CA2369244C - An integrated method for steam-enhanced bitumen production using a process waste stream for flue gas desulphurization - Google Patents
An integrated method for steam-enhanced bitumen production using a process waste stream for flue gas desulphurization Download PDFInfo
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- CA2369244C CA2369244C CA 2369244 CA2369244A CA2369244C CA 2369244 C CA2369244 C CA 2369244C CA 2369244 CA2369244 CA 2369244 CA 2369244 A CA2369244 A CA 2369244A CA 2369244 C CA2369244 C CA 2369244C
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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
- C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
- C10G1/047—Hot water or cold water extraction processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/083—Mineral agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
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- Treating Waste Gases (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention is in the area of thermal recovery of bitumen from an underground reservoir using steam. More specifically, it relates to a method for integrating bitumen production with steam generation by burning a portion of the produced high-sulfur bitumen and then using a waste stream from a boiler feed water treatment process to clean the flue gas.
Description
AN INTEGRATED METHOD FOR STEAM-ENHANCED BITUMEN
PRODUCTION USING A PROCESS WASTE STREAM FOR FLUE GAS
DE SULPHURIZATION
Field of the Invention The invention is in the area of thermal recovery of bitumen from an underground reservoir using steam. More specifically, it relates to a method for integrating bitumen production with steam generation by burning a portion of the produced high-sulfur bitumen and then using a waste stream from a boiler feed water treatment process to clean the flue gas.
Background of the Invention In the thermal recovery of bitumen, natural gas is normally used as a fuel to generate steam. This fuel has little or no sulfur and hence its use does not require SOZ removal from the flue gas. Fuel cost constitutes the majority share of the bitumen lifting cost at many production sites including places such as Cold Lake and Athabasca in Alberta, Canada. With increasing demand for and a generally upward trend in the price of natural gas, the need for an alternative, less expensive fuel is strong.
Many alternative fuel sources have been considered including coal and bitumen which may include both whole bitumen and/or the heavier fractions of bitumen. Of these, whole bitumen and water emulsions of the whole bitumen and/or the heavier fractions of bitumen are the most promising. However, significant problems exist with the use of bitumen as a fuel because of the high cost associated with removing SOZ from the flue gas which results from burning bitumen.
Furthermore, in a commercial thermal bitumen recovery operation large volumes of water are needed to make steam. This water becomes contaminated with bitumen and underground minerals during underground injection and subsequent recovery. The produced water from bitumen recovery therefore requires treatment before it can be reused to make steam. That is, it is a requirement that contaminated water from the production of bitumen be treated with chemicals to remove contaminants to enable the water to be re-used in a steam generator and that the contaminants are properly disposed of. Accordingly, past bitumen recovery operations utilize water treatment facilities which introduce treatment chemicals to the produced water to remove the contaminating hardness ions, silica and/or clay minerals.
The treatment chemicals enable most contaminants to be removed as precipitated solids which are subsequently removed from the facility as waste to a slurry pit.
Accordingly, there is a continuing need to improve the operating cost structure at a bitumen production operation of which fuel is a major component. One way this can be achieved is by efficiently combining the bitumen burning, the water treatment and the SOZ
removal processes wherein the waste slurry from treatment of the produced water, containing the precipitated contaminants, is used within the SOZ scrubbing facilities in order to reduce the S02 removal cost.
A review of the prior art reveals that such a solution has not been provided.
For example, Canadian Patent No. 1,339,531 discusses a process of producing and burning a natural-emulsified liquid fuel in which the alkali metal level in the liquid fuel is adjusted to reduce SOz emissions and Canadian Patent No. 2,105,166 relates to scrubbing SOZ with mixtures of hydroxides and carbonates of calcium and magnesium in coal-fired boilers; and Canadian Patent Application No. 2,335,771 describes a process that uses hydrovisbreaking in the reservoir, and fractionates the produced visbroken hydrocarbons into a heavier fraction, which is then partially oxidized to generate,hydrogen and fuel gas. In this latter patent, the fuel gas is used for steam generation and the steam is then injected with hydrogen for in situ hydrovisbreaking.
Summary of the Invention In accordance with the invention, there is provided an integrated process for producing bitumen and removing sulfur dioxide from a flue gas said process comprising:
(a) burning whole bitumen or a heavier fraction thereof to generate steam to extract bitumen from a bitumen reservoir in a bitumen and produced water stream, said burning yielding said flue gas;
(b) removing SOZ from said flue gas by contacting said flue gas with a waste slurry resulting from treatment of water separated from said bitumen and produced water stream.
PRODUCTION USING A PROCESS WASTE STREAM FOR FLUE GAS
DE SULPHURIZATION
Field of the Invention The invention is in the area of thermal recovery of bitumen from an underground reservoir using steam. More specifically, it relates to a method for integrating bitumen production with steam generation by burning a portion of the produced high-sulfur bitumen and then using a waste stream from a boiler feed water treatment process to clean the flue gas.
Background of the Invention In the thermal recovery of bitumen, natural gas is normally used as a fuel to generate steam. This fuel has little or no sulfur and hence its use does not require SOZ removal from the flue gas. Fuel cost constitutes the majority share of the bitumen lifting cost at many production sites including places such as Cold Lake and Athabasca in Alberta, Canada. With increasing demand for and a generally upward trend in the price of natural gas, the need for an alternative, less expensive fuel is strong.
Many alternative fuel sources have been considered including coal and bitumen which may include both whole bitumen and/or the heavier fractions of bitumen. Of these, whole bitumen and water emulsions of the whole bitumen and/or the heavier fractions of bitumen are the most promising. However, significant problems exist with the use of bitumen as a fuel because of the high cost associated with removing SOZ from the flue gas which results from burning bitumen.
Furthermore, in a commercial thermal bitumen recovery operation large volumes of water are needed to make steam. This water becomes contaminated with bitumen and underground minerals during underground injection and subsequent recovery. The produced water from bitumen recovery therefore requires treatment before it can be reused to make steam. That is, it is a requirement that contaminated water from the production of bitumen be treated with chemicals to remove contaminants to enable the water to be re-used in a steam generator and that the contaminants are properly disposed of. Accordingly, past bitumen recovery operations utilize water treatment facilities which introduce treatment chemicals to the produced water to remove the contaminating hardness ions, silica and/or clay minerals.
The treatment chemicals enable most contaminants to be removed as precipitated solids which are subsequently removed from the facility as waste to a slurry pit.
Accordingly, there is a continuing need to improve the operating cost structure at a bitumen production operation of which fuel is a major component. One way this can be achieved is by efficiently combining the bitumen burning, the water treatment and the SOZ
removal processes wherein the waste slurry from treatment of the produced water, containing the precipitated contaminants, is used within the SOZ scrubbing facilities in order to reduce the S02 removal cost.
A review of the prior art reveals that such a solution has not been provided.
For example, Canadian Patent No. 1,339,531 discusses a process of producing and burning a natural-emulsified liquid fuel in which the alkali metal level in the liquid fuel is adjusted to reduce SOz emissions and Canadian Patent No. 2,105,166 relates to scrubbing SOZ with mixtures of hydroxides and carbonates of calcium and magnesium in coal-fired boilers; and Canadian Patent Application No. 2,335,771 describes a process that uses hydrovisbreaking in the reservoir, and fractionates the produced visbroken hydrocarbons into a heavier fraction, which is then partially oxidized to generate,hydrogen and fuel gas. In this latter patent, the fuel gas is used for steam generation and the steam is then injected with hydrogen for in situ hydrovisbreaking.
Summary of the Invention In accordance with the invention, there is provided an integrated process for producing bitumen and removing sulfur dioxide from a flue gas said process comprising:
(a) burning whole bitumen or a heavier fraction thereof to generate steam to extract bitumen from a bitumen reservoir in a bitumen and produced water stream, said burning yielding said flue gas;
(b) removing SOZ from said flue gas by contacting said flue gas with a waste slurry resulting from treatment of water separated from said bitumen and produced water stream.
Further still, the invention provides a process for producing bitumen from a subsurface reservoir comprising the steps of:
(a) inj ecting steam into a reservoir to recover bitumen;
(b) producing a stream of bitumen and produced water from the reservoir;
(c) separating the produced water and the bitumen;
(d) treating the produced water to form a boiler-feed quality water and a waste slurry;
(e) burning at least a portion of the bitumen and using at least a portion of the boiler-feed quality water to produce steam and a flue gas; and (fj contacting the flue gas with the waste slurry to remove sulfur dioxide from the flue gas.
In another embodiment, the invention provides a process for scrubbing sulfur dioxide from a flue gas comprising contacting the flue gas with a waste slurry from a water treatment process, the waste slurry chemically active in removing sulfur dioxide from the flue gas.
In further embodiments, the water treatment process is operatively connected to a bitumen recovery operation and/or the waste slurry comprises at least one of calcium hydroxide, magnesium hydroxide, calcium carbonate and a magnesium silicate mineral and one or more alkaline compounds. It is also preferred that the total solids concentration in the waste slurry is 4-20% by weight and more preferably 5-15% by weight.
In another preferred embodiment, the process is integrated with a bitumen-fired steam generation process and the flue gas originates from the bitumen-fired steam generation process.
Brief Description of the Drawings Preferred embodiments of the present invention will now be described with reference to the attached figures, wherein:
Figure 1 is a schematic diagram of the presently practiced process of bitumen production in accordance with the prior art;
Figure 2 is a configuration for a high sulfur fuel bitumen production operation; and Figure 3 is a schematic diagram of an integrated bitumen production, waste-water treatment and SOZ scrubbing process in accordance with the invention.
Detailed Description of the Invention As shown in Figure 1, in a conventional commercial bitumen recovery operation l, steam 2 is generated from water 3 and treated water 3a by burning a natural gas fuel 4 in a steam generator or boiler 16. The steam 2 is injected into an underground reservoir 6 to reduce the viscosity of the underground bitumen by heat thereby enabling the bitumen to be recovered as a bitumen/water mixture 7~ The steam 2 and condensed water also react with the naturally occurring minerals in the reservoir 6 and pick up hardness ions, silica, and clay minerals which contaminate the water portion of the bitumen/water mixture 7.
Separation of the mixture in a separator 8 provides product bitumen 9 and produced water 9a.
The produced water 9a is treated in a water treatment facility 7a with chemicals 7c which remove the contaminants as a sludge/slurry 7b enabling re-use of the treated water 3 in the production of steam 2. The flue gas 16a does not require scrubbing.
Figure 2 shows a variation 1 a of the conventional bitumen recovery operation in which the natural gas fuel can be substituted for by a high sulfur fuel such as bitumen or an emulsion of bitumen or its heavier fractions 4a. Unlike burning natural gas, the burning of a high sulfur fuel produces a high sulfur flue gas 16a which requires scrubbing of SOZ in a conventional scrubber 5. Scrubber 5, using techniques known in the art, removes SOZ by reacting the SOz with scrubbing chemicals 5a which will produce a scrubber slurry Sb which is disposed in a slurry pit. The cost of the chemicals 5a is such that the process is not always cost-competitive with burning natural gas, depending on the price of natural gas.
In accordance with the invention, an integrated process 10 of water treatment and scrubbing is shown in Figure 3 for a high sulfur fuel fired steam generation and bitumen recovery process. As shown, and as in a conventional bitumen recovery operation described above, steam 12 is generated from water 14 and treated water 14a by burning a fuel (including whole bitumen or heavy fractions thereof) in a steam generator 16 for injection into the reservoir 24. Recovered bitumen and produced water 24a are separated from each other in a bitumen-water separator 26 to produce bitumen 28 and produced water 30. The produced water 30 is treated in a water treatment facility 32 to remove contaminants including hardness ions, silica and clay through the addition of chemicals 32a. A portion of the bitumen 28b is preferably used as fuel for the steam generator 16 and a portion 28a is directed to sales.
The produced water 30 is treated by techniques known in the art. Within the water treatment facility 32, chemicals including calcium hydroxide, magnesium hydroxide, sodium hydroxide, sodium carbonate, and a flocculant are added to the water, as necessary, to react with or provide adsorption sites for the hardness ions, silica and clay minerals thereby forming a waste slurry 22 which has both a liquid and a precipitated solids component.
The waste slurry 22 generally comprises unreacted chemicals and reacted product. The typical solid concentration range in the waste slurry is 4 to 20% by weight with the corresponding water concentration range as 96 to 80% by weight. A preferred concentration range of the solids is 5 to 15% by weight with the corresponding water concentration range as 95 to 85% by weight.
The SOZ laden flue gas 18 from the generator 16 is directed to a flue gas cleaner or scrubber 20 where, in accordance with the invention, it is contacted with the waste slurry 22 from the water treatment facility 32 thus utilizing both the reacted and unreacted chemicals of the waste slurry 22 within the scrubbing process. In most circumstances, no additional chemicals need to be added. After treatment of the SOz-laden flue gas 18, the spent slurry 34 is sent to disposal 36.
The precise composition of the chemicals added to the produced water in the water treatment facility may be varied as is known by those skilled in the art for effecting water treatment and will depend on the particular contaminants that may result from a particular reservoir. In order to provide effective scrubbing capabilities, it is preferred that the waste slurry composition include calcium hydroxide, magnesium hydroxide, calcium carbonate and a magnesium silicate mineral, some of which may be present in the water produced from the reservoir before treatment. A representative composition of this slurry is shown in the examples.
Accordingly, the system provides an effective way of combining the use of bitumen as a fuel and scrubbing SOz gas from combustion with chemicals contained in the slurry generated by treating the produced water from bitumen extraction.
As a result, an advantage of the invention is that the chemicals for SOZ
scrubbing are continuously generated in the water treatment facility. Moreover, no additional slurry pit is required as per other conventional flue gas desulfizrization processes.
Further still, the fuel for the process is generated internally.
In another embodiment where bitumen is used as a fuel, part of the total produced bitumen 28 may be used in the generator 16 and the remainder shipped to market 28a. In one embodiment, further separation of the bitumen 28 is provided to produce heavier and lighter bitumen fractions where the heavier fraction 28b is used as a fuel in the generator 16 and the lighter fraction is shipped to market. As a fuel, the heavier fraction 28b is may be emulsified in water and used as an emulsion fuel in the generator 16.
Moreover, the utilization of the waste stream for SOZ scrubbing offers a cost-effective method for utilizing sulfur-rich fuel that is cheaper than natural gas. The fuel is also internally generated as whole or a fraction of the produced bitumen; in the latter case also improving the viscosity and gravity of the remaining marketable bitumen.
The invention is illustrated by the following example.
EXAMPLE
Two litres of waste slurry from the Imperial Oil water treatment facility at Cold Lake, Alberta were separated into a water portion and a solids portion for analysis.
The water portion of the waste slurry had the following representative properties and composition as shown in Table 1:
Table 1- Water Composition of Waste Slurry Properties/Composition Preferred Range General Range pH at 22C 9.5 to 10 9 to 11 Total Dissolved Solids 10000 to 12000 ppm 8000 to 14000 ppm Total Hardness 80 to 160 ppm 70 to 180 ppm Tannin and Lignin 60 to 65 ppm 50 to 80 ppm Alkalinity Phen. 8.3 300 to 400 ppm 250 to 500 ppm as CaC03 Alkalinity Total as 500 to 650 ppm 400 to 800 ppm CaC03 Carbonate Ions 200 to 300 ppm 150 to 400 ppm Hydroxyl Ions 40 to 70 ppm 30 to 100 ppm Chloride Dissolved 5000 to 7000 ppm 4000 to 10000 ppm Total Organic Carbon 140 to 160 ppm 120 to 200 ppm Silica 10 to 50 ppm 5 to 100 ppm Sulfate 60 to 100 ppm 50 to 120 ppm Magnesium Ions 10 to 30 ppm 5 to 40 ppm Calcium Ions 14 to 15 ppm 10 to 40 ppm Potassium Ions 150 to 180 ppm 130 to 200 ppm -6_ Sodium Ions 3500 to 4500 ppm 3000 to 5000 ppm Sulfur Dissolved 30 to 40 ppm 25 to 50 ppm The slurry may also contain a non-ionic flocculating agent, such as NALCO
86070.
The solid portion of the waste slurry contained the following metal ions as shown in Table 2A:
Table 2A- Solids Portion Composition of Waste Slurry Properties/CompositionPreferred Range General Range Mg 10 to 20 wt% 5 to 25 wt%
Ca 20 to 25 wt% 15 to 35 wt%
Si 5 to 6 wt% 4 to 8 wt%
Na 0:45 to 0.80 wt% 0.4 to 1.0 wt%
A1 0:04 to 0.08 wt% 0.03 to 0.10 wt%
K 0:04 to 0.05 wt% 0.03 to 0.06 wt%
Fe 0.15 to 0.25 wt% 0.10 to 0.40 wt%
Sr 1500 to 2400 ppm 1200 to 3000 ppm Ba 500 to 700 ppm 400 to 1000 ppm By mineralogical analysis, the solid portion of the waste slurry contains the minerals shown in Table 2B and their typical proportions. These minerals were identified by X-ray diffraction and scanning electron microscope and their relative amounts determined using elemental analysis and mineral quantification software. The adsorbed water in the solid was not measured which explains why the sum of the mineral proportions is less than 100%. Some of these minerals were formed in the water treatment process, while others were either leached out from the reservoir sand or formed in the reservoir following steam inj ection.
Table 2B- Mineral Analysis of Solid Portion of Waste Slurry Minerals Name Formula wt%
Quartz Si02 4.6 - 6.0 wt%
K-spar KA1Si308 0.3 - 0.4 wt%
Albite NaA1Si30g 0.1 - 0.4 wt%
Calcite CaC03 55.5 - 59.3 wt%
_7_ Magnesite MgC03 1.5 3.6 wt%
-Siderite FeC03 0.4 0.5 wt%
-Halite NaCl 1.2 1.9 wt%
-Serpentine Mg6Si40,(OH) $ 8.2 9.2 wt%
-Brucite Mg(OH) 2 9.8 11.5 - wt%
Sepiolite Mg4Si60,5(OH)2.6H20 7.6 8.2 wt%
-Organic Carbon 1.0 2.3 wt%
-Total 95.8 - 97.9 wt%
Assuming a water concentration of 85-95% by weight, the whole waste slurry would have a composition representative of that shown in Table 3.
Table 3-Whole Waste Slurry Composition Properties/Composition Preferred Range General Range Solid 5 to 15 wt % 4 to 20 wt%
pH at 22C 9.5 to 10 9 to 11 Total Dissolved Solids 8500 to 11400 ppm 6400 to 13440 ppm Total Hardness 68 to 152 ppm 56 to 173 ppm Tannin and Lignin 51 to 62 ppm 40 to 77 ppm Alkalinity Phen. 8.3 255 to 380 ppm 200 to 480 ppm as CaC03 Alkalinity Total as 425 to 618 ppm 320 to 768 ppm CaC03 Carbonate Ions 170 to 285 ppm 120 to 384 ppm Hydroxyl Ions 34 to 67 ppm 24 to 96 ppm Chloride Ions 4250 to 6650 ppm 3200 to 9600 ppm Total Organic Carbon 119 to 152 ppm 96 to 192 ppm Dissolved Silica 3 to 5 ppm 0 to 48 ppm Sulfate Ions 51 to 95 ppm 40 to 115 ppm Magnesium Ions 9 to 29 ppm 4 to 38 ppm Calcium Ions 12 to 14 ppm 8 to 38 ppm Potassium Ions 128 to 171 ppm 104 to 192 ppm Sodium Ions 3000 to 4275 ppm 2400 to 4800 ppm Sulfur Dissolved 26 to 38 ppm 20 to 48 ppm Mg in solid 0.5 to 3 wt% 0.2 to 4 wt%
Ca in solid 1 to 4 wt% 0.6 to 7 wt%
Si in solid 0.3 to 0.9 wt% 0.16 to 1.6 wt A1 in solid 0.002 to 0.012 wt% 0.0012 to 0.02 wt K in solid 0.002 to 0.0075 0.0012 to 0.012 wt% wt%
Fe in solid 0.0075 to 0.0375 0.004 to 0.08%
wt % wt%
Sr in solid 75 to 360 ppm 48 to 600 ppm Ba in solid 25 to 105 ppm 16 to 200 ppm _g_ Pure SOZ from a gas cylinder was bubbled through the waste slurry at room temperature. The SOZ volume was measured with a Dry Test meter. Using a Drager tube, the SOZ in the effluent gas was monitored and recorded as a :function of the volume of SOZ
bubbled through. As shown in Table 4, the SOZ concentration in the effluent gas was only 6 ppm after 20 litres of SOZ at standard temperature and pressure conditions (STP) was bubbled through. At this point, the test was terminated. The pH of the slurry dropped from 9.9 to 4.3 at the end of the test.
Table 4- SOz Concentration in Effluent Gas Volume SOZ Bubbled (L@STP) SOZ Concentration in Effluent Gas (ppm) 8 Trace 16 Trace This test shows that two litres of Cold Lake waste slurry is capable of removing 20 litres of pure SOZ at STP.
The above-described embodiments of the invention are intended to be examples of the present invention. Alterations, modifications and variations may be effected to the particular embodiments by those of skill in the art, without departing from the scope of the invention which is defined solely by the claims appended hereto.
(a) inj ecting steam into a reservoir to recover bitumen;
(b) producing a stream of bitumen and produced water from the reservoir;
(c) separating the produced water and the bitumen;
(d) treating the produced water to form a boiler-feed quality water and a waste slurry;
(e) burning at least a portion of the bitumen and using at least a portion of the boiler-feed quality water to produce steam and a flue gas; and (fj contacting the flue gas with the waste slurry to remove sulfur dioxide from the flue gas.
In another embodiment, the invention provides a process for scrubbing sulfur dioxide from a flue gas comprising contacting the flue gas with a waste slurry from a water treatment process, the waste slurry chemically active in removing sulfur dioxide from the flue gas.
In further embodiments, the water treatment process is operatively connected to a bitumen recovery operation and/or the waste slurry comprises at least one of calcium hydroxide, magnesium hydroxide, calcium carbonate and a magnesium silicate mineral and one or more alkaline compounds. It is also preferred that the total solids concentration in the waste slurry is 4-20% by weight and more preferably 5-15% by weight.
In another preferred embodiment, the process is integrated with a bitumen-fired steam generation process and the flue gas originates from the bitumen-fired steam generation process.
Brief Description of the Drawings Preferred embodiments of the present invention will now be described with reference to the attached figures, wherein:
Figure 1 is a schematic diagram of the presently practiced process of bitumen production in accordance with the prior art;
Figure 2 is a configuration for a high sulfur fuel bitumen production operation; and Figure 3 is a schematic diagram of an integrated bitumen production, waste-water treatment and SOZ scrubbing process in accordance with the invention.
Detailed Description of the Invention As shown in Figure 1, in a conventional commercial bitumen recovery operation l, steam 2 is generated from water 3 and treated water 3a by burning a natural gas fuel 4 in a steam generator or boiler 16. The steam 2 is injected into an underground reservoir 6 to reduce the viscosity of the underground bitumen by heat thereby enabling the bitumen to be recovered as a bitumen/water mixture 7~ The steam 2 and condensed water also react with the naturally occurring minerals in the reservoir 6 and pick up hardness ions, silica, and clay minerals which contaminate the water portion of the bitumen/water mixture 7.
Separation of the mixture in a separator 8 provides product bitumen 9 and produced water 9a.
The produced water 9a is treated in a water treatment facility 7a with chemicals 7c which remove the contaminants as a sludge/slurry 7b enabling re-use of the treated water 3 in the production of steam 2. The flue gas 16a does not require scrubbing.
Figure 2 shows a variation 1 a of the conventional bitumen recovery operation in which the natural gas fuel can be substituted for by a high sulfur fuel such as bitumen or an emulsion of bitumen or its heavier fractions 4a. Unlike burning natural gas, the burning of a high sulfur fuel produces a high sulfur flue gas 16a which requires scrubbing of SOZ in a conventional scrubber 5. Scrubber 5, using techniques known in the art, removes SOZ by reacting the SOz with scrubbing chemicals 5a which will produce a scrubber slurry Sb which is disposed in a slurry pit. The cost of the chemicals 5a is such that the process is not always cost-competitive with burning natural gas, depending on the price of natural gas.
In accordance with the invention, an integrated process 10 of water treatment and scrubbing is shown in Figure 3 for a high sulfur fuel fired steam generation and bitumen recovery process. As shown, and as in a conventional bitumen recovery operation described above, steam 12 is generated from water 14 and treated water 14a by burning a fuel (including whole bitumen or heavy fractions thereof) in a steam generator 16 for injection into the reservoir 24. Recovered bitumen and produced water 24a are separated from each other in a bitumen-water separator 26 to produce bitumen 28 and produced water 30. The produced water 30 is treated in a water treatment facility 32 to remove contaminants including hardness ions, silica and clay through the addition of chemicals 32a. A portion of the bitumen 28b is preferably used as fuel for the steam generator 16 and a portion 28a is directed to sales.
The produced water 30 is treated by techniques known in the art. Within the water treatment facility 32, chemicals including calcium hydroxide, magnesium hydroxide, sodium hydroxide, sodium carbonate, and a flocculant are added to the water, as necessary, to react with or provide adsorption sites for the hardness ions, silica and clay minerals thereby forming a waste slurry 22 which has both a liquid and a precipitated solids component.
The waste slurry 22 generally comprises unreacted chemicals and reacted product. The typical solid concentration range in the waste slurry is 4 to 20% by weight with the corresponding water concentration range as 96 to 80% by weight. A preferred concentration range of the solids is 5 to 15% by weight with the corresponding water concentration range as 95 to 85% by weight.
The SOZ laden flue gas 18 from the generator 16 is directed to a flue gas cleaner or scrubber 20 where, in accordance with the invention, it is contacted with the waste slurry 22 from the water treatment facility 32 thus utilizing both the reacted and unreacted chemicals of the waste slurry 22 within the scrubbing process. In most circumstances, no additional chemicals need to be added. After treatment of the SOz-laden flue gas 18, the spent slurry 34 is sent to disposal 36.
The precise composition of the chemicals added to the produced water in the water treatment facility may be varied as is known by those skilled in the art for effecting water treatment and will depend on the particular contaminants that may result from a particular reservoir. In order to provide effective scrubbing capabilities, it is preferred that the waste slurry composition include calcium hydroxide, magnesium hydroxide, calcium carbonate and a magnesium silicate mineral, some of which may be present in the water produced from the reservoir before treatment. A representative composition of this slurry is shown in the examples.
Accordingly, the system provides an effective way of combining the use of bitumen as a fuel and scrubbing SOz gas from combustion with chemicals contained in the slurry generated by treating the produced water from bitumen extraction.
As a result, an advantage of the invention is that the chemicals for SOZ
scrubbing are continuously generated in the water treatment facility. Moreover, no additional slurry pit is required as per other conventional flue gas desulfizrization processes.
Further still, the fuel for the process is generated internally.
In another embodiment where bitumen is used as a fuel, part of the total produced bitumen 28 may be used in the generator 16 and the remainder shipped to market 28a. In one embodiment, further separation of the bitumen 28 is provided to produce heavier and lighter bitumen fractions where the heavier fraction 28b is used as a fuel in the generator 16 and the lighter fraction is shipped to market. As a fuel, the heavier fraction 28b is may be emulsified in water and used as an emulsion fuel in the generator 16.
Moreover, the utilization of the waste stream for SOZ scrubbing offers a cost-effective method for utilizing sulfur-rich fuel that is cheaper than natural gas. The fuel is also internally generated as whole or a fraction of the produced bitumen; in the latter case also improving the viscosity and gravity of the remaining marketable bitumen.
The invention is illustrated by the following example.
EXAMPLE
Two litres of waste slurry from the Imperial Oil water treatment facility at Cold Lake, Alberta were separated into a water portion and a solids portion for analysis.
The water portion of the waste slurry had the following representative properties and composition as shown in Table 1:
Table 1- Water Composition of Waste Slurry Properties/Composition Preferred Range General Range pH at 22C 9.5 to 10 9 to 11 Total Dissolved Solids 10000 to 12000 ppm 8000 to 14000 ppm Total Hardness 80 to 160 ppm 70 to 180 ppm Tannin and Lignin 60 to 65 ppm 50 to 80 ppm Alkalinity Phen. 8.3 300 to 400 ppm 250 to 500 ppm as CaC03 Alkalinity Total as 500 to 650 ppm 400 to 800 ppm CaC03 Carbonate Ions 200 to 300 ppm 150 to 400 ppm Hydroxyl Ions 40 to 70 ppm 30 to 100 ppm Chloride Dissolved 5000 to 7000 ppm 4000 to 10000 ppm Total Organic Carbon 140 to 160 ppm 120 to 200 ppm Silica 10 to 50 ppm 5 to 100 ppm Sulfate 60 to 100 ppm 50 to 120 ppm Magnesium Ions 10 to 30 ppm 5 to 40 ppm Calcium Ions 14 to 15 ppm 10 to 40 ppm Potassium Ions 150 to 180 ppm 130 to 200 ppm -6_ Sodium Ions 3500 to 4500 ppm 3000 to 5000 ppm Sulfur Dissolved 30 to 40 ppm 25 to 50 ppm The slurry may also contain a non-ionic flocculating agent, such as NALCO
86070.
The solid portion of the waste slurry contained the following metal ions as shown in Table 2A:
Table 2A- Solids Portion Composition of Waste Slurry Properties/CompositionPreferred Range General Range Mg 10 to 20 wt% 5 to 25 wt%
Ca 20 to 25 wt% 15 to 35 wt%
Si 5 to 6 wt% 4 to 8 wt%
Na 0:45 to 0.80 wt% 0.4 to 1.0 wt%
A1 0:04 to 0.08 wt% 0.03 to 0.10 wt%
K 0:04 to 0.05 wt% 0.03 to 0.06 wt%
Fe 0.15 to 0.25 wt% 0.10 to 0.40 wt%
Sr 1500 to 2400 ppm 1200 to 3000 ppm Ba 500 to 700 ppm 400 to 1000 ppm By mineralogical analysis, the solid portion of the waste slurry contains the minerals shown in Table 2B and their typical proportions. These minerals were identified by X-ray diffraction and scanning electron microscope and their relative amounts determined using elemental analysis and mineral quantification software. The adsorbed water in the solid was not measured which explains why the sum of the mineral proportions is less than 100%. Some of these minerals were formed in the water treatment process, while others were either leached out from the reservoir sand or formed in the reservoir following steam inj ection.
Table 2B- Mineral Analysis of Solid Portion of Waste Slurry Minerals Name Formula wt%
Quartz Si02 4.6 - 6.0 wt%
K-spar KA1Si308 0.3 - 0.4 wt%
Albite NaA1Si30g 0.1 - 0.4 wt%
Calcite CaC03 55.5 - 59.3 wt%
_7_ Magnesite MgC03 1.5 3.6 wt%
-Siderite FeC03 0.4 0.5 wt%
-Halite NaCl 1.2 1.9 wt%
-Serpentine Mg6Si40,(OH) $ 8.2 9.2 wt%
-Brucite Mg(OH) 2 9.8 11.5 - wt%
Sepiolite Mg4Si60,5(OH)2.6H20 7.6 8.2 wt%
-Organic Carbon 1.0 2.3 wt%
-Total 95.8 - 97.9 wt%
Assuming a water concentration of 85-95% by weight, the whole waste slurry would have a composition representative of that shown in Table 3.
Table 3-Whole Waste Slurry Composition Properties/Composition Preferred Range General Range Solid 5 to 15 wt % 4 to 20 wt%
pH at 22C 9.5 to 10 9 to 11 Total Dissolved Solids 8500 to 11400 ppm 6400 to 13440 ppm Total Hardness 68 to 152 ppm 56 to 173 ppm Tannin and Lignin 51 to 62 ppm 40 to 77 ppm Alkalinity Phen. 8.3 255 to 380 ppm 200 to 480 ppm as CaC03 Alkalinity Total as 425 to 618 ppm 320 to 768 ppm CaC03 Carbonate Ions 170 to 285 ppm 120 to 384 ppm Hydroxyl Ions 34 to 67 ppm 24 to 96 ppm Chloride Ions 4250 to 6650 ppm 3200 to 9600 ppm Total Organic Carbon 119 to 152 ppm 96 to 192 ppm Dissolved Silica 3 to 5 ppm 0 to 48 ppm Sulfate Ions 51 to 95 ppm 40 to 115 ppm Magnesium Ions 9 to 29 ppm 4 to 38 ppm Calcium Ions 12 to 14 ppm 8 to 38 ppm Potassium Ions 128 to 171 ppm 104 to 192 ppm Sodium Ions 3000 to 4275 ppm 2400 to 4800 ppm Sulfur Dissolved 26 to 38 ppm 20 to 48 ppm Mg in solid 0.5 to 3 wt% 0.2 to 4 wt%
Ca in solid 1 to 4 wt% 0.6 to 7 wt%
Si in solid 0.3 to 0.9 wt% 0.16 to 1.6 wt A1 in solid 0.002 to 0.012 wt% 0.0012 to 0.02 wt K in solid 0.002 to 0.0075 0.0012 to 0.012 wt% wt%
Fe in solid 0.0075 to 0.0375 0.004 to 0.08%
wt % wt%
Sr in solid 75 to 360 ppm 48 to 600 ppm Ba in solid 25 to 105 ppm 16 to 200 ppm _g_ Pure SOZ from a gas cylinder was bubbled through the waste slurry at room temperature. The SOZ volume was measured with a Dry Test meter. Using a Drager tube, the SOZ in the effluent gas was monitored and recorded as a :function of the volume of SOZ
bubbled through. As shown in Table 4, the SOZ concentration in the effluent gas was only 6 ppm after 20 litres of SOZ at standard temperature and pressure conditions (STP) was bubbled through. At this point, the test was terminated. The pH of the slurry dropped from 9.9 to 4.3 at the end of the test.
Table 4- SOz Concentration in Effluent Gas Volume SOZ Bubbled (L@STP) SOZ Concentration in Effluent Gas (ppm) 8 Trace 16 Trace This test shows that two litres of Cold Lake waste slurry is capable of removing 20 litres of pure SOZ at STP.
The above-described embodiments of the invention are intended to be examples of the present invention. Alterations, modifications and variations may be effected to the particular embodiments by those of skill in the art, without departing from the scope of the invention which is defined solely by the claims appended hereto.
Claims (14)
1. A process for producing bitumen and removing sulfur dioxide from a flue gas said process comprising:
(a) burning whole bitumen or a heavier fraction thereof to generate steam to extract bitumen from a bitumen reservoir in a bitumen and produced water stream, said burning yielding said flue gas; and (b) removing SO2 from said flue gas by contacting said flue gas with a waste slurry resulting from a water treatment process for treatment of water separated from said bitumen and produced water stream.
(a) burning whole bitumen or a heavier fraction thereof to generate steam to extract bitumen from a bitumen reservoir in a bitumen and produced water stream, said burning yielding said flue gas; and (b) removing SO2 from said flue gas by contacting said flue gas with a waste slurry resulting from a water treatment process for treatment of water separated from said bitumen and produced water stream.
2. A process for producing bitumen from a subsurface reservoir comprising the steps of:
(a) injecting steam into a reservoir to recover bitumen;
(b) producing a stream of bitumen and produced water from the reservoir;
(c) separating the produced water and the bitumen;
(d) treating the produced water in a water treatment process to form a boiler-feed quality water and a waste slurry;
(e) burning at least a portion of the bitumen and using at least a portion of the boiler-feed quality water to produce steam and a flue gas; and (f) contacting the flue gas with the waste slurry to remove sulfur dioxide from the flue gas.
(a) injecting steam into a reservoir to recover bitumen;
(b) producing a stream of bitumen and produced water from the reservoir;
(c) separating the produced water and the bitumen;
(d) treating the produced water in a water treatment process to form a boiler-feed quality water and a waste slurry;
(e) burning at least a portion of the bitumen and using at least a portion of the boiler-feed quality water to produce steam and a flue gas; and (f) contacting the flue gas with the waste slurry to remove sulfur dioxide from the flue gas.
3. A process for scrubbing sulfur dioxide from a flue gas generated in the bitumen recovery process comprising contacting the said flue gas with a waste slurry from a water treatment process, wherein the waste slurry results from treatment of produced water in the said water treatment process within the said bitumen recovery process using steam to recover bitumen from an underground reservoir.
4. A process as in claim 3 wherein the process is integrated with a bitumen-fired steam generation process and the flue gas originates from the bitumen-fired steam generation process.
5. A process as in any one of claims 1-4 wherein said waste slurry comprises at least one of calcium hydroxide, magnesium hydroxide, calcium carbonate and magnesium silicate.
6. A process as in any one of claims 1-5 wherein said waste slurry comprises one or more alkaline compounds.
7. A process as in any one of claims 1-6 wherein the total solids concentration in the waste slurry is 4-20% by weight.
8. A process as in any one of claims 1-7 wherein the total solids concentration in the waste slurry is 5-15% by weight.
9. A process as in any one of claims 1-8 wherein the water treatment process includes the addition of chemicals for the precipitation of contaminants dissolved within water extracted from the reservoir.
10. A process as in any one of claims 1-9 wherein the waste slurry has a solids component having a metal ions composition including 5 to 25% by weight Mg, 15 to 35% by weight Ca, 4 to 8% by weight Si, 0.4 to 1.0% by weight Na, 0.03 to 0.10% by weight Al, 0.03 to 0.06% by weight K, 0.1 to 0.4% by weight Fe, 1200 to 3000 ppm, Sr, and 400 to 1000 ppm Ba.
11. A process as in any one of claims 1-9 wherein the waste slurry has a solids component having a metal ions composition including 10 to 20% by weight Mg, 20 to 25% by weight Ca, 5 to 6% by weight Si, 0.45 to 0.8% by weight Na, 0.04 to 0.08% by weight Al, 0.04 to 0.05% by weight K, 0.15 to 0.25% by weight Fe, 1500 to 2400 ppm Sr and 500 to 700 ppm Ba.
12. A process as in any one of claims 1-9 wherein the waste slurry has a liquid component including the following properties:
pH at 22°C ~9 to 11 Total Dissolved Solids 8000 to 14000 ppm Total Hardness ~70 to 180 ppm Tannin and Lignin ~~50 to 80 ppm Alkalinity Phen. 8.3 as CaCO3 ~250 to 500 ppm Alkalinity Total as CaCO3 ~~400 to 800 ppm Carbonate Ions ~~150 to 400 ppm Hydroxyl Ions ~~30 to 100 ppm Dissolved Chloride ~~4000 to 10000 ppm Total Organic Carbon ~~120 to 200 ppm Silica ~~5 to 100 ppm Sulfate ~~50 to 120 ppm Magnesium Ions ~~5 to 40 ppm Calcium Ions ~~10 to 40 ppm Potassium Ions ~~130 to 200 ppm Sodium Ions ~~3000 to 5000 ppm Sulfur Dissolved ~~25 to 50 ppm.
pH at 22°C ~9 to 11 Total Dissolved Solids 8000 to 14000 ppm Total Hardness ~70 to 180 ppm Tannin and Lignin ~~50 to 80 ppm Alkalinity Phen. 8.3 as CaCO3 ~250 to 500 ppm Alkalinity Total as CaCO3 ~~400 to 800 ppm Carbonate Ions ~~150 to 400 ppm Hydroxyl Ions ~~30 to 100 ppm Dissolved Chloride ~~4000 to 10000 ppm Total Organic Carbon ~~120 to 200 ppm Silica ~~5 to 100 ppm Sulfate ~~50 to 120 ppm Magnesium Ions ~~5 to 40 ppm Calcium Ions ~~10 to 40 ppm Potassium Ions ~~130 to 200 ppm Sodium Ions ~~3000 to 5000 ppm Sulfur Dissolved ~~25 to 50 ppm.
13. A process as in any one of claims 1-9 wherein the waste slurry has a liquid component including the following properties:
pH at 22°C ~9.5 to 10 Total Dissolved Solids ~~10000 to 12000 ppm Total Hardness ~~80 to 160 ppm Tannin and Lignin ~~60 to 65 ppm Alkalinity Phen. 8.3 as CaCO3~~300 to 400 ppm Alkalinity Total as CaCO3~~500 to 650 ppm Carbonate Ions ~~200 to 300 ppm Hydroxyl Ions ~~40 to 70 ppm Chloride Dissolved ~~5000 to 7000 ppm Total Organic Carbon ~~140 to 160 ppm Silica ~~10 to 50 ppm Sulfate ~~60 to 100 ppm Magnesium Ions ~~10 to 30 ppm Calcium Ions ~~14 to 15 ppm Potassium Ions ~~150 to 180 ppm Sodium Ions ~~3500 to 4500 ppm Sulfur Dissolved ~~30 to 40 ppm.
pH at 22°C ~9.5 to 10 Total Dissolved Solids ~~10000 to 12000 ppm Total Hardness ~~80 to 160 ppm Tannin and Lignin ~~60 to 65 ppm Alkalinity Phen. 8.3 as CaCO3~~300 to 400 ppm Alkalinity Total as CaCO3~~500 to 650 ppm Carbonate Ions ~~200 to 300 ppm Hydroxyl Ions ~~40 to 70 ppm Chloride Dissolved ~~5000 to 7000 ppm Total Organic Carbon ~~140 to 160 ppm Silica ~~10 to 50 ppm Sulfate ~~60 to 100 ppm Magnesium Ions ~~10 to 30 ppm Calcium Ions ~~14 to 15 ppm Potassium Ions ~~150 to 180 ppm Sodium Ions ~~3500 to 4500 ppm Sulfur Dissolved ~~30 to 40 ppm.
14. A process as in any one of claims 1-10 wherein the waste slurry has a solids component including the following properties:
Quartz ~SiO2 ~~4.6 - 6.0 % (wt%) K-spar ~KAlSi3O8 ~0.3 - 0.4 % (wt%) Albite ~NaAlSi3O8 ~0.1 - 0.4 % (wt%) Calcite CaCO3 55.5 - 59.3 % (wt%) Magnesite MgCO3 1.5 - 3.6 % (wt%) Siderite FeCO3 0.4 - 0.5 % (wt%) Halite NaCl 1.2 - 1.9 % (wt%) Serpentine Mg6Si4O10(OH)8 8.2 - 9.2 % (wt%) Brucite Mg(OH)2 9.8 - 11.5 % (wt%) Sepiolite Mg4Si6O15(OH)2.6H2O 7.6 - 8.2 % (wt%) Organic Carbon ~~~ 1.0 - 2.3 % (wt%).
Quartz ~SiO2 ~~4.6 - 6.0 % (wt%) K-spar ~KAlSi3O8 ~0.3 - 0.4 % (wt%) Albite ~NaAlSi3O8 ~0.1 - 0.4 % (wt%) Calcite CaCO3 55.5 - 59.3 % (wt%) Magnesite MgCO3 1.5 - 3.6 % (wt%) Siderite FeCO3 0.4 - 0.5 % (wt%) Halite NaCl 1.2 - 1.9 % (wt%) Serpentine Mg6Si4O10(OH)8 8.2 - 9.2 % (wt%) Brucite Mg(OH)2 9.8 - 11.5 % (wt%) Sepiolite Mg4Si6O15(OH)2.6H2O 7.6 - 8.2 % (wt%) Organic Carbon ~~~ 1.0 - 2.3 % (wt%).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10487636B2 (en) | 2017-07-27 | 2019-11-26 | Exxonmobil Upstream Research Company | Enhanced methods for recovering viscous hydrocarbons from a subterranean formation as a follow-up to thermal recovery processes |
| US11002123B2 (en) | 2017-08-31 | 2021-05-11 | Exxonmobil Upstream Research Company | Thermal recovery methods for recovering viscous hydrocarbons from a subterranean formation |
| US11142681B2 (en) | 2017-06-29 | 2021-10-12 | Exxonmobil Upstream Research Company | Chasing solvent for enhanced recovery processes |
| US11261725B2 (en) | 2017-10-24 | 2022-03-01 | Exxonmobil Upstream Research Company | Systems and methods for estimating and controlling liquid level using periodic shut-ins |
-
2002
- 2002-01-24 CA CA 2369244 patent/CA2369244C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11142681B2 (en) | 2017-06-29 | 2021-10-12 | Exxonmobil Upstream Research Company | Chasing solvent for enhanced recovery processes |
| US10487636B2 (en) | 2017-07-27 | 2019-11-26 | Exxonmobil Upstream Research Company | Enhanced methods for recovering viscous hydrocarbons from a subterranean formation as a follow-up to thermal recovery processes |
| US11002123B2 (en) | 2017-08-31 | 2021-05-11 | Exxonmobil Upstream Research Company | Thermal recovery methods for recovering viscous hydrocarbons from a subterranean formation |
| US11261725B2 (en) | 2017-10-24 | 2022-03-01 | Exxonmobil Upstream Research Company | Systems and methods for estimating and controlling liquid level using periodic shut-ins |
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| CA2369244A1 (en) | 2003-07-24 |
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