CN101680294B - Utilization of low btu gas generated during in situ heating of organic-rich rock - Google Patents
Utilization of low btu gas generated during in situ heating of organic-rich rock Download PDFInfo
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- CN101680294B CN101680294B CN200880017507.0A CN200880017507A CN101680294B CN 101680294 B CN101680294 B CN 101680294B CN 200880017507 A CN200880017507 A CN 200880017507A CN 101680294 B CN101680294 B CN 101680294B
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Classifications
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- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/34—Arrangements for separating materials produced by the well
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
- E21B43/24—Enhanced recovery methods for obtaining hydrocarbons using heat, e.g. steam injection
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
- C10G31/09—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by filtration
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G7/00—Distillation of hydrocarbon oils
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B23/00—Apparatus for displacing, setting, locking, releasing or removing tools, packers or the like in boreholes or wells
- E21B23/04—Apparatus for displacing, setting, locking, releasing or removing tools, packers or the like in boreholes or wells operated by fluid means, e.g. actuated by explosion
- E21B23/0417—Down-hole non-explosive gas generating means, e.g. by chemical reaction
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B41/00—Equipment or details not covered by groups E21B15/00 - E21B40/00
- E21B41/005—Waste disposal systems
- E21B41/0057—Disposal of a fluid by injection into a subterranean formation
- E21B41/0064—Carbon dioxide sequestration
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
- F01K23/00—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids
- F01K23/02—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled
- F01K23/06—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled combustion heat from one cycle heating the fluid in another cycle
- F01K23/067—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled combustion heat from one cycle heating the fluid in another cycle the combustion heat coming from a gasification or pyrolysis process, e.g. coal gasification
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
- F01K23/00—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids
- F01K23/02—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled
- F01K23/06—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled combustion heat from one cycle heating the fluid in another cycle
- F01K23/10—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled combustion heat from one cycle heating the fluid in another cycle with exhaust fluid of one cycle heating the fluid in another cycle
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
- F01K23/00—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids
- F01K23/02—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled
- F01K23/06—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled combustion heat from one cycle heating the fluid in another cycle
- F01K23/10—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled combustion heat from one cycle heating the fluid in another cycle with exhaust fluid of one cycle heating the fluid in another cycle
- F01K23/103—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled combustion heat from one cycle heating the fluid in another cycle with exhaust fluid of one cycle heating the fluid in another cycle with afterburner in exhaust boiler
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/16—Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/16—Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
- Y02E20/18—Integrated gasification combined cycle [IGCC], e.g. combined with carbon capture and storage [CCS]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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- Engineering & Computer Science (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Mining & Mineral Resources (AREA)
- Geology (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Fluid Mechanics (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method for utilizing gas produced from an in situ conversion process is provided. The method may include heating an organic-rich rock formation, for example an oil shale formation, in situ. The method may further include producing a production fluid from the organic-rich rock formation where the production fluid having been at least partially generated as a result of pyrolysis of formation hydrocarbons, for example oil shale, located in the organic-rich rock formation. The method may include obtaining a gas stream from the production fluid, where the gas stream comprises combustible hydrocarbon fluids. The method may include separating the gas stream into a first composition gas stream and a second composition gas stream, where the composition of the first composition gas stream is a low BTU gas stream maintained in a substantially constant condition and passing the first composition gas stream through a first gas turbine to form a first gas turbine exhaust stream, where the first gas turbine being configured to provide energy to a first electrical generator.
Description
The cross reference of related application
The application requires the rights and interests in the U.S. Provisional Patent Application series number 60/931,820 of submission on May 25th, 2007.The name of this application is called " Utilization of Low BTU Gas Generated DuringIn Situ Heating of Organic-Rich Rock (application that the low BTU gas producing during organic matter rock is rich in heating in position) ", and it is incorporated to herein with its full content by reference.
This application with jointly unsettled, simultaneously submit to and U.S. Patent application [lawyer's case 2007EM146] that the common name of transferring the possession of is called " A Process forProducing Hydrocarbon Fluids Combining In Situ Heating; a Power Plant and a GasPlant " relevant, this U.S. Patent application requires the U.S. Provisional Patent Application series number 60/931 of submitting on May 25th, 2007,940 rights and interests, are incorporated to their disclosure herein with its full content accordingly by reference.
Background of invention
Technical field
The present invention relates to reclaim from subsurface formations the field of hydrocarbon.More specifically, the present invention relates to reclaim hydrocarbon fluid from being rich in organic matter rock stratum original position, described rock stratum comprises for example oil shale formation, coal stratum and tar sand formation.
Background technology
Known some geo-logical terrain comprises the organic matter that is called as " kerogen (kerogen) ".Kerogen is solid carbonaceous substance.When kerogen is embedded in rock stratum, this mixture is called as oil shale.The fact is that it is all the rock forming from leck no matter in fact this mineral matter is shale technically.
Kerogen is exposed to hot a period of time by going through decomposition.After heating, kerogen decomposes to produce oil, gas and carbon containing coke on molecular level.Can also produce a small amount of water.Oil, G&W fluid can flow in this rock matrix, and the maintenance of carbon containing coke is substantially motionless.
Each area worldwide comprises that the U.S. has all found oil shale formation.Oil shale formation is often positioned at the relatively shallow degree of depth.In the U.S., oil shale the most significantly in the Wyoming State, the state of Colorado and the Utah State find.These stratum are common is characterised in that limited permeability.Some think that oil shale formation is such hydrocarbon deposit, and it does not also experience and think to form required heat for many years and the pressure of conventional oily gentle reserves.
Kerogen decomposition produces the rate dependent of the hydrocarbon that flows in temperature.During many years, the general temperature that surpasses 270 ℃ (518 °F) may be essential for substance transforms.At higher temperature, substantive conversion can occur within the shorter time.When kerogen is heated, chemical reaction becomes the less gentle molecule of oil by forming the kerogenic larger molecular breakdown of solid.Thermal conversion process is called as pyrolysis or destructive distillation.
From oil shale formation, extracting oil has attempted many years.Near surface oil shale is exploited on earth's surface and destructive distillation century more than one.In 1862, James Young started to process Scotland oil shale.This industry has continued about 100 years.Commercial oil shale retorting of exploiting by earth's surface is also carried out in other country as Australia, Brazil, China, Estonia, France, Russia, South Africa, Spain and Sweden.Yet, because its confirms it is environmental limitations uneconomic or that process due to spent shale, this practice recent years major part stop.(referring to T.F.Yen and G.V.Chilingarian, " Oil Shale, " Amsterdam, Elsevier, p.292, its whole disclosures are incorporated herein by reference.) in addition, earth's surface destructive distillation needs producing oil shale, this is limited to the application to very shallow stratum.
In the U.S., since the 00's of 20th century is early stage, just know that the northwest state of Colorado exists oil shale deposit thing.Although often conduct a research project in this area, also do not carry out real business development.Most of research that oil shale is produced was carried out in the later stage the 00's of 20th century.This research is mainly for shale oil geology, geochemistry and the destructive distillation in the facility of earth's surface.
In nineteen forty-seven, U.S. Patent number 2,732,195 authorize Ljungstrom.This denomination of invention is that the patent of " Method of Treating Oil Shale and Recovery of Oil and Other Mineral ProductsTherefrom (method of processing oil shale and therefrom recovered oil and other mineral products) " proposes at high temperature hot in-place to be applied to oil shale formation with distillation and generation hydrocarbon.Be somebody's turn to do ' 195 Ljungstrom patents incorporated herein by reference.
Ljungstrom has fabricated phrase " heat supply passage (heat supply channels) " to describe the pit shaft getting in stratum.This pit shaft receives and transfers heat to the electrothermal conductor of oil shale around.Therefore, heat supply passage serves as hot Injection Well.Heating in hot Injection Well is placed in sand or cement or other Heat Conduction Material, to allow hot Injection Well to transfer heat in oil shale around, prevents the inflow of fluid simultaneously.According to Ljungstrom, in some applications, should " aggregate (aggregate) " be heated between 500 ℃ and 1,000 ℃.
Together with hot Injection Well, fluid production well is near completion hot Injection Well also.After thermal conductance is entered in rock matrix, kerogen is by pyrolysis, and the oil of generation is gentle is recovered the producing well by contiguous.
Ljungstrom by Swedish Shale Oil Company implemented he from heating pit shaft carry out heat conducting method.The factory of full scale is established, and it moves to the 1950's from nineteen forty-four.(referring to G.Salamonsson, " The Ljungstrom In Situ Method for Shale-Oil Recovery, " 2
ndoilShale and Cannel Coal Conference, v.2, Glasgow, Scotland, Institute of Petroleum, London, p.260-280 (1951), its whole disclosures mode is by reference incorporated to herein).
Other in-situ method is suggested.These methods relate generally to heat and/or solvent to inject subterranean oil shale.Heat can be with the form of methane (referring to the U.S. Patent number 3,241,611 of J.L.Dougan), flue gas or superheated steam (referring to the U.S. Patent number 3,400,762 of D.W.Peacock) of heating.Heat can also be with resistance heated, dielectric heating, radio frequency (RF) heating (U.S. Patent number 4,140,180, it is transferred to the ITT Research Institute that is positioned at Chicago, Illinois) or the form of oxidant injection, to support situ combustion.In some cases, artificial permeation's property forms to contribute to the motion of pyrolyzation fluid in this basement rock.Permeability production method comprises that excavation, rubblization (rubblization), fracturing are (referring to the U.S. Patent number 3 of M.L.Slusser, 468,376 and the U.S. Patent number 3,513,914 of J.V.Vogel), explosive fracturing is (referring to the U.S. Patent number 1 of W.W.Hoover etc., 422,204), hot pressing is split (referring to the U.S. Patent number 3,284,281 of R.W.Thomas) and steam pressure break (referring to the U.S. Patent number 2 of H.Purre, 952,450).
In 1989, U.S. Patent number 4,886,118 authorize Shell Oil Company (Shell Oil Company), and its whole disclosures mode is by reference incorporated to herein.Patent states that the name is "Conductively Heatinga Subterranean Oil Shale to Create Permeability and Subsequently Produce Oil (conductive heating underground oil shale to produce the permeability and the subsequent production of oil)," the "[c] ontrary to theimplications of ... prior teachings and beliefs ... the presently described conductiveheating process is economically feasible for use even in a substantially impermeablesubterranean Oil Shale. (and ... earlier teachings and views imply the opposite ... conductive heating process described in the present even in the essentially impermeable underground oil shale application is economically feasible.) " (the 6th hurdle, 50-54 is capable).Although there is this statement, it should be noted that except the application of Ljungstrom almost do not have and---occur if any---commercial original position shale oil production.Thermal conduction rate in these each hot Injection Wells of ' 118 patents proposition control rock is around to provide uniform heat front.
The other history that oil shale retorting and shale oil reclaim can be called in name " Methods ofTreating a Subterranean Formation to Convert Organic Matter into ProducibleHydrocarbons, (process subsurface formations with organic matter is changed into can extraction hydrocarbon method) " joint patent publication WO 2005/010320 and name be called " Hydrocarbon Recovery from Impermeable oil shale, (from impenetrability oil shale, reclaiming hydrocarbon) " patent publications WO 2005/045192 in find.The background parts of these two pieces of patent publications and technology disclosure are incorporated herein by reference.
To producing the modification method of shale oil, there is demand.In addition, to producing the modification method of the shale oil with improvement characteristic, there is demand.In addition, to using by the thermogenetic low quality gas of add in-place and/or the method that changes in time the gas of quality, there are needs.In addition, to can be from there are needs by the thermogenetic low quality gas of add in-place and/or the method that changes in time the gas generating of quality.
Summary of the invention
In one embodiment, the present invention includes the method for using the gas producing from converted in-situ process.The method comprises that In Situ Heating is rich in organic matter rock stratum and is rich in organic matter formation production Produced Liquid (production fluid) from this, and wherein said Produced Liquid produces as the result that is arranged in the stratum hydrocarbon pyrolysis of being rich in organic matter rock stratum at least partly.Produced Liquid can comprise hydrocarbon fluid.The method can further comprise that wherein air-flow comprises flammable hydrocarbon fluid from Produced Liquid acquisition air-flow.The method can further comprise that this air-flow is divided into the first composition air-flow and second forms air-flow, and wherein the first composition that forms air-flow remains under the condition of substantial constant, and the first composition air-flow has the low heat value below 800BTU/SCF.The method can further comprise makes the first composition air-flow by the first gas-turbine (gas turbine, gas turbine), and to form the first gas-turbine waste stream, wherein the first gas-turbine is configured to provide energy to the first generator.
In one embodiment, the present invention includes the method for using the gas producing from converted in-situ process.The method comprises that In Situ Heating is rich in organic matter rock stratum and is rich in organic matter formation production Produced Liquid from this, and wherein said Produced Liquid produces as the result that is arranged in the stratum hydrocarbon pyrolysis of being rich in organic matter rock stratum at least partly.Produced Liquid can comprise hydrocarbon fluid.The method can comprise that wherein air-flow comprises wobbe index (Wobbe Index) temporal evolution of flammable hydrocarbon fluid and described air-flow from Produced Liquid acquisition air-flow.The method can further comprise that this air-flow is divided into the first composition air-flow and second forms air-flow, and wherein the first wobbe index that forms air-flow is held substantially constant, and the first composition air-flow has the low heat value below 800BTU/SCF.The method can further comprise makes the first composition air-flow by the first gas-turbine, and to form the first gas-turbine waste stream, wherein the first gas-turbine is configured to provide energy to the first generator.
In one embodiment, the present invention includes the method that produces hydrocarbon fluid.The method comprises that In Situ Heating is rich in organic matter rock stratum and is rich in organic matter formation production Produced Liquid from this, and wherein said Produced Liquid produces as the result that is arranged in the stratum hydrocarbon pyrolysis of being rich in organic matter rock stratum at least partly.Produced Liquid can comprise hydrocarbon fluid.The method can further comprise that wherein air-flow comprises flammable hydrocarbon fluid from Produced Liquid acquisition air-flow.The method can further comprise that this air-flow is divided into the first composition air-flow and second forms air-flow, and wherein the first composition that forms air-flow remains under the condition of substantial constant, and the first composition air-flow has the low heat value below 800BTU/SCF.The method can further comprise makes the first composition air-flow by the first gas-turbine, and to form the first gas-turbine waste stream, wherein the first gas-turbine is configured to provide energy to the first generator.
Accompanying drawing explanation
In order to understand better feature of the present invention, at this, enclose some figure, curve map and flow chart.Yet, it should be noted that these figure only illustrate the selected embodiment of the present invention and therefore not will be understood that the scope of having limited, because the present invention can allow embodiment and application that other is equivalent.
Fig. 1 is the cross section isometric view (isomeric view) of illustrative subterranean zone.This subterranean zone comprise limit subsurface formations be rich in organic matter rock matrix.
Fig. 2 means in one embodiment from being rich in the flow chart of the gentle conventional method of organic matter rock stratum original position heat utilization oil.
Fig. 3 is in aquifer or is connected to the illustrative oil shale formation of aquifer and the cross-sectional side view of stratum leaching operation.
Fig. 4 is the plan view in producing well illustrative heated well pattern around.What show is two-layer heated well.
Fig. 5 is a block diagram, and it has compared one ton of GreenRiver oil shale before and after the original position distillation process of simulation.
Fig. 6 is the process chart for the exemplary earth's surface process equipment of subsurface formations exploitation.
Fig. 7 is the percetage by weight figure of each carbon number pseudocomponent of occurring from C6 to C38 for the laboratory experiment carrying out under three different stress levels.
Fig. 8 compares the percetage by weight ratio chart of C20 pseudocomponent for the laboratory experiment carrying out under three different stress levels from each carbon number pseudocomponent of C6 to C38 appearance.
Fig. 9 compares the percetage by weight ratio chart of C25 pseudocomponent for the laboratory experiment carrying out under three different stress levels from each carbon number pseudocomponent of C6 to C38 appearance.
Figure 10 compares the percetage by weight ratio chart of C29 pseudocomponent for the laboratory experiment carrying out under three different stress levels from each carbon number pseudocomponent of C6 to C38 appearance.
Figure 11 is for the laboratory experiment carrying out under three different stress levels and the percetage by weight figure of n-alkane (normal alkane, the normal alkane) compound that the extremely positive C38 of Yan Congzheng (or positive structure) C6 occurs.
Figure 12 is that the n-alkane Compound Phase that occurs from positive C6 to positive C38 for the laboratory experiment carrying out under three different stress levels is than the percetage by weight figure of positive C20 hydrocarbon compound.
Figure 13 is that the n-alkane Compound Phase that occurs from positive C6 to positive C38 for the laboratory experiment carrying out under three different stress levels is than the percetage by weight figure of positive C25 hydrocarbon compound.
Figure 14 is that the n-alkane Compound Phase that occurs from positive C6 to positive C38 for the laboratory experiment carrying out under three different stress levels is than the percetage by weight figure of positive C29 hydrocarbon compound.
Figure 15 is from the n-alkane compound of each carbon number of C6 to C38 and the weight ratio figure of pseudocomponent for the laboratory experiment carrying out under three different stress levels.
Figure 16 is a block diagram, and it is presented at the molar percentage concentration of the hydrocarbon kind existing in the gaseous sample of taking from the repetition laboratory experiment carrying out under three different stress levels.
Figure 17 is the schematic diagram of the golden tube apparatus of use in the unstressed Pa Er heating test (unstressed Parrheating test) of describing in embodiment 1.
Figure 18 is the cross-sectional view of the Pa Er container that uses in embodiment 1-5.
Figure 19 is the gas chromatogram of the gas of taking-up from embodiment 1.
Figure 20 is the complete oily gas chromatogram of the liquid of taking-up from embodiment 1.
Figure 21 is the schematic diagram of the Berea cylinder that uses of embodiment 2-5, Berea plug and oil shale core sample.
Figure 22 is the miniature Load brackets that uses in embodiment 2-5 and the schematic diagram of sample assembly.
Figure 23 is the gas chromatogram of the gas of taking-up from embodiment 2.
Figure 24 is the gas chromatogram of the gas of taking-up from embodiment 3.
Figure 25 is the complete oily gas chromatogram of the liquid of taking-up from embodiment 3.
Figure 26 is the gas chromatogram of the gas of taking-up from embodiment 4.
Figure 27 is the complete oily gas chromatogram of the liquid of taking-up from embodiment 4.
Figure 28 is the gas chromatogram of the gas of taking-up from embodiment 5.
Figure 29 is the process chart that can be used for the exemplary process equipment of some embodiments of the present invention.
Figure 30 is the optional process chart that can be used for the exemplary process equipment of some embodiments of the present invention.
Figure 31 is the optional process chart that can be used for the exemplary process equipment of some embodiments of the present invention.
The curve map of the several species of gasses kind that Figure 32 discharges from the heating of oil shale laboratory, Colorado.Left side y axle is reported in the concentration of 12-hour experiment measurement gas kind that discharge, that represent with mol%, and it comprises CO
2, H
2, methane, ethane and CO.X-axle represents the time, and with hour representing.
Figure 33 is the optional process chart that can be used for the exemplary process equipment of some embodiments of the present invention.
Figure 34 is the optional process chart that can be used for the exemplary process equipment of some embodiments of the present invention.
Figure 35 is the optional process chart that can be used for the exemplary process equipment of some embodiments of the present invention.
Some embodiment describes in detail
Definition
As used herein, term " hydrocarbon (one or more) " refers to the organic matter with the molecular structure that comprises the carbon of being combined with hydrogen.Hydrocarbon also can comprise other element, such as but not limited to halogen, metallic element, nitrogen, oxygen and/or sulphur.
As used herein, term " hydrocarbon fluid " refers to hydrocarbon or the hydrocarbon mixture into gas or liquid.For example, hydrocarbon fluid can be included under formation condition, under processing conditions or at ambient conditions (15 ℃ and 1 atmospheric pressure) lower hydrocarbon or hydrocarbon mixture for gas or liquid.Hydrocarbon fluid can comprise for example thermal decomposition product and other hydrocarbon in gaseous state or liquid state of oil, natural gas, coal bed methane, shale oil, pyrolysis oil, pyrolysis gas, coal.
As used herein, term " Produced Liquid (produced fluids) " and " production fluid (productionfluids) " refer to and from comprising, are for example rich in liquid and/or the gas that the subsurface formations of organic matter rock stratum shifts out.Produced Liquid can comprise hydrocarbon fluid and non-hydrocarbon fluids.Produced Liquid can include but not limited to thermal decomposition product, carbon dioxide, hydrogen sulfide and the water (comprising steam) of pyrolysis shale oil, synthesis gas, coal.Produced Liquid can comprise hydrocarbon fluid and non-hydrocarbon fluids.
As used herein, term " condensable hydrocarbons " refers to those hydrocarbon of condensation under 25 ℃ and an atmosphere absolute pressure.Condensable hydrocarbons can comprise that carbon number is greater than the mixture of 4 hydrocarbon.
As used herein, term " non-condensing hydrocarbon " refers to uncondensable those hydrocarbon under 25 ℃ and an atmosphere absolute pressure.Non-condensing hydrocarbon can comprise the hydrocarbon that carbon number is less than 5.
As used herein, term " heavy hydrocarbon (heavy hydrocarbons) " refers to the hydrocarbon fluid in the lower high viscosity of ambient conditions (15 ℃ and 1 atmospheric pressure).Heavy hydrocarbon can comprise high viscosity hydrocarbon fluid, such as heavy oil, tar and/or pitch.Heavy hydrocarbon can comprise carbon and hydrogen and compared with the sulphur of small concentration, oxygen and nitrogen.Other element also can be present in heavy hydrocarbon by trace.Heavy hydrocarbon can be classified according to API (American Petroleum Institute (API)) proportion.The api gravity of heavy hydrocarbon is generally below approximately 20 degree.For example, the api gravity of heavy oil is generally about 10-20 degree, and the api gravity of tar is generally below approximately 10 degree.The viscosity of heavy hydrocarbon is generally greater than approximately 100 centipoises at 15 ℃.
As used herein, term " hydrocarbon solid " refers under formation condition any hydrocarbon materials with the natural discovery of basic solid form.Limiting examples comprises kerogen, coal, shungite, natural rock asphalt and ozocerite.
As used herein, term " stratum hydrocarbon (rock stratum hydrocarbon) " refers to the heavy hydrocarbon and the hydrocarbon solid that in being rich in organic matter rock stratum, comprise.Stratum hydrocarbon can be but be not limited to kerogen, oil shale, coal, pitch, tar, ozocerite and natural rock asphalt.
As used herein, term " tar " refers to that at 15 ℃ viscosity is generally greater than the viscous hydrocarbon of approximately 10,000 centipoises.The proportion of tar is generally greater than 1.000.The api gravity of tar can be less than 10 degree.
As used herein, term " kerogen " refers to the insoluble hydrocarbon of solid that mainly contains carbon, hydrogen, nitrogen, oxygen and sulphur.Oil shale contains kerogen.
As used herein, term " pitch " refers to amorphous solid or the viscous hydrocarbon material that can fully dissolve in carbon disulfide.
As used herein, term " oil " refers to the hydrocarbon fluid that contains condensable hydrocarbons mixture.
As used herein, term " underground (subsurface) " refers to the geo-logical terrain appearing at below earth surface.
As used herein, term " rich hydrocarbon containing formation " refers to any stratum of containing the above hydrocarbon of trace.For example, rich hydrocarbon containing formation can comprise being greater than the part that the level of 5 percentage by volumes contains hydrocarbon.The hydrocarbon that is arranged in rich hydrocarbon containing formation can comprise for example oil, natural gas, heavy hydrocarbon and hydrocarbon solid.
As used herein, term " is rich in organic matter rock " and refers to any rock matrix that has hydrocarbon solid and/or heavy hydrocarbon.Rock matrix can include but not limited to sedimentary rock, shale, siltstone, sand, silicilyte, carbonate and kieselguhr.
As used herein, term " stratum " refers to any limited subterranean zone.This stratum can comprise one or more layers that contain hydrocarbon on any subsurface geology stratum, layer, overlying rock and/or the underlying stratum of one or more not hydrocarbonaceous." overlying rock " and/or " underlying stratum " is ground metallic substance above formation at target locations or below.Overlying rock or underlying stratum can comprise one or more dissimilar materials of impenetrability substantially.For example, overlying rock and/or underlying stratum can comprise rock, shale, mud stone or wet/tight carbonate (not the impermeable acid carbonate of hydrocarbonaceous).Overlying rock and/or underlying stratum can comprise relatively impermeable hydrocarbon bearing formation.In some cases, overlying rock and/or underlying stratum can be infiltrative.
As used herein, term " is rich in organic matter rock stratum " and refers to any stratum of being rich in organic matter rock of containing.Be rich in organic matter rock stratum and comprise, for example, oil shale formation, coal stratum and tar sand formation.
As used herein, term " pyrolysis " refers to by applying heat by chemical bond rupture.For example, pyrolysis only can comprise by heat or by heat and is combined with oxidant and converts compound to one or more other material.Pyrolysis can comprise that described hydrogen atom can obtain from molecular hydrogen, water, carbon dioxide or carbon monoxide by adding hydrogen atom that the character of compound is changed.Heat can be transferred to a part of stratum to cause pyrolysis.
As used herein, term " water-soluble mineral " refers to soluble mineral in water.Water-soluble mineral comprise, for example, and nahcolite (sodium acid carbonate), sode ash (sodium carbonate), dawsonite (NaAl (CO
3) (OH)
2) or its combination.A large amount of dissolvings can need hot water and/or non-neutral pH solution.
As used herein, term " formation water dissolubility mineral " refers to the water-soluble mineral of natural discovery in stratum.
As used herein, term " migration stain species (migratory contaminant species) " refers to solvable in water or aqueous fluid or kind movably, and is considered to human health or environment have potential hazard or have a stake.Migration stain species can comprise inorganic and organic pollution.Organic pollution can comprise saturated hydrocarbons, aromatic hydrocarbons and oxygen-containing hydrocarbon.Inorganic pollution can comprise various types of metal pollutants and ionic contamination, and it can significantly change pH or formation fluid chemistry.Aromatic hydrocarbons can comprise, for example, and benzene,toluene,xylene, ethylbenzene and trimethylbenzene, and various types of polyaromatic such as anthracene, naphthalene,
and pyrene.Oxygen-containing hydrocarbon can comprise, for example alcohol, ketone, phenol and organic acid are as carboxylic acid.Metal pollutant can comprise, for example, and arsenic, boron, chromium, cobalt, molybdenum, mercury, selenium, lead, vanadium, nickel or zinc.Ionic contamination comprises, for example, and sulfide, sulfate, chloride, fluoride, ammonia, nitrate, Determination, lithium, boron and strontium.
As used herein, term " cracking (cracking) " refers to such process, and it includes the decomposition of organic compounds and molecular recombination to produce number than the larger molecule existing at first.In cracking, series reaction is accompanied by hydrogen atom and occurs in intermolecular transfer.For example, naphtha can experience heat cracking reaction to form ethene and H
2and other molecule.
As used herein, term " cut deposit (sequestration) " refers to that storage is the fluid of process byproducts, rather than by this fluid drainage in atmosphere or open environment.
As used herein, term " sinking " refers to that earth's surface moves down with respect to the original height above sea level on this earth's surface.
As used herein, " thickness " of term layer refers to the distance between the up-and-down boundary of layer cross section, and wherein this distance is vertically to measure with the common inclined-plane of this cross section.
As used herein, term " (thermal fracture) split in hot pressing " refers to the pressure break producing in stratum, described pressure break is directly or indirectly to cause by the expansion of a part of stratum and/or stratum inner fluid or contraction, and this expansion or contraction are again because heating is by increasing/reduce the temperature of this stratum and/or this stratum inner fluid and/or causing by increasing/reduce the pressure of this stratum inner fluid.Hot pressing is split can propagate into than the cold a lot of near zone of heating region or at this near zone and is formed.
As used herein, term " fracturing (hydraulic fracture) " refers to the pressure break propagating at least partly in stratum, and wherein said pressure break is by being expelled to pressure fluid in stratum and producing.This pressure break can keep open by injecting proppant material artificially.Fracturing can be in direction basic horizontal, basic vertical or directed along any other plane in direction.
As used herein, term " pit shaft " refers to underground by holing or pipeline being inserted into underground made hole.Pit shaft can have substantially circular cross section, or other shape of cross section (for example circle, ellipse, square, rectangle, triangle, crack or Else Rule or irregularly shaped).As used herein, during perforate in mentioning stratum, term " well " can be used with term " pit shaft " exchange.
The description of the specific embodiment
The present invention is described herein together with some specific embodiment.Yet just detailed description is below specific to the degree of specific implementations or application-specific, this intention is illustrative and should not be construed as limiting the scope of the invention.
As discussed herein, some embodiments of the present invention comprise or have an application relevant to the in-situ method that reclaims natural resource.Natural resource can comprise that for example oil shale formation reclaims from being rich in organic matter rock stratum.Be rich in organic matter rock stratum and can comprise stratum hydrocarbon, it comprises for example kerogen, coal and heavy hydrocarbon.In some embodiments of the present invention, natural resource can comprise hydrocarbon fluid, and it comprises, for example, and the thermal decomposition product of stratum hydrocarbon such as shale oil.In some embodiments of the present invention, natural resource also can comprise water-soluble mineral, and it comprises, for example, and nahcolite (sodium acid carbonate or 2NaHCO
3), sode ash (sodium carbonate or Na
2cO
3) and dawsonite (NaAl (CO
3) (OH)
2).
Fig. 1 has presented the phantom drawing of illustrative oil shale developing zone 10.The earth's surface 12 of developing zone 10 is shown.Below earth's surface, be to be rich in organic matter rock stratum 16.Illustrative subsurface formations 16 comprise stratum hydrocarbon (for example, such as, kerogen) and may valuable water-soluble mineral (for example, such as, nahcolite).Should be appreciated that representative stratum 16 can be to be rich in arbitrarily organic matter rock stratum, for example, it comprises the rock matrix that contains coal or Tar sands.In addition, the rock matrix on formation stratum 16 can be infiltrative, semi-permeable or impermeability.The present invention has at first very limited or without the oil shale developing zone of fluid permeability, is being in fact particularly advantageous.
In order to enter stratum 16 and therefrom to reclaim natural resource, a plurality of pit shafts have been formed.Pit shaft in Fig. 1 with 14 demonstrations.Representative pit shaft 14 is with respect to earth's surface 12 perpendicular in direction.Yet, should be appreciated that some or all pit shafts 14 can depart from into obtuse angle or the direction of level even.In the arrangement of Fig. 1, each pit shaft 14 completes in oil shale formation 16.Completion can be open hole well or cased hole.Well completes also can comprise support or the unsupported fracturing of therefrom dispersing.
In the view of Fig. 1, only have seven pit shafts 14 shown.Yet, should be appreciated that in oil shale exploration project, many additional pit shafts 14 will most possibly be got out.Pit shaft 14 can be positioned on relatively near vicinity, and it separates 10 feet to as high as 300 feet.In some embodiments, provide the well interval of 15 to 25 feet.Typically, pit shaft 14 can also complete at shallow depth, and its total depth is 200 to 5,000 feet.In some embodiments, take oil shale formation that original position destructive distillation is target more than 200 feet depths or 400 feet of places under earth's surface alternatively under earth's surface.Alternatively, conversion and production occur in the depth between 500 and 2,500 feet.
For the water-soluble mineral of recovered oil, gas and sodium (or other), can take series of steps.Fig. 2 has presented in one embodiment from being rich in the flow chart of the gentle method of organic matter rock stratum 100 original position heat utilization oil.The order that should be appreciated that some steps in Fig. 2 can change, and this step order is only for explanation.
First, 10 interior discriminating oil shale (or other is rich in organic matter rock) stratum 16 in developing zone.This step is presented in square frame 110.Optionally, oil shale formation can comprise nahcolite or other sodium mineral.Target developing region in oil shale formation can be by measuring or the degree of depth, thickness and the organic matter richness of simulated oil shale and evaluation are rich in organic matter rock stratum and for example, are differentiated with respect to position, architectural feature (tomography, anticlinal strata or swally) or the geohydrologic unit (being aquifer) of other rock type.This is by the figure from effective test and data foundation and interpreted depth, thickness, organic matter richness and other data and/or model realization.This can comprise that carrying out geology surface exploration, research appears, carries out seismic survey and/or drilling well cylinder to obtain core sample from subsurface rock.The ability that rock sample can be analyzed to evaluate kerogen content and produce fluid hydrocarbon.
The kerogen content that is rich in organic matter rock stratum can utilize various data from appear or core sample determine.Such data can comprise the Fischer analysis of experiments of organic carbon content, hydrogen index and correction.Subsurface wastewater infiltration system can also be by rock sample, appear or the research of underflow, assesses.In addition can evaluate the connectedness of developing zone and underground water source.
Secondly, a plurality of pit shafts 14 form across target developing district 10.This step is schematically presented in square frame 115.The object of pit shaft 14 is illustrated in the above and needn't be repeated.Yet, it should be noted that the object that forms step for square frame 115 pit shafts, initial only some well need to complete.For example, when project starts, hot Injection Well needs, and most of hydrocarbon producing well does not also need.For example, once producing well can be introduced after conversion starts, after heating 4-12 is individual month.
Should be appreciated that Petroleum Engineer will work out the scheme of pit shaft 14 optimum depth and arrangement, this depends on expection reservoir characteristics, economic restriction factor and work scheduling constraint.In addition, engineering staff will determine which kind of pit shaft 14 should be for 16 heating of initial stratum.This selection step is described by square frame 120.
About hot Injection Well, there is the multiple method that is rich in organic matter rock stratum 16 that heat is applied to.Unless explicit state in claims, this method is not limited to applied heating technique.Heating steps is generally described by square frame 130.Preferably, for in-situ process, the heating of production area occurs several months or even 4 years or years more.Stratum 16 is heated to is enough to pyrolysis at least a portion oil shale to cheese root is changed into the temperature of hydrocarbon fluid.The major part of target area, stratum can be heated between 270 ℃ to 800 ℃.Alternatively, the target volume that is rich in organic matter stratum is heated at least 350 ℃ to form Produced Liquid.Switch process is described in Fig. 2 by square frame 135.Formed liquid and the hydrocarbon gas can be refined into the product of similar common commercial oil product.Such fluid product comprises transport fuel such as diesel engine, jet fuel and naphtha.The gas producing comprises light alkane, light olefin, H
2, CO
2, CO and NH
3.
The conversion of oil shale will produce permeability in the oil shale location in impermeable rock originally.Preferably, square frame 130 and 135 heating and conversion process occur in long time durations.On the one hand, between the period of heating, be 3 months to 4 years or more for many years.Also have the optional part as square frame 135, stratum 16 can be heated to the temperature that is enough at least a portion nahcolite to be converted into sode ash, if there is nahcolite.Gentle the applied heat of slaking oil shale and recovered oil also can change into nahcolite sodium carbonate (sode ash)---a kind of relevant sodium mineral.The method that nahcolite (sodium acid carbonate) is changed into sode ash (sodium carbonate) is described in this article.
Relevant with heating steps 130, rock stratum 16 can be optionally by pressure break to contribute to conduct heat or hydrocarbon fluid extraction subsequently.Optional pressure break step is presented in square frame 125.Pressure break can produce hot pressing and splits and realize by applying heat in stratum.It is gentle by heating, to be rich in organic matter rock and to be converted kerogen to oil, and the extraction of the formation that the permeability on part stratum is split by hot pressing and the hydrocarbon fluid that produces from kerogen with rear portion increases.Alternatively, can use the technique that is called as fracturing.Fracturing is known technique in the gentle recovery of oil field, and fracturing fluid pressurized frac pressure that surpasses stratum in pit shaft wherein produces fracture planes thus with by the earth pressure release producing in pit shaft in stratum.Fracturing can be used in part stratum, produce additional permeability and/or be used to provide plane heating source.
As the part of production of hydrocarbon fluids technique 100, some well 14 can be designated as oil and gas production well.This step is described by square frame 140.Until determine that kerogen, by fully destructive distillation is gentle with permission peak discharge recovered oil from stratum 16, just can start oily gentle production.In some cases, special-purpose producing well until hot Injection Well (square frame 130) moved after several weeks or several months just by drilling well.Therefore, square frame 140 can comprise the formation of additional pit shaft 14.In other example, selected heated well is transformed into producing well.
Some pit shaft 14 designated as oil and gas production well after, oil and/or gas are plucked out of from pit shaft 14.Oil and/or gas extraction technique are displayed in square frame 145.At this stage (square frame 145), crystal or agglomerate that the sode ash of any water-soluble mineral such as nahcolite and conversion can be used as fine dispersion in oil shale bed keep being substantially limited in rock stratum 16, and are not plucked out of.Yet some nahcolites and/or sode ash can be dissolved in the water producing during thermal transition in stratum (square frame 135).
Secondly, optionally, water or aqueous fluid are injected into and enter oil shale formation 16 by water Injection Well.Changing step is presented in square frame 155.Water can be in steam or pressurized hot water form.Alternatively, injected water can be cold and along with it contacts pre-heated stratum and heating.Injection technology can further cause pressure break.This technique can produce finger-like hole and dust region injecting the interval with nahcolite of some distances of pit shaft outside for example up to 200 feet apart from water.On the one hand, pneumatic jack, such as nitrogen, can be maintained at each " hole " top to prevent vertical-growth.
Along with some pit shaft 14 is designated as water Injection Well, design engineer can also be appointed as some pit shaft 14 water or water-soluble mineral solution producing well.This step is presented in square frame 160.These wells can be with identical for previously producing hydrocarbon or injecting hot well.These recovery wells can be used to produce the water-soluble mineral that dissolve and comprise for example aqueous solution of other kind of migration stain species.For example, this solution can be mainly the solution of the sode ash of dissolving.This step is presented in square frame 165.Alternatively, single pit shaft can be used to injected water and then reclaim sodium mineral solution.Therefore, square frame 165 comprises that the same pit shaft 14 of use injects for water and the selection (square frame 165) of solution production.
The interim migration of controlling migration stain species, especially during pyrolytic process, can inject with producing well 14 so that the fluid stream of outflow heating region minimizes obtains by layouts.Typically, this relates to Injection Well is placed in to heating region around to cause barometric gradient, and this barometric gradient prevents that the fluid stream of heating region inside from leaving this region.
Fig. 3 is in aquifer or is connected to the illustrative oil shale formation of aquifer and the cross-sectional view of stratum leaching operation.Four oil shale formation regions that separate (23,24,25 and 26) are depicted in oil shale formation.Aquifer, below ground surface 27, and is divided into aquifer, 20He bottom, aquifer, top 22.In the middle of aquifer, upper and lower, it is aquitard 21.Can find out, some region on stratum is aquifer or aquitard and oil shale region.A plurality of wells (28,29,30 and 31) are shown to be crossed by aquifer vertically downward.In these wells, one is as water Injection Well 31, and another one is served as water producing well 30.By this way, water circulates 32 by least lower aquifer 22.
Fig. 3 diagram has shown the water circulation 32 through heated oil shale volume 33, and described oil shale volume is positioned at aquifer 22 or is connected with aquifer 22, and hydrocarbon fluid previously reclaimed from oil shale volume 33.By water Injection Well 31, water is injected and impels water to enter pre-heated oil shale 33, thereby water-soluble mineral and migration stain species are flushed to water producing well 30.Then water can be processed in equipment 34, and wherein water-soluble mineral (for example nahcolite or sode ash) and migration stain thing can be removed substantially from current.Then water be then injected in oil shale volume 33, and repeat stratum leaching.Leaching that this water carries out intention continue until in the level of pre-heated oil shale region 33 interior migration pollutant kinds in environmentally acceptable level.This may need 1 circulation, 2 circulations, 5 circulations, 10 circulations or the leaching of more multicycle stratum, the wherein water of single cyclic representation injection and the about pore volume of extraction.Should be appreciated that in actual oil shale exploitation to have much water to inject and water producing well.In addition, this system can comprise can be used in oil shale heating period, shale oil production phase, leaching stage or the monitoring well (28 and 29) during these stage any combination, so that monitoring migration stain species and/or water-soluble mineral.
For each feature and the method for shale oil exploitation are described in detail in detail, some cross section is specifically named below.
At some Zhong， stratum, oil field hydrocarbon, such as oil shale, may reside in more than one subsurface formations.In some cases, being rich in organic matter rock stratum can be by the rock stratum of hydrocarbonaceous not or the rock stratum in addition seldom or do not have with commercial value separately.Therefore, the operator for oil field in hydrocarbon exploitation, can expect to analyze which underground organic matter rock stratum of being rich in should sequentially be developed with what as target or they.
Being rich in organic matter rock stratum can select to develop based on different factors.Such factor is the thickness of hydrocarbon bearing formation in stratum.Larger payzone thickness can show the production of hydrocarbon fluids of larger potential volume.Each hydrocarbon bearing formation can have such thickness, and described thickness depends on the condition that for example should form containing stratum hydrocarbon layer and changes.Therefore, if be rich in organic matter rock stratum comprise at least one thickness be enough to economical production Produced Liquid containing stratum hydrocarbon layer, this stratum will generally be selected and process so.
If the tight spacing thickness of several layers is together enough to carry out the economical production of Produced Liquid, is rich in so organic matter rock stratum and also can be selected.For example, the converted in-situ process of stratum hydrocarbon can comprise select and process thickness be greater than approximately 5 meters, 10 meters, 50 meters or even 100 meters be rich in the layer in organic matter rock stratum.By this way, above being rich in organic matter rock stratum and below form layer heat waste (as the hot part of total injection) can be less than this heat waste from skim stratum hydrocarbon.Yet process described herein also can comprise selects and process such layer, it can comprise layer or the stratum hydrocarbon thin layer that is substantially free of stratum hydrocarbon.
One or more richness that are rich in organic matter rock stratum also can be considered.Richness can be depending on factors, comprises the composition containing stratum hydrocarbon in the amount of stratum hydrocarbon in the formation condition of stratum hydrocarbon layer, this layer and/or this layer.Thin and abundant stratum hydrocarbon layer can produce than the obvious how valuable hydrocarbon of thicker, not too abundant stratum hydrocarbon layer.Certainly, from not only thick but also abundant stratum, producing hydrocarbon expects.
The kerogen content that is rich in organic matter rock stratum can be used various data from appearing or core sample is determined.Such data can comprise the Fischer analysis of experiments of organic carbon content, hydrogeneous index and correction.Fischer test is such standard method, and it relates in one hour the sample containing stratum hydrocarbon layer is heated to approximately 500 ℃, collects the fluid producing from heated sample, and the amount that quantizes the fluid of institute's output.
Subsurface formations permeability also can be by rock sample, appear or the research of underflow is assessed.In addition, the connectedness of developing zone and underground water source can be assessed.Therefore, being rich in organic matter rock stratum can permeability or degree of porosity based on formation matrix select to develop, even the thickness relative thin on stratum.
The known other factors of Petroleum Engineer can be considered when selecting exploitation stratum.Such factor comprises the degree of depth of the payzone of discovery, fresh underground water and contains the stratigraphy proximity in kerogen region, continuity and the other factors of thickness.For example, in stratum, evaluated fluid production content is also produced the last volume life of impact.
From the figure hydrocarbon fluid of oil shale oil field, migration that can desired control pyrolyzation fluid.In some cases, this comprises the use of Injection Well, especially in this oil field around.Such well can injected water, steam, CO
2, heating methane or other fluid, to order about the kerogen fluid of cracking, inwardly enter producing well.In some embodiments, physical baffle can be placed on around the region of being rich in organic matter rock stratum of exploitation.An example of physical baffle relates to the generation of freeze wall.Freeze wall forms greatly to reduce the temperature of rock stratum by the well circulating refrigerant through periphery.This kerogen pyrolysis and oil that has prevented that again oil field periphery from existing is gentle to external migration.Freeze wall electricity will cause natural water in the stratum of periphery to freeze.
By underground, freezingly for the poor soil of stabilization and reinforcement or to fluid, flow and to provide baffle plate to be well known in the art.Shell Exploration and Production Company (shell exploration and production company) has discussed application freeze wall and has produced for oil shale in several patents, comprises U.S. Patent number 6,880, and 633 and U.S. Patent number 7,032,660.Shell ' 660 patents are used underground freezing to prevent original position shale oil production period Groundwater Flow and groundwater pollution.The other patent that discloses the application of so-called freeze wall is U.S. Patent number 3,528,252, U.S. Patent number 3,943,722, U.S. Patent number 3,729,965, U.S. Patent number 4,358,222, U.S. Patent number 4,607,488 and the WO patent No. 98996480.
Another example that can be used for the physical baffle in limit fluid inflow or effluent oil shale oil field is to form grouting wall.Grouting wall forms to be full of permeability passage by cement being injected to stratum.In the environment in oil shale oil field, cement is injected into the periphery along oil field.This prevents that the fluid of pyrolysis from moving to develop oil fields outside and water and moving to oil field from contiguous aquifer.
As implied above, several dissimilar wells can be used to be rich in the exploitation of organic matter rock stratum, comprise for example oil shale oil field.For example, being rich in the heating of organic matter rock stratum can be by using heated well complete.Heated well can comprise, for example, and stratie.The completion that the production of hydrocarbon fluid from stratum can be used for fluid production by use realizes.The injection of aqueous fluid can be by being used Injection Well to realize.Finally, the production of aqueous solution can be by being used solution producing well to realize.
Different wells listed above can be for more than one object.Changing a kind of saying is exactly, and the well initially completing for a kind of object can be used for another object afterwards, reduces thus project cost and/or reduces and carry out the time that some required by task is wanted.For example, one or more producing wells also can be used as subsequently water being injected to the Injection Well that is rich in organic matter rock stratum.Alternatively, one or more producing wells also can be used as subsequently from being rich in the solution producing well of organic matter formation production aqueous solution.
In other side, producing well (and in some cases heated well) can be used as dewatering well (for example, before heating starts and/or when heating is activated at first) at first.In addition, in some cases, dewatering well can be used as producing well (and in some cases as heated well) subsequently.Therefore, dewatering well can be placed and/or design so that this well can be used as producing well and/or heated well subsequently.Heated well can be placed and/or design so that this well can be used as producing well and/or dewatering well subsequently.Producing well can be placed and/or design so that this well can be used as dewatering well and/or heated well subsequently.Similarly, Injection Well can be the well that is used as at first other object (such as heating, production, dehydration, monitoring etc.), and Injection Well can be used to other object subsequently.Similarly, monitoring well can be to be used as at first the well of other object (such as heating, production, dehydration, injection etc.).Finally, monitoring well can be used to other object, for example aquatic product subsequently.
The pit shaft of different wells can relatively closely be located, and separates 10 feet to as high as 300 feet.Alternatively, pit shaft can interval 30 to 200 feet or 50 to 100 feet.Typically, pit shaft also completes at shallow depth, 200 to 5,000 feet of total depths.Alternatively, pit shaft can complete at the depth of from 1,000 to 4,000 foot or 1,500 to 3,500 foot.In some embodiments, target be the oil shale formation of original position destructive distillation in earth's surface lower more than 200 feet depth.In optional embodiment, target is oil shale formation 500,1,000 or 1,500 feet of above depths under earth's surface of original position destructive distillation.In optional embodiment, target is oil shale formation depth between 200 and 5,000 feet under earth's surface of original position destructive distillation, alternatively between 1,000 and 4,000 foot, between 1,200 and 3,700 foot or between 1,500 and 3,500 foot.
Expectation be to take preplanned hole pattern to arrange different wells as oil shale oil field.For example, heated well can, with various hole pattern arrangements, include but not limited to triangle, square, hexagon and other polygon.This hole pattern can comprise that regular polygon is to promote that heating is through at least part of stratum of having placed heated well uniformly.This hole pattern can also be that ranks drive well pattern.Ranks drive well pattern and generally comprise the first heated well linear array, the second heated well linear array, and the producing well between the first and second heated well linear arraies or producing well linear array.The one or more producing wells typically that scatter between heated well.Injection Well can be disposed in the unit of repeated hole pattern equally, and it can be similar to or be different from heated well hole pattern used.
A method that reduces well number is to use single well, not only as heated well but also as producing well.By reducing project cost with the number that single well reduces well for continuous object.One or more monitoring wells can be disposed on the position of selecting in oil field.Monitoring well can be configured with the device of temperature, pressure and/or fluid behaviour in one or more measurement pit shafts.In some cases, heated well can also conduct be monitored well, or uses in addition instrument and equipment.
The other method that reduces heated well number is to adopt well pattern.Can use the regular well pattern with the heated well of producing well equidistant intervals.This well pattern can form triangular arranged, hexagonal array or other arrangement well pattern.The arrangement of heated well can be placed like this, makes the distance between each heated well be less than approximately 70 feet (21 meters).Part stratum can be heated with heated well, and described heated well is placed abreast with the border on hydrocarbon stratum substantially.
In optional embodiment, the arrangement of heated well can be placed like this, makes the distance between each heated well can be less than approximately 100 feet or 50 feet or 30 feet.Regardless of the arrangement of heated well or between distance, in some embodiments, heated well and the ratio between producing well of in being rich in organic matter rock stratum, placing can be greater than approximately 5,8,10,20 or more.
In one embodiment, single producing well by one deck heated well at the most around.This can comprise arranges such as 5 points, 7 or 9 lattice arrays, and wherein production and heated well are embarked on journey alternately.In another embodiment, two-layer heated well can be around producing well, and still wherein heated well is stagger arrangement, to exist Wheelchair Accessible to flow for the major part of the heated well away from other.Can apply passage and the temperature history of hydrocarbon fluid mobile and that reservoir simulation produces with assessment original position when they move to producing well from its original place.
The plan view that the heated well of the above heated well of use one deck of furnishing an example property of Fig. 4 is arranged.The use that this heated well is arranged is with from shale oil development zone, 400 production hydrocarbon phases close.In Fig. 4, heated well arrange to be used first floor heated well 410, its by second layer heated well 420 around.Heated well in first floor 410 is mentioned with 431, and heated well in first floor 420 is cited with 432.
Producing well 440 is displayed on well layer 410 and 420 central authorities.It should be noted that with respect to producing well 440, the heated well 432 in the well second layer 420 is offset to some extent with the heated well 431 in well first floor 410.Object is that the hydrocarbon for transforming provides such flow channel, and it minimizes near the stroke heated well in heated well first floor 410.This makes again when hydrocarbon flow to producing well 440 from second layer well 420 secondary cracking of the hydrocarbon that transforms from kerogen minimize.
In the illustrative arrangement of Fig. 4, each limits 5 well spacing first floor 410 and the second layer 420.Yet, be to be understood that and can use other well spacing, such as 3 or 6 well spacing.In any situation, comprise that a plurality of heated wells 431 of heated well first floor 410 are placed in around producing well 440, comprising the heated well second layer 420 around more than second interior heated well 432 is placed in first floor 410.
Heated well in two-layer also can be arranged like this, makes the most of hydrocarbon producing in each heated well 432 from the second layer 420 by heating can move to producing well 440, and substantially not by near the heated well 431 in first floor 410.Heated well 431,432 in two-layer 410,420 further can be arranged like this, makes the most of hydrocarbon producing in each heated well 432 from the second layer 420 by heating can move to producing well 440, and not by substantially increasing the region of formation temperature.
A kind of method that reduces heated well number is to adopt well pattern, and described well pattern is extended on specific direction, especially in the direction of effective thermal conductivity, extends.Thermal convection current can be affected by different factors, such as the stress in aspect and stratum.For example, thermal convection current can be more effective with the direction that on stratum, minimum level main stress bar is vertical.In some cases, thermal convection current can be more effective in the direction parallel with minimum level main stress bar.
Relevant to the exploitation in oil shale oil field, can expect, according to step 130 and 135 heat, by underground advancing, be uniform.Yet due to many reasons, although heated well and producing well regulation arrangement, in subsurface formations, the heating of stratum hydrocarbon and slaking can not evenly be carried out.The inhomogeneities of oil shale characteristic and earth formation can be so that some regional area be more voluminous or still less produce.And, because the formation breakdown that oil shale heats and slaking occurs may cause preferred passage uneven distribution, and increased thus flowing and having reduced flowing to other producing well to some producing well.Inhomogeneous fluid slaking may be less desirable condition, and because some subterranean zone may receive than required more heat energy, other region than expectation still less.This causes again inhomogeneous the flowing and reclaim of Produced Liquid.Extraction oil quality, total throughput rate and/or final recovery may reduce.
In order to detect inhomogeneous flox condition, production and heated well can be mounted sensor.Sensor can comprise the equipment of measuring temperature, pressure, flow velocity and/or forming information.From the data of these sensors simply rule process or be transfused to and carry out detailed simulation, how to regulate heating and producing well to descend with improvement the decision-making of performance.Producing well performance can regulate by the back pressure on control well or throttling.Heated well performance also can regulate by controlling energy input.Sensor reading also can be indicated sometimes needs repairing, replacement or discarded well or the mechanical problem of underground equipment.
In one embodiment, utilize from flow velocity, composition, temperature and/or the pressure data of two or more wells as the input of computerized algorithm to control the rate of heat addition and/or throughput rate.Near unmeasured condition in well or well is then evaluated and for control well.For example, heat based on from one group of well of the behavior of original position pressure break and the slaking of cheese root, flow and form data and assess.In another example, the in situ stress of well integrality based on pressure data, well temperature data and estimation evaluated.In related embodiment, the number of sensor is by only making a subgroup well be equipped with equipment and using result interpolation, calculating or estimate that not instrumented aboveground condition is reduced.Some well can only have one group of limited sensor (such as only wellhead temperature and pressure) and other well has one group of larger sensor (such as wellhead temperature and pressure, bottom hole temperature (BHT) and pressure, production composition, flow velocity, the signal of telecommunication, sleeve pipe strain etc.).
As implied above, there is the multiple method that is rich in organic matter rock stratum that heat is applied to.For example, a kind of method can comprise the resistance heater being placed in outside pit shaft or pit shaft.A kind of such method relates to stratie is used in setting of casing pit shaft or uncased wellbore.Resistance heated relates to directly passes through conductive material by electricity, thereby resistance loss makes its electric conduction of heating material.Other heating means comprise uses downhole burner, situ combustion, radio frequency (RF) electric energy or microwave energy.The heating means that remain other comprise hot fluid are directly injected in oil shale formation to be directly heated.Hot fluid can circulate or can not circulate.A kind of method can comprise by subsurface formations outside or internal-combustion fuel produce heat.For example, heat can or be supplied with in stratum by passing for example pit shaft thermal fluid circulation (such as methane gas or naphtha) via for example natural or artificial pressure break by earth's surface burner or downhole burner.Some burners can be configured to carry out non-flaming combustion.Alternatively, certain methods can comprise such as passing through natural distributed formula burner in stratum combust fuel, described large right distributed burner generally refer to use oxidant with in oxidation stratum at least partly carbon to produce hot heater, and wherein oxidation occur in approach most pit shaft near.Unless so statement in claims, this method is not limited to applied heating technique.
A kind of method of ground layer for heating relates to the use of resistor, and wherein electric current is through resistance material, and described resistance material will disperse electric energy with heat.This method is different from dielectric heating, at dielectric heating medium-high frequency oscillating current, nearby in material, induces electric current and they are heated.Electric heater can comprise insulated electric conductor, be placed in the elongated member of perforate and/or be placed in the conductor of conduit.Disclosing and having used resistance heater is U.S. Patent number 1,666 with the early stage patent of produced in situ oil shale, 488.' 488 patents are authorized Crawshaw in nineteen twenty-eight.Since nineteen twenty-eight, the design of various downhole electric heaters has been proposed.Illustrative design is at U.S. Patent number 1,701, and 884, introduce in U.S. Patent number 3,376,403, U.S. Patent number 4,626,665, U.S. Patent number 4,704,514 and U.S. Patent number 6,023,554.
The commentary of heavy oil reservoir electrical heating method application by R.Sierra and S.M.Farouq Ali at " Promising Progress in Field Application of Reservoir Electrical Heating Methods ", in Society of Petroleum Engineers Paper 69709,2001, provide.Whole disclosures of this list of references are incorporated to herein by reference.
Some of In-situ resistance heater formerly designs has utilized solid, laser heating element (for example wire or bar).Yet such element may lack for a long time, high temperature application toughness as necessary in oil shale slaking.Along with ground layer for heating and oil shale slaking, there is significant expansion in rock.This causes the aboveground stress that intersects with stratum high.These stress can cause the crooked of wellbore tubular and internal component and stretch.In position cementing (for example U.S. Patent number 4,886,118) or filling (for example U.S. Patent number 2,732,195) heating element can provide some protections for stress, but some stress still can be transmitted to heating element.
As possibility, International Patent Publication No. W WO2005/010320 instruction makes electricity consumption pilot split heating oil shale.Heating element by form pit shaft and then fracturing pit shaft oil shale formation around construct.In pressure break, be filled with the conducting material that forms heating element.Calcined petroleum coke is exemplary suitable conductive material.Preferably, pressure break along by horizontal wellbore, form longitudinally, produce in the vertical direction of horizontal plane.Electricity can be transmitted to by conductibility pressure break the toe of each well from the root of each well.Electric current can by with near the one or more vertical pressure break of toe, intersect, for providing the other horizontal well of opposite electrode to form.This WO 2005/010320 method produces " original position baker ", and described original position baker is artificial ageing's oil shale by applying electric heating.Heat conduction heating oil shale is to the conversion temperature that surpasses 300 ℃, and it causes artificial ageing.
International Patent Publication No. W WO 2005/045192 has instructed optional heating means, and it utilizes the circulation that adds hot fluid in oil shale formation.In the method for WO 2005/045192, the naphtha of supercritical heated can circulate by the pressure break in stratum.This means that oil shale heats through a series of intensive fracturings by the dense hot hydrocarbon steam that circulates.On the one hand, pressure break is that level forms and supported by convention.The pressure break temperature of 320 ℃-400 ℃ is held to reach five to ten years.The naphtha of vaporization can be preferred heat medium, and this is due to its high volumetric heat capacity, easily obtains and relative low degradation rate under heating-up temperature.In WO 2005/045192 method, along with kerogen slaking, fluid pressure will drive the oil producing in the pressure break of heating, and wherein it is plucked out of the hydrocarbon steam along with circulation.
The object that organic matter rock stratum is rich in heating is that pyrolysis at least a portion solid formations hydrocarbon is to produce hydrocarbon fluid.Solid formations hydrocarbon can by being rich in that organic matter rock stratum (or region) in stratum is increased to pyrolysis temperature, original position produces.In some embodiments, formation temperature can slowly raise and reach pyrolysis temperature range.For example, converted in-situ process can comprise that the average temperature that heating at least a portion is rich in Yi Jianggai region, organic matter rock stratum for example, is increased to about more than 270 ℃ to be less than the speed of selected amount every day (about 10 ℃, 5 ℃, 3 ℃, 1 ℃, 0.5 ℃ or 0.1 ℃).In further embodiment, this part can be heated, so that the average temperature of selection area can be less than approximately 375 ℃, or in some embodiments, is less than approximately 400 ℃.This stratum can be heated, for example, so that the temperature in stratum (at least) reaches initial pyrolysis temperature (pyrolysis starts the temperature at the temperature range lower bound place of generation).
Pyrolysis temperature range can distribute and change according to the kind of stratum hydrocarbon in stratum, heating means and thermal source.For example, pyrolysis temperature range can comprise the temperature between approximately 270 ℃ and approximately 900 ℃.Alternatively, the body of target area, stratum can be heated between 300 ℃ and 600 ℃ mutually.In optional embodiment, pyrolysis temperature range can comprise the temperature between approximately 270 ℃ and approximately 500 ℃.
Preferably, for in-situ method, the heating of production area occurs in some months or even 4 years or more in years.Alternatively, stratum can be heated 1 year to 15 years, alternatively, 3 to 10 years, 1.5 to 7 years, or 2 to 5 years.The body of target area, stratum can be heated between 270 ℃ and 800 ℃ mutually.Preferably, the body of target area, stratum can be heated between 300 ℃ and 600 ℃ mutually.Alternatively, the body of target area can finally be heated to 400 ℃ (752 °F) following temperature mutually.
In some embodiment of the inventive method, downhole burner can be used to add thermal target oil shale section.The downhole burner of different designs comes into question in patent documentation, for oil shale and other main firmware hydrocarbon deposit.Example comprises U.S. Patent number 2,887,160; U.S. Patent number 2,847,071; U.S. Patent number 2,895,555; U.S. Patent number 3,109,482; U.S. Patent number 3,225,829; U.S. Patent number 3,241,615; U.S. Patent number 3,254,721; U.S. Patent number 3,127,936; U.S. Patent number 3,095,031; U.S. Patent number 5,255,742; With U.S. Patent number 5,899,269.Downhole burner moves by the underground position that ignitable fuel (typically natural gas) and oxidant (typically air) are transported in pit shaft.Fuel and oxidant react to produce heat in down-hole.Burning gases are removed (generally by being transported to earth's surface, but may by being injected in stratum).Usually, downhole burner utilizes pipe-in-pipe to arrange with transport fuel and oxidant to down-hole, and then removes combustion gas and turn back to above earth's surface.Some downhole burners produce flames, and other can not produce flame.
The use of downhole burner is the replacement scheme of the down-hole heating that is called as steam generation of another kind of form.In underground steam occurs, the burner in well is used to boil the water that is placed in pit shaft to be injected in stratum.The application of underground heat disaster technology has been described in F.M.Smith, " ADown-hole burner-Versatiletool for well heating, " 25
thtechnical Conference on Petroleum Production, Pennsylvania State University, pp 275-285 (Oct.19-21,1966); H.Brandt, W.G.Poynter and J.D.Hummell, " Stimulating Heavy Oil Reservoirs with Downhole Air-Gas Burners, " World Oil.pp.91-95 (Sept.1965); With C.I.DePriester and A.J.Pantaleo, " Well Stimulationby Downhole Gas-Air Burner, " Journal of Petroleum Technology, in pp.1297-1302 (Dec.1963).
Downhole burner is because the infrastructure cost reducing has advantage with respect to electrical heating method.In this respect, do not need expensive power plant and electrical distribution system.And, there is the thermal efficiency of increase, because avoided the energy loss of intrinsic experience during generating electricity.
There is downhole burner application seldom.Downhole burner design problem comprises that temperature is controlled and metallurgy restriction.In this respect, flame temperature may make pipe and burner hardware is overheated and by fusing, thermal stress, hot strength heavy losses or creep make their inefficacy.Some stainless steel, it typically has high chromium content, can tolerate the long-term time of temperature up to～700 ℃.(referring to for example H.E.Boyer and T.L.Gall (eds.), Metals Handbook, " Chapter 16:Heat-Resistant Materials ", American Society forMetals, the existence of (1985.) flame may cause focus in the stratum in burner with around burner.This is because the radiativity from luminous flame part conducts heat.Yet typical gas flame can produce the temperature up to about 1,650 ℃.Therefore, the material of structure burner must be enough to tolerate the temperature of these focuses.Heater is therefore more expensive than fireless similar heater.
For downhole burner application, heat transfer one of can be in several ways occurs.These comprise conduction, convection current and method of radiating.Radiant heat transfer can be especially strong for naked light.In addition, flue gas is due to CO
2with water content may be corrosive.The use of refractory metal or pottery can contribute to address these problems, but general cost is higher.Surpassing, at the temperature of 900 ℃, to have the ceramic materials that can accept intensity be generally high alumina content pottery.Other pottery that can be useful comprises chromic oxide-based pottery, zirconia-based ceramics and magnesium oxide-based pottery.In addition, according to down-hole aptitude to burn, NO
xgeneration may be a large amount of.
Heat transfer in the pipe-in-pipe of downhole burner is arranged also can cause difficulty.The fuel of advancing downwards and air carry out interchange of heat by the hot flue gases with upwards advancing.In well, for high-insulation, there is minimum space, be therefore generally expected that a large amount of heat transfers.This intersection interchange of heat, along with fuel and air preheat, can cause higher flame temperature.In addition, the interchange of heat that intersects can limit the transmission of burner downstream heat because the flue gas of heat can rapidly heat-energy losses be given rising compared with cool flue gas.
The method that for example heats by pyrolysis the stratum hydrocarbon being rich in organic matter rock stratum can produce fluid.The fluid that heat generates can comprise the water of evaporation in stratum.In addition, heat the pyrolyzation fluid that tends to expansion after kerogenic effect generation is heated.The pyrolyzation fluid generating not only can comprise water, and can comprise for example oxide, ammonia, dinitrogen and the molecular hydrogen of hydrocarbon, carbon.Therefore,, along with the temperature in ground layer for heating part increases, the pressure in heating part increases because fluid produces, molecule expands and evaporation of water also may increase.Therefore, some corollaries are present between the fluid pressure producing during subsurface pressure in oil shale formation and pyrolysis.This shows again, and strata pressure can be monitored to detect the progress of kerogen conversion process.
The pressure being rich in the heating part of organic matter rock stratum depends on other reservoir characteristic.These can comprise, for example, depth of stratum, the distance with heated well, the richness that is rich in stratum hydrocarbon in organic matter rock stratum, degree of heat and/or with the distance of producing well.
The developer in oil shale oil field can expect to monitor between development period strata pressure.Pressure in stratum can be measured at a plurality of diverse locations place.Such position can include but not limited to the different depth place in well head place and pit shaft.In some embodiments, pressure can be measured at producing well place.In optional embodiment, pressure can be measured at heated well place.In remaining another embodiment, the down-hole that pressure can be monitored well in special use is measured.
Organic matter rock stratum to the process of pyrolysis temperature range is rich in heating not only will increase strata pressure, and will increase stratum permeability.Pyrolysis temperature range reaches before should having produced basic permeability in being rich in organic matter rock stratum.The initial permeability that lacks can prevent that the fluid producing from pyrolysis section from transmitting in stratum.Mode like this, along with heat is transferred to and is rich in organic matter rock stratum from heated well at first, the fluid pressure being rich in organic matter rock stratum can raise more close to this heated well.This fluid pressure increase may be by for example in stratum the fluid during the pyrolysis of at least some stratum hydrocarbon produce and to cause.
The pressure that alternatively, can make to be produced by the expansion of the pyrolyzation fluid generating in stratum or other fluid increases.Open channel or other Pressure Drop of this supposition producing well are not also present in stratum.On the one hand, fluid pressure can be allowed to be increased to rock static stress or on.In this case, when fluid pressure equals or exceeds rock static stress, the pressure break in hydrocarbon containing formation can form.For example, pressure break can be formed into producing well from heated well.In heating part, the generation of pressure break can reduce the pressure in this part, and this is owing to passing through the production of producing well Produced Liquid.
Once pyrolysis starts in being rich in organic matter rock stratum, fluid pressure can change according to different factors.These comprise for example thermal expansion of hydrocarbon, the fluid of the generation of pyrolyzation fluid, conversion rate and taking-up generation from stratum.For example, along with fluid produces in stratum, the fluid pressure in hole may increase.Near the fluid pressure of the fluid that shifts out generation from stratum in can reducing the shaft area of stratum.
In some embodiments, the quality that at least a portion is rich in organic matter rock stratum can be lowered, and this is due to the pyrolysis of for example stratum hydrocarbon and from stratum, produces hydrocarbon fluid.Therefore, the permeability at least a portion stratum and degree of porosity may increase.Anyly effectively from oil shale, produce the gentle in-situ method of oil and will the rock of original very hypotonicity, produce permeability.The degree of this generation is illustrated by large swell increment, if the fluid producing from kerogen can not flow, must have described expansion.This viewpoint is illustrated in Fig. 5.
Fig. 5 provides a block diagram, and it has compared one ton of Green River oil shale of 50 and afterwards 51 before the original position distillation process of simulation.The process of simulation is to be that 22wt.% and Fisher test on the oil shale of 42 Gallons Per Tons and carry out under 2,400psi and 750 °F, at total content of organic carbon.Before conversion, there is 15.3ft altogether
3rock matrix 52.This matrix comprises the 7.2ft being embedded in shale
3mineral 53, i.e. dolomite, limestone etc. and 8.1ft
3kerogen 54.Owing to transforming this material, be expanded to 26.1ft
355.This provides 7.2ft
3mineral 56 (with transform before identical number), 6.6ft
3hydrocarbon fluid 57,9.4ft
3hydrocarbon steam 58 and 2.9ft
3coke 59.Can find out, during basic volume expansion occurs in conversion process.This has increased again the permeability of rock texture.
In one embodiment, an In Situ Heating part is rich in organic matter rock stratum and can increases the permeability of heating part to pyrolysis temperature.For example, permeability can be owing to increasing by applying the formation that in the heating part that heat causes, hot pressing is split.Along with the temperature increase of heating part, water can be removed due to evaporation.The water of vaporization can overflow and/or remove from stratum.In addition, the permeability of heating part also can increase, and this is in macroscopic scale, due to the pyrolysis of at least some stratum hydrocarbon in heating part, to produce the result of hydrocarbon fluid.
Some system described herein can be used for processing the stratum hydrocarbon on (for example, in " densification " stratum of containing stratum hydrocarbon) in the relative low permeability formation of at least a portion with method.Such stratum hydrocarbon can be heated at least some stratum hydrocarbon of pyrolysis in the selected district on stratum.Heating also can increase the permeability in the selected district of at least a portion.The hydrocarbon fluid producing from pyrolysis can produce from stratum, further increases thus stratum permeability.
The permeability that is rich in the interior selected district of heating part of organic matter rock stratum also can increase sharply when this selected district is heated due to conduction.For example, the impermeable permeability that is rich in organic matter rock stratum can be less than approximately 0.1 millidarcy before heating.In some embodiments, pyrolysis at least a portion is rich in that organic matter rock stratum can be increased to the permeability in the selected district of this part approximately 10 millidarcies, 100 millidarcies, 1 darcy, 10 darcies, 20 darcies or more than 50 darcies.Therefore, the permeability in the selected district of this part can increase about more than 10,100,1,000,10,000 or 100,000 factor.In one embodiment, this has the initial total permeability below 1 millidarcy before being rich in organic matter rock stratum in heating to be rich in organic matter rock stratum, alternatively below 0.1 or 0.01 millidarcy.In one embodiment, this has more than 1 millidarcy heating total permeability afterwards after being rich in organic matter rock stratum in heating to be rich in organic matter rock stratum, alternatively, and more than 10,50 or 100 millidarcies.
To be rich in organic matter rock stratum relevant to heating, is rich in organic matter rock stratum and optionally by pressure break, conducted heat or production of hydrocarbon fluids contributing to.In a kind of situation, pressure break can produce in stratum that hot pressing is split and realization naturally by applying heat.Hot pressing is split the thermal expansion that form to be by rock and fluid and kerogen and is transformed into that the gentle chemically expansible of oil causes.Hot pressing is split to occur in and is stood the zone line of heating and colder near zone.It is the caused tensile stress that spreads and more expand in thermal region due to pressure break that hot pressing near zone is split.Therefore, it is gentle by heating, to be rich in organic matter rock and kerogen is transformed into oil, and permeability not only forms by fluid and evaporates but also split to form by hot pressing and increases.The permeability increasing contributes to the extraction of the hydrocarbon fluid mobile and that produce from kerogen of the fluid in stratum.
In addition, can use the method that is called as fracturing.Fracturing is known method in oily gentle recovery field, and wherein fracturing fluid is pressurized on the frac pressure on stratum in pit shaft, therefore in stratum, forms fracture planes to discharge the pressure producing in pit shaft.The geometry that fracturing can be used to produce additional permeability and/or be used to provide stretching to heated well.WO 2005/010320 patent publications that is incorporated to has above been described a kind of such method.
Close with produce hydrocarbon phase from those of the especially shallow degree of depth of rock matrix, may have the misgivings of sinking about ground.This heats especially in position, and to be rich in organic matter rock be actual conditions, and wherein a part of matrix itself is by thermal transition and remove.At first, the stratum hydrocarbon that this stratum can comprise solid form such as, for example, kerogen.This stratum also can comprise water-soluble mineral at first.At first, this stratum can fluid flow be also substantially impermeable.
This matrix pyrolysis of In Situ Heating at least a portion stratum hydrocarbon to produce hydrocarbon fluid.This again the slaking in being rich in organic matter rock stratum (pyrolysis) be rich in organic matter petrographic province and produce permeability.Pyrolysis and permeability increase combined permission hydrocarbon fluid and produce from stratum.Meanwhile, the loss of the material of support substrate also produces the possibility with respect to surface subsidence.
In some cases, for fear of environment or hydrogeology impact, sink to being sought to minimize.In this respect, change the isohypse on earth's surface and landform even several inches all may change runoff (runoff) pattern, affect vegetation pattern and affect dividing ridge.In addition, sink have damage the production that forms or heated well in Production Regional may.This sinking can produce destructive endless belt and compressive stress to wellbore casing, cement workpiece and underground equipment.
For fear of or minimize sinking, propose to stay the stratum hydrocarbon of pyrolysis not substantially of selected part.What this contributed to protect one or more not slakings is rich in organic matter petrographic province.In some embodiments, the organic matter petrographic province of being rich in of slaking not can be shaped as substantially vertical post, and it extends through the major part of the thickness that is rich in organic matter rock stratum.
Firing rate in stratum and heat distribution can be designed and carry out, to leave enough not slaking posts to prevent from.On the one hand, heat is injected pit shaft and is formed at well spacing, so that the untreated post of oil shale is left on wherein to support overlying rock and to prevent from.
Preferably, the nahcolite that the gentle heat utilization of oil exists in stratum or any solution mining (solution mining) of other water-soluble mineral carry out before.Solution mining can produce large hole and in oil shale developing zone, make breccia landslide in rock stratum.These holes and dust section throw into question to original position and mining recovered oil shale, and this has further increased the effectiveness of support column.
The constituent and properties of the hydrocarbon fluid producing by converted in-situ process in some embodiments, can change according to the condition being for example rich in organic matter rock stratum.The firing rate of controlling heat and/or being rich in selected part in organic matter rock stratum can increase or reduce the production of selected Produced Liquid.
In one embodiment, at least one characteristic that operating condition can be rich in organic matter rock stratum by measurement is determined.The characteristic of measuring can be imported in computer executable program.At least one characteristic of the selected Produced Liquid of producing from stratum also can be imported in computer executable program.This program can be exercisable, to determine one group of operating condition the characteristic from least one or more measurement.This program also can be configured to determine this group operating condition from least one characteristic of selected Produced Liquid.Like this, determined this group operating condition can be configured to increase and from this stratum, produce selected Produced Liquid.
Some heated well embodiment can comprise such operating system, and described operating system is for example connected with any heated well by the circuit of insulated electric conductor or other type.This operating system can be configured to dock with heated well.Operating system can receive the signal (for example electromagnetic signal) from heater, and it represents the Temperature Distribution of heated well.In addition, operating system can be further configured with this locality and control or remote heating well.For example, operating system can, by changing the parameter of the equipment being connected with heated well, change the temperature of heated well.Therefore, the heating at least a portion stratum can be monitored, changes and/or be controlled to operating system.
In some embodiments, the average temperature in stratum may reach after selected temperature, and heated well can be turned down and/or close.Turn and/or close heated well down and can reduce input cost of energy, substantially suppressed the overheated of stratum, and allow to be delivered to Geng Leng region, stratum in hot radical basis.
The temperature (and average temperature) being rich in organic matter rock stratum of heating can change, and this for example depends on the degree of approach of heated well, the type of the heat conductivity on stratum and heat diffusivity, the type reacting, stratum hydrocarbon and the existence of being rich in water in organic matter rock stratum.In oil field, set up the position of monitoring well, temperature survey can directly be carried out in pit shaft.In addition,, at heated well place, on stratum, immediately temperature is around understood quite fully.Yet expectation is inserted into temperature on the position in stratum medium temperature sensor and heated well.
An aspect of process produced according to the invention, the Temperature Distribution being rich in organic matter rock stratum can adopt numerical simulator to calculate.Numerical simulator can distribute by the interpolation of known data point and the assumed calculation surface temperature of stratum conductivity.In addition, numerical simulator can be used to measure other characteristic of dividing the stratum planting in evaluate temperature.For example, the various characteristics on stratum can include but not limited to the permeability on stratum.
Numerical simulator also can comprise that assessment divides in evaluate temperature the various characteristics that is rich in the fluid forming in organic matter rock stratum planting.For example, the various characteristics of the fluid that forms can include but not limited in stratum the composition of the fluid of formation in cumulative volume, fluid viscosity, fluid density and the stratum of the fluid that forms.This simulation can be used to assess the performance of commercial size operation or small-scale field test.For example, based on, but be not limited to, the product cumulative volume that can produce from research scale operations, can assess the performance that commercial size is developed.
Some embodiments comprise from being rich in organic matter formation production at least a portion hydrocarbon fluid.Hydrocarbon fluid can be produced by producing well.Producing well can be cased hole or open hole well and carry out drilling and well completion by method as known in the art.
Some embodiments further comprise that wherein Produced Liquid comprises hydrocarbon fluid and aqueous fluid from being rich in organic matter formation production Produced Liquid.Aqueous fluid can comprise water-soluble mineral and/or migration stain species.In such a case, Produced Liquid can be separated into hydrocarbon stream and aqueous stream in landscape apparatus.After this water-soluble mineral and/or migration stain species can reclaim from aqueous stream.This embodiment can combine with any aspect in the other side of invention discussed in this article.
The hydrocarbon fluid of producing can comprise pyrolysis oil composition (or condensable composition) and pyrolysis gas composition (or non-condensing composition).The condensable hydrocarbons of producing from stratum will generally comprise paraffin, cycloalkanes, mononuclear aromatics and double ring arene as composition.This condensable hydrocarbons also can comprise other composition such as thrcylic aromatic hydrocarbon and other hydrocarbon kind.
In some embodiments, in Produced Liquid, most of hydrocarbon can have the carbon number that is less than approximately 25.Alternatively, in fluid, be less than by weight approximately 15% hydrocarbon and can there is the carbon number that is greater than approximately 25.Non-condensing hydrocarbon can include but not limited to the hydrocarbon that carbon number is less than 5.
In some embodiments, in Produced Liquid, the api gravity of condensable hydrocarbons can be about 20 or above (such as 25,30,40,50 etc.).In some embodiments, in Produced Liquid, hydrogen and carbon atomic ratio can be at least about 1.7 (such as 1.8,1.9 etc.).
One embodiment of the present invention comprise the in-situ method from being rich in organic matter formation production with the hydrocarbon fluid that improves characteristic.Applicant has been surprised to find is rich in from In Situ Heating and pyrolysis that In Situ Heating is carried out in the location of being rich in organic matter rock stratum that the quality of the hydrocarbon fluid that organic matter rock stratum produces can have a higher lithostatic stress by selection and pyrolysis is improved.
The method can comprise that In Situ Heating has the location of being rich in organic matter rock stratum of high rock static stress, to form, has the hydrocarbon fluid that improves characteristic.The method can comprise that the hydrocarbon solid and/or the heavy hydrocarbon that by pyrolysis, in being rich in organic matter rock stratum, exist produce hydrocarbon fluid.Embodiment can comprise partly, mainly or the hydrocarbon fluid that produces of the hydrocarbon solid substantially fully existing in being rich in organic matter rock stratum by pyrolysis and/or heavy hydrocarbon.The method can comprise that by any method heating is rich in the location of organic matter rock stratum, and it comprises any method as herein described.For example, the method can comprise by resistance heated and heats the location of being rich in organic matter rock stratum.In addition, the method can comprise that the heat-transfer fluid heating by use heats the location of being rich in organic matter rock stratum.More than the method can comprise that the location to 270 ℃ of organic matter rock stratum is rich in heating.Alternatively, the method can be included between 270 ℃ and 500 ℃ the location that organic matter rock stratum is rich in heating.
The method can comprise that In Situ Heating rock static stress is greater than being rich in location, organic matter rock stratum and being rich in organic matter rock stratum location extraction hydrocarbon fluid from this heating of 200psi.In optional embodiment, being rich in location, organic matter rock stratum and can thering is the rock static stress that is greater than 400psi of this heating.In optional embodiment, being rich in location, organic matter rock stratum and can thering is the 800psi of being greater than, be greater than 1,000psi, be greater than 1,200psi, be greater than 1,500psi or be greater than the rock static stress of 2,000psi of this heating.Applicant has been found that In Situ Heating and pyrolysis have to be increased the organic matter rock stratum of being rich in of amount of stress and causes producing and have the hydrocarbon fluid that improves characteristic.
The rock static stress that is rich in the location on organic matter stratum conventionally can be by approving that it generally estimates the weight that equals to cover the rock on stratum.The density of upper overlying strata stone can represent with the psi/ft of unit.Generally, this value will drop on 0.8 and 1.1psi/ft between and often can be approximately 0.9psi/ft.Therefore, being rich in the degree of depth that the rock static stress in location, organic matter stratum can be rich in organic matter rock stratum interval by use is multiplied by 0.9psi/ft and estimates.Therefore, about 1, the rock static stress that is rich in location, organic matter stratum that 000ft occurs can be estimated as approximately (0.9psi/ft) be multiplied by (1,000ft) or be about 900psi.If rock static stress is more accurately estimated in expectation, go up so the density of overlying strata stone and can utilize wireline logging technology or measure by the sample reclaiming from core hole is carried out to laboratory measurement.The method can comprise that heating is rich in the location of organic matter rock stratum, and it is positioned at the depth that is greater than 200ft (foot) under earth surface.Alternatively, the method can comprise that heating is rich in location, organic matter rock stratum, it is positioned under earth surface and is greater than under 500ft (foot), earth surface and is greater than 1, under 000ft (foot), earth surface, be greater than 1, under 200ft (foot), earth surface, be greater than 1, under 500ft (foot) or earth surface, be greater than the depth of 2,000ft (foot).
Be rich in organic matter rock stratum and can be for example heavy hydrocarbon stratum or hydrocarbon solid stratum.The instantiation on such stratum can comprise oil shale formation, tar sand formation or coal stratum.The concrete stratum hydrocarbon existing in such stratum can comprise oil shale, kerogen, coal and/or pitch.
From being rich in the hydrocarbon fluid of organic matter formation production, can comprise condensable hydrocarbons part (for example liquid) and non-condensing hydrocarbon part (for example gas).Hydrocarbon fluid can be produced in addition together with non-hydrocarbon fluids.Exemplary non-hydrocarbon fluids comprises for example water, carbon dioxide, hydrogen sulfide, hydrogen, ammonia and/or carbon monoxide.
The condensable hydrocarbons part of hydrocarbon fluid can be the fluid existing in the diverse location relevant to being rich in organic matter rock exploration project.For example, the condensable hydrocarbons of hydrocarbon fluid part can be the fluid existing in producing well, described producing well be rich in organic matter formation fluid and be communicated with.Producing well can serve as the device that the hydrocarbon fluid of extraction is extracted out from being rich in organic matter rock stratum.Alternatively, condensable hydrocarbons part can be the fluid existing in treatment facility, and described treatment facility is suitable for processing from being rich in the hydrocarbon fluid of organic matter formation production.Exemplary process equipment is described in this article.Alternatively, condensable hydrocarbons part can be the fluid existing in fluid-storing container.Fluid-storing container can comprise fluid reservoir, gas-liquid separation container and other middle, interim or product reservoir vessel for example with fixing or the top of floating.Alternatively, condensable hydrocarbons part can be the fluid existing in fluid-transporting tubing.Fluid-transporting tubing for example can comprise from producing well to treatment facility or the pipeline of fluid-storing container, the pipeline from treatment facility to fluid-storing container or to arrive or from the collection of the fluid of middle or central storage location or carry relevant pipeline.
Following discussion to Fig. 7-16 relates to the data that obtain in embodiment 1-5, and it comes into question in the part that is labeled as " experiment ".Data obtain by experimental arrangement, gas and fluid sample collection procedure, hydrocarbon gas sample gas-chromatography (GC) analytical method, gaseous sample GC peak integration method, gaseous sample GC peak authentication method, complete oily gas-chromatography (WOGC) analytical method, complete oily gas-chromatography (WOGC) peak integration method, complete oily gas-chromatography (WOGC) peak authentication method and the pseudocomponent analytical method of discussing in experimental section.For clarity sake, when speaking of the gas-chromatography chromatogram of hydrocarbon gas sample, for a unstressed experiment by embodiment 1, by two stressed experiments of 400psi of embodiment 2 and 3 and by two 1 of embodiment 4 and 5, the stressed experiment of 000psi provides graphical data.When speaking of complete oily gas-chromatography (WOGC) chromatogram of liquid hydrocarbon sample, for a unstressed experiment by embodiment 1, by stressed experiment of 400psi of embodiment 3 and by one 1 of embodiment 4, the stressed experiment of 000psi provides graphical data.
Fig. 7 is in test in the laboratory experiment of discussing herein and three stress levels analyzing for each, the percetage by weight figure of each the carbon number pseudocomponent occurring from C6 to C38.Pseudocomponent percetage by weight obtains by experimental arrangement, fluid sample collection procedure, complete oily gas-chromatography (WOGC) analytical method, complete oily gas-chromatography (WOGC) peak evaluation and integration method and the pseudocomponent analytical method of discussing in experimental section.For clarity sake, pseudocomponent percetage by weight is calculated as whole C3 to the percentage of the complete oily gas-chromatography area of false C38 and calculated weight.Therefore graphic C6 to C38 percetage by weight does not comprise the weight quota from the relevant gaseous products of the experiment of any independent processing.In addition, graphic percetage by weight does not comprise than the weight quota of any liquid hydrocarbon compound of C38 pseudocomponent heavier (having longer retention time than C38 pseudocomponent).The concentration that y-axle 2000 represents with regard to each C6 to C38 pseudocomponent percetage by weight in liquid phase.X-axle 2001 comprises from the identity of each hydrocarbon pseudocomponent of C6 to C38.The data point occurring on line 2002 represents the percetage by weight of each C6 to C38 pseudocomponent for the unstressed experiment of embodiment 1.The data point occurring on line 2003 represents the percetage by weight of each C6 to C38 pseudocomponent for the stressed experiment of 400psi of embodiment 3.And the data point occurring on line 2004 represents for 1 of embodiment 4, the percetage by weight of each C6 to C38 pseudocomponent of the stressed experiment of 000psi.As can be seen from Figure 7, compare 400psi stress test hydrocarbon liquid and 1,000psi stress test hydrocarbon liquid, the light hydrocarbon component that contains more low weight percentage C8 to C17 pseudocomponent within the scope of by the represented hydrocarbon liquid producing of data point on line 2002 in unstressed experiment and the heavy hydrocarbon component that contains the larger percetage by weight within the scope of C20 to C29 pseudocomponent.See now on line 2003 data point occurring, clearly, by-level 400psi stress test produce the online 2002 represented unstressed experiments of C8 to C17 pseudocomponent concentration and line 2004 represented 1, the hydrocarbon liquid between the stressed experiment of 000psi.The C17 pseudocomponent data that it should be noted that 400psi and the stressed experiment of 1,000psi are approximately equal.In addition, clearly, for the represented intermediate stress level of line 2003 is tested, the percetage by weight of the heavy hydrocarbon component within the scope of C20 to C29 pseudocomponent drops between unstressed experiment (line 2002) hydrocarbon liquid and 1,000psi stress test (line 2004) hydrocarbon liquid.Finally, clearly, high level 1,000psi stress test produces all large hydrocarbon liquid of the represented unstressed experiment of C8 to C17 pseudocomponent concentration ratio line 2002 and the represented stressed experiment of 400psi of line 2003.In addition, clearly, for the represented great horizontal stress of line 2004 is tested, the percetage by weight of the heavy hydrocarbon component within the scope of C20 to C29 pseudocomponent is less than unstressed experiment (line 2002) hydrocarbon liquid and 400psi stress test (line 2003) hydrocarbon liquid.Therefore under the rock static stress level increasing, pyrolysis oil shale presents the hydrocarbon liquid that generation has further lighter carbon number distribution.
Fig. 8 is that each the carbon number pseudocomponent occurring from C6 to C38 is compared the percetage by weight ratio chart of C20 pseudocomponent in test in the laboratory experiment of discussing herein and three stress levels analyzing for each.Pseudocomponent percetage by weight obtains as described in Figure 7.In y-axle 2020 expression liquid phases, each C6 to C38 pseudocomponent is compared the weight ratio of C20 pseudocomponent.X-axle 2021 comprises from the identity of each hydrocarbon pseudocomponent ratio of C6/C20 to C38/C20.The data point occurring on line 2022 represents the weight ratio of each C6 to C38 pseudocomponent and C20 pseudocomponent for the unstressed experiment of embodiment 1.The data point occurring on line 2023 represents the weight ratio of each C6 to C38 pseudocomponent and C20 pseudocomponent for the stressed experiment of 400psi of embodiment 3.And the data point occurring on line 2024 represents the weight ratio of each C6 to C38 pseudocomponent and C20 pseudocomponent for the stressed experiment of 1000psi of embodiment 4.As can be seen from Figure 8, compare 400psi stress test hydrocarbon liquid and 1,000psi stress test hydrocarbon liquid, the light hydrocarbon component that on line 2022, the represented hydrocarbon liquid producing in unstressed experiment of data point contains the more low weight percentage within the scope of C8 to the C18 pseudocomponent of comparing C20 pseudocomponent, and contain at the heavy hydrocarbon component of comparing the larger percetage by weight within the scope of C22 to the C29 pseudocomponent of C20 pseudocomponent.See now the data point occurring on line 2023, clearly, by-level 400psi stress test produce compare the online 2022 represented unstressed experiments of C8 to the C18 pseudocomponent concentration of C20 pseudocomponent and line 2024 represented 1, the hydrocarbon liquid between the stressed experiment of 000psi.In addition, clearly, for the represented intermediate stress level of line 2023 is tested, in the percetage by weight of comparing the heavy hydrocarbon component within the scope of C22 to the C29 pseudocomponent of C20 pseudocomponent, drop between unstressed experiment (line 2022) hydrocarbon liquid and 1,000psi stress test (line 2024) hydrocarbon liquid.Finally, clearly, high level 1,000psi stress test produces compares all large hydrocarbon liquid of the represented unstressed experiment of C8 to the C18 pseudocomponent concentration ratio line 2022 of C20 pseudocomponent and the represented stressed experiment of 400psi of line 2023.In addition, clearly, for the represented great horizontal stress of line 2024 is tested, in the percetage by weight of comparing the heavy hydrocarbon component within the scope of C22 to the C29 pseudocomponent of C20 pseudocomponent, be less than unstressed experiment (line 2022) hydrocarbon liquid and 400psi stress test (line 2023) hydrocarbon liquid.Following relationship has further been supported in this analysis: under the rock static stress level increasing, pyrolysis oil shale produces the hydrocarbon liquid with further lighter carbon number distribution.
Fig. 9 is that each the carbon number pseudocomponent occurring from C6 to C38 is compared the percetage by weight ratio chart of C25 pseudocomponent in test in the laboratory experiment of discussing herein and three stress levels analyzing for each.Pseudocomponent percetage by weight obtains as described in Figure 7.In y-axle 2040 expression liquid phases, each C6 to C38 pseudocomponent is compared the weight ratio of C25 pseudocomponent.X-axle 2041 comprises from the identity of each hydrocarbon pseudocomponent ratio of C6/C25 to C38/C25.The data point occurring on line 2042 represents the weight ratio of each C6 to C38 pseudocomponent and C25 pseudocomponent for the unstressed experiment of embodiment 1.The data point occurring on line 2043 represents the weight ratio of each C6 to C38 pseudocomponent and C25 pseudocomponent for the stressed experiment of 400psi of embodiment 3.And the data point occurring on line 2044 represents the weight ratio of each C6 to C38 pseudocomponent and C25 pseudocomponent for the stressed experiment of 1000psi of embodiment 4.As can be seen from Figure 9, compare 400psi stress test hydrocarbon liquid and 1,000psi stress test hydrocarbon liquid, the light hydrocarbon component that on line 2042, the represented hydrocarbon liquid producing in unstressed experiment of data point contains the more low weight percentage within the scope of C7 to the C24 pseudocomponent of comparing C25 pseudocomponent, and contain at the heavy hydrocarbon component of comparing the larger percetage by weight within the scope of C26 to the C29 pseudocomponent of C25 pseudocomponent.See now the data point occurring on line 2043, clearly, by-level 400psi stress test produce compare the online 2042 represented unstressed experiments of C7 to the C24 pseudocomponent concentration of C25 pseudocomponent and line 2044 represented 1, the hydrocarbon liquid between the stressed experiment of 000psi.In addition, clearly, for the represented intermediate stress level of line 2043 is tested, in the percetage by weight of comparing the heavy hydrocarbon component within the scope of C26 to the C29 pseudocomponent of C25 pseudocomponent, drop between unstressed experiment (line 2042) hydrocarbon liquid and 1,000psi stress test (line 2044) hydrocarbon liquid.Finally, clearly, high level 1,000psi stress test produces compares all large hydrocarbon liquid of the represented unstressed experiment of C7 to the C24 pseudocomponent concentration ratio line 2042 of C25 pseudocomponent and the represented stressed experiment of 400psi of line 2043.In addition, clearly, for the represented great horizontal stress of line 2044 is tested, in the percetage by weight of comparing the heavy hydrocarbon component within the scope of C26 to the C29 pseudocomponent of C25 pseudocomponent, be less than unstressed experiment (line 2042) hydrocarbon liquid and 400psi stress test (line 2043) hydrocarbon liquid.Following relationship has further been supported in this analysis: under the rock static stress level increasing, pyrolysis oil shale produces the hydrocarbon liquid with further lighter carbon number distribution.
Figure 10 is that each the carbon number pseudocomponent occurring from C6 to C38 is compared the percetage by weight ratio chart of C29 pseudocomponent in test in the laboratory experiment of discussing herein and three stress levels analyzing for each.Pseudocomponent percetage by weight obtains as described in Figure 7.In y-axle 2060 expression liquid phases, each C6 to C38 pseudocomponent is compared the weight ratio of C29 pseudocomponent.X-axle 2061 comprises from the identity of each hydrocarbon pseudocomponent ratio of C6/C29 to C38/C29.The data point occurring on line 2062 represents the weight ratio of each C6 to C38 pseudocomponent and C29 pseudocomponent for the unstressed experiment of embodiment 1.The data point occurring on line 2063 represents the weight ratio of each C6 to C38 pseudocomponent and C29 pseudocomponent for the stressed experiment of 400psi of embodiment 3.And the data point occurring on line 2064 represents the weight ratio of each C6 to C38 pseudocomponent and C29 pseudocomponent for the stressed experiment of 1000psi of embodiment 4.As can be seen from Figure 10, compare 400psi stress test hydrocarbon liquid and 1,000psi stress test hydrocarbon liquid, the light hydrocarbon component that on line 2062, the represented hydrocarbon liquid producing in unstressed experiment of data point contains the more low weight percentage within the scope of C6 to the C28 pseudocomponent of comparing C29 pseudocomponent.See now the data point occurring on line 2063, clearly, by-level 400psi stress test produce compare the online 2062 represented unstressed experiments of C6 to the C28 pseudocomponent concentration of C29 pseudocomponent and line 2064 represented 1, the hydrocarbon liquid between the stressed experiment of 000psi.Finally, clearly, high level 1,000psi stress test produces compares all large hydrocarbon liquid of the represented unstressed experiment of C6 to the C28 pseudocomponent concentration ratio line 2062 of C29 pseudocomponent and the represented stressed experiment of 400psi of line 2063.Following relationship has further been supported in this analysis: under the rock static stress level increasing, pyrolysis oil shale produces the hydrocarbon liquid with further lighter carbon number distribution.
Figure 11 is in test in the laboratory experiment of discussing herein and three stress levels analyzing for each, the percetage by weight figure of the n-alkane compound occurring from positive C6 alkane to positive C38 alkane.N-alkane compound percetage by weight obtains as described in Figure 7, except each independent n-alkane compound peaks area integral is used to determine that each is separately n-alkane compound percetage by weight.For clarity sake, n-alkane percetage by weight is calculated as whole C3 to the percentage of the complete oily gas-chromatography area of false C38 and calculated weight, as used in the pseudo-compound data that presented in Fig. 7.Y-axle 2080 represents the concentration with regard to the extremely positive C38 compound percetage by weight of each the positive C6 with regard to finding in liquid phase.The identity that x-axle 2081 comprises each the n-alkane compound from positive C6 to positive C38.The data point occurring on line 2082 represents that each positive C6 is to the percetage by weight of positive C38 hydrocarbon compound for the unstressed experiment of embodiment 1.The data point occurring on line 2083 represents that each positive C6 is to the percetage by weight of positive C38 hydrocarbon compound for the stressed experiment of 400psi of embodiment 3.And the data point occurring on line 2084 represents that each positive C6 is to the percetage by weight of positive C38 hydrocarbon compound for the stressed experiment of 1000psi of embodiment 4.As can be seen from Figure 11, compare 400psi stress test hydrocarbon liquid and 1,000psi stress test hydrocarbon liquid, on line 2082, the represented hydrocarbon liquid producing in unstressed experiment of data point is included in the hydrocarbon compound of the larger percetage by weight within the scope of the extremely positive C30 compound of positive C12.See now on line 2083 data point occurring, clearly, by-level 400psi stress test produce positive C12 to the online 2082 represented unstressed experiments of positive C30 compound concentration and line 2084 represented 1, the hydrocarbon liquid between the stressed experiment of 000psi.Finally, clearly, high level 1,000psi stress test produce positive C12 to positive C30 compound concentration than the represented unstressed experiment of line 2082 and all little hydrocarbon liquid of the represented stressed experiment of 400psi of line 2083.Therefore under the rock static stress level increasing, pyrolysis oil shale presents the hydrocarbon liquid that produces the n-alkane with low concentration.
Figure 12 is that the n-alkane Compound Phase occurring from positive C6 to positive C38 is than the percetage by weight figure of positive C20 hydrocarbon compound in test in the laboratory experiment of discussing herein and three stress levels analyzing for each.Normal compound percetage by weight obtains as described in Figure 11.Y-axle 3000 represent each positive C6 with regard to finding in liquid phase to positive C38 Compound Phase than the concentration with regard to the weight ratio of positive C20 compound.The identity that x-axle 3001 comprises each the n-alkane compound ratio from the positive C20 of positive C6/ to the positive positive C20 of C38/.The data point occurring on line 3002 represents that each positive C6 compares the weight ratio of positive C20 compound to positive C38 hydrocarbon compound for the unstressed experiment of embodiment 1.The data point occurring on line 3003 represents that each positive C6 compares the weight ratio of positive C20 compound to positive C38 hydrocarbon compound for the stressed experiment of 400psi of embodiment 3.And the data point occurring on line 3004 represents to compare the weight ratio of positive C20 compound to positive C38 hydrocarbon compound for each positive C6 of the stressed experiment of 1000psi of embodiment 4.As can be seen from Figure 12, compare 400psi stress test hydrocarbon liquid and 1,000psi stress test hydrocarbon liquid, on line 3002, the represented hydrocarbon liquid producing in unstressed experiment of data point is included in the light normal paraffin component of the more low weight percentage within the scope of the extremely positive C17 compound of positive C6 of comparing positive C20 compound, and the heavy hydrocarbon component that is included in the larger percetage by weight within the scope of the extremely positive C34 compound of positive C22 of comparing positive C20 compound.See now the data point occurring on line 3003, clearly, by-level 400psi stress test produce the positive C6 compare positive C20 compound to the online 3002 represented unstressed experiments of positive C17 compound concentration and line 3004 represented 1, the hydrocarbon liquid between the stressed experiment of 000psi.In addition, clearly, for the represented intermediate stress level of line 3003 is tested, in the percetage by weight of comparing the heavy hydrocarbon component within the scope of C22 to the C34 compound of positive C20 compound, drop between unstressed experiment (line 3002) hydrocarbon liquid and 1,000psi stress test (line 3004) hydrocarbon liquid.Finally, clearly, high level 1,000psi stress test produce the positive C6 that compares positive C20 compound to positive C17 compound concentration than the represented unstressed experiment of line 3002 and the represented stressed experiment of 400psi of line 3003 large hydrocarbon liquid all.In addition, clearly, for the represented great horizontal stress of line 3004 is tested, in the percetage by weight of comparing the heavy hydrocarbon component within the scope of C22 to the C34 compound of positive C20 compound, be less than unstressed experiment (line 3002) hydrocarbon liquid and 400psi stress test (line 3003) hydrocarbon liquid.Following relationship has further been supported in this analysis: under the rock static stress level increasing, pyrolysis oil shale produces the hydrocarbon liquid of the n-alkane with low concentration.
Figure 13 is that the n-alkane Compound Phase occurring from positive C6 to positive C38 is than the percetage by weight figure of positive C25 hydrocarbon compound in test in the laboratory experiment of discussing herein and three stress levels analyzing for each.Normal compound percetage by weight obtains as described in Figure 11.Y-axle 3020 represent each positive C6 with regard to finding in liquid phase to positive C38 Compound Phase than the concentration with regard to the weight ratio of positive C25 compound.The identity that x-axle 3021 comprises each the n-alkane compound ratio from the positive C25 of positive C6/ to the positive positive C25 of C38/.The data point occurring on line 3022 represents that each positive C6 compares the weight ratio of positive C25 compound to positive C38 hydrocarbon compound for the unstressed experiment of embodiment 1.The data point occurring on line 3023 represents that each positive C6 compares the weight ratio of positive C25 compound to positive C38 hydrocarbon compound for the stressed experiment of 400psi of embodiment 3.And the data point occurring on line 3024 represents that each positive C6 compares the weight ratio of positive C25 compound to positive C38 hydrocarbon compound for the stressed experiment of 1000psi of embodiment 4.As can be seen from Figure 13, compare 400psi stress test hydrocarbon liquid and 1,000psi stress test hydrocarbon liquid, on line 3022, the represented hydrocarbon liquid producing in unstressed experiment of data point is included in the light normal paraffin component of the more low weight percentage within the scope of the extremely positive C24 compound of positive C6 of comparing positive C25 compound, and the heavy hydrocarbon component that is included in the larger percetage by weight within the scope of the extremely positive C30 compound of positive C26 of comparing positive C25 compound.See now the data point occurring on line 3023, clearly, by-level 400psi stress test produce the positive C6 compare positive C25 compound to the online 3022 represented unstressed experiments of positive C24 compound concentration and line 3024 represented 1, the hydrocarbon liquid between the stressed experiment of 000psi.In addition, clearly, for the represented intermediate stress level of line 3023 is tested, the percetage by weight of the heavy hydrocarbon component within the scope of the extremely positive C30 compound of the positive C26 that compares positive C25 compound drops between unstressed experiment (line 3022) hydrocarbon liquid and 1,000psi stress test (line 3024) hydrocarbon liquid.Finally, clearly, high level 1,000psi stress test produce the positive C6 that compares positive C25 compound to positive C24 compound concentration than the represented unstressed experiment of line 3022 and the represented stressed experiment of 400psi of line 3023 large hydrocarbon liquid all.In addition, clearly, for the represented great horizontal stress of line 3024 is tested, the percetage by weight of the heavy hydrocarbon component within the scope of the extremely positive C30 compound of the positive C26 that compares positive C25 compound is less than unstressed experiment (line 3022) hydrocarbon liquid and 400psi stress test (line 3023) hydrocarbon liquid.Following relationship has further been supported in this analysis: under the rock static stress level increasing, pyrolysis oil shale produces the hydrocarbon liquid of the n-alkane with low concentration.
Figure 14 is that the n-alkane Compound Phase occurring from positive C6 to positive C38 is than the percetage by weight figure of positive C29 hydrocarbon compound in test in the laboratory experiment of discussing herein and three stress levels analyzing for each.Normal compound percetage by weight obtains as described in Figure 11.Y-axle 3040 represent each positive C6 with regard to finding in liquid phase to positive C38 Compound Phase than the concentration with regard to the weight ratio of positive C29 compound.The identity that x-axle 3041 comprises each the n-alkane compound ratio from the positive C29 of positive C6/ to the positive positive C29 of C38/.The data point occurring on line 3042 represents that each positive C6 compares the weight ratio of positive C29 compound to positive C38 hydrocarbon compound for the unstressed experiment of embodiment 1.The data point occurring on line 3043 represents that each positive C6 compares the weight ratio of positive C29 compound to positive C38 hydrocarbon compound for the stressed experiment of 400psi of embodiment 3.And the data point occurring on line 3044 represents that each positive C6 compares the weight ratio of positive C29 compound to positive C38 hydrocarbon compound for the stressed experiment of 1000psi of embodiment 4.As can be seen from Figure 14, compare 400psi stress test hydrocarbon liquid and 1,000psi stress test hydrocarbon liquid, on line 3042, the represented hydrocarbon liquid producing in unstressed experiment of data point comprises the light normal paraffin component within the scope of the extremely positive C26 compound of positive C6 more low weight percentage, that comparing positive C29 compound.See now the data point occurring on line 3043, clearly, by-level 400psi stress test produce the positive C6 compare positive C29 compound to the online 3042 represented unstressed experiments of positive C26 compound concentration and line 3044 represented 1, the hydrocarbon liquid between the stressed experiment of 000psi.Finally, clearly, high level 1,000psi stress test produce the positive C6 that compares positive C29 compound to positive C26 compound concentration than the represented unstressed experiment of line 3042 and the represented stressed experiment of 400psi of line 3043 large hydrocarbon liquid all.Following relationship has further been supported in this analysis: under the rock static stress level increasing, pyrolysis oil shale produces the hydrocarbon liquid of the n-alkane with low concentration.
Figure 15 is in test in the laboratory experiment of discussing herein and three stress levels analyzing for each, from the n-alkane compound of each carbon number of C6 to C38 and the weight ratio figure of pseudocomponent.Normal compound and pseudocomponent percetage by weight obtain as described in Fig. 7 & 11.For clarity sake, n-alkane and pseudocomponent percetage by weight are calculated as whole C3 to the percentage of the complete oily gas-chromatography area of false C38 and calculated weight, as used in the pseudo-compound data that presented in Fig. 7.Y-axle 3060 represents the concentration with regard to the false C38 compound of the extremely positive C38/ of the false C6 of each the positive C6/ weight ratio with regard to finding in liquid phase.X-axle 3061 comprises from the false C6 of positive C6/ to false each the n-alkane compound of C38 of positive C38/ and the identity of pseudocomponent ratio.The data point occurring on line 3062 represents that the false C6 of each positive C6/ is to the weight ratio of the false C38 ratio of positive C38/ for the unstressed experiment of embodiment 1.The data point occurring on line 3063 represents that the false C6 of each positive C6/ is to the weight ratio of the false C38 ratio of positive C38/ for the stressed experiment of 400psi of embodiment 3.And the data point occurring on line 3064 represents that the false C6 of each positive C6/ is to the weight ratio of the false C38 ratio of positive C38/ for the stressed experiment of 1000psi of embodiment 4.As can be seen from Figure 15, compare 400psi stress test hydrocarbon liquid and 1,000psi stress test hydrocarbon liquid, on line 3062, the represented hydrocarbon liquid producing in unstressed experiment of data point comprises n-alkane compound larger, in C10 to C26 scope than the percetage by weight of pseudocomponent.See now the data point occurring on line 3063, clearly, by-level 400psi stress test be created in n-alkane compound in C10 to C26 scope and pseudocomponent than online 3062 represented unstressed experiments and line 3064 represented 1, the hydrocarbon liquid between the stressed experiment of 000psi.Finally, clearly, high level 1,000psi stress test be created in n-alkane compound in C10 to C26 scope with pseudocomponent than the hydrocarbon liquid that is less than the represented stressed experiment of 400psi of the represented unstressed experiment of line 3062 and line 3063.Therefore under the rock static stress level increasing, pyrolysis oil shale presents and produces the hydrocarbon liquid of comparing the n-alkane with low concentration with the total hydrocarbon of given carbon number occurring between C10 and C26.
From above-described data, can find out the lighter condensable hydrocarbons fluid product of under the stress level increasing heating and the generation of pyrolysis oil shale (with respect to higher carbon number compound or component, more more low carbon number compound or the component of vast scale) and the n-alkane compound that comprises lower concentration.Such product can be more suitable in being refined into gasoline and distillate product.In addition, such product further can have the effectiveness as the raw material of some chemical technology before or after fractionation.
In some embodiments, the hydrocarbon fluid of production comprises condensable hydrocarbons part.In some embodiments, condensable hydrocarbons part can have in following one or more: total C7 is greater than 0.8 with total C20 weight ratio, total C8 is greater than 1.7 with total C20 weight ratio, total C9 is greater than 2.5 with total C20 weight ratio, total C10 is greater than 2.8 with total C20 weight ratio, total C11 is greater than 2.3 with total C20 weight ratio, total C12 is greater than 2.3 with total C20 weight ratio, total C13 is greater than 2.9 with total C20 weight ratio, total C14 is greater than 2.2 with total C20 weight ratio, total C15 is greater than 2.2 with total C20 weight ratio, and total C16 is greater than 1.6 with total C20 weight ratio.In optional embodiment, condensable hydrocarbons partly has in following one or more: total C7 is greater than 2.5 with total C20 weight ratio, total C8 is greater than 3.0 with total C20 weight ratio, total C9 is greater than 3.5 with total C20 weight ratio, total C10 is greater than 3.5 with total C20 weight ratio, total C11 is greater than 3.0 with total C20 weight ratio, and total C12 is greater than 3.0 with total C20 weight ratio.In optional embodiment, condensable hydrocarbons partly has in following one or more: total C7 is greater than 3.5 with total C20 weight ratio, total C8 is greater than 4.3 with total C20 weight ratio, total C9 is greater than 4.5 with total C20 weight ratio, total C10 is greater than 4.2 with total C20 weight ratio, total C11 is greater than 3.7 with total C20 weight ratio, and total C12 is greater than 3.5 with total C20 weight ratio.As used in this paragraph and claims, phrase " one or more (one or more) "---and then it is the ratio of a series of different compounds or component, wherein last ratio is drawn by conjunction " with (and) "---and intention comprises such condensable hydrocarbons part, and it has in listed ratio at least one or has in listed ratio two or more or three or more or four or more etc. or all.In addition, specific condensable hydrocarbons partly also can have other different compounds or component ratio, and it is not included in specific sentence or claim but still drops in the scope of such sentence or claim.The embodiment of describing in this paragraph can be with in other side of the present invention discussed in this article, any one be combined.
In some embodiments, condensable hydrocarbons partly has the total C7 and total C20 weight ratio that is greater than 0.8.Alternatively, condensable hydrocarbons part can have following total C7 and total C20 weight ratio: it is greater than 1.0, is greater than 1.5, is greater than 2.0, is greater than 2.5, is greater than 3.5 or be greater than 3.7.In optional embodiment, condensable hydrocarbons part can have following total C7 and total C20 weight ratio: it is less than 10.0, is less than 7.0, is less than 5.0 or be less than 4.0.In some embodiments, condensable hydrocarbons partly has the total C8 and total C20 weight ratio that is greater than 1.7.Alternatively, condensable hydrocarbons part can have following total C8 and total C20 weight ratio: it is greater than 2.0, is greater than 2.5, is greater than 3.0, is greater than 4.0, is greater than 4.4 or be greater than 4.6.In optional embodiment, condensable hydrocarbons part can have so total C8 and total C20 weight ratio: it is less than 7.0 or be less than 6.0.In some embodiments, condensable hydrocarbons partly has the total C9 and total C20 weight ratio that is greater than 2.5.Alternatively, condensable hydrocarbons part can have so total C9 and total C20 weight ratio: it is greater than 3.0, is greater than 4.0, is greater than 4.5 or be greater than 4.7.In optional embodiment, condensable hydrocarbons part can have so total C9 and total C20 weight ratio: it is less than 7.0 or be less than 6.0.In some embodiments, condensable hydrocarbons partly has the total C10 and total C20 weight ratio that is greater than 2.8.Alternatively, condensable hydrocarbons part can have so total C10 and total C20 weight ratio, and it is greater than 3.0, is greater than 3.5, is greater than 4.0 or be greater than 4.3.In optional embodiment, condensable hydrocarbons part can have so total C10 and total C20 weight ratio, and it is less than 7.0 or be less than 6.0.In some embodiments, condensable hydrocarbons partly has the total C11 and total C20 weight ratio that is greater than 2.3.Alternatively, condensable hydrocarbons part can have so total C11 and total C20 weight ratio, and it is greater than 2.5, is greater than 3.5, is greater than 3.7, is greater than 4.0.In optional embodiment, condensable hydrocarbons part can have so total C11 and total C20 weight ratio, and it is less than 7.0 or be less than 6.0.In some embodiments, condensable hydrocarbons partly has the total C12 and total C20 weight ratio that is greater than 2.3.Alternatively, condensable hydrocarbons part can have so total C12 and total C20 weight ratio, and it is greater than 2.5, is greater than 3.0, is greater than 3.5 or be greater than 3.7.In optional embodiment, condensable hydrocarbons part can have so total C12 and total C20 weight ratio, and it is less than 7.0 or be less than 6.0.In some embodiments, condensable hydrocarbons partly has so total C13 and total C20 weight ratio, and it is greater than 2.9.Alternatively, condensable hydrocarbons part can have so total C13 and total C20 weight ratio, and it is greater than 3.0, is greater than 3.1 or be greater than 3.2.In optional embodiment, condensable hydrocarbons part can have so total C13 and total C20 weight ratio, and it is less than 6.0 or be less than 5.0.In some embodiments, condensable hydrocarbons partly has so total C14 and total C20 weight ratio, and it is greater than 2.2.Alternatively, condensable hydrocarbons part can have so total C14 and total C20 weight ratio, and it is greater than 2.5, is greater than 2.6 or be greater than 2.7.In optional embodiment, condensable hydrocarbons part can have so total C14 and total C20 weight ratio, and it is less than 6.0 or be less than 4.0.In some embodiments, condensable hydrocarbons partly has so total C15 and total C20 weight ratio, and it is greater than 2.2.Alternatively, condensable hydrocarbons part can have so total C15 and total C20 weight ratio, and it is greater than 2.3, is greater than 2.4 or be greater than 2.6.In optional embodiment, condensable hydrocarbons part can have so total C15 and total C20 weight ratio, and it is less than 6.0 or be less than 4.0.In some embodiments, condensable hydrocarbons partly has so total C16 and total C20 weight ratio, and it is greater than 1.6.Alternatively, condensable hydrocarbons part can have so total C16 and total C20 weight ratio, and it is greater than 1.8, is greater than 2.3 or be greater than 2.5.In optional embodiment, condensable hydrocarbons part can have so total C16 and total C20 weight ratio, and it is less than 5.0 or be less than 4.0.In the paragraph of some feature of the present invention above, for example, for example, according to one group of numerical upper limits (" being less than ") and one group of numerical lower limits (" being greater than "), be described.Should be appreciated that scope that any combination by these boundaries forms within the scope of the invention, except as otherwise noted.The embodiment of describing in this paragraph can with other side of the present invention discussed in this article in any one combines.
In some embodiments, condensable hydrocarbons part can have in following one or more: total C7 is greater than 2.0 with total C25 weight ratio, total C8 is greater than 4.5 with total C25 weight ratio, total C9 is greater than 6.5 with total C25 weight ratio, total C10 is greater than 7.5 with total C25 weight ratio, total C11 is greater than 6.5 with total C25 weight ratio, total C12 is greater than 6.5 with total C25 weight ratio, total C13 is greater than 8.0 with total C25 weight ratio, total C14 is greater than 6.0 with total C25 weight ratio, total C15 is greater than 6.0 with total C25 weight ratio, total C16 is greater than 4.5 with total C25 weight ratio, total C17 is greater than 4.8 with total C25 weight ratio, be greater than 4.5 with total C18 with total C25 weight ratio.In optional embodiment, condensable hydrocarbons partly has in following one or more: total C7 is greater than 7.0 with total C25 weight ratio, total C8 is greater than 10.0 with total C25 weight ratio, total C9 is greater than 10.0 with total C25 weight ratio, total C10 is greater than 10.0 with total C25 weight ratio, total C11 is greater than 8.0 with total C25 weight ratio, and total C12 is greater than 8.0 with total C25 weight ratio.In optional embodiment, condensable hydrocarbons partly has in following one or more: total C7 is greater than 13.0 with total C25 weight ratio, total C8 is greater than 17.0 with total C25 weight ratio, total C9 is greater than 17.0 with total C25 weight ratio, total C10 is greater than 15.0 with total C25 weight ratio, total C11 is greater than 14.0 with total C25 weight ratio, and total C12 is greater than 13.0 with total C25 weight ratio.As used in this paragraph and claims, phrase " one or more "---and then it be a series of different compounds or component ratio, wherein last ratio by conjunction " with " draw---intention comprises such condensable hydrocarbons part, and it has in listed ratio at least one or has in listed ratio two or more or three or more or four or more etc. or all.In addition, specific condensable hydrocarbons partly also can have other different compounds or component ratio, and it is not included in specific sentence or claim but still drops in the scope of such sentence or claim.The embodiment of describing in this paragraph can be with in other side of the present invention discussed in this article, any one be combined.
In some embodiments, condensable hydrocarbons partly has the total C7 and total C25 weight ratio that is greater than 2.0.Alternatively, condensable hydrocarbons part can have so total C7 and total C25 weight ratio, and it is greater than 3.0, is greater than 5.0, is greater than 10.0, is greater than 13.0 or be greater than 15.0.In optional embodiment, condensable hydrocarbons part can have so total C7 and total C25 weight ratio, and it is less than 30.0 or be less than 25.0.In some embodiments, condensable hydrocarbons partly has so total C8 and total C25 weight ratio, and it is greater than 4.5.Alternatively, condensable hydrocarbons part can have so total C8 and total C25 weight ratio, and it is greater than 5.0, is greater than 7.0, is greater than 10.0, is greater than 15.0 or be greater than 17.0.In optional embodiment, condensable hydrocarbons part can have so total C8 and total C25 weight ratio, and it is less than 35.0 or be less than 30.0.In some embodiments, condensable hydrocarbons partly has so total C9 and total C25 weight ratio, and it is greater than 6.5.Alternatively, condensable hydrocarbons part can have so total C9 and total C25 weight ratio, and it is greater than 8.0, is greater than 10.0, is greater than 15.0, is greater than 17.0 or be greater than 19.0.In optional embodiment, condensable hydrocarbons part can have so total C9 and total C25 weight ratio, and it is less than 40.0 or be less than 35.0.In some embodiments, condensable hydrocarbons partly has so total C10 and total C25 weight ratio, and it is greater than 7.5.Alternatively, condensable hydrocarbons part can have so total C10 and total C25 weight ratio, and it is greater than 10.0, is greater than 14.0 or be greater than 17.0.In optional embodiment, condensable hydrocarbons part can have so total C10 and total C25 weight ratio, and it is less than 35.0 or be less than 30.0.In some embodiments, condensable hydrocarbons partly has so total C11 and total C25 weight ratio, and it is greater than 6.5.Alternatively, condensable hydrocarbons part can have so total C11 and total C25 weight ratio, and it is greater than 8.5, is greater than 10.0, is greater than 12.0 or be greater than 14.0.In optional embodiment, condensable hydrocarbons part can have so total C11 and total C25 weight ratio, and it is less than 35.0 or be less than 30.0.In some embodiments, condensable hydrocarbons partly has so total C12 and total C25 weight ratio, and it is greater than 6.5.Alternatively, condensable hydrocarbons part can have the total C12 and total C25 weight ratio that is greater than 8.5, is greater than 10.0, is greater than 12.0 or be greater than 14.0 total C12 and total C25 weight ratio.In optional embodiment, condensable hydrocarbons part can have so total C12 and total C25 weight ratio, and it is less than 30.0 or be less than 25.0.In some embodiments, condensable hydrocarbons partly has so total C13 and total C25 weight ratio, and it is greater than 8.0.Alternatively, condensable hydrocarbons part can have so total C13 and total C25 weight ratio, and it is greater than 10.0, is greater than 12.0 or be greater than 14.0.In optional embodiment, condensable hydrocarbons part can have so total C13 and total C25 weight ratio, and it is less than 25.0 or be less than 20.0.In some embodiments, condensable hydrocarbons partly has so total C14 and total C25 weight ratio, and it is greater than 6.0.Alternatively, condensable hydrocarbons part can have so total C14 and total C25 weight ratio, and it is greater than 8.0, is greater than 10.0 or be greater than 12.0.In optional embodiment, condensable hydrocarbons part can have so total C14 and total C25 weight ratio, and it is less than 25.0 or be less than 20.0.In some embodiments, condensable hydrocarbons partly has so total C15 and total C25 weight ratio, and it is greater than 6.0.Alternatively, condensable hydrocarbons part can have so total C15 and total C25 weight ratio, and it is greater than 8.0 or be greater than 10.0.In optional embodiment, condensable hydrocarbons part can have so total C15 and total C25 weight ratio, and it is less than 25.0 or be less than 20.0.In some embodiments, condensable hydrocarbons partly has so total C16 and total C25 weight ratio, and it is greater than 4.5.Alternatively, condensable hydrocarbons part can have so total C16 and total C25 weight ratio, and it is greater than 6.0, is greater than 8.0 or be greater than 10.0.In optional embodiment, condensable hydrocarbons part can have so total C16 and total C25 weight ratio, and it is less than 20.0 or be less than 15.0.In some embodiments, condensable hydrocarbons partly has so total C17 and total C25 weight ratio, and it is greater than 4.8.Alternatively, condensable hydrocarbons part can have so total C17 and total C25 weight ratio, and it is greater than 5.5 or be greater than 7.0.In optional embodiment, condensable hydrocarbons part can have so total C17 and total C25 weight ratio, and it is less than 20.0.In some embodiments, condensable hydrocarbons partly has so total C18 and total C25 weight ratio, and it is greater than 4.5.Alternatively, condensable hydrocarbons part can have so total C18 and total C25 weight ratio, and it is greater than 5.0 or be greater than 5.5.In optional embodiment, condensable hydrocarbons part can have so total C18 and total C25 weight ratio, and it is less than 15.0.In the paragraph of some feature of the present invention above, for example, for example, according to one group of numerical upper limits (" being less than ") and one group of numerical lower limits (" being greater than "), be described.Should be appreciated that scope that any combination by these boundaries forms within the scope of the invention, except as otherwise noted.The embodiment of describing in this paragraph can with other side of the present invention discussed in this article in any one combines.
In some embodiments, condensable hydrocarbons part can have in following one or more: total C7 is greater than 3.5 with total C29 weight ratio, total C8 is greater than 9.0 with total C29 weight ratio, total C9 is greater than 12.0 with total C29 weight ratio, total C10 is greater than 15.0 with total C29 weight ratio, total C11 is greater than 13.0 with total C29 weight ratio, total C12 is greater than 12.5 with total C29 weight ratio, total C13 is greater than 16.0 with total C29 weight ratio, total C14 is greater than 12.0 with total C29 weight ratio, total C15 is greater than 12.0 with total C29 weight ratio, total C16 is greater than 9.0 with total C29 weight ratio, total C17 is greater than 10.0 with total C29 weight ratio, total C18 is greater than 8.8 with total C29 weight ratio, total C19 is greater than 7.0 with total C29 weight ratio, total C20 is greater than 6.0 with total C29 weight ratio, total C21 is greater than 5.5 with total C29 weight ratio, be greater than 4.2 with total C22 with total C29 weight ratio.In optional embodiment, condensable hydrocarbons partly has in following one or more: total C7 is greater than 16.0 with total C29 weight ratio, total C8 is greater than 19.0 with total C29 weight ratio, total C9 is greater than 20.0 with total C29 weight ratio, total C10 is greater than 18.0 with total C29 weight ratio, total C11 is greater than 16.0 with total C29 weight ratio, total C12 is greater than 15.0 with total C29 weight ratio, total C13 is greater than 17.0 with total C29 weight ratio, total C14 is greater than 13.0 with total C29 weight ratio, total C15 is greater than 13.0 with total C29 weight ratio, total C16 is greater than 10.0 with total C29 weight ratio, total C17 is greater than 11.0 with total C29 weight ratio, total C18 is greater than 9.0 with total C29 weight ratio, total C19 is greater than 8.0 with total C29 weight ratio, total C20 is greater than 6.5 with total C29 weight ratio, be greater than 6.0 with total C21 with total C29 weight ratio.In optional embodiment, condensable hydrocarbons partly has in following one or more: total C7 is greater than 24.0 with total C29 weight ratio, total C8 is greater than 30.0 with total C29 weight ratio, total C9 is greater than 32.0 with total C29 weight ratio, total C10 is greater than 30.0 with total C29 weight ratio, total C11 is greater than 27.0 with total C29 weight ratio, total C12 is greater than 25.0 with total C29 weight ratio, total C13 is greater than 22.0 with total C29 weight ratio, total C14 is greater than 18.0 with total C29 weight ratio, total C15 is greater than 18.0 with total C29 weight ratio, total C16 is greater than 16.0 with total C29 weight ratio, total C17 is greater than 13.0 with total C29 weight ratio, total C18 is greater than 10.0 with total C29 weight ratio, total C19 is greater than 9.0 with total C29 weight ratio, be greater than 7.0 with total C20 with total C29 weight ratio.As used in this paragraph and claims, phrase " one or more "---and then it be a series of different compounds or component ratio, wherein last ratio by conjunction " with " draw---intention comprises such condensable hydrocarbons part, and it has in listed ratio at least one or has in listed ratio two or more or three or more or four or more etc. or all.In addition, specific condensable hydrocarbons partly also can have other different compounds or component ratio, and it is not included in specific sentence or claim but still drops in the scope of such sentence or claim.The embodiment of describing in this paragraph can be with in other side of the present invention discussed in this article, any one be combined.
In some embodiments, condensable hydrocarbons partly has the total C7 and total C29 weight ratio that is greater than 3.5.Alternatively, condensable hydrocarbons part can have so total C7 and total C29 weight ratio, and it is greater than 5.0, is greater than 10.0, is greater than 18.0, is greater than 20.0 or be greater than 24.0.In optional embodiment, condensable hydrocarbons part can have so total C7 and total C29 weight ratio, and it is less than 60.0 or be less than 50.0.In some embodiments, condensable hydrocarbons partly has so total C8 and total C29 weight ratio, and it is greater than 9.0.Alternatively, condensable hydrocarbons part can have so total C8 and total C29 weight ratio, and it is greater than 10.0, is greater than 18.0, is greater than 20.0, is greater than 25.0 or be greater than 30.0.In optional embodiment, condensable hydrocarbons part can have so total C8 and total C29 weight ratio, and it is less than 85.0 or be less than 75.0.In some embodiments, condensable hydrocarbons partly has so total C9 and total C29 weight ratio, and it is greater than 12.0.Alternatively, condensable hydrocarbons part can have so total C9 and total C29 weight ratio, and it is greater than 15.0, is greater than 20.0, is greater than 23.0, is greater than 27.0 or be greater than 32.0.In optional embodiment, condensable hydrocarbons part can have so total C9 and total C29 weight ratio, and it is less than 85.0 or be less than 75.0.In some embodiments, condensable hydrocarbons partly has so total C10 and total C29 weight ratio, and it is greater than 15.0.Alternatively, condensable hydrocarbons part can have so total C10 and total C29 weight ratio, and it is greater than 18.0, is greater than 22.0 or be greater than 28.0.In optional embodiment, condensable hydrocarbons part can have so total C10 and total C29 weight ratio, and it is less than 80.0 or be less than 70.0.In some embodiments, condensable hydrocarbons partly has so total C11 and total C29 weight ratio, and it is greater than 13.0.Alternatively, condensable hydrocarbons part can have so total C11 and total C29 weight ratio, and it is greater than 16.0, is greater than 18.0, is greater than 24.0 or be greater than 27.0.In optional embodiment, condensable hydrocarbons part can have so total C11 and total C29 weight ratio, and it is less than 75.0 or be less than 65.0.In some embodiments, condensable hydrocarbons partly has so total C12 and total C29 weight ratio, and it is greater than 12.5.Alternatively, condensable hydrocarbons part can have so total C12 and total C29 weight ratio, and it is greater than 14.5, is greater than 18.0, is greater than 22.0 or be greater than 25.0.In optional embodiment, condensable hydrocarbons part can have so total C12 and total C29 weight ratio, and it is less than 75.0 or be less than 65.0.In some embodiments, condensable hydrocarbons partly has so total C13 and total C29 weight ratio, and it is greater than 16.0.Alternatively, condensable hydrocarbons part can have so total C13 and total C29 weight ratio, and it is greater than 18.0, is greater than 20.0 or be greater than 22.0.In optional embodiment, condensable hydrocarbons part can have so total C13 and total C29 weight ratio, and it is less than 70.0 or be less than 60.0.In some embodiments, condensable hydrocarbons partly has so total C14 and total C29 weight ratio, and it is greater than 12.0.Alternatively, condensable hydrocarbons part can have so total C14 and total C29 weight ratio, and it is greater than 14.0, is greater than 16.0 or be greater than 18.0.In optional embodiment, condensable hydrocarbons part can have so total C14 and total C29 weight ratio, and it is less than 60.0 or be less than 50.0.In some embodiments, condensable hydrocarbons partly has so total C15 and total C29 weight ratio, and it is greater than 12.0.Alternatively, condensable hydrocarbons part can have so total C15 and total C29 weight ratio, and it is greater than 15.0 or be greater than 18.0.In optional embodiment, condensable hydrocarbons part can have so total C15 and total C29 weight ratio, and it is less than 60.0 or be less than 50.0.In some embodiments, condensable hydrocarbons partly has so total C16 and total C29 weight ratio, and it is greater than 9.0.Alternatively, condensable hydrocarbons part can have so total C16 and total C29 weight ratio, and it is greater than 10.0, is greater than 13.0 or be greater than 16.0.In optional embodiment, condensable hydrocarbons part can have so total C16 and total C29 weight ratio, and it is less than 55.0 or be less than 45.0.In some embodiments, condensable hydrocarbons partly has so total C17 and total C29 weight ratio, and it is greater than 10.0.Alternatively, condensable hydrocarbons part can have so total C17 and total C29 weight ratio, and it is greater than 11.0 or be greater than 12.0.In optional embodiment, condensable hydrocarbons part can have so total C17 and total C29 weight ratio, and it is less than 45.0.In some embodiments, condensable hydrocarbons partly has so total C18 and total C29 weight ratio, and it is greater than 8.8.Alternatively, condensable hydrocarbons part can have so total C18 and total C29 weight ratio, and it is greater than 9.0 or be greater than 10.0.In optional embodiment, condensable hydrocarbons part can have so total C18 and total C29 weight ratio, and it is less than 35.0.In some embodiments, condensable hydrocarbons partly has so total C19 and total C29 weight ratio, and it is greater than 7.0.Alternatively, condensable hydrocarbons part can have so total C19 and total C29 weight ratio, and it is greater than 8.0 or be greater than 9.0.In optional embodiment, condensable hydrocarbons part can have so total C19 and total C29 weight ratio, and it is less than 30.0.In the paragraph of some feature of the present invention above, for example, for example, according to one group of numerical upper limits (" being less than ") and one group of numerical lower limits (" being greater than "), be described.Should be appreciated that scope that any combination by these boundaries forms within the scope of the invention, except as otherwise noted.The embodiment of describing in this paragraph can with other side of the present invention discussed in this article in any one combines.
In some embodiments, condensable hydrocarbons part can have in following one or more: total C9 with total C20 weight ratio between 2.5 and 6.0, total C10 and total C20 weight ratio are between 2.8 and 7.3, total C11 and total C20 weight ratio are between 2.6 and 6.5, total C12 with total C20 weight ratio between 2.6 and 6.4, and always C13 and always C20 weight ratio between 3.2 and 8.0.In optional embodiment, condensable hydrocarbons partly has in following one or more: total C9 with total C20 weight ratio between 3.0 and 5.5, total C10 and total C20 weight ratio are between 3.2 and 7.0, total C11 and total C20 weight ratio are between 3.0 and 6.0, total C12 with total C20 weight ratio between 3.0 and 6.0, and always C13 and always C20 weight ratio between 3.3 and 7.0.In optional embodiment, condensable hydrocarbons partly has in following one or more: total C9 with total C20 weight ratio between 4.6 and 5.5, total C10 and total C20 weight ratio are between 4.2 and 7.0, total C11 and total C20 weight ratio are between 3.7 and 6.0, total C12 with total C20 weight ratio between 3.6 and 6.0, and always C13 and always C20 weight ratio between 3.4 and 7.0.As used in this paragraph and claims, phrase " one or more "---and then it be a series of different compounds or component ratio, wherein last ratio by conjunction " with " draw---intention comprises such condensable hydrocarbons part, and it has in listed ratio at least one or has in listed ratio two or more or three or more or four or more etc. or all.In addition, specific condensable hydrocarbons partly also can have other different compounds or component ratio, and it is not included in specific sentence or claim but still drops in the scope of such sentence or claim.The embodiment of describing in this paragraph can be with in other side of the present invention discussed in this article, any one be combined.
In some embodiments, condensable hydrocarbons partly has so total C9 and total C20 weight ratio, and they are between 2.5 and 6.0.Alternatively, condensable hydrocarbons part can have so total C9 and total C20 weight ratio, and they are between 3.0 and 5.8, between 3.5 and 5.8, between 4.0 and 5.8, between 4.5 and 5.8, between 4.6 and 5.8, or between 4.7 and 5.8.In some embodiments, condensable hydrocarbons partly has so total C10 and total C20 weight ratio, and they are between 2.8 and 7.3.Alternatively, condensable hydrocarbons part can have so total C10 and total C20 weight ratio, and they are between 3.0 and 7.2, between 3.5 and 7.0, between 4.0 and 7.0, between 4.2 and 7.0, between 4.3 and 7.0, or between 4.4 and 7.0.In some embodiments, condensable hydrocarbons partly has so total C11 and total C20 weight ratio, and they are between 2.6 and 6.5.Alternatively, condensable hydrocarbons part can have so total C11 and total C20 weight ratio, and they are between 2.8 and 6.3, between 3.5 and 6.3, between 3.7 and 6.3, between 3.8 and 6.3, between 3.9 and 6.2, or between 4.0 and 6.2.In some embodiments, condensable hydrocarbons partly has so total C12 and total C20 weight ratio, and they are between 2.6 and 6.4.Alternatively, condensable hydrocarbons part can have so total C12 and total C20 weight ratio, and they are between 2.8 and 6.2, between 3.2 and 6.2, between 3.5 and 6.2, between 3.6 and 6.2, between 3.7 and 6.0, or between 3.8 and 6.0.In some embodiments, condensable hydrocarbons partly has so total C13 and total C20 weight ratio, and they are between 3.2 and 8.0.Alternatively, condensable hydrocarbons part can have so total C13 and total C20 weight ratio, and they are between 3.3 and 7.8, between 3.3 and 7.0, between 3.4 and 7.0, between 3.5 and 6.5, or between 3.6 and 6.0.The embodiment of describing in this paragraph can with other side of the present invention discussed in this article in any one combines.
In some embodiments, condensable hydrocarbons part can have in following one or more: total C10 with total C25 weight ratio between 7.1 and 24.5, total C11 and total C25 weight ratio are between 6.5 and 22.0, total C12 with total C25 weight ratio between 6.5 and 22.0, and always C13 and always C25 weight ratio between 8.0 and 27.0.In optional embodiment, condensable hydrocarbons partly has in following one or more: total C10 with total C25 weight ratio between 10.0 and 24.0, total C11 and total C25 weight ratio are between 10.0 and 21.5, total C12 with total C25 weight ratio between 10.0 and 21.5, and always C13 and always C25 weight ratio between 9.0 and 25.0.In optional embodiment, condensable hydrocarbons partly has in following one or more: total C10 with total C25 weight ratio between 14.0 and 24.0, total C11 and total C25 weight ratio are between 12.5 and 21.5, total C12 with total C25 weight ratio between 12.0 and 21.5, and always C13 and always C25 weight ratio between 10.5 and 25.0.As used in this paragraph and claims, phrase " one or more "---and then it be a series of different compounds or component ratio, wherein last ratio by conjunction " with " draw---intention comprises such condensable hydrocarbons part, and it has in listed ratio at least one or has in listed ratio two or more or three or more or four or more etc. or all.In addition, specific condensable hydrocarbons partly also can have other different compounds or component ratio, and it is not included in specific sentence or claim but still drops in the scope of such sentence or claim.The embodiment of describing in this paragraph can be with in other side of the present invention discussed in this article, any one be combined.
In some embodiments, condensable hydrocarbons partly has so total C10 and total C25 weight ratio, and they are between 7.1 and 24.5.Alternatively, condensable hydrocarbons part can have so total C10 and total C25 weight ratio, and they are between 7.5 and 24.5, between 12.0 and 24.5, between 13.8 and 24.5, between 14.0 and 24.5, or between 15.0 and 24.5.In some embodiments, condensable hydrocarbons partly has so total C11 and total C25 weight ratio, and they are between 6.5 and 22.0.Alternatively, condensable hydrocarbons part can have so total C11 and total C25 weight ratio, and they are between 7.0 and 21.5, between 10.0 and 21.5, between 12.5 and 21.5, between 13.0 and 21.5, between 13.7 and 21.5, or between 14.5 and 21.5.In some embodiments, condensable hydrocarbons partly has so total C12 and total C25 weight ratio, and they are between 10.0 and 21.5.Alternatively, condensable hydrocarbons part can have so total C12 and total C25 weight ratio, and they are between 10.5 and 21.0, between 11.0 and 21.0, between 12.0 and 21.0, between 12.5 and 21.0, between 13.0 and 21.0, or between 13.5 and 21.0.In some embodiments, condensable hydrocarbons partly has so total C13 and total C25 weight ratio, and they are between 8.0 and 27.0.Alternatively, condensable hydrocarbons part can have so total C13 and total C25 weight ratio, and they are between 9.0 and 26.0, between 10.0 and 25.0, between 10.5 and 25.0, between 11.0 and 25.0, or between 11.5 and 25.0.The embodiment of describing in this section can be with in other side of the present invention discussed in this article, any one be combined.
In some embodiments, condensable hydrocarbons part can have in following one or more: total C10 with total C29 weight ratio between 15.0 and 60.0, total C11 and total C29 weight ratio are between 13.0 and 54.0, total C12 with total C29 weight ratio between 12.5 and 53.0, and always C13 and always C29 weight ratio between 16.0 and 65.0.In optional embodiment, condensable hydrocarbons partly has in following one or more: total C10 with total C29 weight ratio between 17.0 and 58.0, total C11 and total C29 weight ratio are between 15.0 and 52.0, total C12 with total C29 weight ratio between 14.0 and 50.0, and always C13 and always C29 weight ratio between 17.0 and 60.0.In optional embodiment, condensable hydrocarbons partly has in following one or more: total C10 with total C29 weight ratio between 20.0 and 58.0, total C11 and total C29 weight ratio are between 18.0 and 52.0, total C12 with total C29 weight ratio between 18.0 and 50.0, and always C13 and always C29 weight ratio between 18.0 and 50.0.As used in this section and claims, phrase " one or more "---and then it be a series of different compounds or component ratio, wherein last ratio by conjunction " with " draw---intention comprises such condensable hydrocarbons part, and it has in listed ratio at least one or has in listed ratio two or more or three or more or four or more etc. or all.In addition, specific condensable hydrocarbons partly also can have other different compounds or component ratio, and it is not included in specific sentence or claim but still drops in the scope of such sentence or claim.The embodiment of describing in this section can be with in other side of the present invention discussed in this article, any one be combined.
In some embodiments, condensable hydrocarbons partly has so total C10 and total C29 weight ratio, and they are between 15.0 and 60.0.Alternatively, condensable hydrocarbons part can have so total C10 and total C29 weight ratio, and they are between 18.0 and 58.0, between 20.0 and 58.0, between 24.0 and 58.0, between 27.0 and 58.0, or between 30.0 and 58.0.In some embodiments, condensable hydrocarbons partly has so total C11 and total C29 weight ratio, and they are between 13.0 and 54.0.Alternatively, condensable hydrocarbons part can have so total C11 and total C29 weight ratio, and they are between 15.0 and 53.0, between 18.0 and 53.0, between 20.0 and 53.0, between 22.0 and 53.0, between 25.0 and 53.0, or between 27.0 and 53.0.In some embodiments, condensable hydrocarbons partly has so total C12 and total C29 weight ratio, and they are between 12.5 and 53.0.Alternatively, condensable hydrocarbons part can have so total C12 and total C29 weight ratio, and they are between 14.5 and 51.0, between 16.0 and 51.0, between 18.0 and 51.0, between 20.0 and 51.0, between 23.0 and 51.0, or between 25.0 and 51.0.In some embodiments, condensable hydrocarbons partly has so total C13 and total C29 weight ratio, and they are between 16.0 and 65.0.Alternatively, condensable hydrocarbons part can have so total C13 and total C29 weight ratio, and they are between 17.0 and 60.0, between 18.0 and 60.0, between 20.0 and 60.0, between 22.0 and 60.0, or between 25.0 and 60.0.The embodiment of describing in this section can with other side of the present invention discussed in this article in any one combines.
In some embodiments, condensable hydrocarbons part can have in following one or more: positive C7 is greater than 0.9 with positive C20 weight ratio, positive C8 is greater than 2.0 with positive C20 weight ratio, positive C9 is greater than 1.9 with positive C20 weight ratio, positive C10 is greater than 2.2 with positive C20 weight ratio, positive C11 is greater than 1.9 with positive C20 weight ratio, positive C12 is greater than 1.9 with positive C20 weight ratio, positive C13 is greater than 2.3 with positive C20 weight ratio, positive C14 is greater than 1.8 with positive C20 weight ratio, positive C15 is greater than 1.8 with positive C20 weight ratio, and positive C16 is greater than 1.3 with positive C20 weight ratio.In optional embodiment, condensable hydrocarbons partly has in following one or more: positive C7 is greater than 4.4 with positive C20 weight ratio, positive C8 is greater than 3.7 with positive C20 weight ratio, positive C9 is greater than 3.5 with positive C20 weight ratio, positive C10 is greater than 3.4 with positive C20 weight ratio, positive C11 is greater than 3.0 with positive C20 weight ratio, and positive C12 is greater than 2.7 with positive C20 weight ratio.In optional embodiment, condensable hydrocarbons partly has in following one or more: positive C7 is greater than 4.9 with positive C20 weight ratio, positive C8 is greater than 4.5 with positive C20 weight ratio, positive C9 is greater than 4.4 with positive C20 weight ratio, positive C10 is greater than 4.1 with positive C20 weight ratio, positive C11 and positive 20 weight ratios are greater than 3.7, and positive C12 is greater than 3.0 with positive C20 weight ratio.As used in this section and claims, phrase " one or more "---and then it be a series of different compounds or component ratio, wherein last ratio by conjunction " with " draw---intention comprises such condensable hydrocarbons part, and it has in listed ratio at least one or has in listed ratio two or more or three or more or four or more etc. or all.In addition, specific condensable hydrocarbons partly also can have other different compounds or component ratio, and it is not included in specific sentence or claim but still drops in the scope of such sentence or claim.The embodiment of describing in this section can be with in other side of the present invention discussed in this article, any one be combined.
In some embodiments, condensable hydrocarbons partly has so positive C7 and positive C20 weight ratio, and it is greater than 0.9.Alternatively, condensable hydrocarbons part can have so positive C7 and positive C20 weight ratio, and it is greater than 1.0, is greater than 2.0, is greater than 3.0, is greater than 4.0, is greater than 4.5 or be greater than 5.0.In optional embodiment, condensable hydrocarbons part can have so positive C7 and positive C20 weight ratio, and it is less than 8.0 or be less than 7.0.In some embodiments, condensable hydrocarbons partly has so positive C8 and positive C20 weight ratio, and it is greater than 1.7.Alternatively, condensable hydrocarbons part can have so positive C8 and positive C20 weight ratio, and it is greater than 2.0, is greater than 2.5, is greater than 3.0, is greater than 3.5, is greater than 4.0 or be greater than 4.4.In optional embodiment, condensable hydrocarbons part can have so positive C8 and positive C20 weight ratio, and it is less than 8.0 or be less than 7.0.In some embodiments, condensable hydrocarbons partly has so positive C9 and positive C20 weight ratio, and it is greater than 1.9.Alternatively, condensable hydrocarbons part can have so positive C9 and positive C20 weight ratio, and it is greater than 2.0, is greater than 3.0, is greater than 4.0 or be greater than 4.5.In optional embodiment, condensable hydrocarbons part can have so positive C9 and positive C20 weight ratio, and it is less than 7.0 or be less than 6.0.In some embodiments, condensable hydrocarbons partly has so positive C10 and positive C20 weight ratio, and it is greater than 2.2.Alternatively, condensable hydrocarbons part can have so positive C10 and positive C20 weight ratio, and it is greater than 2.8, is greater than 3.3, is greater than 3.5 or be greater than 4.0.In optional embodiment, condensable hydrocarbons part can have so positive C10 and positive C20 weight ratio, and it is less than 7.0 or be less than 6.0.In some embodiments, condensable hydrocarbons partly has so positive C11 and positive C20 weight ratio, and it is greater than 1.9.Alternatively, condensable hydrocarbons part can have so positive C11 and positive C20 weight ratio, and it is greater than 2.5, is greater than 3.0, is greater than 3.5 or be greater than 3.7.In optional embodiment, condensable hydrocarbons part can have so positive C11 and positive C20 weight ratio, and it is less than 7.0 or be less than 6.0.In some embodiments, condensable hydrocarbons partly has so positive C12 and positive C20 weight ratio, and it is greater than 1.9.Alternatively, condensable hydrocarbons part can have so positive C12 and positive C20 weight ratio, and it is greater than 2.0, is greater than 2.2, is greater than 2.6 or be greater than 3.0.In optional embodiment, condensable hydrocarbons part can have so positive C12 and positive C20 weight ratio, and it is less than 7.0 or be less than 6.0.In some embodiments, condensable hydrocarbons partly has so positive C13 and positive C20 weight ratio, and it is greater than 2.3.Alternatively, condensable hydrocarbons part can have so positive C13 and positive C20 weight ratio, and it is greater than 2.5, is greater than 2.7 or be greater than 3.0.In optional embodiment, condensable hydrocarbons part can have so positive C13 and positive C20 weight ratio, and it is less than 6.0 or be less than 5.0.In some embodiments, condensable hydrocarbons partly has so positive C14 and positive C20 weight ratio, and it is greater than 1.8.Alternatively, condensable hydrocarbons part can have so positive C14 and positive C20 weight ratio, and it is greater than 2.0, is greater than 2.2 or be greater than 2.5.In optional embodiment, condensable hydrocarbons part can have so positive C14 and positive C20 weight ratio, and it is less than 6.0 or be less than 4.0.In some embodiments, condensable hydrocarbons partly has so positive C15 and positive C20 weight ratio, and it is greater than 1.8.Alternatively, condensable hydrocarbons part can have so positive C15 and positive C20 weight ratio, and it is greater than 2.0, is greater than 2.2 or be greater than 2.4.In optional embodiment, condensable hydrocarbons part can have so positive C15 and positive C20 weight ratio, and it is less than 6.0 or be less than 4.0.In some embodiments, condensable hydrocarbons partly has so positive C16 and positive C20 weight ratio, and it is greater than 1.3.Alternatively, condensable hydrocarbons part can have so positive C16 and positive C20 weight ratio, and it is greater than 1.5, is greater than 1.7 or be greater than 2.0.In optional embodiment, condensable hydrocarbons part can have so positive C16 and positive C20 weight ratio, and it is less than 5.0 or be less than 4.0.In the paragraph of some feature of the present invention above, for example, for example, according to one group of numerical upper limits (" being less than ") and one group of numerical lower limits (" being greater than "), be described.Should be appreciated that scope that any combination by these boundaries forms within the scope of the invention, except as otherwise noted.The embodiment of describing in this paragraph can with other side of the present invention discussed in this article in any one combines.
In some embodiments, condensable hydrocarbons part can have in following one or more: positive C7 is greater than 1.9 with positive C25 weight ratio, positive C8 is greater than 3.9 with positive C25 weight ratio, positive C9 is greater than 3.7 with positive C25 weight ratio, positive C10 is greater than 4.4 with positive C25 weight ratio, positive C11 is greater than 3.8 with positive C25 weight ratio, positive C12 is greater than 3.7 with positive C25 weight ratio, positive C13 is greater than 4.7 with positive C25 weight ratio, positive C14 is greater than 3.7 with positive C25 weight ratio, positive C15 is greater than 3.7 with positive C25 weight ratio, positive C16 is greater than 2.5 with positive C25 weight ratio, positive C17 is greater than 3.0 with positive C25 weight ratio, be greater than 3.4 with positive C18 with positive C25 weight ratio.In optional embodiment, condensable hydrocarbons partly has in following one or more: positive C7 is greater than 10 with positive C25 weight ratio, positive C8 is greater than 8.0 with positive C25 weight ratio, positive C9 is greater than 7.0 with positive C25 weight ratio, positive C10 is greater than 7.0 with positive C25 weight ratio, positive C11 is greater than 7.0 with positive C25 weight ratio, and positive C12 is greater than 6.0 with positive C25 weight ratio.In optional embodiment, condensable hydrocarbons partly has in following one or more: positive C7 is greater than 10.0 with positive C25 weight ratio, positive C8 is greater than 12.0 with positive C25 weight ratio, positive C9 is greater than 11.0 with positive C25 weight ratio, positive C10 is greater than 11.0 with positive C25 weight ratio, positive C11 is greater than 9.0 with positive C25 weight ratio, and positive C12 is greater than 8.0 with positive C25 weight ratio.As used in this section and claims, phrase " one or more "---and then it be a series of different compounds or component ratio, wherein last ratio by conjunction " with " draw---intention comprises such condensable hydrocarbons part, and it has in listed ratio at least one or has in listed ratio two or more or three or more or four or more etc. or all.In addition, specific condensable hydrocarbons partly also can have other different compounds or component ratio, and it is not included in specific sentence or claim but still drops in the scope of such sentence or claim.The embodiment of describing in this section can be with in other side of the present invention discussed in this article, any one be combined.
In some embodiments, condensable hydrocarbons partly has so positive C7 and positive C25 weight ratio, and it is greater than 1.9.Alternatively, condensable hydrocarbons part can have so positive C7 and positive C25 weight ratio, and it is greater than 3.0, is greater than 5.0, is greater than 8.0, is greater than 10.0 or be greater than 13.0.In optional embodiment, condensable hydrocarbons part can have so positive C7 and positive C25 weight ratio, and it is less than 35.0 or be less than 25.0.In some embodiments, condensable hydrocarbons partly has so positive C8 and positive C25 weight ratio, and it is greater than 3.9.Alternatively, condensable hydrocarbons part can have so positive C8 and positive C25 weight ratio, and it is greater than 4.5, is greater than 6.0, is greater than 8.0, is greater than 10.0 or be greater than 13.0.In optional embodiment, condensable hydrocarbons part can have so positive C8 and positive C25 weight ratio, and it is less than 35.0 or be less than 25.0.In some embodiments, condensable hydrocarbons partly has so positive C9 and positive C25 weight ratio, and it is greater than 3.7.Alternatively, condensable hydrocarbons part can have so positive C9 and positive C25 weight ratio, and it is greater than 4.5, is greater than 7.0, is greater than 10.0, is greater than 12.0 or be greater than 13.0.In optional embodiment, condensable hydrocarbons part can have so positive C9 and positive C25 weight ratio, and it is less than 35.0 or be less than 25.0.In some embodiments, condensable hydrocarbons partly has so positive C10 and positive C25 weight ratio, and it is greater than 4.4.Alternatively, condensable hydrocarbons part can have so positive C10 and positive C25 weight ratio, and it is greater than 6.0, is greater than 8.0 or be greater than 11.0.In optional embodiment, condensable hydrocarbons part can have so positive C10 and positive C25 weight ratio, and it is less than 35.0 or be less than 25.0.In some embodiments, condensable hydrocarbons partly has so positive C11 and positive C25 weight ratio, and it is greater than 3.8.Alternatively, condensable hydrocarbons part can have so positive C11 and positive C25 weight ratio, and it is greater than 4.5, is greater than 7.0, is greater than 8.0 or be greater than 10.0.In optional embodiment, condensable hydrocarbons part can have so positive C11 and positive C25 weight ratio, and it is less than 35.0 or be less than 25.0.In some embodiments, condensable hydrocarbons partly has so positive C12 and positive C25 weight ratio, and it is greater than 3.7.Alternatively, condensable hydrocarbons part can have so positive C12 and positive C25 weight ratio, and it is greater than 4.5, is greater than 6.0, is greater than 7.0 or be greater than 8.0.In optional embodiment, condensable hydrocarbons part can have so positive C12 and positive C25 weight ratio, and it is less than 30.0 or be less than 20.0.In some embodiments, condensable hydrocarbons partly has so positive C13 and positive C25 weight ratio, and it is greater than 4.7.Alternatively, condensable hydrocarbons part can have so positive C13 and positive C25 weight ratio, and it is greater than 5.0, is greater than 6.0 or be greater than 7.5.In optional embodiment, condensable hydrocarbons part can have so positive C13 and positive C25 weight ratio, and it is less than 25.0 or be less than 20.0.In some embodiments, condensable hydrocarbons partly has so positive C14 and positive C25 weight ratio, and it is greater than 3.7.Alternatively, condensable hydrocarbons part can have so positive C14 and positive C25 weight ratio, and it is greater than 4.5, is greater than 5.5 or be greater than 7.0.In optional embodiment, condensable hydrocarbons part can have so positive C14 and positive C25 weight ratio, and it is less than 25.0 or be less than 20.0.In some embodiments, condensable hydrocarbons partly has so positive C15 and positive C25 weight ratio, and it is greater than 3.7.Alternatively, condensable hydrocarbons part can have so positive C15 and positive C25 weight ratio, and it is greater than 4.2 or be greater than 5.0.In optional embodiment, condensable hydrocarbons part can have so positive C15 and positive C25 weight ratio, and it is less than 25.0 or be less than 20.0.In some embodiments, condensable hydrocarbons partly has so positive C16 and positive C25 weight ratio, and it is greater than 2.5.Alternatively, condensable hydrocarbons part can have so positive C16 and positive C25 weight ratio, and it is greater than 3.0, is greater than 4.0 or be greater than 5.0.In optional embodiment, condensable hydrocarbons part can have so positive C16 and positive C25 weight ratio, and it is less than 20.0 or be less than 15.0.In some embodiments, condensable hydrocarbons partly has so positive C17 and positive C25 weight ratio, and it is greater than 3.0.Alternatively, condensable hydrocarbons part can have so positive C17 and positive C25 weight ratio, and it is greater than 3.5 or be greater than 4.0.In optional embodiment, condensable hydrocarbons part can have so positive C17 and positive C25 weight ratio, and it is less than 20.0.In some embodiments, condensable hydrocarbons partly has so positive C18 and positive C25 weight ratio, and it is greater than 3.4.Alternatively, condensable hydrocarbons part can have so positive C18 and positive C25 weight ratio, and it is greater than 3.6 or be greater than 4.0.In optional embodiment, condensable hydrocarbons part can have so positive C18 and positive C25 weight ratio, and it is less than 15.0.In the paragraph of some feature of the present invention above, for example, for example, according to one group of numerical upper limits (" being less than ") and one group of numerical lower limits (" being greater than "), be described.Should be appreciated that scope that any combination by these boundaries forms within the scope of the invention, except as otherwise noted.The embodiment of describing in this paragraph can with other side of the present invention discussed in this article in any one combines.
In some embodiments, condensable hydrocarbons part can have in following one or more: positive C7 is greater than 18.0 with positive C29 weight ratio, positive C8 is greater than 16.0 with positive C29 weight ratio, positive C9 is greater than 14.0 with positive C29 weight ratio, positive C10 is greater than 14.0 with positive C29 weight ratio, positive C11 is greater than 13.0 with positive C29 weight ratio, positive C12 is greater than 11.0 with positive C29 weight ratio, positive C13 is greater than 10.0 with positive C29 weight ratio, positive C14 is greater than 9.0 with positive C29 weight ratio, positive C15 is greater than 8.0 with positive C29 weight ratio, positive C16 is greater than 8.0 with positive C29 weight ratio, positive C17 is greater than 6.0 with positive C29 weight ratio, positive C18 is greater than 6.0 with positive C29 weight ratio, positive C19 is greater than 5.0 with positive C29 weight ratio, positive C20 is greater than 4.0 with positive C29 weight ratio, positive C21 is greater than 3.6 with positive C29 weight ratio, be greater than 2.8 with positive C22 with positive C29 weight ratio.In optional embodiment, condensable hydrocarbons partly has in following one or more: positive C7 is greater than 20.0 with positive C29 weight ratio, positive C8 is greater than 18.0 with positive C29 weight ratio, positive C9 is greater than 17.0 with positive C29 weight ratio, positive C10 is greater than 16.0 with positive C29 weight ratio, positive C11 is greater than 15.0 with positive C29 weight ratio, positive C12 is greater than 12.5 with positive C29 weight ratio, positive C13 is greater than 11.0 with positive C29 weight ratio, positive C14 is greater than 10.0 with positive C29 weight ratio, positive C15 is greater than 8.0 with positive C29 weight ratio, positive C16 is greater than 8.0 with positive C29 weight ratio, positive C17 is greater than 7.0 with positive C29 weight ratio, positive C18 is greater than 6.5 with positive C29 weight ratio, positive C19 is greater than 5.5 with positive C29 weight ratio, positive C20 is greater than 4.5 with positive C29 weight ratio, be greater than 4.0 with positive C21 with positive C29 weight ratio.In optional embodiment, condensable hydrocarbons partly has in following one or more: positive C7 is greater than 23.0 with positive C29 weight ratio, positive C8 is greater than 21.0 with positive C29 weight ratio, positive C9 is greater than 20.0 with positive C29 weight ratio, positive C10 is greater than 19.0 with positive C29 weight ratio, positive C11 is greater than 17.0 with positive C29 weight ratio, positive C12 is greater than 14.0 with positive C29 weight ratio, positive C13 is greater than 12.0 with positive C29 weight ratio, positive C14 is greater than 11.0 with positive C29 weight ratio, positive C15 is greater than 9.0 with positive C29 weight ratio, positive C16 is greater than 9.0 with positive C29 weight ratio, positive C17 is greater than 7.5 with positive C29 weight ratio, positive C18 is greater than 7.0 with positive C29 weight ratio, positive C19 is greater than 6.5 with positive C29 weight ratio, positive C20 is greater than 4.8 with positive C29 weight ratio, be greater than 4.5 with positive C21 with positive C29 weight ratio.As used in this section and claims, phrase " one or more "---and then it be a series of different compounds or component ratio, wherein last ratio by conjunction " with " draw---intention comprises such condensable hydrocarbons part, and it has in listed ratio at least one or has in listed ratio two or more or three or more or four or more etc. or all.In addition, specific condensable hydrocarbons partly also can have other different compounds or component ratio, and it is not included in specific sentence or claim but still drops in the scope of such sentence or claim.The embodiment of describing in this section can be with that any one is discussed in other side of the present invention be herein combined.
In some embodiments, condensable hydrocarbons partly has so positive C7 and positive C29 weight ratio, and it is greater than 18.0.Alternatively, condensable hydrocarbons part can have so positive C7 and positive C29 weight ratio, and it is greater than 20.0, is greater than 22.0, is greater than 25.0, is greater than 30.0 or be greater than 35.0.In optional embodiment, condensable hydrocarbons part can have so positive C7 and positive C29 weight ratio, and it is less than 70.0 or be less than 60.0.In some embodiments, condensable hydrocarbons partly has so positive C8 and positive C29 weight ratio, and it is greater than 16.0.Alternatively, condensable hydrocarbons part can have so positive C8 and positive C29 weight ratio, and it is greater than 18.0, is greater than 22.0, is greater than 25.0, is greater than 27.0 or be greater than 30.0.In optional embodiment, condensable hydrocarbons part can have so positive C8 and positive C29 weight ratio, and it is less than 85.0 or be less than 75.0.In some embodiments, condensable hydrocarbons partly has so positive C9 and positive C29 weight ratio, and it is greater than 14.0.Alternatively, condensable hydrocarbons part can have so positive C9 and positive C29 weight ratio, and it is greater than 18.0, is greater than 20.0, is greater than 23.0, is greater than 27.0 or be greater than 30.0.In optional embodiment, condensable hydrocarbons part can have so positive C9 and positive C29 weight ratio, and it is less than 85.0 or be less than 75.0.In some embodiments, condensable hydrocarbons partly has so positive C10 and positive C29 weight ratio, and it is greater than 14.0.Alternatively, condensable hydrocarbons part can have so positive C10 and positive C29 weight ratio, and it is greater than 20.0, is greater than 25.0 or be greater than 30.0.In optional embodiment, condensable hydrocarbons part can have so positive C10 and positive C29 weight ratio, and it is less than 80.0 or be less than 70.0.In some embodiments, condensable hydrocarbons partly has so positive C11 and positive C29 weight ratio, and it is greater than 13.0.Alternatively, condensable hydrocarbons part can have so positive C11 and positive C29 weight ratio, and it is greater than 16.0, is greater than 18.0, is greater than 24.0 or be greater than 27.0.In optional embodiment, condensable hydrocarbons part can have so positive C11 and positive C29 weight ratio, and it is less than 75.0 or be less than 65.0.In some embodiments, condensable hydrocarbons partly has so positive C12 and positive C29 weight ratio, and it is greater than 11.0.Alternatively, condensable hydrocarbons part can have so positive C12 and positive C29 weight ratio, and it is greater than 14.5, is greater than 18.0, is greater than 22.0 or be greater than 25.0.In optional embodiment, condensable hydrocarbons part can have so positive C12 and positive C29 weight ratio, and it is less than 75.0 or be less than 65.0.In some embodiments, condensable hydrocarbons partly has so positive C13 and positive C29 weight ratio, and it is greater than 10.0.Alternatively, condensable hydrocarbons part can have so positive C13 and positive C29 weight ratio, and it is greater than 18.0, is greater than 20.0 or be greater than 22.0.In optional embodiment, condensable hydrocarbons part can have so positive C13 and positive C29 weight ratio, and it is less than 70.0 or be less than 60.0.In some embodiments, condensable hydrocarbons partly has so positive C14 and positive C29 weight ratio, and it is greater than 9.0.Alternatively, condensable hydrocarbons part can have so positive C14 and positive C29 weight ratio, and it is greater than 14.0, is greater than 16.0 or be greater than 18.0.In optional embodiment, condensable hydrocarbons part can have so positive C14 and positive C29 weight ratio, and it is less than 60.0 or be less than 50.0.In some embodiments, condensable hydrocarbons partly has so positive C15 and positive C29 weight ratio, and it is greater than 8.0.Alternatively, condensable hydrocarbons part can have so positive C15 and positive C29 weight ratio, and it is greater than 12.0 or be greater than 16.0.In optional embodiment, condensable hydrocarbons part can have so positive C15 and positive C29 weight ratio, and it is less than 60.0 or be less than 50.0.In some embodiments, condensable hydrocarbons partly has so positive C16 and positive C29 weight ratio, and it is greater than 8.0.Alternatively, condensable hydrocarbons part can have so positive C16 and positive C29 weight ratio, and it is greater than 10.0, is greater than 13.0 or be greater than 15.0.In optional embodiment, condensable hydrocarbons part can have so positive C16 and positive C29 weight ratio, and it is less than 55.0 or be less than 45.0.In some embodiments, condensable hydrocarbons partly has so positive C17 and positive C29 weight ratio, and it is greater than 6.0.Alternatively, condensable hydrocarbons part can have so positive C17 and positive C29 weight ratio, and it is greater than 8.0 or be greater than 12.0.In optional embodiment, condensable hydrocarbons part can have so positive C17 and positive C29 weight ratio, and it is less than 45.0.In some embodiments, condensable hydrocarbons partly has so positive C18 and positive C29 weight ratio, and it is greater than 6.0.Alternatively, condensable hydrocarbons part can have so positive C18 and positive C29 weight ratio, and it is greater than 8.0 or be greater than 10.0.In optional embodiment, condensable hydrocarbons part can have so positive C18 and positive C29 weight ratio, and it is less than 35.0.In some embodiments, condensable hydrocarbons partly has so positive C19 and positive C29 weight ratio, and it is greater than 5.0.Alternatively, condensable hydrocarbons part can have so positive C19 and positive C29 weight ratio, and it is greater than 7.0 or be greater than 9.0.In optional embodiment, condensable hydrocarbons part can have so positive C19 and positive C29 weight ratio, and it is less than 30.0.In some embodiments, condensable hydrocarbons partly has so positive C20 and positive C29 weight ratio, and it is greater than 4.0.Alternatively, condensable hydrocarbons part can have so positive C20 and positive C29 weight ratio, and it is greater than 6.0 or be greater than 8.0.In optional embodiment, condensable hydrocarbons part can have so positive C20 and positive C29 weight ratio, and it is less than 30.0.In some embodiments, condensable hydrocarbons partly has so positive C21 and positive C29 weight ratio, and it is greater than 3.6.Alternatively, condensable hydrocarbons part can have so positive C21 and positive C29 weight ratio, and it is greater than 4.0 or be greater than 6.0.In optional embodiment, condensable hydrocarbons part can have so positive C21 and positive C29 weight ratio, and it is less than 30.0.In some embodiments, condensable hydrocarbons partly has so positive C22 and positive C29 weight ratio, and it is greater than 2.8.Alternatively, condensable hydrocarbons part can have so positive C22 and positive C29 weight ratio, and it is greater than 3.0.In optional embodiment, condensable hydrocarbons part can have so positive C22 and positive C29 weight ratio, and it is less than 30.0.In the paragraph of some feature of the present invention above, for example, for example, according to one group of numerical upper limits (" being less than ") and one group of numerical lower limits (" being greater than "), be described.Should be appreciated that scope that any combination by these boundaries forms within the scope of the invention, except as otherwise noted.The embodiment of describing in this paragraph can with other side of the present invention discussed in this article in any one combines.
In some embodiments, condensable hydrocarbons part can have in following one or more: positive C10 is less than 0.31 with total C10 weight ratio, positive C11 is less than 0.32 with total C11 weight ratio, positive C12 is less than 0.29 with total C12 weight ratio, positive C13 is less than 0.28 with total C13 weight ratio, positive C14 is less than 0.31 with total C14 weight ratio, positive C15 is less than 0.27 with total C15 weight ratio, positive C16 is less than 0.31 with total C16 weight ratio, positive C17 is less than 0.31 with total C17 weight ratio, positive C18 is less than 0.37 with total C18 weight ratio, positive C19 is less than 0.37 with total C19 weight ratio, positive C20 is less than 0.37 with total C20 weight ratio, positive C21 is less than 0.37 with total C21 weight ratio, positive C22 is less than 0.38 with total C22 weight ratio, positive C23 is less than 0.43 with total C23 weight ratio, positive C24 is less than 0.48 with total C24 weight ratio, be less than 0.53 with positive C25 with total C25 weight ratio.In optional embodiment, condensable hydrocarbons partly has in following one or more: positive C11 is less than 0.30 with total C11 weight ratio, positive C12 is less than 0.27 with total C12 weight ratio, positive C13 is less than 0.26 with total C13 weight ratio, positive C14 is less than 0.29 with total C14 weight ratio, positive C15 is less than 0.24 with total C15 weight ratio, positive C16 is less than 0.25 with total C16 weight ratio, positive C17 is less than 0.29 with total C17 weight ratio, positive C18 is less than 0.31 with total C18 weight ratio, positive C19 is less than 0.35 with total C19 weight ratio, positive C20 is less than 0.33 with total C20 weight ratio, positive C21 is less than 0.33 with total C21 weight ratio, positive C22 is less than 0.35 with total C22 weight ratio, positive C23 is less than 0.40 with total C23 weight ratio, positive C24 is less than 0.45 with total C24 weight ratio, be less than 0.49 with positive C25 with total C25 weight ratio.In optional embodiment, condensable hydrocarbons partly has in following one or more: positive C11 is less than 0.28 with total C11 weight ratio, positive C12 is less than 0.25 with total C12 weight ratio, positive C13 is less than 0.24 with total C13 weight ratio, positive C14 is less than 0.27 with total C14 weight ratio, positive C15 is less than 0.22 with total C15 weight ratio, positive C16 is less than 0.23 with total C16 weight ratio, positive C17 is less than 0.25 with total C17 weight ratio, positive C18 is less than 0.28 with total C18 weight ratio, positive C19 is less than 0.31 with total C19 weight ratio, positive C20 is less than 0.29 with total C20 weight ratio, positive C21 is less than 0.30 with total C21 weight ratio, positive C22 is less than 0.28 with total C22 weight ratio, positive C23 is less than 0.33 with total C23 weight ratio, positive C24 is less than 0.40 with total C24 weight ratio, be less than 0.45 with positive C25 with total C25 weight ratio.As used in this section and claims, phrase " one or more "---and then it be a series of different compounds or component ratio, wherein last ratio by conjunction " with " draw---intention comprises such condensable hydrocarbons part, and it has in listed ratio at least one or has in listed ratio two or more or three or more or four or more etc. or all.In addition, specific condensable hydrocarbons partly also can have other different compounds or component ratio, and it is not included in specific sentence or claim but still drops in the scope of such sentence or claim.The embodiment of describing in this section can be with in other side of the present invention discussed in this article, any one be combined.
In some embodiments, condensable hydrocarbons partly has the positive C10 and total C10 weight ratio that is less than 0.31.Alternatively, condensable hydrocarbons part can have so positive C10 and total C10 weight ratio, and it is less than 0.30 or be less than 0.29.In optional embodiment, condensable hydrocarbons part can have so positive C10 and total C10 weight ratio, and it is greater than 0.15 or be greater than 0.20.In some embodiments, condensable hydrocarbons partly has so positive C11 and total C11 weight ratio, and it is less than 0.32.Alternatively, condensable hydrocarbons part can have so positive C11 and total C11 weight ratio, and it is less than 0.31, is less than 0.30 or be less than 0.29.In optional embodiment, condensable hydrocarbons part can have so positive C11 and total C11 weight ratio, and it is greater than 0.15 or be greater than 0.20.In some embodiments, condensable hydrocarbons partly has so positive C12 and total C12 weight ratio, and it is less than 0.29.Alternatively, condensable hydrocarbons part can have so positive C12 and total C12 weight ratio, and it is less than 0.26 or be less than 0.24.In optional embodiment, condensable hydrocarbons part can have so positive C12 and total C12 weight ratio, and it is greater than 0.10 or be greater than 0.15.In some embodiments, condensable hydrocarbons partly has so positive C13 and total C13 weight ratio, and it is less than 0.28.Alternatively, condensable hydrocarbons part can have so positive C13 and total C13 weight ratio, and it is less than 0.27, is less than 0.25 or be less than 0.23.In optional embodiment, condensable hydrocarbons part can have so positive C13 and total C13 weight ratio, and it is greater than 0.10 or be greater than 0.15.In some embodiments, condensable hydrocarbons partly has so positive C14 and total C14 weight ratio, and it is less than 0.31.Alternatively, condensable hydrocarbons part can have so positive C14 and total C14 weight ratio, and it is less than 0.30, is less than 0.28 or be less than 0.26.In optional embodiment, condensable hydrocarbons part can have so positive C14 and total C14 weight ratio, and it is greater than 0.10 or be greater than 0.15.In some embodiments, condensable hydrocarbons partly has so positive C15 and total C15 weight ratio, and it is less than 0.27.Alternatively, condensable hydrocarbons part can have so positive C15 and total C15 weight ratio, and it is less than 0.26, is less than 0.24 or be less than 0.22.In optional embodiment, condensable hydrocarbons part can have so positive C15 and total C15 weight ratio, and it is greater than 0.10 or be greater than 0.15.In some embodiments, condensable hydrocarbons partly has so positive C16 and total C16 weight ratio, and it is less than 0.31.Alternatively, condensable hydrocarbons part can have so positive C16 and total C16 weight ratio, and it is less than 0.29, is less than 0.26 or be less than 0.24.In optional embodiment, condensable hydrocarbons part can have so positive C16 and total C16 weight ratio, and it is greater than 0.10 or be greater than 0.15.In some embodiments, condensable hydrocarbons partly has so positive C17 and total C17 weight ratio, and it is less than 0.31.Alternatively, condensable hydrocarbons part can have so positive C17 and total C17 weight ratio, and it is less than 0.29, is less than 0.27 or be less than 0.25.In optional embodiment, condensable hydrocarbons part can have so positive C17 and total C17 weight ratio, and it is greater than 0.10 or be greater than 0.15.In some embodiments, condensable hydrocarbons partly has so positive C18 and total C18 weight ratio, and it is less than 0.37.Alternatively, condensable hydrocarbons part can have so positive C18 and total C18 weight ratio, and it is less than 0.35, is less than 0.31 or be less than 0.28.In optional embodiment, condensable hydrocarbons part can have so positive C18 and total C18 weight ratio, and it is greater than 0.10 or be greater than 0.15.In some embodiments, condensable hydrocarbons partly has so positive C19 and total C19 weight ratio, and it is less than 0.37.Alternatively, condensable hydrocarbons part can have so positive C19 and total C19 weight ratio, and it is less than 0.36, is less than 0.34 or be less than 0.31.In optional embodiment, condensable hydrocarbons part can have so positive C19 and total C19 weight ratio, and it is greater than 0.10 or be greater than 0.15.In some embodiments, condensable hydrocarbons partly has so positive C20 and total C20 weight ratio, and it is less than 0.37.Alternatively, condensable hydrocarbons part can have so positive C20 and total C20 weight ratio, and it is less than 0.35, is less than 0.32 or be less than 0.29.In optional embodiment, condensable hydrocarbons part can have so positive C20 and total C20 weight ratio, and it is greater than 0.10 or be greater than 0.15.In some embodiments, condensable hydrocarbons partly has so positive C21 and total C21 weight ratio, and it is less than 0.37.Alternatively, condensable hydrocarbons part can have so positive C21 and total C21 weight ratio, and it is less than 0.35, is less than 0.32 or be less than 0.30.In optional embodiment, condensable hydrocarbons part can have so positive C21 and total C21 weight ratio, and it is greater than 0.10 or be greater than 0.15.In some embodiments, condensable hydrocarbons partly has so positive C22 and total C22 weight ratio, and it is less than 0.38.Alternatively, condensable hydrocarbons part can have so positive C22 and total C22 weight ratio, and it is less than 0.36, is less than 0.34 or be less than 0.30.In optional embodiment, condensable hydrocarbons part can have so positive C22 and total C22 weight ratio, and it is greater than 0.10 or be greater than 0.15.In some embodiments, condensable hydrocarbons partly has so positive C23 and total C23 weight ratio, and it is less than 0.43.Alternatively, condensable hydrocarbons part can have so positive C23 and total C23 weight ratio, and it is less than 0.40, is less than 0.35 or be less than 0.29.In optional embodiment, condensable hydrocarbons part can have so positive C23 and total C23 weight ratio, and it is greater than 0.15 or be greater than 0.20.In some embodiments, condensable hydrocarbons partly has so positive C24 and total C24 weight ratio, and it is less than 0.48.Alternatively, condensable hydrocarbons part can have so positive C24 and total C24 weight ratio, and it is less than 0.46, is less than 0.42 or be less than 0.40.In optional embodiment, condensable hydrocarbons part can have so positive C24 and total C24 weight ratio, and it is greater than 0.15 or be greater than 0.20.In some embodiments, condensable hydrocarbons partly has so positive C25 and total C25 weight ratio, and it is less than 0.48.Alternatively, condensable hydrocarbons part can have so positive C25 and total C25 weight ratio, and it is less than 0.46, is less than 0.42 or be less than 0.40.In optional embodiment, condensable hydrocarbons part can have so positive C25 and total C25 weight ratio, and it is greater than 0.20 or be greater than 0.25.In the paragraph of some feature of the present invention above, for example, for example, according to one group of numerical upper limits (" being less than ") and one group of numerical lower limits (" being greater than "), be described.Should be appreciated that scope that any combination by these boundaries forms within the scope of the invention, except as otherwise noted.The embodiment of describing in this paragraph can with other side of the present invention discussed in this article in any one combines.
Use " total C_ " (for example always C10) to mean the amount of the specific pseudocomponent found herein and in claims in condensable hydrocarbons fluid, this amount is as described herein especially to be measured as described in the part of mark " experiment " herein.That is to say, " total C_ " measures according to the complete oily gas-chromatography of the step utilization of describing in the experimental section of this application (WOGC) analytical method.In addition, " total C_ " measures from complete oily gas-chromatography (WOGC) the peak integration method for the identification of with each pseudocomponent of quantification and peak authentication method, as described in this paper experimental section.In addition, " total C_ " percetage by weight of pseudocomponent and mole percent value are to utilize the pseudocomponent analytical method (Katz relating to by the correlation of Katz and Firoozabadi exploitation, D.L. and A.Firoozabadi, 1978.Predicting phase behavior of condensate/crude-oil systems using methane interactioncoefficients, J.Petroleum Technology (Nov.1978), 1649-1655) obtain, described at experimental section, it comprises exemplary mole and percetage by weight mensuration.
Use " positive C_ " (for example just C10) to mean the amount of the specific n-alkane compound found herein and in claims in condensable hydrocarbons fluid, this amount is as described herein especially to be measured as described in the part of mark " experiment " herein.That is to say, " positive C_ " is that the GC peak area of measuring from the complete oily gas-chromatography of the step utilization according to describing the application's experimental section (WOGC) analytical method is measured.In addition, " total C_ " measures from the evaluation of complete oily gas-chromatography (WOGC) peak and integration method for the identification of with the single compound peaks of quantification, as described in this paper experimental section.In addition, " positive C_ " percetage by weight of n-alkane compound and mole percent value are to utilize to be similar to exemplary mole of the pseudocomponent of explaining and percetage by weight method for measuring acquisition in experimental section, just use density and the molecular weight of interested specific n-alkane compound, then make itself and the sum obtaining in pseudocomponent method compare to obtain weight and mole percent.
The discussion of Figure 16 is related to the data that obtain in embodiment 1-5 below, embodiment 1-5 comes into question in the part of mark " experiment ".These data identify by experimental arrangement, gaseous sample collection procedure, hydrocarbon gas sample gas-chromatography (GC) analytical method and the gaseous sample GC peak discussed in experimental section and integration method obtains.For clarity sake, when speaking of the gas chromatogram of gaseous hydrocarbon sample, for a unstressed experiment of being undertaken by embodiment 1, two stressed experiments of 400psi being undertaken by embodiment 2 and 3 and two 1 of being undertaken by embodiment 4 and 5, the stressed experiment of 000psi provides chart data.
Figure 16 is a block diagram, and it shows the molar percentage concentration of the hydrocarbon kind existing in gaseous sample, and described gaseous sample is taken from each in three stress levels testing in the laboratory experiment of discussing and analyze herein.Gaseous compound mole percent obtains by experimental arrangement as herein described, gaseous sample collection procedure, hydrocarbon gas sample gas-chromatography (GC) analytical method, gaseous sample GC peak integration method and molar concentration mensuration program.For clarity sake, hydrocarbon mole percent is calculated as the sum and the percentage that calculates molar concentration of the hydrocarbon gas GC area (namely for methane, ethane, propane, iso-butane, normal butane, isopentane, pentane, 2-methylpentane and n-hexane) of all having identified.Therefore,, for all experiments, graphic methane to positive C6 mole percent does not comprise following mole share: any relevant nonhydrocarbon gaseous products (for example hydrogen, CO
2or H
2s), listed any unidentified hydrocarbon gas kind (for example numbering of the peak in table 22,6,8-11,13,15-22,24-26 and 28-78) or be dissolved in any gaseous species being processed independently in liquid phase, in liquid phase GC in table 2,4,5,7 or 9.The concentration that y-axle 3080 represents with regard to every kind of gaseous compound mole percent in gas phase.The identity that x-axle 3081 comprises every kind of hydrocarbon compound from methane to n-hexane.Post 3082A-I represents the mole percent of every kind of gaseous compound in the unstressed experiment of embodiment 1.That is to say, 3082A represents methane, and 3082B represents ethane, and 3082C represents propane, and 3082D represents iso-butane, and 3082E represents normal butane, and 3082F represents isopentane, and 3082G represents pentane, and 3082H represents that 2-methylpentane and 3082I represent n-hexane.Post 3083A-I and 3084A-I represent the mole percent from every kind of gaseous compound in the sample of the stressed experiment of repetition 400psi of embodiment 2 and 3, and wherein letter is to distribute for the described mode of unstressed experiment.And post 3085A-I and 3086A-I represent the repetition 1 from embodiment 4 and 5, the mole percent of every kind of gaseous compound in the sample of the stressed experiment of 000psi, wherein letter is to distribute for the described mode of unstressed experiment.As can be seen from Figure 16, the hydrocarbon gas producing in all experiments is mainly methane, ethane and propane, in mole.In addition, clearly, compare the 400psi stress test hydrocarbon gas and 1, the 000psi stress test hydrocarbon gas, the represented unstressed experiment of post 3082A-I comprises maximum methane 3082A and minimum propane 3082C.See now post 3083A-I and 3084A-I, clearly, by-level 400psi stress test produces such hydrocarbon gas, the unstressed experiment that its methane 3083A & 3084A and propane 3083C & 3084C concentration represent between post 3082A & 3082C and post 3085A & 3085C and 3086A & 3086C represent 1, between the stressed experiment of 000psi.Finally, clearly, high level 1,000psi stress test produces such hydrocarbon gas, and it is compared post 3082A & the 3082C unstressed experiment representing and the stressed experiment of 400psi that post 3083A & 3084A and 3083C & 3084C represent and has minimum methane 3085A & 3086A concentration and the highest propane concentration 3085C & 3086C.Therefore under the rock static stress level increasing, pyrolysis oil shale presents to produce and has the methane that reduces concentration and the hydrocarbon gas that increases the propane of concentration.
From being rich in the hydrocarbon fluid of organic matter formation production, can comprise condensable hydrocarbons part (for example liquid) and non-condensing hydrocarbon part (for example gas).In some embodiments, non-condensing hydrocarbon partly comprises methane and propane.In some embodiments, the propane in non-condensing hydrocarbon part and the mol ratio of methane are greater than 0.32.In optional embodiment, the propane in non-condensing hydrocarbon part and the mol ratio of methane are greater than 0.34,0.36 or 0.38.As used herein, " mol ratio of propane and methane " is can the mol ratio of especially measuring described in the part of this paper mark " experiment " as described herein.That is to say, " mol ratio of propane and methane " is to utilize hydrocarbon gas sample gas-chromatography (GC) analytical method, gaseous sample GC peak evaluation and integration method and the molar concentration in the application's experimental section, described to measure program determination.
In some embodiments, the condensable hydrocarbons of hydrocarbon fluid partly comprises benzene.In some embodiments, condensable hydrocarbons partly has the benzene content between 0.1 and 0.8 percetage by weight.Alternatively, condensable hydrocarbons part can have benzene content between 0.15 and 0.6 percetage by weight, the benzene content between 0.15 and 0.5 or at 0.15 and 0.5 benzene content.
In some embodiments, the condensable hydrocarbons of hydrocarbon fluid partly comprises cyclohexane.In some embodiments, condensable hydrocarbons partly has such cyclohexane content, and it is less than 0.8 percetage by weight.Alternatively, condensable hydrocarbons part can have such cyclohexane content, and it is less than 0.6 percetage by weight or is less than 0.43 percetage by weight.Alternatively, condensable hydrocarbons part can have such cyclohexane content, and it is greater than 0.1 percetage by weight or is greater than 0.2 percetage by weight.
In some embodiments, the condensable hydrocarbons of hydrocarbon fluid partly comprises hexahydrotoluene.In some embodiments, condensable hydrocarbons partly has such hexahydrotoluene content, and it is greater than 0.5 percetage by weight.Alternatively, condensable hydrocarbons part can have such hexahydrotoluene content, and it is greater than 0.7 percetage by weight or is greater than 0.75 percetage by weight.Alternatively, condensable hydrocarbons part can have such hexahydrotoluene content, and it is less than 1.2 or be less than 1.0 percetages by weight.
The application of the percetage by weight content of benzene, cyclohexane and hexahydrotoluene means the amount of benzene, cyclohexane and the hexahydrotoluene found in condensable hydrocarbons fluid herein and in claims, and this amount is as described herein especially to be measured as described in the part of mark " experiment " herein.That is to say, each compound percetage by weight is that complete oily gas-chromatography (WOGC) analytical method discussed from this paper experimental section and complete oily gas-chromatography (WOGC) peak are identified and integration method mensuration.In addition, each compound percetage by weight obtains as described in Figure 11, except each each independent compound peaks area integral is used to measure each compound percetage by weight separately.For clarity sake, compound percetage by weight is calculated as whole C3 to the percentage of the complete oily gas-chromatography area of false C38 and calculated weight, as used in the pseudo-compound data that presented in Fig. 7.
In some embodiments, the condensable hydrocarbons of hydrocarbon fluid partly has the api gravity that is greater than 30.Alternatively, condensable hydrocarbons part can have such api gravity, and it is greater than 30,32,34,36,40,42 or 44.As used in this paper and claims, api gravity can be measured by the method for any generally accepted mensuration api gravity.
In some embodiments, the condensable hydrocarbons of hydrocarbon fluid partly has such basic nitrogen and total nitrogen ratio, and it is between 0.1 and 0.50.Alternatively, condensable hydrocarbons part can have such basic nitrogen and total nitrogen ratio, and it is between 0.15 and 0.40.As used in this paper and claims, basic nitrogen and total nitrogen can be measured by the method for any generally accepted mensuration basic nitrogen and total nitrogen.The in the situation that of outcome conflict, follow generally accepted more accurate method.
Rock static stress can affect the rock static stress that composition that this discovery of composition by heating and the Produced Liquid that produces in being rich in organic rock of pyrolysis means the hydrocarbon fluid of extraction also can be rich in organic matter rock stratum by change and change.For example, the rock static stress that is rich in organic matter rock stratum can and/or be heated with pyrolysis subterranean formation zone thickness and/or heating sequencing and be changed by selection by selection pillar (pillar) geometry and/or position.
Pillar is to be rich in organic matter rock stratum and to leave not pyrolysis to alleviate or relax the region of surface subsidence in preset time.Pillar can be the region in stratum, and it is surrounded by the pyrolysis zone in same stratum.Alternatively, pillar can be a part for the not heating region outside general developing zone or be attached thereto.Some region of serving as in early days pillar in the production fields life-span can be converted to Production Regional late period at this oilfield life.
Generally, in its nature, the weight of the overlying rock on stratum is extremely evenly distributed on stratum.Under this state, the rock static stress that in stratum, locality exists is controlled by the thickness of overlying rock and density to a great extent.The rock static stress of expectation can be by analyzing overlying rock geology and selecting the position with appropriate depth and position to select.
Although rock static stress is assumed to be that in stratum, the rock static stress of particular locations can be by redistributing upper overlying strata stone weight so that it is no longer supported and adjust equably by stratum by naturally determining and being unmodifiable overlying strata stone on removing all or part conventionally.For example, this redistribution of upper overlying strata stone weight can realize by two kinds of illustrative methods.One of these methods or both can be used in single stratum.In some cases, a kind of method mainly can be used in early days, and another kind of method mainly can be used in the later stage.Advantageously changing rock static stress that subterranean formation zone experiences carries out and also can before producing significant hydrocarbon fluid, carry out can cause significant pyrolysis in subterranean formation zone before.Alternatively, advantageously changing rock static stress can carry out with pyrolysis simultaneously.
The method of the first change rock static stress relates to manufactures one not as the hard areas of subsurface formation of its adjacent domain.Along with specific region becomes not harder, therefore adjacent domain little by little serves as the pillar that supports upper overlying strata stone.The rock static stress that these post area experience increase, and the rock static stress that not harder region experience reduces.The variable quantity of rock static stress depends on many factors, and it for example comprises: the variation of processing region hardness, the size of processing region, pillar size, pillar spacer, rock compressed and rock strength.Can in this region, produce empty space its experience machinery is weakened by this region of pyrolysis and by removing Produced Liquid being rich in Zhong， stratum, organic matter rock stratum inner region.Can make by this way region in stratum not as do not experience pyrolysis experience the still less pyrolysis of degree or the adjacent domain of production hard.
The method that the second changes rock static stress relate to areas of subsurface formation is expanded and with neighbour near field larger try hard to recommend the overlying strata stone that makes progress.This expansion can be removed overlying strata stone weight a part from adjacent domain, has therefore increased the rock static stress of heating region experience and has reduced the rock static stress that adjacent domain experiences.If it is enough expanding, horizontal pressure break will reduce formation and these regions in adjacent domain to the contribution of overlying strata stone on supporting.The variable quantity of rock static stress depends on many factors, and it for example comprises: the swell increment of processing region, the size of processing region, pillar size, pillar spacer, rock compressed and rock strength.By the region in heating stratum, can make its expansion to cause the thermal expansion of rock.If fluid is intercepted and captured in this region in a large number, fluid expansion or fluid produce and also can contribute to expand.Overall expansion amount can be proportional with the thickness of heating region.It should be noted that if pyrolysis occurs in heating region and removed enough fluids, heating region can mechanically weaken and therefore can change the rock static stress that adjacent domain experiences, described in the first illustrative methods.
The embodiment of the method can comprise by be rich in the second adjacent domain extraction fluid in organic matter rock stratum so that the young's modulus of elasticity of second area (being hardness) is lowered by first heating and the stratum hydrocarbon that exists of pyrolysis and from this in being rich in organic matter rock stratum, increases the rock static stress in first area and controls by heating and pyrolysis from being rich in the composition of the extraction hydrocarbon fluid of the first area generation in organic matter rock stratum.
The embodiment of the method can comprise the composition of controlling the extraction hydrocarbon fluid producing from the first area of being rich in organic matter rock stratum by heating and pyrolysis by the rock static stress in increase first area, the rock static stress increasing in first area is carried out as follows: before the adjacent domain in being rich in organic matter rock stratum, heat first area, or this first area is heated to than the larger degree of adjacent domain being rich in organic matter rock stratum, makes the thermal expansion in first area be greater than the thermal expansion in the adjacent domain that is rich in organic matter rock stratum.
The embodiment of the method can comprise the composition of controlling the extraction hydrocarbon fluid producing from the first area of being rich in organic matter rock stratum by heating and pyrolysis by the rock static stress in reduction first area, the rock static stress reducing in first area is carried out as follows: before first area, one or more adjacent domains of organic matter rock stratum are rich in heating, or the one or more adjacent domains that are rich in organic matter rock stratum are heated to the degree larger than this first area, make the thermal expansion in adjacent domain be greater than the thermal expansion in first area.
The embodiment of the method can comprise makes to be rich in heating location, sizing and/or the timing of heating region in organic matter rock stratum to change the original position rock static stress that is rich in current in organic matter rock stratum or following heating and pyrolysis zone, thus the composition of control extraction hydrocarbon fluid.
Some manufacturing processes are included in from being rich in before organic matter rock stratum removes formation water dissolubility mineral substantially, and what In Situ Heating comprised stratum hydrocarbon and formation water dissolubility mineral is rich in organic matter rock stratum.In some embodiments of the present invention, before heating, do not need in position partly, substantially or completely remove water-soluble mineral.For example, in the oil shale formation of the nahcolite that contains natural generation, oil shale can be heated before substantially removing nahcolite by solution mining.Substantially remove the removal degree that water-soluble mineral can represent water-soluble mineral, it occurs from any business solution mining operation as known in the art.Substantially removing water-soluble mineral can be approximately to remove and be rich in by weight more than 5% of specific water soluble mineral total amount existing in the target area of production of hydrocarbon fluids in organic matter rock stratum.In optional embodiment, the In Situ Heating that is rich in organic matter rock stratum with pyrolysis stratum hydrocarbon can from be rich in organic matter rock stratum remove by weight more than 3% formation water dissolubility mineral before, alternatively, by weight 7%, by weight 10% or by weight 13%.
Before extraction nahcolite, heating oil shale is that nahcolite is changed into more recyclable form (sode ash) with the gentle effect that produces oil, and permeability is provided, and contributes to its recovery subsequently.Water-soluble mineral reclaim and can after empyreumatic oil is produced, just occur, or its period that can be left the several years is for recovery below.If desired, sode ash can easily be transformed back nahcolite on earth's surface.This conversion can easily be carried out two kinds of mineral can be exchanged effectively.
In some production methods, heating is rich in organic matter rock stratum and is comprised that the decomposition by nahcolite produces sode ash.The method can be included in landscape apparatus, process containing water-soluble mineral aqueous solution to remove a part of water-soluble mineral.This treatment step can comprise by removing water-soluble mineral owing to changing the precipitation that the temperature of aqueous solution causes.
Water-soluble mineral can comprise sodium.Water-soluble mineral also can comprise nahcolite (sodium acid carbonate), sode ash (sodium carbonate), dawsonite (NaAl (CO
3) (OH)
2) or its combination.Surfacing can further be included in landscape apparatus by with CO
2reaction changes into sodium acid carbonate (nahcolite) by sode ash.After partially or completely removing water-soluble mineral, aqueous solution can be then injected into subsurface formations, and it can be by hidden there.This subsurface formations can be identical or different with the original organic matter rock stratum of being rich in.
In some production methods, heating is rich in not only pyrolysis at least a portion stratum, organic matter rock stratum hydrocarbon to produce hydrocarbon fluid but also the migration stain species of formerly combination in being rich in organic matter rock stratum can be obtained.Migration stain species can form by the pyrolysis of stratum hydrocarbon, can be after heating from stratum, itself discharges, or the permeability that can increase by generation behind heating stratum can approach it.That in being rich in organic matter rock stratum, exist or inject water or other aqueous fluid wherein, migration stain species can be soluble.
From the oil shale of pyrolysis, produce hydrocarbon and will generally leave some water-soluble migration stain species at least partly.Depend on that pyrolysis shale oil is connective with the hydrology of more shallow section, it is in the unacceptable underground water of environment that these compositions can finally move to concentration.The type of potential migration stain species depends on the characteristic of oil shale pyrolysis and the composition of the oil shale that is just being converted.If pyrolysis is carried out in the presence of not at oxygen or air, pollutant kind can comprise aromatic hydrocarbons (for example benzene, toluene, ethylbenzene, dimethylbenzene), polyaromatic (for example anthracene, pyrene, naphthalene,
), metal pollutant (for example As, Co, Pb, Mo, Ni and Zn), and other kind such as sulfate, ammonia, Al, K, Mg, chloride, fluoride and phenol.If application oxygen or air, pollutant kind also can comprise ketone, alcohol and cyanide.In addition, the concrete migration stain species of existence can comprise any group or the combination of mentioned kind.
Oil field development person can expect to assess the connectedness that is rich in organic matter rock stratum and aquifer.This can carry out determining whether the original position pyrolysis of the stratum hydrocarbon being rich in organic matter rock stratum can produce the migration kind of tending to move to aquifer, or its degree.If being rich in organic matter rock stratum is that the hydrology is connected with aquifer, can take the precautionary measures to reduce or prevent that the kind that produces or discharge from entering aquifer during pyrolysis.Alternatively, be rich in organic matter rock stratum can be after pyrolysis as described herein water or aqueous fluid rinse to remove water-soluble mineral and/or migration stain species.In other embodiments, be rich in organic matter rock stratum can with any underground water source substantially the hydrology be not connected.In such a case, rinse and to be rich in organic matter rock stratum and may for the removal of migration stain species, expect, still however for the recovery of water-soluble mineral, may expect.
From being rich in organic matter stratum, producing hydrocarbon, some migration stain species can remain in rock stratum.Under these circumstances, can expect that aqueous fluid is injected into the aqueous fluid that is rich in organic matter rock stratum and makes to inject is dissolved to the water-soluble mineral of small part and/or migration stain species to form aqueous solution.Aqueous solution then can be by for example solution producing well extraction from be rich in organic matter rock stratum.Aqueous fluid can regulate to increase the solubility of migration stain species and/or water-soluble mineral.Adjusting can comprise and adds acid or alkali with the pH of regulator solution.Then gained aqueous solution can be processed to earth's surface from be rich in organic matter rock stratum in extraction.
After the extraction of initial aqueous fluid, can further expect with aqueous fluid rinse slaking be rich in organic matter petrographic province and not slaking be rich in organic matter petrographic province.Aqueous fluid can be used to further dissolved water dissolubility mineral and migration stain species.Flushing can be optionally most hydrocarbon fluid from slaking be rich in the extraction of organic matter rock section complete.In some embodiments, after rinsing step can be delayed to production of hydrocarbon fluids step.Flushing can be delayed to allow the heat that generates from heating steps to transmit to depths more, and what enter around not slaking is rich in organic matter rock section, so as by around not the nahcolite being rich in organic matter rock section of slaking change into sode ash.Alternatively, flushing can be delayed to allow the heat that generates from heating steps around being not rich in organic matter rock section of slaking produce permeability.In addition, flushing can based on sodium acid carbonate, sode ash or both at present and/or the market price of prediction and being delayed, as further discussed herein.The method can combine with any one of other side of the present invention discussed in this article.
After aqueous solution rinses, can be desirably in landscape apparatus and process aqueous solution to remove at least some migration stain species.Migration stain species can be by being used for example sorbing material, counter-infiltration, chemical oxidation, biological oxidation and/or ion-exchange to remove.The example of these methods is all known in the art.Exemplary sorbing material can comprise active carbon, clay or bleaching earth.
In the production of oil and source of the gas, can expect the energy as ongoing operation by the hydrocarbon of extraction.This can be applied to from oil shale exploitation oil and source of the gas.In this respect, when resistance heater and original position shale oil reclaim while being combined with, need a large amount of electric power.
Electric energy can obtain from the turbine of rotating generator.By utilizing the extraction gas from oil field to be provided with gas-turbine power, can be favourable economically.Yet this extraction gas must carefully be controlled so that maximum efficiency, and to do not damage turbine, cause turbine misfire or produce excessive pollutant (NO for example
x).
A source of gas-turbine problem is in fuel, to have pollutant.Pollutant comprises solid, water, the heavy constituent and the hydrogen sulfide that as liquid, exist.In addition, the burning behavior of fuel is important.The combustion parameter of considering comprises calorific value, proportion, adiabatic flame temperature, flammable limit, autoignition temperature, nature time delay and flame speed.Wobbe index (Wobbe index, WI) is through being often used as the critical metrics of fuel mass.WI equals the subduplicate ratio of low heat value and specific gravity of gas.By the wobbe index of fuel control to desired value and for example+10% or ± 20% scope can allow turbine design to simplify and performance optimization increases.Generally speaking, gas-turbine is the machine of height optimization, and the variation of gas feed can cause periodically closing turbine and carries out great maintenance and replacement part again to optimize the needs of turbine.Usually, directly cost and loss operating time this aspect two, it is all expensive operation.Therefore, wish to minimize the needs to this maintenance.
Fuel mass is controlled and be can be used for shale oil exploitation, and wherein extraction gas composition may change during oilfield life, and wherein gas generally also has a large amount of CO except lighter hydrocarbons
2, CO and H
2.Commercial-scale oil shale retorting is expected and produces time dependent gas composition.Gas composition temporal evolution comes from simultaneous a plurality of and competitive decomposition reaction when pyrolysis oil shale.
Inert gas in turbine fuel can keep flame temperature in expected range, to increase generating by increasing flow of matter simultaneously.In addition inert gas can reduce flame temperature and reduce thus NO
xpollutant produces.The gas producing from oil shale slaking can have a large amount of CO
2content.Therefore, in some embodiment of production method, the CO of fuel gas
2content is by separated in landscape apparatus or add and regulate so that turbine performance is optimized.CO
2all remove not necessarily desirable.
For low BTU (British Thermal Units, British thermal unit) fuel, reach certain hydrogen content and also can expect, to realize suitable combustibility.In some embodiment of this paper method, the H of fuel gas
2content is by separated in landscape apparatus or add and regulate so that turbine performance is optimized.Utilize the H in the non-shale oil landscape apparatus of low BTU fuel adjusting
2content for example, is discussed in patent documentation (U.S. Patent number 6,684,644 and U.S. Patent number 6,858,049, its whole disclosures are incorporated to herein by reference).
In some region in oil shale source, other oil shale source or other hydrocarbon source may reside in lower depth.Other hydrocarbon source can be included in the natural gas (so-called " tight gas ") in low permeability formation or be entrained in coal neutralization and be adsorbed onto the natural gas (so-called " coal bed methane ") on coal.At some, have in the embodiment in a plurality of oil shales source, first the darker region of exploitation then sequentially the more shallow region of exploitation may be favourable.By this way, well is by the rock region not needing through thermal region or weakening.In other embodiments, by drilling well, pass that to be just used as developing darker region compared with the region of the pillar of shallow depth shale oil exploitation may be favourable.
In the same area, exploitation can utilize some equipment and logistics running collaboratively when shale oil sources and gas source.For example, gas treatment can be carried out in single factory.Equally, office worker can under developmently share.
Fig. 6 illustrates the schematic diagram of a kind of embodiment of landscape apparatus 70, and described landscape apparatus 70 can be configured to process Produced Liquid.Produced Liquid 85 can be produced by producing well 71 from subsurface formations 84, as described herein.Produced Liquid can comprise any Produced Liquid of producing by any method described herein.Subsurface formations 84 can be any subsurface formations, and it comprises, for example, comprises such as any organic matter rock stratum of being rich in oil shale, coal or Tar sands.Production decision can relate to 72 to 300 °F, 200 °F of Produced Liquid chillings or the temperature below 100 °F even, in oil eliminator 73, isolate condensable composition (i.e. oil 74 and water 75), in air processing unit 77, process non-condensing composition 76 (i.e. gas) to remove water 78 and sulphur kind 79, in natural gas plant 81, for example, from gas (propane and butane), remove the heavier composition of a part to form the liquefied petroleum gas (LPG) 80 that will sell, and from remaining gas 83, produce electric energy 82 in power plant 88.Electric energy 82 can be used through any method described herein energy of sub-surface 84 heatedly.For example, electric energy 82 can be at high pressure input transformer 86 under 132kV for example, and progressively drops to for example 6600V of lower voltage before being imported into be arranged in heated well 87 resistive heater of---it is arranged in subsurface formations 84---.By this way, the required all or part of energy of sub-surface 84 can produce from the non-condensing part of Produced Liquid 85 heatedly.Excessive gas---can be output sale if any---.
The Produced Liquid of producing from original position oil shale comprises multiple composition that can be separated in landscape apparatus.Condensable hydrocarbons kind, CO that Produced Liquid typically comprises water, non-condensing hydrocarbon alkane kind (such as methane, ethane, propane, normal butane, iso-butane), non-condensing hydrocarbon alkene kind (such as ethene, propylene), (alkane, alkene, aromatic hydrocarbons and polyaromatic etc.), consists of
2, CO, H
2, H
2s and NH
3.
In landscape apparatus, condensable composition can be separated by reducing temperature and/or increasing pressure from non-condensing composition.Temperature reduction can utilize by ambient air or available water-cooled heat interchanger and realize.Alternatively, the Produced Liquid of heat can be by carrying out cooling with previously cooling extraction hydrocarbon fluid interchange of heat.Pressure can increase by centrifugal or reciprocating compressor.Alternatively, or jointly, diffuser-expander device can be used to go out liquid from condensation.Separation can relate to several stages cooling and/or that pressure changes.
When reducing temperature or increasing pressure, except condensable hydrocarbons, water can ooze from gas.Aqueous water can separate with condensable hydrocarbons by gravitational settler or whizzer.Demulsifier can be used to promote water separated.
From the hydrocarbon gas of producing, remove CO
2and other so-called acid gas is (as H
2s) method comprises uses chemical reaction method and physical solvent process.Chemical reaction method generally comprises the aqueous solution that makes air-flow contact amine under high pressure and/or low temperature.This makes acid gas kind and amine generation chemical reaction and enters into solution.By heating up and/or step-down, chemical reaction can be reversed and concentrated acid flow can be recovered.Optional chemical reaction method relates to hot carbonate solution, is generally potash.The carbonate solution of heat is reproduced, and concentrated acid flow is by reclaiming this solution contact air-flow.Physical solvent process relates generally to make air-flow contact dihydroxylic alcohols under high pressure and/or low temperature.Be similar to amine method, step-down or heat up permission solvent reclamation and acid gas recovery.Certain amine or dihydroxylic alcohols can have more or less selective in the type of the acid gas kind of removing.The scale adjustment of any these methods need to be measured the required energy input of amount, cycle rate, the regeneration of the chemicals that will circulate and size and the type of gas chemicals contact arrangement.Contact arrangement can comprise packed tower or multistage column plate countercurrent tower.In these aspects, the concentration of acid gas in speed that gas is produced from stratum and air-flow is highly depended in the optimal size adjustment of every aspect.Alternatively, iron oxidation-reduction method (for example, Low-Cat
tM) can be available, particularly when the carbon monoxide of some and low-level sulphur are present in hydrocarbon stream.In liquid oxidation reducing process, the solution that contains iron compound is recycled reduction and oxidation, and during the reduction part of circulation, the gas that contains hydrogen sulfide reacts forming element sulphur with iron compound like this.By the reduction in circulation and the in-line filter in the solution circulation between oxidized portion, remove elementary sulfur.
Acid gas is removed can also be by using destilling tower to realize.This tower can comprise middle freezing section, wherein allows freezing CO
2and H
2s particle forms.Freezing particle and the mixture of liquid fall downwards and enter stripping section, and wherein the lighter hydrocarbon gas is overflowed and risen in tower.Rectifying section may be provided in the upper end of tower further to promote the purification of overhead gas stream.The other details of these class methods and correlation technique is found in United States Patent (USP) 3,724, and 225,4,511,382,4,533,372,4,923,493,5,120,338,5,956,971, its full content is incorporated to herein by reference.
The hydrogen content of air-flow can be by removing that all or part of hydrogen reduces or for example, by removing all or part of non-hydrogen kind (CO
2, CH
4deng) and increase.Separation can utilize cryogenic condensation, transformation or Temp .-changing adsorption or selective diffusion barrier to realize.If need other hydrogen, hydrogen can be by making by typical water conversion reaction reforming methane.
In one embodiment, provide the method for using the gas producing from converted in-situ process.The method can comprise that In Situ Heating is rich in organic matter rock stratum.Further, the method can comprise from being rich in organic matter rock stratum generation Produced Liquid.Produced Liquid can comprise hydrocarbon fluid, and it produces as the result that is arranged in the stratum hydrocarbon pyrolysis of being rich in organic matter rock stratum at least partly.The air-flow that comprises flammable hydrocarbon fluid can obtain from Produced Liquid.Air-flow can be divided into the first composition air-flow and second and form air-flow, and wherein the first composition that forms air-flow remains under the condition of substantial constant.First forms air-flow can pass through the first gas-turbine, to form the first gas-turbine waste stream.This first gas-turbine is configured to provide energy to the first generator, and object is generating.
As what describe, be rich in organic matter rock stratum and can be for example heavy hydrocarbon stratum or hydrocarbon solid stratum in other embodiment herein.The instantiation on such stratum can comprise oil shale formation, tar sand formation or coal stratum.The concrete stratum hydrocarbon existing in such stratum can comprise heavy hydrocarbon, oil shale, kerogen, coal and/or pitch.
From being rich in the Produced Liquid of organic matter rock stratum generation, can comprise hydrocarbon fluid.Hydrocarbon fluid can comprise condensable hydrocarbons part (for example liquid) and non-condensing hydrocarbon part (for example gas).The hydrocarbon fluid of Produced Liquid can be plucked out of in addition together with non-hydrocarbon fluids.Exemplary non-hydrocarbon fluids comprises for example water, carbon dioxide (CO
2), hydrogen sulfide (H
2s), hydrogen (H
2), ammonia (NH
3) and/or carbon monoxide (CO).In position in heating operation, the composition temporal evolution of expection Produced Liquid.At first, expection Produced Liquid flow velocity and forming be all different from heating 1 year or more for many years after flow velocity and composition.For example, in early days, in the pyrolysis of the oil shale of certain volume, the composition of extraction gas can have high CO
2molar fraction and low H
2molar fraction.Along with pyrolysis continues, the composition of extraction gas is changed into wherein CO
2low and the H of concentration
2concentration is high.In the middle period, alkanes (for example, methane and ethane) can show maximum concentration in cracking gas.(referring to, for example " Isothermal Decomposition of Colorado Oil Shale ", DOE/FE/60177-2288.)
The composition temporal evolution of the air-flow of organic matter rock stratum generation is rich in expection from In Situ Heating.Particularly, the ratio of expection hydrogen and carbon dioxide is at the life period of business In Situ Heating oil field development by marked change, and described oil field development will last 3 years by 10 years or more for many years.And the relative scale that expection gaseous hydrocarbon kind---comprises methane, ethane, ethene, propane, isopropyl alkane and propylene---will change at the life period of oil field development.These change the exploitation for Commercial Oil shale may be significant especially.In oil shale exploitation, the density of hydrogen in expection extraction gas increases in time, and expection CO
2concentration reduce in time.Be expected at these expection variations in total extraction gas composition and will propose to process challenge (processing challenges), particularly, when extraction gas or its part are burnt in gas-turbine, this is when keeping stable operation, can not adapt to the larger variation that air inlet forms because have the gas-turbine of specific combustion furnace.Embodiments of the present invention comprise from Produced Liquid acquisition air-flow, wherein the composition temporal evolution of air-flow.During time dependent air-flow composition can be included in 1 year, more than average day change in concentration 5mol% of the one or more kinds in air-flow.In optional embodiment, during 1 year, average day concentration of the one or more kinds in air-flow can change 10,15 or more than 20mol%.In optional embodiment, during 2 years, average day concentration of the one or more kinds in air-flow can change 5,10,15 or more than 20mol%.In the specific embodiment, the kind of change in concentration can be CO
2, methane, hydrogen or their combination.In optional embodiment, during 1 year, average day wobbe index or the improved wobbe index of air-flow can change more than 5,10,15 or 20%.In optional embodiment, during 2 years, average day wobbe index or the improved wobbe index of air-flow can change more than 5,10,15 or 20%.
Figure 32 provides the diagram of the several species of gasses kind of disengaging from the heating of oil shale laboratory, Colorado to describe.This figure is based on from Miknis, F.P.; Conn, P.J.; And Turner, T.F., " IsothermalDecomposition of Colorado Oil Shale ", the data of DOE/FE/60177-2288 (DE87009043).This experiment is by heating Colorado oil shale sample under the steady temperature at 368 ℃, and form the period being kept at least 12 hours.Left side y axle 351 is reported in the concentration of the gaseous species of experiment measurement that disengage, that represent with mol% in 12-hour, and it comprises CO
2352, H
2353, methane 354, ethane 355 and CO 356.X-axle 350 represents the time, and with a hour expression.Data representation in this figure consists of to obtain the value that the estimated value of instant gas composition obtains the accumulation of differential measurement.The wobbe index that BTU/SCF is unit is take in y-axle 358 reports in the right.Based on non-sulphur kind in gas, calculate wobbe index 357.Lower BTU/SCF calorific value and be used to wobbe index with respect to the proportion of air and calculate.As shown in the figure, initial (0-2 hour), the gas disengaging is mainly CO
2, from the CO of 70mol%
2change the CO that drops to 40mol%
2, and there is methane (12-18mol%) and the ethane (2-6mol%) of less amount.Along with Time evolution, the generation of hydrogen increases, almost corresponding to CO
2the minimizing producing.Approach last 7.5 hour period, CO
2concentration has been down to about 4mol%, and hydrogen generation is increased to over 70mol%.Hydrocarbon kind also changed within 7 hour period, yet its intensity of variation is much lower.Methane concentration higher about 22mol% while being changed to 4 hours from initial lower about 12mol%, fell back to about 10mol% by 7.5 hours.Ethane concentration higher about 8mol% while changing to 4.5 hours from initial lower about 2-3mol%, fell back to about 5mol% by 7.5 hours.Time dependent composition causes wobbe index that large variation occurs in time.This value is initially about 210BTU/SCF, and stablizes and be increased to about 890BTU/SCF at the 7.5th hour.These data also show that the gas producing with pyrolysis oil shale from heating will be relative low BTU gas, and it comprises for example a large amount of CO
2.For heating oil shale, the data representation gas composition presenting in Figure 32 potential variation in time, however due to the lower for example 270-350 ℃ of in-situ temperature, the time scale in commercial operation will be crossed over the much longer time limit.The application of low temperature reflects the unrealistic property of Fast Heating large volume rock and increases in the relevant efficiency of underground application to harmonic(-)mean temperature.For example, in the exploitation of commercialization oil shale, may spend 1 to 3 year and produce to obtain significant hydrocarbon, this depends on the geometry of energy input, the rate of heat addition, formation at target locations density, formation at target locations thickness, heated well interval and heated well.In addition, in commercialization In Situ Heating oil shale exploitation, may spend 6 to 10 years or more for many years the kerogen in oil shale is converted into completely to recoverable fluid hydrocarbon, this also depends on above-mentioned concrete development parameters.
The air-flow that comprises flammable hydrocarbon fluid can obtain from Produced Liquid.Air-flow can be further divided into the first composition air-flow and second and form air-flow.In some embodiments, the first composition air-flow and second forms air-flow and all contains hydrocarbon fluid.The first identity that forms hydrocarbon kind in air-flow can be identical or different with the identity of hydrocarbon kind in the second composition air-flow.In addition, in each air-flow, the concentration of identical hydrocarbon kind can be similar or very different.Exemplary gaseous hydrocarbon kind in each air-flow can comprise methane, ethane, ethene, propane, propylene, butane, iso-butane, butylene, and pentane, isopentane, amylene, C6+ hydrocarbon kind and their any combination of possibility less amount.In some embodiments, the first air-flow is the hydrocarbon gas more than 5 molar percentages.In optional embodiment, the first air-flow is the hydrocarbon gas more than 10,15,20,25,30,35 or 40 molar percentages.In some embodiments, the first composition air-flow is methane more than 15 molar percentages.In optional embodiment, the first composition air-flow is methane more than 20,25,30,35 or 40 molar percentages.
In some embodiments, the first composition air-flow and second forms air-flow and all contains fuel gas.Fuel gas can comprise the hydrocarbon gas and the non-hydrocarbon gas, for example hydrogen.In some embodiments, first forms that air-flow, second forms air-flow or both are considered to low heat value or low BTU gas.This stream is considered to low BTU air-flow, because they have the lower low heat value of low heat value (LHV) than typical pipeline gas, it is about 1 that described typical pipeline gas has, the low heat value of 000BTU/SCF.Yet this stream can have the sufficiently high calorific value that can be used for gas-turbine and/or boiler, and therefore different from the gas of accessory substance for burning or burn incompletely, and described accessory substance can have the low heat values within the scope of 50 to 150BTU/SCF.In some embodiments, first forms that air-flow, second forms air-flow or both have low heat value more than 200BTU/SCF.In optional embodiment, the first composition air-flow, second forms air-flow or both have 300BTU/SCF, 400BTU/SCF, 500BTU/SCF or low heat value more than 600BTU/SCF.In other embodiments, first forms that air-flow, second forms air-flow or both have the low heat value below 800BTU/SCF.In optional embodiment, the first composition air-flow, second forms air-flow or both have 700BTU/SCF, 600BTU/SCF or the low heat value below 500BTU/SCF.
Air-flow, first forms air-flow, the second composition air-flow or their any combination can comprise at least one inert gas, for example CO
2.As zero calorific value gas, CO
2existence as the thinner of calorific value object, and promote to reduce total low heat value of air-flow.In some embodiments, the CO that utilization of the present invention exists in Produced Liquid
2pressure and mass flow, and make this class CO
2can be used in the first air-flow finally to process in the first gas-turbine.Can consider that Produced Liquid can be under rising pressure produces from being rich in organic matter rock stratum, described pressure is for example 300,400,500,600psig is above or more than 700psig.After processing, the gas part of pressurization Produced Liquid can be sent to gas-turbine to recover energy from passing through the pressure decreased of this kind of forced air of this gas-turbine.Like this, energy not only reclaims from the burning of the incendivity part of the first air-flow, and incombustible partially recycled from the pressurization of the first air-flow.In some embodiments, air-flow, the first composition air-flow, the second composition air-flow or their any combination can have CO more than 10 molar percentages
2content.Alternatively, air-flow, the first composition air-flow, the second composition air-flow or their any combination can have CO more than 15,20,25,30,35 or 40 molar percentages
2content.Alternatively, air-flow, the first composition air-flow, the second composition air-flow or their any combination can have the CO below 70,60,50 or 45 molar percentages
2content.
In one embodiment, the first composition air-flow is hydrogen more than 5 molar percentages.Alternatively, the first composition air-flow can be hydrogen more than 10,20,30,40,50,60,70,80 or 90 molar percentages.Alternatively, the second composition air-flow can be hydrogen more than 30,50,70 or 90 molar percentages.First forms air-flow, second forms air-flow or both hydrogen contents and also can be conditioned to compensate high inert content in these air-flows (CO for example
2), particularly when such air-flow burns in gas-turbine.CO along with gas-turbine incoming flow
2concentration increases, and has corresponding reduction in this incoming flow flame speed.Hydrogen has relatively high flame speed and can be used to compensate CO high in gas-turbine incoming flow
2concentration, thus the gas-turbine incoming flow that flame speed changes in particular turbine designs acceptable parameter obtained.Alternatively, if need other hydrogen, hydrogen can by via classical steam-reforming then water-gas shift reaction reforming methane prepare, thereby increase the hydrogen concentration of gas-turbine incoming flow, or make other hydrogen can be used for mixing with gas-turbine incoming flow.Water-gas shift reaction provides below: steam-reforming: CH
4+ H
2o → CO+3H
2aqueous vapor conversion: H
2o+CO → H
2+ CO
2
In one embodiment, first forms the H that air-flow has substantial constant
2with CO
2mol ratio, thus relatively constant flame speed in gas-turbine, obtained.In optional embodiment, first forms air-flow has between the H between 0.1 to 2.0,0.3 to 1.8,0.5 to 1.6 or between 0.7 to 1.4
2with CO
2mol ratio.Alternatively, first forms ethane and the CO that air-flow can have substantial constant
2mol ratio.Particularly, during 7 days, on per day basis, first forms ethane and the CO of air-flow
2the variation of mol ratio can be below 15%.Further, during 7 days, on per day basis, first forms ethane and the CO of air-flow
2mol ratio changes below 10% or 5%.
The method comprises at least makes the first composition air-flow through gas-turbine.In optional embodiment, second forms air-flow also optionally passes through gas-turbine.In either case, gas-turbine is included as the combustion tool of burner.Generally speaking, burner comprises for injected gas charging with by this charging and the nozzle or the syringe that mix containing air or oxygen stream.Then, formed mixture burnt before the turbine portion that enters gas-turbine is divided, and in the turbine portion of energy of gas-turbine, from hot combustion product stream, was extracted.Gas burner and their syringe are generally designed to certain gas composition or compositing range, at this situation gas-turbine, will stablize and operation effectively.If changing, gas composition exceeded scope of design, gas-turbine can experience irregular operation, invalid operation so, reliability reduces and/or the discharge of Environmental Regulation kind (environmentally regulated species) increases, and it comprises for example nitrogen oxide (NO
x), carbon monoxide (CO) and/or sulphur (oxysulfide (SO for example
x)) discharge.In some embodiments, the first gas-turbine is equipped with the two gas burners that are comprised of the first gas syringe and the second gas syringe, wherein the first gas syringe is optimised or be designed to the first composition air-flow, and the second gas syringe is optimised or be designed to the second composition air-flow.In optional embodiment, the first gas-turbine and/or the second gas-turbine can be equipped with the burner of geometry-variable.Still further in embodiment, the first gas-turbine and/or the second gas-turbine can be equipped with catalytic burner.Still further in embodiment, the first gas-turbine and/or the second gas-turbine can be equipped with thin premix burner (lean pre-mixed combustor) (one or more), the low NO of dry type
x(DLN) burner (one or more) or dry low emissions (DLE) burner (one or more).Further, steam injection or water inject and can be used to reduce NO
x.
Generally speaking, gas-turbine manufacturer specifies preferred pressure or pressure limit to carry the gas-turbine feed stream of further processing in the burning of gas-turbine burner and the turbine at gas-turbine.If gas-turbine feed stream has exceeded specified pressure scope, be transported to gas-turbine, gas-turbine can experience the discharge increase of irregular operation, Efficiency Decreasing and/or Environmental Regulation component so.Therefore, usefully, the In Situ Heating operation of organic matter rock stratum is rich in operation, not only to provide and to form in the almost gas-turbine air inlet of controlled condition to gas-turbine, and provides the air inlet within the scope of goal pressure to it.In some embodiments, the first composition air-flow can offer the first gas-turbine with substantially constant pressure.In some embodiments, the first composition air-flow can be transported to the first gas-turbine with the pressure in 200 to 1,000 pounds/square inch of gauge pressures (psig) scope.Alternatively, first forms air-flow and can be transported to the first gas-turbine with the pressure within the scope of 300 to 800,350 to 650 or 400 to 600psig.In some embodiments, during 7 days, on per day basis, the variation of the pressure of the first composition air-flow is below 20% gauge pressure.In optional embodiment, during 7 days, on per day basis, the first pressure that forms air-flow changes below 15,10 or 5% gauge pressure.
A feature of the present invention is that at least the first composition that forms air-flow remains under the condition of substantial constant.The first composition that forms air-flow remains under the condition of substantial constant, to meet the desirable operational parameters of the first gas-turbine.Generally speaking, modern gas-turbine is equipped with low emission combustor, to meet modern environment regulations.Turbine needs relatively constant fuel composition like this, and therefore to adapting to the extensive variation of fuel gas composition, has very little flexibility.This is because majority of gas turbine cartridge has the fact that the burner of fixed geometry---is generally one group of circular orifice---.For gas-turbine moves reliably according to generally accepted performance standard, fuel gas must be with supplies such as the flow velocity that regulates, pressure ratio, composition, temperature.If fuel composition changes, and therefore improved wobbe index variation, the fuel energy of so in liberal supply amount will change to the required pressure ratio of turbine (to keeping load).Yet the concrete required pressure ratio of burner geometry is set by the aerodynamic design of this burner, this design is generally fixing geometry.Therefore any variation that, fuel gas forms will make burner move outside its optimum design point.When the operation off-target design point of hope is to surpassing can accept the point of scope of design time, so generally run into negative results.The gas with the condition of substantial constant refers to such fuel gas compositing range: given gas-turbine can be used this scope, keeps fully stable behavior in service simultaneously.For example, the gas with a set condition of substantial constant can be by specific gas turbine applications, and does not experience unacceptable kinetics of combustion, and this comprises pressure fluctuation, and it can cause the unreliability being caused by fire extinguishing, and this finally causes turbine to be closed.In addition, the gas with the condition of substantial constant can be by specific gas turbine applications, and does not produce discharge (for example, the NO over define objective or environmental regulations
x, CO etc.).In addition, the gas with the condition of substantial constant can be by specific gas turbine applications, turbine can be moved and do not exist frequent maintenance or replace the needs of its inner body, this needs may be to cause due to component wear or fatigue that overfire kinetics causes, or the parts damages that cause due to locational flame back flash (flame flashback) or the flame grappling (flameanchoring) of the rising temperature not being designed to be caused by this class event cause.In addition, the gas with the condition of substantial constant can be employed, and without closing turbine, to use for initial fuel gas design, forms and be designed to adapt to the parts replacement combustion component that different fuel gas forms.It may be essential with new fuel gas composition that this parts are replaced for coupling fuel injection mouth geometry, to reach the essential pressure ratio of the fuel gas that is fed to combustion zone, or the geometry in the diluent air hole in change burner may be essential, to suitable air shunting (air split) is provided between burning and dilution.
Based on gaseous mass, there is the gas-turbine performance of many method assessment expectations.A method comprises the wobbe index that keeps substantial constant.One of wobbe index measures that can use down establishes an equation calculates:
Wherein WI is wobbe index, LHV is the low heat value of fuel gas, its unit is BTU/SCF (or suitable unit), wherein BTU is British thermal unit (British Thermal Units), SCFShi unit's standard cubic foot, SG is for example gaseous fuel, with respect to the proportion of the lower air of standard conditions (1atm and 20 ℃).
Correlated measure is improved wobbe index, and it can use equation below to calculate:
Wherein MWI is improved wobbe index, and LHV is that the low heat value ，Qi unit of gaseous fuel is BTU/SCF, wherein BTU is British thermal unit, SCFShi unit's standard cubic foot, SG be gaseous fuel with respect to the proportion of air, Tgas is the gaseous fuel temperature with thermometer.
In some embodiments of the present invention, during 7 days, by wobbe index or the improved wobbe index of the first composition air-flow are changed below 15% on per day basis, first forms air-flow can remain on substantially invariable condition.In optional embodiment, during 7 days, on per day basis, the first wobbe index or improved wobbe index that forms air-flow changes below 10% or 5%.In further alternative embodiment, during 1 day, on average basis per hour, the first wobbe index or improved wobbe index that forms air-flow changes below 15%.In further alternative embodiment, during 1 day, on average basis per hour, the first wobbe index or improved wobbe index that forms air-flow changes below 10% or 5%.In further embodiment, during 1 hour, on five minutes average bases, the first wobbe index or improved wobbe index that forms air-flow changes below 15%.In further alternative embodiment, during 1 hour, on five minutes average bases, the first wobbe index or improved wobbe index that forms air-flow changes below 10% or 5%.In optional embodiment, during 30 days, on per day basis, the first wobbe index or improved wobbe index that forms air-flow changes below 15%, 10% or 5%.
In further embodiment, for the composition of air-flow is remained under substantially invariable condition, it can be enough the character of air-flow being remained under the condition of substantial constant.For example, in some embodiments, during 7 days, on per day basis, the first proportion that forms air-flow changes below 15,10% or 5%.In optional embodiment, during 30 days, on per day basis, the first proportion that forms air-flow changes below 15,10% or 5%.In optional embodiment, during 1 day, on average basis per hour, the first proportion that forms air-flow changes below 15,10% or 5%.In further alternative embodiment, during 7 days, on per day basis, the first low heat value that forms air-flow changes below 15,10% or 5%.In further alternative embodiment, during 30 days, on per day basis, the first low heat value that forms air-flow changes below 15,10% or 5%.In optional embodiment, during 1 day, on average basis per hour, the first low heat value that forms air-flow changes below 15,10% or 5%.
By the temperature of adjustments of gas turbine incoming flow, improved wobbe index can be by fine tuning.The temperature of adjustments of gas turbine incoming flow will change the density of gas, and therefore, therefore the proportion of gas also also affect wobbe index equation presented above by change.Therefore, embodiments of the present invention comprise the temperature that regulates the first composition air-flow, thereby regulate wobbe index or the improved wobbe index of the first composition air-flow.Can regulate by several different methods the temperature of the first composition air-flow, it comprises makes the first composition air-flow and the interchange of heat of Produced Liquid or derivatives thereof, make the first composition air-flow and steam or boiler feedwater interchange of heat or make the first composition air-flow and any interchange of heat that is included in the various process streams in the process equipment of oil shale exploitation earth's surface.In concrete embodiment, can be by making the first composition air-flow and the first gas-turbine waste stream, Produced Liquid, steam or their combination carry out the temperature that interchange of heat regulates the first composition air-flow.
By optional method, air-flow is formed under the condition that remains on substantial constant, to meet the operating parameter of gas-turbine needs.In some embodiments of the present invention, by the total concentration of particular types or particular types group is changed below the amount of regulation, the composition of the first composition air-flow can be remained on to the condition of substantial constant.In some embodiments of the present invention, during 7 days, by the concentration of the inert species in the first composition air-flow is changed below 15 molar percentages on per day basis, the first composition air-flow can be remained on to the condition of substantial constant.In optional embodiment, during 30 days, on per day basis, the first concentration change that forms the inert species in air-flow is below 10 or 5 molar percentages.In optional embodiment, during 7 days, on per day basis, the first concentration change that forms the inert species in air-flow is below 10 or 5 molar percentages.In further alternative embodiment, during 1 day, on average basis per hour, the first concentration change that forms the inert species in air-flow is below 15,10 or 5 molar percentages.In one embodiment, the concentration of specific inert species carbon dioxide can change below the amount of regulation, to keep air-flow in the condition of substantial constant.In one embodiment, during 7 days, on per day basis, first forms CO in air-flow
2concentration change below 15,10 or 5 molar percentages.In one embodiment, during 30 days, on per day basis, first forms CO in air-flow
2concentration change below 15,10 or 5 molar percentages.In optional embodiment, during 1 day, on average basis per hour, first forms CO in air-flow
2concentration change below 15,10 or 5 molar percentages.
In some embodiments of the present invention, by the total concentration of hydrogen is changed below the amount of regulation, the composition of the first air-flow can be remained on to the condition of substantial constant.In some embodiments of the present invention, during 7 days, by making H in the first air-flow
2concentration on per day basis, change below 15 molar percentages, the first air-flow can be remained on to the condition of substantial constant.In optional embodiment, during 7 days, the H on per day basis in the first air-flow
2concentration change be below 10 or 5 molar percentages.In optional embodiment, during 30 days, the H on per day basis in the first air-flow
2concentration change below 10 or 5 molar percentages.In further alternative embodiment, during 1 day, the H on average basis per hour in the first air-flow
2concentration change 15,10 or below 5 molar percentages.
In some embodiments of the present invention, by the total concentration of particular hydrocarbon kind or hydrocarbon kind group is changed below the amount of regulation, the composition of the first composition air-flow can be remained on to the condition of substantial constant.In some embodiments of the present invention, during 7 days, by the concentration of methane in the first composition air-flow is changed below 15,10 or 5 molar percentages on per day basis, the composition of the first composition air-flow can be remained on to the condition of substantial constant.In optional embodiment, during 30 days, on per day basis, the first concentration that forms methane in air-flow changes below 15,10 or 5 molar percentages.In optional embodiment, during 1 day, on average basis per hour, the first concentration that forms methane in air-flow changes below 15,10 or 5 molar percentages.In optional embodiment, during 7 days, on per day basis, the first concentration that forms ethane in air-flow changes below 15,10 or 5 molar percentages.In optional embodiment, during 30 days, on per day basis, the first concentration that forms ethane in air-flow changes below 15,10 or 5 molar percentages.In optional embodiment, during 1 day, on average basis per hour, the first concentration that forms ethane in air-flow changes below 15,10 or 5 molar percentages.In some embodiments of the present invention, during 7 days, by the concentration of propane in the first air-flow is changed below 15,10 or 5 molar percentages on per day basis, the composition of the first air-flow can be remained on to the condition of substantial constant.In optional embodiment, during 30 days, on per day basis, in the first air-flow, the concentration of propane changes below 15,10 or 5 molar percentages.In optional embodiment, during 1 day, on average basis per hour, in the first air-flow, the concentration of propane changes below 15,10 or 5 molar percentages.
In some embodiments, the second composition that forms air-flow is also maintained under the condition of substantial constant.Such condition is by regulating first to form the relative ratios that air-flow and second forms air-flow, and it can be possible keeping the composition of two kinds of stream substantial constant simultaneously.In such embodiment, second forms air-flow also can be sent to gas-turbine, and for example the second gas-turbine, carries out power recovery.
In some embodiments of the present invention, by monitoring the condition of the first composition air-flow, can contribute to the composition of the first composition air-flow to remain on the condition of substantial constant.For example, can monitor one or more characteristics of the first composition air-flow.Illustrative properties that can be monitored can comprise and is selected from following one or more characteristics: gas composition, temperature, calorific value, proportion, wobbe index, improved wobbe index, dew point, flammability limits, flame speed and their combination.
In some embodiments of the present invention, first forms air-flow can be changed to control one or more operating parameters of the first composition air-flow.In these embodiments, monitoring the condition of the first composition air-flow and in the result of this monitoring, mainly or partly take these changes or control can be useful as basis.Can controlled exemplary operation parameter comprise C
2with higher hydrocarbon, C
3one or more concentration with higher hydrocarbon, carbon dioxide, inert gas, hydrogen, ethane, ethene, propane and their combinations.By mixed airflow and first is formed to air-flow, mix the composition that changes the first composition air-flow, can keep selected operating parameter.Mixed airflow can comprise methane or gaseous hydrocarbon mixture, comprises the mixed airflow from non-Produced Liquid source.In other embodiments, can be by regulating the inert gas content of the first composition air-flow to change the inert gas content of the first composition air-flow, to keep wobbe index or the improved wobbe index of substantial constant in time.
In some embodiments of the present invention, the composition that changes the first composition air-flow comprises hydrogen, ethane, ethene or their combination is joined to the first composition air-flow.Can be used for increasing adding of these compositions the first composition air-flow flame speed, regulate the first composition air-flow burn rate, be stabilized in burning in the first gas-turbine or their combination.
In further embodiment, first forms air-flow can change to produce hydrogen by least a portion methane in the first composition air-flow of reforming.In the gaseous feed that enters into gas-turbine burner, contain a large amount of CO
2and therefore needing other hydrogen to keep the situation of the flame speed of substantial constant in gas-turbine burner, this can be useful especially.In some embodiments, other hydrocarbon compound, for example ethane and/or propane also can be reformed together with methane.The hydrogen content of gas-turbine charging can increase by different reformation configurations.In one embodiment, before reforming, at least a portion methane is shifted out from the first composition air-flow, and the methane shifting out is reformed to produce hydrogen in independent process equipment, and the hydrogen producing is returned to the first composition air-flow, then the first composition air-flow is delivered to gas-turbine.Alternatively, at least a portion methane is reformed online, be present in the first composition air-flow simultaneously, and without shifting out methane and produce hydrogen in the reformer apparatus separating.In any situation, the methane part that is restructured as hydrogen can be controlled to keep the operating parameter of selection, and this for example comprises wobbe index or the improved wobbe index value of substantial constant in time.
In the whole bag of tricks described herein, pressure or temperature that the first composition that forms air-flow can be positioned at one or more gs-oil separators of process equipment by adjusting change.Thereby the adjusting of such pressure or temperature is by the composition changing from the waste gas of such eliminator.This process equipment can comprise several grades of gs-oil separators, and it is generally under continuous low pressure.For a series of eliminators at same temperature, for example, from the waste gas (being rich in methane and hydrogen) of initial elevated pressures eliminator recently for example, from the waste gas (being rich in propane and carbon dioxide) of low pressure separator below lighter.Therefore, first forms air-flow and can comprise at least from the first separator gas of the first gs-oil separator with from the mixture of the second separator gas of the second gs-oil separator.In addition, the method can comprise that by adjusting, forming first forms the composition that the first separator gas of air-flow and the relative quantity of the second separator gas change the first composition air-flow.
In the whole bag of tricks described herein, the first composition that forms air-flow or the second composition air-flow can be by being used vapour-liquid extractive technique change.In this art, air-flow can contact with liquid, to allow to have some component---described component is generally heavier component---mass transfer in the air-flow of optimum solvation degree to shift out and to be dissolved in from air-flow liquid stream in liquid stream, thereby change the composition of the air-flow that forms.Therefore, contact can be used to for example by reducing the amount of heavier component, increase the H of air-flow
2content.In this area, have the multiple known method of carrying out vapour-liquid extraction, it comprises that for example applying plate column or packed column carries out contacting of liquid stream and steam or air-flow.Usually, air-flow was cooled to improve solubility before contact.Also can increase pressure and improve solubility.Produced Liquid or its part can be used as liquid stream.Especially, a part can be recycled and return from the Produced Liquid of fluid handling system below, to form air-flow, second with air-flow, first, forms air-flow or derivatives thereof and contacts to dissolve and remove a part of component in this stream.A kind of method of the Ryan-Holmes of being known as method is open in authorizing the U.S. Patent number 4,318,723 of Holmes etc.This patent is described and is used for example C of nonpolar addition
2-C
5alkane distills acid gas from methane.About other of Ryan/Holmes method, discuss, referring to Holmes etc., Hydrocarbon Processing, May 1982, pp.131-136; With Oil and Gas Journal, Jun.27,1983, pp.85-91.
The method can comprise from gas-turbine generation electricity, and optionally gas-turbine is a part of combined cycle power plant (combined cycle power facilities).In such embodiment, the method can be included in the first composition air-flow by the first gas-turbine and burn after the first composition air-flow, the first gas-turbine waste stream of burning is fed to steam heating boiler, thereby provides heat to produce steam in this steam heating boiler to steam heating boiler.In combined cycle operation, the steam of generation can be supplied to the steamturbine that is configured to provide energy to the second generator subsequently.The second generator can be the identical generator using with the first gas-turbine, or different generators.In different embodiments, steam heating boiler can be aftercombustion formula waste heat boiler (supplementally fired waste heat boiler) or can not comprise supplementary boiler feed stream.By using combined circulation power apparatus, the whole or most electric demand that produces In Situ Heating operation can be possible, and wherein In Situ Heating basically, mainly or is ad hoc undertaken by resistance heated.
In some embodiments, the second composition air-flow is fed to steam heating boiler or fired heater, and carries out power recovery and may expect without first making the second composition air-flow lead to gas-turbine.In some embodiments, in view of keeping first to form air-flow composition substantial constant, second forms air-flow by the vicissitudinous composition of tool.In other embodiments, the second composition air-flow can have the low heat value lower than the low heat value of the first composition air-flow.In order to adapt to, the difference of the second composition air-flow forms and/or low heat value---it may not be enough constant for stablize processing in specific gas turbine, and second forms air-flow can be sent to combustion-type steam heating boiler (firedsteam boiler).The steam producing in this steam heating boiler by applying steam turbine can be used to produce electric energy, therefore further promotes total technique generating capacity.In optional embodiment, steam heating boiler can be super critical boiler or the steam heating boiler that is equipped with catalytic burner, and described catalytic burner is not subject to form in combustion-gas flow the impact of variation especially.
In some embodiments, the Produced Liquid of heat can be with hydrothermal exchange to produce low-pressure steam.Under these circumstances, current are by the current that are boiler feedwater quality.
In other embodiments, the steam producing from the Waste Heat Recovery of the first gas-turbine waste stream, burning from the second composition air-flow steam heating boiler or the part steam producing from one or two source can be used to earth's surface process equipment and/or at least a portion heat is provided, and for heating, are rich in organic matter rock stratum.Depend on production method, that steam can be used as is low, in or high steam miscarriage raw.Low-pressure steam is conventionally under the pressure lower than 150psig, and middle pressure steam is conventionally in the scope of 150-250psig, and high steam is generally over 250psig.In one embodiment, at least a portion steam---high steam particularly, is transported to and is rich in organic matter rock stratum to help this stratum of heating.Lower pressure steam---comprise for example middle pressure steam, also can be used for ground layer for heating by injection.In some embodiments, particularly when steam is low or during middle pressure steam turbine waste stream, low-pressure steam stream can be used as the process heat (process heat, process heat) of Produced Liquid or derivatives thereof in processing.Steam can useful example process be included in regeneration for the sorbent fluid of heavy hydrocarbon or acid gas, in the reboiler of Distallation systm or in the regeneration of the solid absorbent system of removing for acid gas and contaminant trace species.Further example comprises film separation, low temperature distillation and pressure-variable adsorption.In any of above-mentioned application---wherein use Steam Heating, the first gas-turbine waste stream itself can be used as process heat, alternative as steam in Produced Liquid or derivatives thereof is processed.
, to the discharge of controlling from various gas-turbines described herein, may there are needs in the final purpose that depends on gas-turbine waste stream.For example, in some cases, gas-turbine waste stream can, before or after Waste Heat Recovery and/or further gas-turbine waste stream processing subsequently, be emitted in atmosphere.Some gas-turbine burner is available on market, and it is designed to reduce nitrogen oxide (NO in gas-turbine combustion process
x) generation of compound.Therefore, some embodiments of the present invention comprise with thin premix burner (one or more), the low NO of dry type
x(DLN) burner (one or more), dry low emissions (DLE) burner (one or more) or other similar device are equipped the first gas-turbine, to reduce NO
xformation.These technology can be to be also of value to low NO with target
xthe gas-turbine inlet air flow composition producing combines.NO
xform known combustion zone Flame temperature and the nitrogen (N of being subject to
2) time of staying impact.Therefore, NO
xgeneration can be by the N that reduces combustion zone temperature and/or exist in combustion zone
2amount and be reduced.In one embodiment, the first composition that forms air-flow can change by reducing the inert gas content of the first composition air-flow.In such embodiment, the first inert gas concentration that forms air-flow can reduce by reducing nitrogen content of the first composition air-flow.In one embodiment, the first composition that forms air-flow can change by the inert gas content increasing in the first composition air-flow, to be reduced in NO in the first gas-turbine
xproduce.In such embodiment, inert gas concentration can be by increasing the CO of the first composition air-flow
2content and increasing.In such embodiment, can be between 10-60 molar percentage by the first inert gas content that forms air-flow of the first gas-turbine.
Can use other NO
xreduction technology replaces method previously discussed or is combined with method previously discussed.Technology previously discussed makes great efforts to reduce NO
xgeneration, yet, exist and can be used for reducing the NO existing in gas-turbine waste stream
xother method.For example, can pass through gas-turbine waste stream and ammoniacal liquor (NH
3) process stream and contact, from gas-turbine waste stream, remove the NO of generation
x.Optionally, WITH AMMONIA TREATMENT stream can obtain from being derived from wholly or in part the stream of Produced Liquid.An embodiment comprises NH
3separated with Produced Liquid to form NH
3process stream, and by this NH
3process stream and inject the first gas-turbine waste stream, thereby by a part of NO in the first gas-turbine waste stream
xcomponent is converted into N
2.In some embodiments, NH
3process stream and there is NH more than 50 molar percentages
3form.In optional embodiment, NH
3process stream and there is NH more than 90 molar percentages
3form.
Produced Liquid can comprise sulphur compound, and it comprises for example hydrogen sulfide.The air-flow forming from Produced Liquid, hydrogen sulfide is the most general.Conventionally, from air-flow, remove hydrogen sulfide or other sulfur-containing compound is expected, this air-flow with after-combustion for example, to reduce or prevent it being the oxysulfide (SO of Environmental Regulation compound
2) formation.The method can comprise that flow of process air, first forms air-flow, second and forms air-flow or its any combination, at least to remove a part for the sulfur-containing compound existing in this stream, so that resulting each air-flow has the sulfur-containing compound lower than 5 molar percentages.Alternatively, the sulfur-containing compound existing in this stream can be lowered, so that resulting each air-flow has the sulfur-containing compound lower than 1 molar percentage or 1,000ppm.In some embodiments, the method can comprise from air-flow and substantially removes H
2s, can be at the rich H that for example sulfur recovery factory further processes to form
2s stream.Alternatively, rich H
2s can be injected into coal seam, dark aquifer, the fine and close gas area of pressure break substantially exhausting, the oil shale district substantially exhausting, the oil shale district that exhausts sodium mineral matter or their combination.
As discussed earlier, reclaim between exploitation and can have cooperation being rich in organic matter rock exploitation and other hydrocarbon.For example, in some cases, tight gas deposit is arranged in oil shale deposit thing immediate area.Under these circumstances, from the extraction gas of tight gas exploitation, can be used as the charging of the first gas-turbine using in oil shale exploitation.As discussed earlier, from being rich in the complete hydrocarbon gas extraction of In Situ Heating process implementation of organic matter rock exploitation, a period of time may be spent.Therefore, to supplementary gas-turbine gas feed source, may there are needs at first.Under these circumstances, a part for the extraction gas of developing from tight gas can be used as charging a period of time of the first gas-turbine, for example, until the sufficient hydrocarbon gas is developed extraction from being rich in organic matter rock, in the situation of oil shale exploitation.Therefore, in one embodiment, the charging a period of time that is used as the first gas-turbine from the extraction gas of tight gas exploitation, it is rich in organic matter rock stratum in heating and starts after starting, until from being rich in Produced Liquid that the extraction of organic matter rock comprises hydrocarbon fluid at least some times before finishing.In optional embodiment, from being connected to the electricity of the generator generation of the gas-turbine that is rich in the exploitation of organic matter rock stratum, can be used to being used for the compressor power supply of compression from the extraction gas of tight gas exploitation.
The method that organic matter rock stratum is rich in heating described herein can cause the generation of steam, and described steam can produce from having the organic matter rock stratum of being rich in of Produced Liquid.In Situ Heating is rich in the formation that organic matter rock stratum can cause steam.In such a case, can produce steam to earth's surface further to process.The steam producing can condensation on the ground in the process equipment of earth's surface, thereby forms condensation flow.This condensation flow can be high purity water stream, and there is no obvious mineral component.Such condensation flow has many possible application.For example, condensation flow can be used as boiler feedwater.In one embodiment, condensed water or derivatives thereof can be supplied to the waste heat boiler of cogeneration of heat and power combined cycle or combined heat and power system.And condensation flow can be supplied to gas-turbine to improve the performance of gas-turbine.Condensation flow can be fed to gas-turbine together with gas-turbine air inlet, enters in the burner of gas-turbine, or for example, is fed to together gas-turbine with oxidant (, air) incoming flow.In one embodiment, condensed water or derivatives thereof can be supplied to the first gas-turbine, thereby increases the power in the first gas-turbine, controls the discharge from the first gas-turbine, or their combination.In above-mentioned arbitrary situation, condensed water or derivatives thereof can be by making itself and the interchange of heat of Produced Liquid or derivatives thereof and preheating.
The whole bag of tricks that uses air-flow or derivatives thereof to produce power can comprise that the power that use produces is rich in the energy of organic matter rock stratum as heating.As discussed earlier, by the first gas-turbine is connected to the first generator, thereby generate electricity in the first generator, can produce electric energy.In addition, electric energy can produce from being connected to the steamturbine of generator, as described herein.In any of these situations, the electricity of generation can be used to be combined to heat with resistance heater and be rich in organic matter rock stratum.The electricity producing by application, resistance heater can be by power supply partly, substantially or completely.In one embodiment, the electricity of generation accounts in heating and is rich in use in organic matter rock stratum hot more than 60%.In optional embodiment, the electricity of generation accounts in heating and is rich in use in organic matter rock stratum hot more than 70,80,90 or 95%.
In some embodiments, this method makes the method that is heated by resistive heating means in addition.In such a case, a part of air-flow can burn with heating process fluid (process fluid) in heating furnace.In one embodiment, second forms air-flow can be supplied in heating furnace, and in this heating furnace, burns to process stream, to provide heat.Then the process stream or derivatives thereof of heating is used to heating and is rich in organic matter rock stratum.Alternatively, the process stream of heating can be used as heating the heat-transfer fluid in separation of the fluid, and described separation of the fluid is used to heating and is rich in organic matter rock stratum.
In some embodiments, the electricity of generation can be used to optional application.For example, the electricity of generation or its a part ofly can be sold third party, and it comprises for example electric public service.The non-peak value that some embodiments can be included in selection needs time Cong electricity supplier to buy electricity.Electric some or all of buying can be rich in organic matter rock stratum for heating by for example resistance heated.
In some embodiments, Produced Liquid or derivatives thereof can be sold or for other treating apparatus.In one embodiment, air-flow or derivatives thereof can be used to generating object in addition.For example, if electric demand does not need to use whole air-flows---first forms air-flow and/or second forms air-flow---do not generate electricity, a part for these air-flows can be sold or for other process so.In some embodiments, the method can comprise that from Produced Liquid, obtaining liquid flows.This liquid stream can comprise flammable hydrocarbon fluid.Exemplary liquid stream can comprise LPG stream, naphtha stream, distillate flow and heavy oil stream.The one or more of these streams can be sold or further be refined to produce salable hydrocarbon product.
Figure 29 describes the part that exemplary In Situ Heating is rich in the process equipment of organic matter rock stratum oilfield development project.The organic matter rock stratum 89a that is rich in that is arranged in a part of underground 89 is passed by pit shaft 87a.Heating element 87 is placed in pit shaft 87a.Heating element 87 can be the heating element of any type, for example, and stratie.In actual business development, there are several heated well pit shaft 87a, wherein heating element 87 is positioned at such pit shaft 87a.Electricity is supplied to heating element 87 by conductor wire 318, to start heating, is rich in organic matter rock stratum 89a.In heating, be rich in organic matter rock stratum 89a after a period of time, Produced Liquid will, from being rich in the 89a extraction of organic matter rock stratum, for example, by producing well (not shown), and be transferred to process equipment by production line 71.Produced Liquid, it can comprise hydrocarbon fluid and non-hydrocarbon fluids, and described hydrocarbon fluid comprises for example condensable (liquid) part and non-condensing (gas) part, and described non-hydrocarbon fluids comprises for example water, CO
2, H
2s and H
2, being transferred to oil water separator 300, Produced Liquid is divided into three streams there: current 75, hydrocarbon liquid stream 79 and air-flow 76.Although do not illustrate, Produced Liquid can be by chilling (quench) before entering oil water separator 300, thereby to reduce a part of gaseous component of its temperature condensation Produced Liquid.Produced Liquid can by use cooling fluid (for example boiler feedwater) in heat interchanger indirect by chilling, or can be by adding chilling current and mixing to come direct chilling with it.Should be appreciated that oil water separator 300 can comprise multiple air oil actuator, oil-water separator and/or oil-water-gas separating device in business equipment, yet for easy an eliminator is only shown.Current 75 can process to remove and/or reclaim the kind of dissolving in miscellaneous equipment (not shown), then use or water are refilled underground.Hydrocarbon liquid stream 79 can comprise the hydrocarbon kind of wide region and have wide distillation range.Useful hydrocarbon product can further be processed and be refined into hydrocarbon liquid stream 79 in miscellaneous equipment (not shown).
Air-flow 76 is transferred to acid gas contactor 301, and here air-flow contacts to promote to remove H with poor amine stream 326
2s, and in some cases, remove other acid gas kind as CO
2.In acid gas contactor 301, H
2s and other acid gas kind are dissolvable in water in poor amine, form rich amine aqueous solution, and it falls the bottom of acid gas contactor 301, and are shifted out by rich amine stream 319.Rich amine stream 319 is supplied to amine regenerator 320, here the temperature of rich amine stream be raised and rich amine stream in H
2s discharges from amine, and at H
2in S stream 321, reclaim.The H reclaiming
2s Liu321Ke sulfur recovery factory further processes to produce elementary sulfur.Alternatively, H
2s stream 321 can be injected into underground, as discussed earlier.By amine reboiler 323, heat is joined to amine regenerator 320, next this return to heat to stream 325 by reboiler and turn back to amine regenerator 320 by removing the first 322 of amine regenerator 320 bottom streams.The second portion of amine regenerator 320 bottom sediment or poor amine stream 326 are returned to amine contactor 301, are reused for from air-flow 76 and shift out acid gas.The further discussion of amine system is providing herein above.In addition, for shifting out H
2s and/or CO
2distinct methods before discuss, and can be used for replacing the concrete amine system of describing in Figure 29.
Desulfurization air-flow 302 shifts out from amine contactor 301, and cooling in cooler 303, then enters stripping tower (gas stripper tower) 304.Bottom sediments product shifts out from air lift device 304, forms LPG product stream 80.Air lift device 304 comprises that tower top first forms air-flow 83 and side-draw second forms air-flow 327.Should be appreciated that stripping tower 304 can have other extraction stream (draw stream) (not shown), but in order simply only to describe two.In addition, should be appreciated that any extraction stream of describing can have reflux line (not shown).Also should be appreciated that, in commercial operation, air lift device 304 can comprise a plurality of strippers and/or destilling tower, it has a plurality of extraction stream and reflow stream, yet for a tower is simply only shown.
In some embodiments, the first composition and the second composition that forms air-flow 327 that forms air-flow 83 will be different, and needs different gas-turbine structures, as discussed earlier.In the embodiment of describing, next first forms air-flow 83 is supplied to the first gas-turbine 305.And single the first gas-turbine 305 is only described in Figure 29, should be appreciated that and in commercial operation, can have a plurality of the first gas-turbines.The first composition air-flow 83 burns in the first gas-turbine 305 and the combustion-gas flow of energy from the turbine part of the first gas-turbine 305 reclaims.In the embodiment of describing, the first gas-turbine is connected to generator 317, and to generate electricity, it is transferred from generator 317 by conductor wire 332a.The electricity producing can be combined and be transported to transformer 86 by conductor wire 82.Then the electricity of transformation can be used to produce heat in heating element 87, as discussed earlier.In commercialization embodiment, but a plurality of transformers, heating element and well there is, although each has only described one in Figure 29.
The first gas-turbine 305 comprises burner (not shown), and it forms and be optimised for the first composition air-flow, as discussed earlier.That is to say, the first gas-turbine 305 carries out optimization for the compositing range of the first composition air-flow 83 expections.The first relative quantity that forms air-flow 83 and the second composition air-flow 327 can change with the life-span of oil field development, as discussed earlier.
Depend on embodiment, second forms air-flow 327 can further process in many ways.In one embodiment, the second composition air-flow can further be processed in the second gas-turbine (shown in Figure 34).In optional embodiment, the second composition air-flow can be further processed to produce can sell goods.Exemplaryly can comprise hydrogen, methane, ethane, ethene, propane, propylene or their combination by sell goods.In optional embodiment, the steam heating boiler that the second composition air-flow can be used as discussing herein or the fuel of fired heater.In optional embodiment still, second forms air-flow 327 can mix with the first composition air-flow 83 parts, wherein the second unmixed part that forms air-flow 327 is used by any mode with this section of detailed earlier herein, and the first composition air-flow 83 mixing at present burns in the first gas-turbine 305.
The first gas-turbine waste stream 307 comprises burning gases, and is supplied to steam heating boiler 312, and object is to produce steam from hot combustion turbine waste stream.Make gas-turbine waste stream 307 by steam heating boiler 312, emit heat to steam heating boiler 312 systems, and by flowing 309, leave steam heating boiler 312 at reduction temperature.Boiler feedwater 310 is supplied to steam heating boiler 312, and here it,, by 307 heating of hot gas-turbine waste stream, therefore produces the steam that leaves steam heating boiler 312 by vapor stream 311.In some embodiments, vapor stream 311 can be high steam stream.In some embodiments, particularly when vapor stream 311 is high steam stream, the steam producing can be supplied to steamturbine 313, for further power recovery, the power cycle of the type---it comprises gas-turbine and steamturbine, is commonly referred to as combined cycle generation circulation (combined cycle powergeneration cycle).Alternatively, the processing that vapor stream 311 can be used to other needs (not shown).In the embodiment of describing, vapor stream 311 is supplied to steamturbine 313, here the vapor stream from steamturbine 313 311 recovers energy, thereby produce low-pressure steam stream 315, it can be used to other processed and applied (not shown) or again heat (not shown) with finally application in steamturbine 313.Steamturbine 313 is connected to the generator 314 of generating, and electricity is transported to transformer 86 by conductor wire 316 and 82.
Figure 30 describes the optional embodiment of processing the second composition air-flow with the second gas-turbine.For the processing occurring up to air lift device 304 discharge currents (outlet stream), it is identical that the technological process of Figure 30 is described with Figure 29.Choose the description to air lift device 304 gaseous product flows.Air lift device 304 gaseous product flows comprise that tower top first forms air-flow 83 and side-draw second forms air-flow 327.As in Figure 29, should be appreciated that stripping tower 304 can have other extraction stream (not shown), but in order simply only to describe two.In addition, should be appreciated that the extraction stream of describing can have reflux line (not shown).Also should be appreciated that, in commercial operation, air lift device 304 can comprise a plurality of strippers and/or destilling tower, it has a plurality of extraction stream and reflow stream, yet for a tower is simply only shown.
In the embodiment of describing, the first composition air-flow 83 and second forms air-flow 327 and is next supplied to gas-turbine 305 & 328.Although in Figure 30, only described single the first gas-turbine 305 and the second gas-turbine 328, should be appreciated that in commercial operation can there are a plurality of gas-turbines for the gas-turbine of every type.Each air-flow 83 & 327 are burning in gas-turbine 305 & 328 separately, and the combustion-gas flow of energy from the turbine part of each gas-turbine 305 & 328 reclaims.Although do not illustrate, alternatively, two gas-turbines can replace with a gas-turbine, this gas-turbine has double burner, this double burner forms the first gas syringe that air-flow forms and optimizes and for second, form the second gas syringe that air-flow forms and form by being optimized for first, as previously discussed in this paper.In the embodiment of describing, each gas-turbine is connected to generator 317 & 329, and to produce electricity, the electricity of generation is carried from generator by conductor wire 332 & 332a.The electricity producing can be combined and be transported to transformer 86 by conductor wire 82.Then the electricity of transformation can be used to produce heat in heating element 87, as discussed earlier.
Gas-turbine 305 & 328 comprise burner (not shown), and it is optimised for having the different air inlets that form, as discussed earlier.That is to say, the first gas-turbine 305 is optimised for the compositing range of the first composition air-flow 83 expections, and the compositing range that the second gas-turbine 328 is expected for the second composition air-flow 327 is optimised.The relative quantity of expection the first composition air-flow 83 and the second composition air-flow 327 changed with the life-span of oil field development, but formed under the condition that can remain on substantial constant so that turbine performance keeps accepting.
The first gas-turbine waste stream 307 and the second gas-turbine waste stream 330 all comprise burning gases, combination in stream 331, and be supplied to steam heating boiler 312, with the combustion turbine waste stream from hot, produce steam.In conjunction with stream 331 by steam heating boiler 312, emit heat to steam heating boiler 312 systems, and by flowing 309, leave steam heating boiler 312 reducing at temperature.Boiler feedwater 310 is supplied to steam heating boiler 312, and here it,, by hot combination stream 331 heating, therefore produces the steam that leaves steam heating boiler 312 by vapor stream 311.In some embodiments, vapor stream 311 can be high steam stream.In some embodiments, particularly when vapor stream 311 is high steam stream, the steam producing can be supplied to steamturbine 313, for further power recovery, the power cycle of the type---it comprises gas-turbine and steamturbine, is commonly referred to as combined cycle generation circulation (combined cycle power generation cycle).Alternatively, the processing that vapor stream 311 can be used to other needs (not shown).In the embodiment of describing, vapor stream 311 is supplied to steamturbine 313, here the vapor stream 311 of energy from steamturbine 313 reclaims, thereby produce low-pressure steam stream 315, it can be used to other processed and applied (not shown) or again heat (not shown) with finally application in steamturbine 313.Steamturbine 313 is connected to the generator 314 of generating, and described electricity is transported to transformer 86 by conductor wire 316 and 82.
Figure 31 describes and uses combustion-type steam heating boiler to replace the second gas-turbine to process the optional embodiment of the second composition air-flow.For the processing occurring up to stripping tower 304 charging apertures, it is identical that the technological process of Figure 31 is described with Figure 29.Choose leaving the description of the desulfurization air-flow 302 of amine contactor 301, desulfurization air-flow 302 shifts out from amine contactor 301, and cooling in cooler 303, then enters stripping tower 304.Bottom sediments product shifts out from air lift device 304, forms LPG product stream 80, as discussed in Figure 29.Air lift device 304 comprises overhead streams 83.As in Figure 29, should be appreciated that stripping tower 304 can have other extraction stream (not shown), but in order simply only to describe one.In addition, should be appreciated that the extraction stream of describing can have reflux line (not shown).Also should be appreciated that, in commercial operation, air lift device 304 can comprise a plurality of strippers and/or destilling tower, it has a plurality of extraction stream and reflow stream, yet for a tower is simply only shown.Overhead streams is supplied to the second splitter column 333, with further separating feed overhead streams 83.Gas distribution tower 333 comprises that tower top first forms air-flow 334 and bottom is extracted the second composition air-flow 335 out.Although be described as tower bottom flow, alternatively, second forms the side-draw stream that air-flow 335 can be the separative tower bottom flow of tool.When the second composition air-flow 335 is bottom stream, second forms air-flow 335 can be by adding heat by the (not shown) that gasifies again, then burning in combustion-type steam heating boiler 336.
In some embodiments, the first composition that forms air-flow 334 and the second composition air-flow 335 is different, and needs the stream processing in different downstreams, as discussed earlier.In the embodiment of describing, next first forms air-flow 334 is supplied to the first gas-turbine 305.The first composition air-flow 334 burns in the first gas-turbine 305 and the combustion-gas flow of energy from the turbine part of the first gas-turbine 305 reclaims.The first gas-turbine 305 is connected to generator 317, and to produce electricity, the electricity of generation is transferred from generator 317 by conductor wire 332a.The electricity producing can be transferred and be hot for producing at heating element 87, as discussed earlier.
In the embodiment that Figure 31 describes, second forms air-flow 335 is not supplied to gas-turbine, as described in the embodiment of describing at Figure 30, but changes in combustion-type steam heating boiler 336 burning into produce high steam.Second forms air-flow 335 burns in combustion-type steam heating boiler 336, thereby provides heat to steam boiler system, then by waste stream 337, leaves combustion-type steam heating boiler 336.Alternatively, combustion-type steam heating boiler 336 can replace with fired heater (not shown).In such a case, fired heater can be used to heat process fluid rather than steam.The process fluid of heating can be used to other processing needs, and this for example comprises, is rich in the hot fluid that adds of organic matter rock stratum, as discussed earlier as heating.Waste stream 337 can be discharged in atmosphere by as directed, or as for further heat utilization (not shown) or inject the thermal source of underground (not shown).Boiler feedwater 339 is supplied to combustion-type steam heating boiler 336, and it is heated in steam heating boiler 336, thereby produces high steam stream 338.High steam stream 338 is supplied to steamturbine 313 and carries out power recovery, as discussed in Figure 29.
When the composition of the composition of the first composition air-flow and the second composition air-flow not being remained on to the lower time of condition of substantial constant, the embodiment of describing in Figure 31 is available.Under these circumstances, first forms the condition that air-flow can be maintained at substantial constant, and the second composition air-flow allows to change.Because second forms the changeability of air-flow, may be not suitable for using gas-turbine to carry out power recovery, this is because gas-turbine can keep the compositing range of stable operation limited, as discussed earlier.Therefore, the second variable composition air-flow can be processed in combustion-type steam heating boiler (fired stream boiler), and this boiler is still less subject to feed stream to form the impact changing.In the situation of a large amount of generatings of needs, by the steamturbine that uses as describe in Figure 31, the steam producing in combustion-type steam heating boiler can be used to generating.
In some embodiments, the steam that the second burning that forms air-flow produces from the Waste Heat Recovery of the first gas-turbine waste stream, steam heating boiler or the part steam producing from one or two source can be used to earth's surface process equipment and/or for providing at least a portion heating to be rich in the heat of organic matter rock stratum.With reference now to Figure 33,, it has described the optional embodiment of the various application that are included in the steam producing in landscape apparatus.Figure 33 is used the first gas-turbine 305 and combustion-type steam heating boiler 336, as described in Figure 31.The technological process that the technological process of Figure 33 and Figure 31 describe is identical, except Figure 33 comprises for the other technological process of vapor stream and relates to steam treatment and other treatment facility that steam is applied.Choose the description to combustion-type steam heating boiler 336 and steam heating boiler 312, boiler feedwater 339 is supplied to combustion-type steam heating boiler 336, and it heats in combustion-type steam heating boiler 336, thereby produces high steam stream 338.High steam stream 338 is supplied to steamturbine 313 for power recovery, as discussed in Figure 29.Reference vapor boiler 312, by steam heating boiler 312, emits heat to steam heating boiler 312 systems in conjunction with stream 331, and by flowing 309, leave steam heating boiler 312 at reduction temperature.Boiler feedwater 310 is supplied to steam heating boiler 312, and here it,, by hot combination stream 331 heating, therefore produces the steam that leaves steam heating boiler 312 by vapor stream 311.In some embodiments, vapor stream 311 can be high pressure or middle pressure steam stream.In some embodiments, particularly, when vapor stream 311 is high steam stream, the steam of generation can be supplied to steamturbine 313, for further power recovery, as described.In addition, from the vapor stream 311 of steam heating boiler 312 with from the high steam stream 338 of combustion-type steam heating boiler 336, can be used to other process requirements, some of them are described in Figure 33.
As described in Figure 33, the available pipeline 341 of crossing of a part of vapor stream 338 & 311 is sent to high steam drum 342.The first high steam stream 343a can be used as the thermal source that organic matter rock stratum 89a is rich in heating, as previously discussed herein.Steam from steamturbine 313 outlets forms low-pressure steam stream 315, and its steam condensate together with amine reboiler 323 flows out (steam condensate outlet) 344 and is sent to low-pressure steam drum 345.Low-pressure steam can be used to various processing equipment, and it comprises the first low-pressure steam stream 349 for amine contactor preheater 361 of description.Steam condensate outflow 362 from amine contactor preheater 361 can be recycled for other processing needs, or as boiler feedwater stream recycling (not shown).The second low-pressure steam stream 360 can be used as the thermal source of air lift reboiler 363, and described air lift reboiler 363 is as the thermal source of stripping tower 304.Steam condensate outflow 364 from air lift reboiler 363 can be recycled for other processing needs, or as boiler feedwater stream recycling (not shown).The 3rd low-pressure steam stream 343 can be used as the thermal source of the amine reboiler 323 of earlier in respect of figures 29 discussion.As previously discussed herein, in process equipment to high, in and low-pressure steam there is other application, and the graphic example of conduct is above described.Steam can useful example process be included in for the adsorbent of heavy hydrocarbon or the regeneration of absorbent, in the reboiler of Distallation systm or in the regeneration of the solid absorption system of removing for acid gas and contaminant trace species.Further example comprises film separation, low temperature distillation, pressure-variable adsorption and sulfur recovery unit.
In the whole bag of tricks described herein, the first composition or second that forms air-flow forms pressure or the temperature that the composition of air-flow can be arranged in one or more gs-oil separators of process equipment by adjusting and changes.Figure 34 has described the optional illustrated embodiment comprising optionally for the multiple gs-oil separator of earth's surface process equipment.Figure 34 chooses the overhead streams place from acid gas contactor.Desulfurization air-flow 302 shifts out from amine contactor (not shown), and cooling in cooler 303, then enters adsorbent cartridge type charger 500.Adsorbent cartridge type charger 500 comprises liquid stream 501 and vapor stream, and described vapor stream is divided into the first adsorbent cartridge type charger air-flow 502 and adsorbent incoming flow 503.Adsorbent incoming flow 503 contacts with oil stream 530 in absorber 504, its objective is from adsorbent incoming flow 503 and shifts out heavier hydrocarbon kind, is then fed to stripping tower 304 together with adsorbent overhead streams 506.Oil stream 530 can be that oil flows arbitrarily, and it comprises that hydrocarbon liquid flows 79 or derivatives thereofs, as earlier in respect of figures 29 is discussed.Adsorbent bottom sediment 505 can be sent to flash tank 524 after by heat interchanger 520 heating.In flash tank, the charging 523 of this moment having heated can be divided into flash tank gas 525 and flash tank liquid 526.Adsorbent overhead streams 506 is supplied to stripping tower 304, as earlier in respect of figures 29 is discussed.Yet the stripping tower 304 of describing in Figure 34 comprises optional phegma cooler 507a and reflux accumulator 508, and optional tower top distillates cooler 512 and tower top distillates product tank (product drum) 513.Reflux accumulator 508 comprises backflow waste gas streams 516, reflow stream 510 and backflow product stream 509.Optional tower top distillates product tank 513 and comprises that tower top distillates gaseous product 515 and overhead distillate body product 514.One or more previously described the first composition air-flows or second herein that are used as that the first adsorbent cartridge type charger air-flow 502, flash tank gas 525, backflow waste gas streams 516 or tower top distillate gaseous product 515 form air-flow.Therefore, the first or second composition that forms air-flow can regulate by temperature and/or the pressure that regulates adsorbent cartridge type charger 500, flash tank 524, reflux accumulator 508 or tower top to distillate product tank 513, thereby changes the composition from the waste gas of these various gs-oil separators.Although only describe a gs-oil separator for every kind of application type in Figure 34, should be appreciated that process equipment can comprise several grades of gs-oil separators, it is generally under continuous low pressure.For a series of eliminators at same temperature, for example, from the waste gas (being rich in methane and hydrogen) of initial elevated pressures eliminator recently for example, from the waste gas (being rich in propane and carbon dioxide) of low pressure separator below lighter.Therefore, first forms air-flow and can comprise at least from the first separator gas of the first gs-oil separator with from the mixture of the second separator gas of the second gs-oil separator.In addition, the method can comprise that by adjusting, forming first forms the composition that the first separator gas of air-flow and the relative quantity of the second separator gas change the first composition air-flow.Can be selected the concrete exemplary stream that mixes to form the first composition air-flow, comprise that for example the first adsorbent cartridge type charger air-flow 502, flash tank gas 525, backflow waste gas streams 516, tower top distillate one or more of gaseous product 515 and LPG product stream 80.
In the whole bag of tricks described herein, the first composition that forms air-flow or the second composition air-flow can change by use vapour-liquid extractive technique, for example described to adsorbent 504.In this art, air-flow can contact with liquid, to allow to have some component---described component is generally heavier component---mass transfer in the air-flow of optimum solvation degree to shift out and to be dissolved in from air-flow liquid stream in liquid stream, thereby change the composition of the air-flow that forms.Produced Liquid or its part can be used as liquid stream.Especially, a part can be recycled and return from the Produced Liquid of fluid handling system below, to form air-flow, second with air-flow, first, forms air-flow or derivatives thereof and contacts to dissolve and remove a part of component in this stream.
The method that organic matter rock stratum is rich in heating described herein can cause the generation of steam, and described steam can produce from being rich in organic matter rock stratum together with Produced Liquid.In such a case, steam can further processing in process equipment.Figure 35 describes and is included in the optional embodiment of processing the recovered water of recovered water and application condensation in landscape apparatus.Figure 35 applying steam turbine 313 and combustion-type steam heating boiler 336, as described in Figure 31.The technological process of Figure 35 is identical with the technological process that Figure 31 describes, except Figure 35 comprises for the other technological process of recovered water and the other treatment facility that relates to boiler feedwater processing and apply.Choose the description to oil water separator 300, Produced Liquid 71 is divided into three streams there: current 75, hydrocarbon liquid stream 79 and air-flow 76.Although do not illustrate, Produced Liquid can be by chilling before entering oil water separator 300, thereby to reduce a part of gaseous component of its temperature condensation Produced Liquid.Current 75 can be high purity water stream, there is no obvious mineral component, if particularly water enters pit shaft 87a as steam.In the embodiment of describing, current 75 are transferred to boiler feedwater tank 550.Optionally, current can be processed in water treatment facilities 552, then enter boiler feedwater tank 550.The first boiler feedwater stream 339 supply combustion-type steam heating boilers 336.Combustion-type steam heating boiler 336 is discussed with reference to Figure 31 above.The second boiler feedwater stream 310 supply steam heating boilers 312.Steam heating boiler 312 is discussed with reference to Figure 31 above.The 3rd boiler feedwater stream 551 is used as the charging of the first gas-turbine 305.The first gas-turbine 305 is discussed with reference to Figure 31 above.As previously discussed herein, the extraction current of condensation can be supplied to gas-turbine to improve the performance of gas-turbine.The 3rd boiler feedwater stream 551 can be supplied to the first gas-turbine 305 together with gas-turbine air inlet 334, enters in the combustion chamber of gas-turbine, or for example, be supplied to the first gas-turbine 305 together with oxidant (air) incoming flow.
Experiment
Heating Experiment is to carry out for several different oil shale samples and the liquids and gases that discharge from the oil shale of the heating of detailed inspection.What collect is the oil shale sample from the Mahogany stratum in the Piceance Basin of the state of Colorado.The solid that one block size is about 1 cubic feet, continuous oil shale formation are to collect from the small-scale test mine of the position, Colony mine in Parachute Creek east side.This oil shale sillar is called as CM-1B.Take from the core sample of this sillar, as described in the following example, all take from same stratigraphy interval.Heat run utilizes Pa Er container (Parr vessel) to carry out, and described Pa Er container model is 243HC5, and it is presented in Figure 18 and can obtains from Parr Instrument Company.
Oil shale sillar CM-1B is through aspect removal of core to produce 1.391 inches of diameters and about 2 inches of long cylinders.Make the gold pipe 7002 of diameter about 2 inches and 5 inches long crispatura and insert filter screen 7000 to serve as the supporter (Figure 17) of core sample 7001.The oil shale core sample 7001 that weight is 82.46 grams is placed on the filter screen 7000 in gold pipe 7002, and whole assembly is placed in Pa Er heating container.The Pa Er container 7010 showing in Figure 18 has the internal capacity of 565 milliliters.With argon, rinse Pa Er container 7010 several times, to remove the air existing in chamber, and this container is forced into 500psi with argon.Then Pa Er container is placed in smelting furnace, and described smelting furnace is designed to match with Pa Er container.Smelting furnace at room temperature and after Pa Er container is placed in smelting furnace, be heated to 400 ℃ at first.The temperature of Pa Er container reached 400 ℃ and keep 24 hours in 400 ℃ of smelting furnaces after about 3 hours.Then Pa Er container takes out and makes it within the time of about 16 hours, be cooled to room temperature from smelting furnace.
Room temperature Pa Er container is sampled to obtain after Heating Experiment remaining a part of exemplary gases in container.The little gas sample cylinder that volume is 150 milliliters is evacuated, and is connected, and makes pressure equilibrium with Pa Er container.The gas-chromatography of this gaseous sample (GC) analytical test and non-hydrocarbon gas sample gas phase chromatogram (GC) (GC is not shown) are created in the result showing in Figure 19, table 2 and table 1.In Figure 19, the detector response that y-axle 4000 represents in picoampire (pA), and x-axle 4001 represents in minute retention time of (min).In Figure 19, peak 4002 represents the response of methane, and peak 4003 represents the response of ethane, and peak 4004 represents the response of propane, and peak 4005 represents the response of butane, and peak 4006 represents the response of pentane, and peak 4007 represents the response of hexane.From GC result and related known volume and pressure, obtain the total hydrocarbon content (2.09 grams) of this gas, the CO of this gas
2the H of content (3.35 grams) and this gas
2s content (0.06 gram).Peak and the area particulars of table 2. Figure 19-embodiment 1-0 stress-gas GC
Table 2. (continuing)
| Peak numbering | Retention time [min] | Area [pA*s] | |
| 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 | 0.910 0.999 1.077 2.528 4.243 4.922 5.022 5.301 5.446 5.582 6.135 6.375 6.742 6.899 7.023 7.136 7.296 7.383 7.603 8.138 8.223 8.345 8.495 8.651 8.884 9.165 9.444 9.557 9.650 9.714 9.793 9.852 9.914 10.013 10.229 10.302 10.577 11.252 11.490 11.567 | 1.46868e4 148.12119 1.26473e4 1.29459e4 2162.93066 563.11804 5090.54150 437.92255 4.67394 283.92194 15.47334 1159.83130 114.83960 1922.98450 2.44915 264.34424 127.60601 118.79453 3.99227 13.15432 13.01887 103.15615 291.26767 15.64066 91.85989 40.09448 534.44507 2.64731 32.28295 52.42796 42.05001 8.93775 4.43648 24.74299 13.34387 133.95892 2.67224 27.57400 23.41665 8.13992 | Methane? ethane propane iC4? normal butane? iC5? pentane? 2-methylpentane? n-hexane? |
| 41 42 43 44 45 | 11.820 11.945 12.107 12.178 12.308 | 32.80781 4.61821 30.67044 2.58269 13.57769 | ？ ？ ？ ？ ？ |
| Peak numbering | Retention time [min] | Area [pA*s] | Title |
| 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 | 12.403 12.492 12.685 12.937 13.071 13.155 13.204 13.317 13.443 13.525 13.903 14.095 14.322 14.553 14.613 14.730 14.874 14.955 15.082 15.138 15.428 15.518 15.644 15.778 15.855 16.018 16.484 16.559 16.643 17.261 17.439 17.971 18.097 | 12.43018 34.29918 4.71311 183.31729 7.18510 2.01699 7.77467 7.21400 4.22721 35.08374 18.48654 6.39745 3.19935 8.48772 3.34738 5.44062 40.17010 3.41596 3.04766 7.33028 2.71734 11.00256 5.16752 45.12025 3.26920 3.77424 4.66657 5.54783 10.57255 2.19534 10.26123 1.85618 11.42077 | ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ |
Then make Pa Er container ventilate to reach atmospheric pressure, container is opened, and collect liquid from gold pipe inside and Pa Er container bottom.Water is separated with hydrocarbon layer and weigh.The amount of collecting is recorded in table 1.The hydrocarbon liquid of collecting is placed in bottle, sealing and storing in the presence of not at light.On the wall of golden pipe or on Pa Er wall of a container, do not observe solid.Weigh solid core sample and its after measured because heating has been lost 19.21 grams.The result showing in complete oily gas-chromatography (WOGC) test generation Figure 20, table 3 and the table 1 of this liquid.In Figure 20, y-axle 5000 represents the detector response in picoampire (pA), and 5001 expressions of x-axle in minute retention time.GC chromatogram is generally with mark 5002 demonstrations, and wherein the peak of single discriminating carries out mark with abbreviation.Peak and the area particulars of table 3. Figure 20-embodiment 1-0 stress-liquid GC
| Peak # | Retention time [min] | Peak area [pA*s] | |
| 1 | 2.660 | 119.95327 | iC4 |
| 2 | 2.819 | 803.25989 | |
| 3 | 3.433 | 1091.80298 | iC5 |
| 4 | 3.788 | 2799.32520 | nC5 |
| 5 | 5.363 | 1332.67871 | 2-methylpentane (2MP) |
| 6 | 5.798 | 466.35703 | 3-methylpentane (3MP) |
| 7 | 6.413 | 3666.46240 | nC6 |
| 8 | 7.314 | 1161.70435 | Methyl cyclopentane (MCP) |
| 9 | 8.577 | 287.05969 | Benzene (BZ) |
| 10 | 9.072 | 530.19781 | Cyclohexane (CH) |
| 11 | 10.488 | 4700.48291 | |
| 12 | 11.174 | 937.38757 | Hexahydrotoluene (MCH) |
| 13 | 12.616 | 882.17358 | Toluene (TOL) |
| 14 | 14.621 | 3954.29687 | nC8 |
| 15 | 18.379 | 3544.52905 | |
| 16 | 21.793 | 3452.04199 | nC10 |
| 17 | 24.929 | 3179.11841 | |
| 18 | 27.843 | 2680.95459 | nC12 |
| 19 | 30.571 | 2238.89600 | |
| 20 | 33.138 | 2122.53540 | |
| 21 | 35.561 | 1773.59973 | nC15 |
| 22 | 37.852 | 1792.89526 | |
| 23 | 40.027 | 1394.61707 | |
| 24 | 40.252 | 116.81663 | Pristane (Pr) |
| 25 | 42.099 | 1368.02734 | |
| 26 | 42.322 | 146.96437 | Phytane (Ph) |
| 27 | 44.071 | 1130.63342 | |
| 28 | 45.956 | 920.52136 | |
| 29 | 47.759 | 819.92810 | |
| 30 | 49.483 | 635.42065 | nC22 |
| 31 | 51.141 | 563.24316 | |
| 32 | 52.731 | 432.74606 | |
| 33 | 54.261 | 397.36270 | nC25 |
| 34 | 55.738 | 307.56073 | nC26 |
| 35 | 57.161 | 298.70926 | nC27 |
| 36 | 58.536 | 252.60083 | nC28 |
| 37 | 59.867 | 221.84540 | nC29 |
| 38 | 61.154 | 190.29596 | nC30 |
| 39 | 62.539 | 123.65781 | |
| 40 | 64.133 | 72.47668 | nC32 |
| 41 | 66.003 | 76.84142 | nC33 |
| 42 | 68.208 | 84.35004 | nC34 |
| 43 | 70.847 | 36.68131 | nC35 |
| 44 | 74.567 | 87.62341 | nC36 |
| 45 | 77.798 | 33.30892 | nC37 |
| 46 | 82.361 | 21.99784 | nC38 |
| Amount to: | 5.32519e4 |
Embodiment 2
Except what produce, be the rock core of 1 inch diameter, oil shale sillar CM-1B is to be similar to the mode removal of core of embodiment 1.With reference to Figure 21, about 2 inches long of core sample 7050, and weight is 42.47 grams.This core sample 7050 is placed in the Berea sandstone cylinder 7051 of 1 inch of internal diameter, 1.39 inches of external diameters.Berea plug 7052 and 7053 is placed in every one end of this assembly, so that core sample is surrounded completely by Berea.Berea cylinder 7051 and core sample 7050 and Berea end plug 7052 are placed in the stainless steel sleeve pipe of groove and are sandwiched in suitable position together with 7053.Sample assembly 7060 is placed in the miniature Load brackets 7061 that spring is housed as shown in Figure 22.Load is applied in Compress Spring 7064 and 7065 by tightening the nut 7062 and 7063 at Load brackets 7061 tops.Spring 7064 and 7065 is high temperature, inconel spring, and when compression, spring 7064 and 7065 is delivered to the effective stress of 400psi on oil shale sample 7060.Keep-spring 7064 and enough movements of 7065 during heating process are to adapt to any expansion of core sample 7060.In order to ensure the present embodiment, be this situation, goldleaf 7066 is placed on a leg of device to measure mobile degree.Whole spring charging device 7061 is placed in Pa Er container (Figure 18) and carries out as described in Example 1 Heating Experiment.
As described in Example 1, sampled to obtain after Heating Experiment remaining a part of exemplary gases in container after room temperature Pa Er container.The test of gas sample, hydrocarbon gas sample gas-chromatography (GC) and non-hydrocarbon gas sample gas phase chromatogram (GC) are carried out as embodiment 1.Result is presented in Figure 23, table 4 and table 1.In Figure 23, y-axle 4010 represents the detector response in picoampire (pA), and 4011 expressions of x-axle in minute retention time.In Figure 23, peak 4012 represents the response of methane, and peak 4013 represents the response of ethane, and peak 4014 represents the response of propane, and peak 4015 represents the response of butane, and peak 4016 represents the response of pentane, and peak 4017 represents the response of hexane.From gas chromatograph results and related known volume and pressure, the total hydrocarbon content of this gas is determined as the CO of 1.33 grams and this gas
2content is 1.70 grams.Peak and the area particulars of table 4. Figure 23-embodiment 2-400psi stress-gas GC
Table 4. (continuing)
| Peak numbering | Retention time [min] | Area [pA*s] | |
| 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 | 0.910 0.999 1.077 2.528 4.240 4.917 5.022 5.298 5.578 6.125 6.372 6.736 6.898 7.066 7.133 7.293 7.378 7.598 7.758 8.133 8.216 8.339 8.489 8.644 8.878 9.184 9.438 9.549 9.642 9.705 9.784 9.843 9.904 | 1.36178e4 309.65613 1.24143e4 1.41685e4 2103.01929 1035.25513 5689.08887 450.26572 302.56229 33.82201 1136.37097 263.35754 2254.86621 7.12101 258.31876 126.54671 155.60977 6.73467 679.95312 27.13466 24.77329 124.70064 289.12952 19.83309 92.18938 102.25701 664.42584 2.91525 26.86672 49.83235 52.11239 9.03158 6.18217 | Methane? ethane propane iC4? normal butane? iC5? pentane? 2-methylpentane? n-hexane? |
| 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 | 10.004 10.219 10.292 10.411 10.566 11.240 11.478 11.555 11.809 11.935 12.096 12.167 12.297 12.393 12.483 12.669 12.929 13.063 13.196 13.306 13.435 13.516 | 24.84150 13.21182 158.67511 2.49094 3.25252 46.79988 29.59438 12.84377 38.67433 5.68525 31.29068 5.84513 15.52042 13.54158 30.95983 20.21915 229.00655 6.38678 10.89876 7.91553 5.05444 44.42806 | ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ |
| Peak numbering | Retention time [min] | Area [pA*s] | |
| 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 | 13.894 14.086 14.313 14.545 14.605 14.722 14.865 14.946 15.010 15.075 15.131 15.331 15.421 15.511 15.562 15.636 15.771 | 20.61910 8.32365 2.80677 9.18198 4.93703 5.06628 46.53282 6.55945 2.85594 4.05371 9.15954 2.16523 3.03294 9.73797 5.22962 3.73105 54.64651 | ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ |
| 73 74 75 76 77 78 79 80 81 82 | 15.848 16.010 16.477 16.552 16.635 17.257 17.318 17.433 17.966 18.090 | 3.95764 3.39639 5.49586 6.21470 11.08140 2.28673 2.82284 11.11376 2.54065 14.28333 | ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ |
Now, make Pa Er container ventilate to reach atmospheric pressure, container is opened, and collect liquid from Pa Er internal tank.Water is separated with hydrocarbon layer and weigh.The amount of collecting is recorded in table 1.The hydrocarbon liquid of collecting is placed in bottle, sealing and storing in the presence of not at light.Any other liquid facial tissue collecting covering on apparatus surface or Pa Er container limit, and the weight of the liquid of this collection is added on total liquid of collection.Liquid in any Berea of remaining in sandstone extracts with carrene, and its shared weight in total liquid is reported in table 1.Due to heating, Berea sandstone cylinder and the obviously blackening together with organic substance of end plug.The unavailable toluene of organic substance or dichloromethane extraction in Berea, and therefore it is the coke that the cracking by hydrocarbon liquid forms after measured.After Heating Experiment, Berea is pulverized and is measured its total organic carbon (TOC).This measurement is used to estimate the amount of coke in Berea and estimate subsequently to have the cracking of how much liquid in Berea.Invariant 2.283 is used to the TOC of measurement to change into the estimated value of amount of fluid, and it necessarily exists to be created in the carbon of finding in Berea.The liquid of this estimation is " inferring oil (inferred the oil) " value being displayed in Table 1.Weigh solid core sample and its after measured because heating has been lost 10.29 grams.
In the mode similar to embodiment 2, to testing from the core sample of oil shale sillar CM-1B, the effective stress wherein applying is 400psi.The result of the gaseous sample by hydrocarbon gas sample gas-chromatography (GC) and non-hydrocarbon gas sample gas phase chromatogram (GC) (GC is shown) Collection and analysis is presented in Figure 24, table 5 and table 1.In Figure 24, y-axle 4020 represents the detector response in picoampire (pA), and 4021 expressions of x-axle in minute retention time.In Figure 24, peak 4022 represents the response of methane, and peak 4023 represents the response of ethane, and peak 4024 represents the response of propane, and peak 4025 represents the response of butane, and peak 4026 represents the response of pentane, and peak 4027 represents the response of hexane.The result of analyzing the liquid of Collection and analysis by complete oily gas-chromatography (WOGC) is presented in Figure 25, table 6 and table 1.In Figure 25, y-axle 5050 represents the detector response in picoampire (pA), and 5051 expressions of x-axle in minute retention time.GC chromatogram generally shows by mark 5052, and wherein the peak of single discriminating carries out mark with abbreviation.Peak and the area particulars of table 5. Figure 24-embodiment 3-400psi stress-gas GC
Table 5. (continuing)
Peak and the area particulars of table 6. Figure 25-embodiment 3-400psi stress-liquid GC
| Peak numbering | Retention time [min] | Area [pA*s] | |
| 1 | 0.910 | 1.71356e4 | Methane |
| 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 | 0.998 1.076 2.534 4.242 4.919 5.026 5.299 5.579 6.126 6.374 6.737 6.900 7.134 7.294 7.379 7.599 8.132 8.216 8.339 8.490 8.645 | 341.71646 1.52621e4 1.72319e4 2564.04077 1066.90942 6553.25244 467.88803 311.65158 33.61063 1280.77869 250.05510 2412.40918 249.80679 122.60424 154.40988 6.87471 25.50270 22.33015 129.17023 304.97903 18.48411 | Ethane propane iC4? normal butane? iC5? pentane? 2-methylpentane? |
| Peak numbering | Retention time [min] | Area [pA*s] | |
| 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 | 8.879 9.187 9.440 9.551 9.645 9.708 9.786 9.845 9.906 10.007 10.219 10.295 10.413 10.569 11.243 11.482 11.558 11.812 | 98.23043 89.71329 656.02161 3.05892 25.34058 45.14915 48.62077 10.03335 5.43165 22.33582 16.02756 196.43715 2.98115 3.88067 41.63386 28.44063 12.05196 37.83630 | N-hexane? |
| 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 | 11.938 12.100 12.170 12.301 12.397 12.486 12.672 12.931 13.064 13.103 13.149 13.198 13.310 13.437 13.519 13.898 14.089 14.316 14.548 14.608 14.725 14.869 14.949 15.078 15.134 15.335 15.423 15.515 15.565 15.639 15.774 15.850 16.014 16.480 16.555 16.639 17.436 17.969 18.093 | 5.45990 31.03111 4.91053 15.75041 13.75454 30.26099 15.14775 207.50433 3.35393 3.04880 1.62203 7.97665 7.49605 4.64921 41.82572 19.01739 7.34498 2.68912 8.29593 3.93147 4.75483 40.93447 5.30140 5.79979 7.95179 1.91589 2.75893 8.64343 3.76481 3.41854 45.59035 3.73501 5.84199 4.87036 5.12607 9.97469 8.00434 3.86749 9.71661 | ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ |
| Peak # | Retention time [min] | Peak area [pA*s] | |
| 1 | 2.744 | 102.90978 | iC4 |
| 2 | 2.907 | 817.57861 | |
| 3 | 3.538 | 1187.01831 | iC5 |
| 4 | 3.903 | 3752.84326 | nC5 |
| 5 | 5.512 | 1866.25342 | 2MP |
| 6 | 5.950 | 692.18964 | 3MP |
| 7 | 6.580 | 6646.48242 | nC6 |
| 8 | 7.475 | 2117.66919 | MCP |
| 9 | 8.739 | 603.21204 | |
| 10 | 9.230 | 1049.96240 | CH |
| 11 | 10.668 | 9354.29590 | |
| 12 | 11.340 | 2059.10303 | MCH |
| 13 | 12.669 | 689.82861 | |
| 14 | 14.788 | 8378.59375 | nC8 |
| 15 | 18.534 | 7974.54883 | |
| 16 | 21.938 | 7276.47705 | nC10 |
| 17 | 25.063 | 6486.47998 | |
| 18 | 27.970 | 5279.17187 | nC12 |
| 19 | 30.690 | 4451.49902 | |
| 20 | 33.254 | 4156.73389 | |
| 21 | 35.672 | 3345.80273 | nC15 |
| 22 | 37.959 | 3219.63745 | |
| 23 | 40.137 | 2708.28003 | |
| 24 | 40.227 | 219.38252 | |
| 25 | 42.203 | 2413.01929 | |
| 26 | 42.455 | 317.17825 | |
| 27 | 44.173 | 2206.65405 | |
| 28 | 46.056 | 1646.56616 | |
| 29 | 47.858 | 1504.49097 | |
| 30 | 49.579 | 1069.23608 | nC22 |
| 31 | 51.234 | 949.49316 | |
| 32 | 52.823 | 719.34735 | |
| 33 | 54.355 | 627.46436 | nC25 |
| 34 | 55.829 | 483.81885 | nC26 |
| 35 | 57.253 | 407.86371 | nC27 |
| 36 | 58.628 | 358.52216 | nC28 |
| 37 | 59.956 | 341.01791 | nC29 |
| 38 | 61.245 | 214.87863 | nC30 |
| 39 | 62.647 | 146.06461 | |
| 40 | 64.259 | 127.66831 | nC32 |
| 41 | 66.155 | 85.17574 | nC33 |
| 42 | 68.403 | 64.29253 | nC34 |
| 43 | 71.066 | 56.55088 | nC35 |
| 44 | 74.282 | 28.61854 | nC36 |
| 45 | 78.140 | 220.95929 | nC37 |
| 46 | 83.075 | 26.95426 | nC38 |
| Amount to: | 9.84518e4 |
Embodiment 4
In the mode similar to embodiment 2 to testing from the core sample of oil shale sillar CM-1B, yet the effective stress applying is in this embodiment 1,000psi.The result of the gas by hydrocarbon gas sample gas-chromatography (GC) and non-hydrocarbon gas sample gas phase chromatogram (GC) (GC is shown) Collection and analysis is presented in Figure 26, table 7 and table 1.In Figure 26, y-axle 4030 represents the detector response in picoampire (pA), and 4031 expressions of x-axle in minute retention time.In Figure 26, peak 4032 represents the response of methane, and peak 4033 represents the response of ethane, and peak 4034 represents the response of propane, and peak 4035 represents the response of butane, and peak 4036 represents the response of pentane, and peak 4037 represents the response of hexane.The result of the liquid by complete oily gas-chromatography (WOGC) Collection and analysis is presented in Figure 27, table 8 and table 1.In Figure 27, y-axle 6000 represents the detector response in picoampire (pA), and 6001 expressions of x-axle in minute retention time.GC chromatogram generally shows by mark 6002, and wherein the peak of single discriminating carries out mark with abbreviation.Peak and the area particulars of table 7. Figure 26-embodiment 4-1000psi stress-gas GC
Table 7. (continuing)
Peak and the area particulars of table 8. Figure 27-embodiment 4-1000psi stress-liquid GC
| Peak numbering | Retention time [min] | Area [pA*s] | |
| 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 | 0.910 1.000 1.078 2.541 4.249 4.924 5.030 5.303 5.583 6.131 6.376 6.740 6.902 7.071 7.136 7.295 7.381 | 1.43817e4 301.69287 1.37821e4 1.64047e4 2286.08032 992.04395 6167.50000 534.37000 358.96567 27.44937 1174.68872 223.61662 2340.79248 5.29245 309.94775 154.59171 169.53279 | Methane? ethane propane iC4? normal butane? iC5? pentane? |
| 18 19 20 21 22 23 24 25 26 27 | 7.555 7.601 7.751 8.134 8.219 8.342 8.492 8.647 8.882 9.190 | 2.80458 5.22327 117.69164 29.41086 19.39338 133.52739 281.61343 22.19704 99.56919 86.65676 | 2-methylpentane? |
| Peak numbering | Retention time [min] | Area [pA*s] | |
| 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 | 9.443 9.552 9.646 9.710 9.788 9.847 9.909 10.009 10.223 10.298 10.416 10.569 11.246 11.485 11.560 11.702 11.815 11.941 12.103 12.172 12.304 12.399 12.490 12.584 12.675 12.934 13.105 13.151 13.201 13.312 | 657.28754 4.12572 34.33701 59.12064 62.97972 15.13559 6.88310 29.11555 23.65434 173.95422 3.37255 7.64592 47.30062 32.04262 13.74583 2.68917 36.51670 6.45255 28.44484 5.96475 17.59856 15.17446 31.96492 3.27834 14.08259 207.21574 8.29743 2.25476 8.36965 9.49917 | N-hexane? |
| 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 | 13.436 13.521 13.900 14.090 14.318 14.550 14.610 14.727 14.870 14.951 15.080 15.136 15.336 15.425 15.516 15.569 15.641 15.776 16.558 16.641 17.437 18.095 15.853 16.016 16.482 | 6.09893 46.34579 20.53506 8.41120 4.36870 8.68951 4.39150 4.35713 37.17881 5.78219 5.54470 8.07308 2.07075 2.67118 8.47004 3.89987 3.96979 40.75155 5.06379 8.43767 6.00180 7.66881 3.97375 5.68997 3.27234 | ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ |
| Peak # | Retention time [min] | Peak area [pA*s] | |
| 1 | 2.737 | 117.78948 | iC4 |
| 2 | 2.901 | 923.40125 | |
| 3 | 3.528 | 1079.83325 | iC5 |
| 4 | 3.891 | 3341.44604 | nC5 |
| 5 | 5.493 | 1364.53186 | 2MP |
| 6 | 5.930 | 533.68530 | 3MP |
| 7 | 6.552 | 5160.12207 | nC6 |
| 8 | 7.452 | 1770.29932 | MCP |
| 9 | 8.717 | 487.04718 | |
| 10 | 9.206 | 712.61566 | CH |
| 11 | 10.634 | 7302.51123 | |
| 12 | 11. | 1755.92236 | MCH |
| 13 | 12.760 | 2145.57666 | |
| 14 | 14.755 | 6434.40430 | nC8 |
| 15 | 18.503 | 6007.12891 | |
| 16 | 21.906 | 5417.67480 | nC10 |
| 17 | 25.030 | 4565.11084 | |
| 18 | 27.936 | 3773.91943 | nC12 |
| 19 | 30.656 | 3112.23950 | |
| 20 | 33.220 | 2998.37720 | |
| 21 | 35.639 | 2304.97632 | nC15 |
| 22 | 37.927 | 2197.88892 | |
| 23 | 40.102 | 1791.11877 | |
| 24 | 40.257 | 278.39423 | |
| 25 | 42.171 | 1589.64233 | |
| 26 | 42.428 | 241.65131 | |
| 27 | 44.141 | 1442.51843 | |
| 28 | 46.025 | 1031.68481 | |
| 29 | 47.825 | 957.65479 | |
| 30 | 49.551 | 609.59943 | nC22 |
| 31 | 51.208 | 526.53339 | |
| 32 | 52.798 | 383.01022 | |
| 33 | 54.329 | 325.93640 | nC25 |
| 34 | 55.806 | 248.12935 | nC26 |
| 35 | 57.230 | 203.21725 | nC27 |
| 36 | 58.603 | 168.78055 | nC28 |
| 37 | 59.934 | 140.40034 | nC29 |
| 38 | 61.222 | 95.47594 | nC30 |
| 39 | 62.622 | 77.49546 | |
| 40 | 64.234 | 49.08135 | nC32 |
| 41 | 66.114 | 33.61663 | nC33 |
| 42 | 68.350 | 27.46170 | nC34 |
| 43 | 71.030 | 35.89277 | nC35 |
| 44 | 74.162 | 16.87499 | nC36 |
| 45 | 78.055 | 29.21477 | nC37 |
| 46 | 82.653 | 9.88631 | nC38 |
| Amount to: | 7.38198e4 |
Embodiment 5
In the mode similar to embodiment 2 to testing from the core sample of oil shale sillar CM-1B; Yet the effective stress applying is in this embodiment 1,000psi.The result of the gas by hydrocarbon gas sample gas-chromatography (GC) and non-hydrocarbon gas sample gas phase chromatogram (GC) (GC does not show) Collection and analysis is presented in Figure 28, table 9 and table 1.In Figure 28, y-axle 4040 represents the detector response in picoampire (pA), and 4041 expressions of x-axle in minute retention time.In Figure 28, peak 4042 represents the response of methane, and peak 4043 represents the response of ethane, and peak 4044 represents the response of propane, and peak 4045 represents the response of butane, and peak 4046 represents the response of pentane, and peak 4047 represents the response of hexane.Peak and the area particulars of table 9. Figure 28-embodiment 5-1000psi stress-gas GC
Table 9. (continuing)
The combined data of table 1. embodiment 1-5
| Peak numbering | Retention time [min] | Area [pA*s] | |
| 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 | 0.910 0.999 1.077 2.537 4.235 4.907 5.015 5.285 5.564 6.106 6.351 6.712 6.876 7.039 7.109 7.268 7.354 7.527 7.574 7.755 7.818 8.107 8.193 8.317 8.468 8.622 8.858 9.168 9.422 9.531 9.625 9.689 9.767 9.826 9.889 | 1.59035e4 434.21375 1.53391e4 1.86530e4 2545.45850 1192.68970 6814.44678 687.83679 463.25885 30.02624 1295.13477 245.26985 2561.11792 4.50998 408.32999 204.45311 207.92183 4.02397 5.65699 2.35952 2.00382 38.23093 20.54333 148.54445 300.31586 26.06131 113.70123 90.37163 694.74438 4.88323 45.91505 76.32931 77.63214 19.23768 8.54605 | Methane? ethane propane iC4? normal butane? iC5? pentane? 2-methylpentane? n-hexane? |
| Peak numbering | Retention time [min] | Area [pA*s] | Title |
| 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 | 9.989 10.204 10.280 10.397 10.551 10.843 11.231 11.472 11.547 11.691 11.804 11.931 12.094 12.163 12.295 12.391 12.482 12.577 12.618 12.670 12.851 12.929 13.100 13.198 13.310 13.432 13.519 13.898 14.090 14.319 14.551 14.612 14.729 14.872 14.954 15.084 15.139 15.340 15.430 15.521 | 37.74959 30.83943 184.58420 4.43609 10.59880 2.30370 55.64666 35.46931 17.16440 3.30460 39.46368 7.32969 30.59748 6.93754 18.69523 15.96837 33.66422 2.02121 2.32440 12.83803 2.22731 218.23195 14.33166 10.20244 12.02551 8.23884 47.64641 22.63760 9.29738 3.88012 9.26884 4.34914 4.07543 46.24465 6.62461 3.92423 8.60328 2.17899 2.96646 9.66407 | ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ |
| 76 77 78 79 80 81 82 83 84 85 86 87 88 89 | 15.578 15.645 15.703 15.782 15.859 16.022 16.489 16.564 16.648 17.269 17.445 17.925 17.979 18.104 | 4.27190 4.37904 2.68909 46.97895 4.69475 7.36509 3.91073 6.22445 10.24660 2.69753 10.16989 2.28341 2.71101 11.19730 | ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ ？ |
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Effective stress (psi) | 0 | 400 | 400 | 1000 | 1000 |
| Example weight (g) | 82.46 | 42.57 | 48.34 | 43.61 | 43.73 |
| Example weight loss (g) | 19.21 | 10.29 | 11.41 | 10.20 | 9.17 |
| The fluid reclaiming: | |||||
| Oil (g) | 10.91 36.2 Gallons Per Tons | 3.63 23.4 Gallons Per Tons | 3.77 21.0 Gallons Per Tons | 3.02 19.3 Gallons Per Tons | 2.10 13.1 Gallons Per Tons |
| Water (g) | 0.90 2.6 Gallons Per Ton | 0.30 1.74 Gallons Per Ton | 0.34 1.7 Gallons Per Ton | 0.39 2.1 Gallons Per Ton | 0.28 1.5 Gallons Per Ton |
| HC gas (g) | 2.09 683 standard cubic foot/tons | 1.33 811 standard cubic foot/tons | 1.58 862 standard cubic foot/tons | 1.53 905 standard cubic foot/tons | 1.66 974 standard cubic foot/tons |
| ?CO 2(g) | 3.35 700 standard cubic foot/tons | 1.70 690 standard cubic foot/tons | 1.64 586 standard cubic foot/tons | 1.74 690 standard cubic foot/tons | 1.71 673 standard cubic foot/tons |
| ?H 2S(g) | 0.06 | 0.0 | 0.0 | 0.0 | 0.0 |
| The coke reclaiming: | 0.0 | 0.73 | 0.79 | .47 | 0.53 |
| Infer oil (g) | 0.0 0 Gallons Per Tons | 1.67 10.8 Gallons Per Tons | 1.81 10.0 Gallons Per Tons | 1.07 6.8 Gallons Per Tons | 1.21 7.6 Gallons Per Tons |
| Total oil (g) | 10.91 36.2 Gallons Per Tons | 5.31 34.1 Gallons Per Tons | 5.58 31.0 Gallons Per Tons | 4.09 26.1 Gallons Per Tons | 3.30 20.7 Gallons Per Tons |
| Surplus (g) | 1.91 | 2.59 | 3.29 | 3.05 | 2.91 |
Analyze
Gas and fluid sample that the experimental arrangement of describing by embodiment 1-5 and gas and fluid sample collection procedure obtain are by hydrocarbon gas sample gas-chromatography (GC) analytical method, non-hydrocarbon gas sample gas phase chromatogram (GC) analytical method, gaseous sample GC peak discriminating and integration method, complete oily gas-chromatography (WOGC) analytical method below, and complete oily gas-chromatography (WOGC) peak is differentiated and integration method is analyzed.
To as at embodiment 1-5 described in hydrocarbon and the non-hydrocarbon gas of the gaseous sample collected of heating test period analyze, utilization be AgilentModel 6890 gas chromatographs that are connected with Agilent Model 5,973 four utmost point mass selective detectors.6890 GC are configured with two entrances (front and rear) and two detectors (front and rear) with two fixed volume sample loops, for Sample introduction.The Chemstation software that employing is supplied together with GC instrument (revised edition A.03.01) carries out peak discriminating and integration.For the hydrocarbon gas, GC configuration is comprised of following: a) shunting/without minute inflow entrance (back location of a GC) b) FID (flame ionization detector), the back location c of GC) HP Ultra-2 (5% phenyl methyl siloxanes) capillary column (two) (25 meters of x200 μ m ID), guide fid detector into for one, another guides Agilent 5973 mass selective detector d into) 500 μ l fixed volume sample loop e) six logical GSV f) low temperature (liquid nitrogen) insulating box, there is cooling capacity g) insulating box program :-80 ℃ continue 2 minutes, 20 ℃/min to 0 ℃, then 4 ℃/min to 20 ℃, then 10 ℃/min to 100 ℃, keep 1 minute h) helium carrier gas flow velocity 2.2ml/mini) 100 ℃ of j of inlet temperature) entrance pressure 19.35psik) split ratio 25: 1l) FID temperature is 310 ℃
For example, for the non-hydrocarbon gas (argon, carbon dioxide and hydrogen sulfide), GC configuration is comprised of following: a) PTV (Programmable Temperature vaporization) entrance (anterior locations of GC) b) the anterior locations c of TCD (thermal conductivity detector (TCD)) GC) GS-GasPro capillary column (30 meters of x0.32mm ID) d) 100 μ l fixed volume sample loop e) six logical GSV f) insulating box program: 25 ℃ keep 2min., then 10 ℃/min to 200 ℃, keeps 1min.G) helium carrier gas flow velocity 4.1ml/minh) 200 ℃ of i of inlet temperature) inlet pressure 14.9psij) without shunt mode k) 250 ℃ of TCD temperature
For embodiment 1-5, the stainless steel sample cylinder (Figure 18) that comprises the gas of collecting from Pa Er container has been mounted two stage gas conditioners (for thin compressed gas cylinder (lecture bottle) application design) so that gas pressure intensity is down to about 20 pounds per square inch.Dividing plate annex is positioned at demodulator outlet, to allow the 1005 type gastight syringes by Hamilton, takes out gas.Dividing plate annex and syringe are all used the gas purging from stainless steel sample cylinder, to guarantee to collect exemplary gases sample.Then gaseous sample is transferred to stainless steel chamber (baffle chamber), and described stainless steel chamber (baffle chamber) is configured with pressure sensor and dividing plate annex.Baffle chamber is connected with the fixed volume sample loop being arranged on GC by Stainless Steel Capillary pipeline.Baffle chamber and sample loop are evacuated about 5 minutes.Then the baffle chamber of finding time is positioned at the needle valve of baffle chamber outlet and isolates with the sample loop of finding time by closing.Gaseous sample imports baffle chamber by dividing plate annex from tightness syringe, and records pressure.Then the sample loop of finding time is opened to the baffle chamber of pressurization, and makes gaseous sample balance one minute between sample loop and baffle chamber.Then record equilibrium pressure, to allow the calculating gas total mole number existing before being expelled to GC entrance in sample loop.Then sample loop inclusion sweeps into entrance by helium carrier gas, and based on GC calorstat temperature program and flow rate of carrier gas, by the retention time in capillary column, composition is separated.
Utilize the gas standard of identifying, generate the calibration curve that the peak area of integration is associated with concentration, for quantizing gas composition.For the hydrocarbon gas, the standard of methane, ethane, propane, butane, pentane and the hexanes mixtures that contains variable concentrations in helium matrix (every 1,000,000 parts, based on mole) is under atmospheric pressure injected GC by fixed volume sample loop.For the non-hydrocarbon gas,---to be carbon dioxide in helium and the hydrogen sulfide in natural gas---inject GC to produce calibration curve to the standard that comprises single composition in sample loop under different pressure.
The hydrocarbon gas sample mole percent of reporting in Figure 16 adopts following method to obtain.The gas standard of the methane of at least three kinds of variable concentrations, ethane, propane, butane, pentane and hexane moves to obtain the peak area response for these normal concentrations in gas-chromatography.Then in Chemstation software, make concentration known be associated with peak area response separately, to produce the calibration curve of methane, ethane, propane, butane, pentane and hexane.In Chemstation, draw calibration curve, to guarantee linearity good between concentration and peak intensity (R2 > 0.98).For the compound of each calibration, use linear fit, making response factor between peak area and molar concentration is the function of the straight slope measured of Chemstation software.Then Chemstation software program is measured the GC peak area intensity response factor associated with the molal quantity of each calibration compound.Then this software measure from response factor and peak area the molal quantity that each calibrates compound.The peak area using in embodiment 1-5 is reported in table 2,4,5,7 and 9., the molal quantity of undeterminate each authenticating compound of calibration curve (being iso-butane, isopentane and 2-methylpentane) then utilizes immediate calibration compound (is that is butane for iso-butane; For isopentane, it is pentane; And be hexane for 2-methylpentane) the response factor peak area that is multiplied by the undeterminate authenticating compound of calibration curve estimate with the ratio of the peak area of calibration compound.Then the value of reporting in Figure 16 is calculated as the percentage of the molar concentration of all hydrocarbon gas GC areas of having identified (namely for methane, ethane, propane, iso-butane, normal butane, isopentane, pentane, 2-methylpentane and n-hexane) sum and calculating.Therefore the graphic methane of all experiments to positive C6 mole percent is not included in mole share (for example numbering of the peak in table 22,6,8-11,13,15-22,24-26 and 28-78) of unidentified hydrocarbon gas kind listed in table 2,4,5,7 or 9.
Fluid sample in the heating test periods collection of describing as embodiment 1,3 and 4 is analyzed by complete oily gas-chromatography (WOGC) according to following method.Sample, QA/QC standard and blank (carbon disulfide) are utilized Ultra 1 Methyl Siloxane (methylsiloxane) post (long 25m in disposing the Agilent 6890GC of shunting/without split stream injector, Autosampler and flame ionic detector (FID), diameter 0.32 μ m, thickness 0.52 μ m) analyze.Sample is injected on capillary column with shunt mode, and its split ratio is 80: 1.GC calorstat temperature at 20 ℃ by constant maintenance 5min, with 5 ℃ of min
-1speed from 20 ℃ of programme-control, be warming up to 300 ℃, then at 300 ℃, keep 30min (total run time=90min).Injector temperature is maintained at 300 ℃, and FID temperature is set at 310 ℃.Helium is with 2.1mLmin
-1flow velocity be used as carrier gas.The Chemstation software revision that utilization provides with Agilent instrument is originally A.10.02[1757] (Agilent Tech.1990-2003) carry out peak discriminating and integration.
The correct mixture of hydrocarbon is by above-mentioned WOGC method and by disposing shunting/carry out under the same conditions parallel analysis without the Agilent 6890GC of split stream injector, Autosampler and mass selective detector (MS).By analyze the mass spectrum at each peak from GC-MS, carry out the evaluation of hydrocarbon compound.Because condition is identical for two kinds of instruments, the peak therefore carrying out on GC-MS is differentiated can be transferred to the peak obtaining on GC-FID.Utilize these data, make retention time and peak differentiate that associated compound table is set in GC-FID Chemstation.This table is used to peak and differentiates.
Utilize pseudocomponent technology to analyze the gas chromatogram obtaining on fluid sample (Fig. 4,9 and 11).Identify that each pseudocomponent convention used is that wherein pseudocomponent is named by the n-alkane of the wash-out that lags behind by all share integrations from n-alkane to the next n-alkane occurring.For example, C-10 pseudocomponent starts and continues the just integration acquisition of the positive C10 of process from the positive C9 in firm past.The carbon number percetage by weight of the pseudocomponent obtaining by this way and mole percent value are utilized the relational expression assignment (Katz by Katz and Firoozabadi exploitation, D.L., and A.Firoozabadi, 1978.Predicting phase behavior ofcondensate/crude-oil systems using methane interaction coefficients, J.PetroleumTechnology (Nov.1978), 1649-1655).The result of embodiment 1,3 and 4 pseudocomponent analyte is presented in table 10,11 and 12.
In order to illustrate this technology, below the exemplary pseudocomponent percetage by weight computing reference table 10 of the C10 pseudocomponent of embodiment 1 is presented on.First, C-10 pseudocomponent area is that positive C9 from the firm past just starts and continue to obtain through the integration of the area of positive C10 as mentioned above.The total mark area of C10 pseudocomponent was 10551.700 skin ampere-seconds (pAs).Total C10 pseudocomponent integral area (10551.700pAs) is then multiplied by C10 pseudocomponent density (0.7780g/ml), produces " area * density " of 8209.22pAs g/ml.Similarly, determine the peak integral area of each pseudocomponent and all lighter listed compounds (being nC3, iC4, nC4, iC5 & nC5), and be multiplied by its density separately, to produce each " area * density " number of pseudocomponent and listed compound separately.Then " area * density " determined separately number of each pseudocomponent and listed compound is added to determine " gross area * density " number.Embodiment's 1 " gross area * density " number is 96266.96pAs g/ml.C10 pseudocomponent percetage by weight is then by obtaining divided by " gross area * density " number (96266.96pAs g/ml) C10 pseudocomponent " area * density " number (8209.22pAs g/ml) to obtain the C10 pseudocomponent percetage by weight of 8.53 percetages by weight.
In order further to illustrate this pseudocomponent technology, below the exemplary pseudocomponent mole percent computing reference table 10 of the C10 pseudocomponent of embodiment 1 is presented on.First, C-10 pseudocomponent area is that positive C9 from the firm past just starts and continue to obtain through the integration of the area of positive C10 as mentioned above.The total mark area of C10 pseudocomponent was 10551.700 slight ampere-seconds (pAs).Total C10 pseudocomponent integral area (10551.700pAs) is then multiplied by C10 pseudocomponent density (0.7780g/ml), produces " area * density " of 8209.22pAs g/ml.Similarly, determine the integral area of each pseudocomponent and all lighter listed compounds (being nC3, iC4, nC4, iC5 & nC5), and be multiplied by its density separately to produce each " area * density " number of pseudocomponent and listed compound separately.C10 pseudocomponent " area * density " number (8209.22pAs g/ml), then divided by C10 pseudocomponent molecular weight (134.00g/mol), produces C10 pseudocomponent " area * density/molecular weight " number of 61.26pAs mol/ml.Similarly, " area * density " of each pseudocomponent and listed compound number is then divided by these components or compound molecular weight separately, to produce each " area * density/molecular weight " number of pseudocomponent and listed compound separately.Then " area * density/molecular weight " number that each pseudocomponent and listed compound are determined is separately added to determine " gross area * density/molecular weight " number.Total " gross area * density/molecular weight " number of embodiment 1 is 665.28pAsmol/ml.Then C10 pseudocomponent mole percent is by C10 pseudocomponent " area * density/molecular weight " number (61.26pAs mol/ml) is obtained to obtain the C10 pseudocomponent mole percent of 9.21 mole percents divided by " gross area * density/molecular weight " number (665.28pAs mol/ml).The GC-0 stress of pseudocomponent-liquid of table 10. embodiment 1
Table 10. (continuing)
The GC-400psi stress of pseudocomponent-liquid of table 11. embodiment 3
Table 11. (continuing)
The GC-1000psi stress of pseudocomponent-liquid of table 12. embodiment 4
| Component | Area (cts.) | Area % | Mean boiling point (°F) | Density (g/ml) | Molecular weight (g/mol) | Wt. ％ | Mol％ |
| nC 3 | 41.881 | 0.03 | -43.73 | 0.5069 | 44.10 | 0.02 | 0.07 |
| iC 4 | 120.873 | 0.10 | 10.94 | 0.5628 | 58.12 | 0.07 | 0.18 |
| nC 4 | 805.690 | 0.66 | 31.10 | 0.5840 | 58.12 | 0.49 | 1.22 |
| iC 5 | 1092.699 | 0.89 | 82.13 | 0.6244 | 72.15 | 0.71 | 1.42 |
| nC 5 | 2801.815 | 2.29 | 96.93 | 0.6311 | 72.15 | 1.84 | 3.68 |
| False C 6 | 7150.533 | 5.84 | 147.00 | 0.6850 | 84.00 | 5.09 | 8.76 |
| False C 7 | 10372.800 | 8.47 | 197.50 | 0.7220 | 96.00 | 7.78 | 11.73 |
| False C 8 | 11703.500 | 9.56 | 242.00 | 0.7450 | 107.00 | 9.06 | 12.25 |
| False C 9 | 11776.200 | 9.61 | 288.00 | 0.7640 | 121.00 | 9.35 | 11.18 |
| False C 10 | 10551.700 | 8.61 | 330.50 | 0.7780 | 134.00 | 8.53 | 9.21 |
| False C 11 | 9274.333 | 7.57 | 369.00 | 0.7890 | 147.00 | 7.60 | 7.48 |
| False C 12 | 8709.231 | 7.11 | 407.00 | 0.8000 | 161.00 | 7.24 | 6.50 |
| False C 13 | 7494.549 | 6.12 | 441.00 | 0.8110 | 175.00 | 6.31 | 5.22 |
| False C 14 | 6223.394 | 5.08 | 475.50 | 0.8220 | 190.00 | 5.31 | 4.05 |
| False C 15 | 6000.179 | 4.90 | 511.00 | 0.8320 | 206.00 | 5.19 | 3.64 |
| False C 16 | 5345.791 | 4.36 | 542.00 | 0.8390 | 222.00 | 4.66 | 3.04 |
| Component | Area (cts.) | Area % | Mean boiling point (°F) | Density (g/ml) | Molecular weight (g/mol) | Wt.％ | Mol％ |
| False C 17 | 4051.886 | 3.31 | 572.00 | 0.8470 | 237.00 | 3.57 | 2.18 |
| False C 18 | 3398.586 | 2.77 | 595.00 | 0.8520 | 251.00 | 3.01 | 1.73 |
| False C 19 | 2812.101 | 2.30 | 617.00 | 0.8570 | 263.00 | 2.50 | 1.38 |
| False C 20 | 2304.651 | 1.88 | 640.50 | 0.8620 | 275.00 | 2.06 | 1.09 |
| False C 21 | 2038.925 | 1.66 | 664.00 | 0.8670 | 291.00 | 1.84 | 0.91 |
| False C 22 | 1497.726 | 1.22 | 686.00 | 0.8720 | 305.00 | 1.36 | 0.64 |
| False C 23 | 1173.834 | 0.96 | 707.00 | 0.8770 | 318.00 | 1.07 | 0.49 |
| False C 24 | 822.762 | 0.67 | 727.00 | 0.8810 | 331.00 | 0.75 | 0.33 |
| False C 25 | 677.938 | 0.55 | 747.00 | 0.8850 | 345.00 | 0.62 | 0.26 |
| False C 26 | 532.788 | 0.43 | 766.00 | 0.8890 | 359.00 | 0.49 | 0.20 |
| False C 27 | 459.465 | 0.38 | 784.00 | 0.8930 | 374.00 | 0.43 | 0.16 |
| False C 28 | 413.397 | 0.34 | 802.00 | 0.8960 | 388.00 | 0.38 | 0.14 |
| False C 29 | 522.898 | 0.43 | 817.00 | 0.8990 | 402.00 | 0.49 | 0.18 |
| False C 30 | 336.968 | 0.28 | 834.00 | 0.9020 | 416.00 | 0.32 | 0.11 |
| False C 31 | 322.495 | 0.26 | 850.00 | 0.9060 | 430.00 | 0.30 | 0.10 |
| False C 32 | 175.615 | 0.14 | 866.00 | 0.9090 | 444.00 | 0.17 | 0.05 |
| False C 33 | 165.912 | 0.14 | 881.00 | 0.9120 | 458.00 | 0.16 | 0.05 |
| False C 34 | 341.051 | 0.28 | 895.00 | 0.9140 | 472.00 | 0.32 | 0.10 |
| False C 35 | 286.861 | 0.23 | 908.00 | 0.9170 | 486.00 | 0.27 | 0.08 |
| False C 36 | 152.814 | 0.12 | 922.00 | 0.9190 | 500.00 | 0.15 | 0.04 |
| False C 37 | 356.947 | 0.29 | 934.00 | 0.9220 | 514.00 | 0.34 | 0.10 |
| False C 38 | 173.428 | 0.14 | 947.00 | 0.9240 | 528.00 | 0.17 | 0.05 |
| Amount to | 122484.217 | 100.00 | 100.00 | 100.00 |
| Component | Area | Area % | Mean boiling point (°F) | Density (g/ml) | Molecular weight (g/mol) | Wt. ％ | Mol ％ |
| nC 3 | 35.845 | 0.014 | -43.730 | 0.5069 | 44.10 | 0.01 | 0.03 |
| iC 4 | 103.065 | 0.041 | 10.940 | 0.5628 | 58.12 | 0.03 | 0.07 |
| nC 4 | 821.863 | 0.328 | 31.100 | 0.5840 | 58.12 | 0.24 | 0.62 |
| iC 5 | 1187.912 | 0.474 | 82.130 | 0.6244 | 72.15 | 0.37 | 0.77 |
| nC 5 | 3752.655 | 1.498 | 96.930 | 0.6311 | 72.15 | 1.20 | 2.45 |
| False C 6 | 12040.900 | 4.805 | 147.000 | 0.6850 | 84.00 | 4.17 | 7.34 |
| False C 7 | 20038.600 | 7.997 | 197.500 | 0.7220 | 96.00 | 7.31 | 11.26 |
| False C 8 | 24531.500 | 9.790 | 242.000 | 0.7450 | 107.00 | 9.23 | 12.76 |
| False C 9 | 25315.000 | 10.103 | 288.000 | 0.7640 | 121.00 | 9.77 | 11.94 |
| False C 10 | 22640.400 | 9.035 | 330.500 | 0.7780 | 134.00 | 8.90 | 9.82 |
| False C 11 | 20268.100 | 8.089 | 369.000 | 0.7890 | 147.00 | 8.08 | 8.13 |
| False C 12 | 18675.600 | 7.453 | 407.000 | 0.8000 | 161.00 | 7.55 | 6.93 |
| False C 13 | 16591.100 | 6.621 | 441.000 | 0.8110 | 175.00 | 6.80 | 5.74 |
| False C 14 | 13654.000 | 5.449 | 475.500 | 0.8220 | 190.00 | 5.67 | 4.41 |
| False C 15 | 13006.300 | 5.191 | 511.000 | 0.8320 | 206.00 | 5.47 | 3.92 |
| False C 16 | 11962.200 | 4.774 | 542.000 | 0.8390 | 222.00 | 5.07 | 3.38 |
| False C 17 | 8851.622 | 3.533 | 572.000 | 0.8470 | 237.00 | 3.79 | 2.36 |
| False C 18 | 7251.438 | 2.894 | 595.000 | 0.8520 | 251.00 | 3.12 | 1.84 |
| False C 19 | 5946.166 | 2.373 | 617.000 | 0.8570 | 263.00 | 2.57 | 1.45 |
| False C 20 | 4645.178 | 1.854 | 640.500 | 0.8620 | 275.00 | 2.02 | 1.09 |
| False C 21 | 4188.168 | 1.671 | 664.000 | 0.8670 | 291.00 | 1.83 | 0.93 |
| False C 22 | 2868.636 | 1.145 | 686.000 | 0.8720 | 305.00 | 1.26 | 0.61 |
| False C 23 | 2188.895 | 0.874 | 707.000 | 0.8770 | 318.00 | 0.97 | 0.45 |
| False C 24 | 1466.162 | 0.585 | 727.000 | 0.8810 | 331.00 | 0.65 | 0.29 |
| False C 25 | 1181.133 | 0.471 | 747.000 | 0.8850 | 345.00 | 0.53 | 0.23 |
| False C 26 | 875.812 | 0.350 | 766.000 | 0.8890 | 359.00 | 0.39 | 0.16 |
| False C 27 | 617.103 | 0.246 | 784.000 | 0.8930 | 374.00 | 0.28 | 0.11 |
| False C 28 | 538.147 | 0.215 | 802.000 | 0.8960 | 388.00 | 0.24 | 0.09 |
| False C 29 | 659.027 | 0.263 | 817.000 | 0.8990 | 402.00 | 0.30 | 0.11 |
| False C 30 | 1013.942 | 0.405 | 834.000 | 0.9020 | 416.00 | 0.46 | 0.16 |
| Component | Area | Area % | Mean boiling point (°F) | Density (g/ml) | Molecular weight (g/mol) | Wt.％ | Mol％ |
| False C 31 | 761.259 | 0.304 | 850.000 | 0.9060 | 430.00 | 0.35 | 0.12 |
| False C 32 | 416.031 | 0.166 | 866.000 | 0.9090 | 444.00 | 0.19 | 0.06 |
| False C 33 | 231.207 | 0.092 | 881.000 | 0.9120 | 458.00 | 0.11 | 0.03 |
| False C 34 | 566.926 | 0.226 | 895.000 | 0.9140 | 472.00 | 0.26 | 0.08 |
| False C 35 | 426.697 | 0.170 | 908.000 | 0.9170 | 486.00 | 0.20 | 0.06 |
| False C 36 | 191.626 | 0.076 | 922.000 | 0.9190 | 500.00 | 0.09 | 0.03 |
| False C 37 | 778.713 | 0.311 | 934.000 | 0.9220 | 514.00 | 0.36 | 0.10 |
| False C 38 | 285.217 | 0.114 | 947.000 | 0.9240 | 528.00 | 0.13 | 0.04 |
| Amount to | 250574.144 | 100.000 | 100.00 | 100.00 |
| Component | Area | Area % | Mean boiling point (°F) | Density (g/ml) | Molecular weight (g/mol) | Wt.％ | Mol％ |
| nC 3 | 44.761 | 0.023 | -43.730 | 0.5069 | 44.10 | 0.01 | 0.05 |
| iC 4 | 117.876 | 0.060 | 10.940 | 0.5628 | 58.12 | 0.04 | 0.11 |
| nC 4 | 927.866 | 0.472 | 31.100 | 0.5840 | 58.12 | 0.35 | 0.87 |
| iC 5 | 1082.570 | 0.550 | 82.130 | 0.6244 | 72.15 | 0.44 | 0.88 |
| nC 5 | 3346.533 | 1.701 | 96.930 | 0.6311 | 72.15 | 1.37 | 2.74 |
| False C 6 | 9579.443 | 4.870 | 147.000 | 0.6850 | 84.00 | 4.24 | 7.31 |
| False C 7 | 16046.200 | 8.158 | 197.500 | 0.7220 | 96.00 | 7.49 | 11.29 |
| False C 8 | 19693.300 | 10.012 | 242.000 | 0.7450 | 107.00 | 9.48 | 12.83 |
| False C 9 | 20326.300 | 10.334 | 288.000 | 0.7640 | 121.00 | 10.04 | 12.01 |
| False C 10 | 18297.600 | 9.302 | 330.500 | 0.7780 | 134.00 | 9.20 | 9.94 |
| False C 11 | 16385.600 | 8.330 | 369.000 | 0.7890 | 147.00 | 8.36 | 8.23 |
| False C 12 | 15349.000 | 7.803 | 407.000 | 0.8000 | 161.00 | 7.94 | 7.14 |
| False C 13 | 13116.500 | 6.668 | 441.000 | 0.8110 | 175.00 | 6.88 | 5.69 |
| False C 14 | 10816.100 | 5.499 | 475.500 | 0.8220 | 190.00 | 5.75 | 4.38 |
| False C 15 | 10276.900 | 5.225 | 511.000 | 0.8320 | 206.00 | 5.53 | 3.88 |
| False C 16 | 9537.818 | 4.849 | 542.000 | 0.8390 | 222.00 | 5.17 | 3.37 |
| False C 17 | 6930.611 | 3.523 | 572.000 | 0.8470 | 237.00 | 3.79 | 2.32 |
| False C 18 | 5549.802 | 2.821 | 595.000 | 0.8520 | 251.00 | 3.06 | 1.76 |
| False C 19 | 4440.457 | 2.257 | 617.000 | 0.8570 | 263.00 | 2.46 | 1.35 |
| False C 20 | 3451.250 | 1.755 | 640.500 | 0.8620 | 275.00 | 1.92 | 1.01 |
| False C 21 | 3133.251 | 1.593 | 664.000 | 0.8670 | 291.00 | 1.76 | 0.87 |
| False C 22 | 2088.036 | 1.062 | 686.000 | 0.8720 | 305.00 | 1.18 | 0.56 |
| False C 23 | 1519.460 | 0.772 | 707.000 | 0.8770 | 318.00 | 0.86 | 0.39 |
| False C 24 | 907.473 | 0.461 | 727.000 | 0.8810 | 331.00 | 0.52 | 0.23 |
| False C 25 | 683.205 | 0.347 | 747.000 | 0.8850 | 345.00 | 0.39 | 0.16 |
| False C 26 | 493.413 | 0.251 | 766.000 | 0.8890 | 359.00 | 0.28 | 0.11 |
| False C 27 | 326.831 | 0.166 | 784.000 | 0.8930 | 374.00 | 0.19 | 0.07 |
| False C 28 | 272.527 | 0.139 | 802.000 | 0.8960 | 388.00 | 0.16 | 0.06 |
| False C 29 | 291.862 | 0.148 | 817.000 | 0.8990 | 402.00 | 0.17 | 0.06 |
| False C 30 | 462.840 | 0.235 | 834.000 | 0.9020 | 416.00 | 0.27 | 0.09 |
| False C 31 | 352.886 | 0.179 | 850.000 | 0.9060 | 430.00 | 0.21 | 0.07 |
| False C 32 | 168.635 | 0.086 | 866.000 | 0.9090 | 444.00 | 0.10 | 0.03 |
| False C 33 | 67.575 | 0.034 | 881.000 | 0.9120 | 458.00 | 0.04 | 0.01 |
| False C 34 | 95.207 | 0.048 | 895.000 | 0.9140 | 472.00 | 0.06 | 0.02 |
| False C 35 | 226.660 | 0.115 | 908.000 | 0.9170 | 486.00 | 0.13 | 0.04 |
| False C 36 | 169.729 | 0.086 | 922.000 | 0.9190 | 500.00 | 0.10 | 0.03 |
| False C 37 | 80.976 | 0.041 | 934.000 | 0.9220 | 514.00 | 0.05 | 0.01 |
| False C 38 | 42.940 | 0.022 | 947.000 | 0.9240 | 528.00 | 0.03 | 0.01 |
| Amount to | 196699.994 | 100.000 | 100.00 | 100.00 |
TOC and Rock-eval (Rock-eval) test is what on the sample from oil shale sillar CM-1B, to carry out, and this sample is interval acquisition of the identical geology of the sample with by the test of Pa Er heating means described in embodiment 1-5.The Rock-eval hydrogen index of the TOC of these test generations 21% and 872mg/g-toc.
Following TOC and Rock-eval program pin carry out the rear remaining oil shale sample of Pa Er heating test of describing in embodiment 1-5.Result is presented in table 13.
Above-mentioned Rock-eval pyrolysis analysis adopts the following step to carry out.Rock-eval pyrolysis analysis utilizes Delsi Rock-eval II instrument to carry out on calibration rock standard (IFP standard #55000), blank and sample.Rock sample was pulverized before being loaded into Rock-eval crucible, micronizing and air-dry.25 and 100mg between Powdered rock sample be loaded onto in crucible, this depends on this sample total organic carbon (TOC) content.When start every day, move two or three blank to purify this system and equilibrium temperature.Two or three weight are that the sample of the IFP calibration criterion #55000 of 100+/-1mg is moved to calibrate this system.If Rock-eval T
maxparameter is 2 ℃ of 419 ℃ of +/-in these standards, just sample is analyzed.This standard is also before every 10 samples and move afterwards to monitor the performance of this instrument.
Rock-eval pyrolytic technique relates to and Powdered rock sample speed program is heated to high temperature in inertia (helium) atmosphere and characterizes the product producing from the thermal destruction of chemical bond.The isothermal at 300 ℃ of pyrolysis baking oven after Sample introduction is being kept three minutes.The hydrocarbon producing in this stage detects by flame ionization detector (FID), produces S
1peak.Then pyrolysis oven temperature is increased to 550 ℃ with the gradient of 25 ℃/min, and wherein baking oven is kept one minute by isothermal.The hydrocarbon producing during this step is detected and is produced S by FID
2peak.
Hydrogen index (HI) is by by S
2peak (is expressed as mg
hydrocarbon/ g
rock) be normalized into that percetage by weight TOC (independent definite total organic carbon) calculates, as follows: HI=(S
2/ TOC) * 100 wherein HI be represented as mg
hydrocarbon/ g
tOC.
Total organic carbon (TOC) determines by being suitable for the well-known process of geology sample, and existing any In Carbonate Rock is then that surplus materials burning is removed by acid treatment, to produce and to measure CO
2the organic group carbon of form.TOC and the Rock-eval result of oil shale sample after table 13. Pa Er heating test
The api gravity of embodiment 1-5 is estimated by estimating the room temperature proportion (SG) of collected liquid, and result is reported in table 14.Api gravity is estimated from definite proportion by application following formula: api gravity=(141.5/SG)-131.5
The proportion of every kind of fluid sample utilizes the following step to estimate.50 empty μ l HamiltonModel 1705 tightness syringes weigh to measure empty syringe weight on Mettler AE 163 digital calculation balances.Then this syringe is loaded by this syringe being filled to the liquid of certain volume.Record the volume of liquid in syringe.Then weigh the syringe loading.Then fluid sample weight estimated by the syringe measurement weight of loading being deducted to the empty syringe weight of measurement.Proportion is then by estimating fluid sample weight divided by the shared syringe volume of fluid sample.Table 14. is from the estimation api gravity of the fluid sample of embodiment 1-5
| | Embodiment | 1 | Embodiment 2 | | Embodiment 4 | Embodiment 5 |
| Api gravity | 29.92 | 30.00 | 27.13 | 32.70 | 30.00 |
Above-mentioned method can have value for reclaiming in the Piceance basin in the state of Colorado aspect hydrocarbon.Some have evaluated in some oil shale deposit things of ， US West, and every earth's surface acre can reclaim up to 1 MMBO.A research has estimated containing the oil shale resources in nahcolite part, to have in position 400,000,000,000 barrels of shale oil in the oil shale formation in Piceance basin.Generally speaking, only in Piceance basin, can exist up to 1,000,000,000,000 barrels of shale oil.
Some feature of the present invention is described with regard to one group of numerical upper limits and one group of numerical lower limits.Should be appreciated that except as otherwise noted, any scope being combined to form by these limiting values within the scope of the invention.Although put into practice according to the U.S., some dependent claims have single subordinate relation, but in these dependent claims each feature of any one can be subordinated to other dependent claims of identical one or more independent claims in one or more each feature combine.
Although clearly invention described herein has been carried out to abundant calculating to realize benefit above-mentioned and advantage, should be understood that the present invention is easy to modify, changes and changes, and do not depart from its spirit.
Claims (47)
1. use the method for the gas producing from converted in-situ process, comprising:
A) In Situ Heating is rich in organic matter rock stratum, and the wherein said organic matter rock stratum of being rich in is oil shale formation;
B) from the described organic matter formation production Produced Liquid that is rich in, the result that is rich in the stratum hydrocarbon pyrolysis of organic matter rock stratum described at least part of conduct of described Produced Liquid is arranged in produces, and described Produced Liquid comprises hydrocarbon fluid;
C) from described Produced Liquid, obtain air-flow, described air-flow comprises flammable hydrocarbon fluid;
D) described air-flow is divided into the first composition air-flow and second and forms air-flow, the wherein said first composition that forms air-flow remains under the condition of substantial constant, and described first forms air-flow comprises that methane and at least one inert gas and described first form air-flow and have the low heat value below 800BTU/SCF; With
E) make described first to form air-flow by the first gas-turbine, to form the first gas-turbine waste stream, described the first gas-turbine is configured to provide energy to the first generator;
F) by described second, form air-flow and be supplied to steam heating boiler;
G) burn described the second composition air-flow to provide heat to described steam heating boiler; With
H) at described steam heating boiler, produce steam; With
I) make described steam process steamturbine to form steamturbine waste stream, wherein said steamturbine is configured to provide energy to the second generator, thereby described steamturbine provides energy to described the second generator.
2. method claimed in claim 1, wherein said first forms air-flow and described second forms air-flow and all comprises hydrocarbon fluid.
3. method claimed in claim 1, wherein said first forms air-flow and described second forms air-flow and all comprises fuel gas.
4. method claimed in claim 1, wherein said first forms air-flow and described second forms air-flow and all has low heat value more than 200BTU/SCF.
5. method claimed in claim 4, wherein said first forms air-flow has the low heat value below 700BTU/SCF.
6. method claimed in claim 1, wherein said first forms air-flow comprises methane more than 15 molar percentages.
7. method claimed in claim 1, wherein said first forms the CO of air-flow
2content is more than 30 molar percentages.
8. method claimed in claim 1, wherein said first forms the H that air-flow has substantial constant
2with CO
2mol ratio.
9. method claimed in claim 8, wherein said first forms air-flow has the H between 0.1 to 2.0
2with CO
2mol ratio.
10. method claimed in claim 1, wherein said first forms ethane and the CO that air-flow has substantial constant
2mol ratio.
11. methods claimed in claim 1, wherein said steam heating boiler is super critical boiler.
12. methods claimed in claim 1, wherein said steam heating boiler is equipped with catalytic burner.
13. methods claimed in claim 1, are rich in organic matter rock stratum described at least a portion of wherein said steam is transported to.
14. use the method for the gas producing from converted in-situ process, comprising:
A) In Situ Heating is rich in organic matter rock stratum, and the wherein said organic matter rock stratum of being rich in is oil shale formation;
B) from the described organic matter formation production Produced Liquid that is rich in, the result that is rich in the stratum hydrocarbon pyrolysis of organic matter rock stratum described at least part of conduct of described Produced Liquid is arranged in produces, and described Produced Liquid comprises hydrocarbon fluid;
C) from described Produced Liquid, obtain air-flow, described air-flow comprises flammable hydrocarbon fluid;
D) described air-flow is divided into the first composition air-flow and second and forms air-flow, the wherein said first composition that forms air-flow remains under the condition of substantial constant, and described first forms air-flow comprises that methane and at least one inert gas and described first form air-flow and have the low heat value below 800BTU/SCF;
E) make described first to form air-flow by the first gas-turbine, to form the first gas-turbine waste stream, described the first gas-turbine is configured to provide energy to the first generator;
F) monitor one or more characteristics of described the first composition air-flow; With
G) change the composition of described the first composition air-flow, thereby control one or more operating parameters of described the first composition air-flow, wherein said first forms air-flow comprises methane, and wherein changes the described first composition that forms air-flow and comprise reforming and described first form at least a portion methane in air-flow to produce hydrogen.
Method described in 15. claims 14, wherein said one or more characteristic is selected from gas composition, temperature, calorific value, proportion, wobbe index, improved wobbe index, dew point, flammability limits, flame speed and their combination, and the low heat value that wherein said improved wobbe index is fuel gas is multiplied by the square root of its temperature divided by the proportion of fuel gas.
Method described in 16. claims 14, wherein said operating parameter is C
2with higher hydrocarbon, C
3one or more concentration with higher hydrocarbon, carbon dioxide, inert gas, hydrogen, ethane, ethene, propane and their combinations.
Method described in 17. claims 14, wherein changes the described first composition that forms air-flow and comprises that mixed airflow and described first is formed to air-flow to be mixed.
Method described in 18. claims 14, wherein before reforming, at least a portion methane is formed air-flow from described first and is shifted out, the methane shifting out is reformed, thereby generation hydrogen, and the hydrogen of generation is turned back to described first and form air-flow, then make described first to form air-flow by described the first gas-turbine.
Method described in 19. claims 14, wherein at least a portion methane is reformed, and is present in described first simultaneously and forms in air-flow, thereby form in air-flow, from being present in the described first at least a portion methane generation hydrogen forming air-flow described first.
Method described in 20. claims 14, the methane that is wherein restructured as hydrogen is partly controlled to keep the wobbe index value of substantial constant in time.
Method described in 21. claims 14, wherein said first forms air-flow comprises inert gas, and wherein changes the described first composition that forms air-flow and comprise and regulate the described first inert gas content that forms air-flow to keep the wobbe index value of substantial constant in time.
Method described in 22. claims 14, wherein changes the described first composition that forms air-flow and comprises pressure or the temperature that regulates one or more gs-oil separators.
Method described in 23. claims 14, wherein change the described first composition that forms air-flow and comprise and add hydrogen, ethane, ethene or their combination, thereby increase by the described first flame speed that forms air-flow, regulate the described first burn rate that forms air-flow, be stabilized in burning in described the first gas-turbine or their combination.
Method described in 24. claims 14, further comprises:
H) regulate described first to form the temperature of air-flow, thereby regulate the wobbe index of described the first composition air-flow.
Method described in 25. claims 14, the wherein said second composition that forms air-flow is also maintained under the condition of substantial constant.
Method described in 26. claims 25, further comprises:
H) make described second form air-flow through the second gas-turbine to form the second gas-turbine waste stream, described the second gas-turbine is configured to provide energy to the second generator.
Method described in 27. claims 14, wherein change the described first composition that forms air-flow and comprise and reduce the described first described inert gas content that forms air-flow, and described the first gas-turbine is equipped with thin premix burner or a plurality of thin premix burner, the low NO of dry type
x(DLN) burner or the low NO of a plurality of dry type
x(DLN) burner or dry low emissions (DLE) burner or a plurality of dry low emissions (DLE) burner.
Method described in 28. claims 14, wherein changes the described first composition that forms air-flow and comprises that increasing described first forms the described inert gas content of air-flow, thereby be reduced in the NO in described the first gas-turbine
xproduce.
Method described in 29. claims 28, wherein by increasing the CO of described the first composition air-flow
2content, increases by the described first described inert gas content that forms air-flow.
30. use the method for the gas producing from converted in-situ process, comprising:
A) In Situ Heating is rich in organic matter rock stratum, and the wherein said organic matter rock stratum of being rich in is oil shale formation;
B) from the described organic matter formation production Produced Liquid that is rich in, the result that is rich in the stratum hydrocarbon pyrolysis of organic matter rock stratum described at least part of conduct of described Produced Liquid is arranged in produces, and described Produced Liquid comprises hydrocarbon fluid;
C) from described Produced Liquid, obtain air-flow, described air-flow comprises flammable hydrocarbon fluid;
D) described air-flow is divided into the first composition air-flow and second and forms air-flow, the wherein said first composition that forms air-flow remains under the condition of substantial constant, and described first forms air-flow comprises that methane and at least one inert gas and described first form air-flow and have the low heat value below 800BTU/SCF;
E) make described first to form air-flow by the first gas-turbine, to form the first gas-turbine waste stream, described the first gas-turbine is configured to provide energy to the first generator;
F) by NH
3separated with described Produced Liquid to form NH
3process stream; With
G) by described NH
3inject the first gas-turbine waste stream, thereby by the NO in described the first gas-turbine waste stream
xa part for component is converted into N
2.
31. methods claimed in claim 1, wherein said the first composition air-flow is hydrogen more than 90 molar percentages.
32. methods claimed in claim 1, wherein said the second composition air-flow is hydrogen more than 90 molar percentages.
Method described in 33. claims 20, further comprises:
H) electricity being produced by described the first generator is sold to third party.
Method described in 34. claims 33, further comprises:
I) at the non-peak value of selecting, need time Cong electricity supplier to buy electricity.
35. methods claimed in claim 1, wherein, during 7 days, on per day basis, the above first wobbe index that forms air-flow changes below 15%.
36. methods claimed in claim 1, wherein, during 7 days, in the above first composition air-flow of per day basis, the total concentration of inert gas changes below 10 molar percentages.
37. methods claimed in claim 1, wherein during 7 days, per day basis the above first form air-flow in CO
2concentration change below 10 molar percentages.
38. methods claimed in claim 1, wherein, during 7 days, in the above first composition air-flow of per day basis, the concentration of methane changes below 10 molar percentages.
39. methods claimed in claim 1, wherein, during 7 days, on per day basis, the above first low heat value that forms air-flow changes below 10%.
40. methods claimed in claim 1, wherein, during 7 days, in the above first composition air-flow of per day basis, the concentration of ethane changes below 10 molar percentages.
Method described in 41. claims 14, wherein, during 7 days, on per day basis, the above first wobbe index that forms air-flow changes below 15%.
Method described in 42. claims 14, wherein, during 7 days, in the above first composition air-flow of per day basis, the total concentration of inert gas changes below 10 molar percentages.
Method described in 43. claims 14, wherein during 7 days, per day basis the above first form air-flow in CO
2concentration change below 10 molar percentages.
Method described in 44. claims 14, wherein, during 7 days, in the above first composition air-flow of per day basis, the concentration of methane changes below 10 molar percentages.
Method described in 45. claims 14, wherein, during 7 days, on per day basis, the above first low heat value that forms air-flow changes below 10%.
Method described in 46. claims 14, wherein, during 7 days, in the above first composition air-flow of per day basis, the concentration of ethane changes below 10 molar percentages.
47. methods claimed in claim 1, the wherein said second composition that forms air-flow is also maintained under the condition of substantial constant.
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| US93182007P | 2007-05-25 | 2007-05-25 | |
| US60/931,820 | 2007-05-25 | ||
| PCT/US2008/006463 WO2008147503A1 (en) | 2007-05-25 | 2008-05-21 | Utilization of low btu gas generated during in situ heating of organic-rich rock |
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| CN101680294A CN101680294A (en) | 2010-03-24 |
| CN101680294B true CN101680294B (en) | 2014-02-19 |
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| CN200880017507.0A Expired - Fee Related CN101680294B (en) | 2007-05-25 | 2008-05-21 | Utilization of low btu gas generated during in situ heating of organic-rich rock |
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| CN (1) | CN101680294B (en) |
| AU (1) | AU2008257396B2 (en) |
| BR (1) | BRPI0810591A2 (en) |
| CA (1) | CA2686565C (en) |
| IL (1) | IL201290A0 (en) |
| JO (1) | JO2731B1 (en) |
| WO (1) | WO2008147503A1 (en) |
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| CN102913222A (en) * | 2012-11-20 | 2013-02-06 | 中国石油集团长城钻探工程有限公司工程服务公司 | Oxidation process completion method of horizontal well for developing coalbed methane |
| CN105793520A (en) * | 2013-10-17 | 2016-07-20 | 西格纳化学有限责任公司 | Alkali metal silicides for high temperature wettability improvement in carbonate reservoirs |
| CN103790563B (en) * | 2013-11-09 | 2016-06-08 | 吉林大学 | A kind of oil shale in-situ topochemistry method extracts the method for shale oil gas |
| EP3444319B1 (en) | 2017-08-14 | 2020-12-02 | Sami Abdulrahman A. Albakri | Indirectly heated retorting reactor with heat pipes and system for retorting oil shale |
| CN108561108B (en) * | 2018-06-15 | 2024-05-14 | 邵洪伟 | Generator for in-situ oil extraction shale |
| CN112761589B (en) * | 2021-01-27 | 2022-04-05 | 中山大学 | A CO2-enhanced gas layer recovery method of deep low-permeability coal seam |
| CN118065850B (en) * | 2024-04-18 | 2024-07-02 | 太原理工大学 | System and method for upgrading oil gas through underground in-situ pyrolysis of oil shale |
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| US7243618B2 (en) * | 2005-10-13 | 2007-07-17 | Gurevich Arkadiy M | Steam generator with hybrid circulation |
| US7654320B2 (en) * | 2006-04-07 | 2010-02-02 | Occidental Energy Ventures Corp. | System and method for processing a mixture of hydrocarbon and CO2 gas produced from a hydrocarbon reservoir |
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2008
- 2008-05-21 BR BRPI0810591-0A2A patent/BRPI0810591A2/en not_active IP Right Cessation
- 2008-05-21 CN CN200880017507.0A patent/CN101680294B/en not_active Expired - Fee Related
- 2008-05-21 CA CA2686565A patent/CA2686565C/en not_active Expired - Fee Related
- 2008-05-21 WO PCT/US2008/006463 patent/WO2008147503A1/en active Application Filing
- 2008-05-21 AU AU2008257396A patent/AU2008257396B2/en not_active Ceased
- 2008-05-26 JO JO2008240A patent/JO2731B1/en active
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| US6055803A (en) * | 1997-12-08 | 2000-05-02 | Combustion Engineering, Inc. | Gas turbine heat recovery steam generator and method of operation |
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| Publication number | Publication date |
|---|---|
| AU2008257396B2 (en) | 2013-08-29 |
| CA2686565A1 (en) | 2008-12-04 |
| JO2731B1 (en) | 2013-09-15 |
| WO2008147503A1 (en) | 2008-12-04 |
| CN101680294A (en) | 2010-03-24 |
| AU2008257396A1 (en) | 2008-12-04 |
| CA2686565C (en) | 2015-11-24 |
| IL201290A0 (en) | 2010-05-31 |
| BRPI0810591A2 (en) | 2014-10-21 |
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