US20130277275A1 - Method for treating heavy oil - Google Patents
Method for treating heavy oil Download PDFInfo
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- US20130277275A1 US20130277275A1 US13/822,818 US200913822818A US2013277275A1 US 20130277275 A1 US20130277275 A1 US 20130277275A1 US 200913822818 A US200913822818 A US 200913822818A US 2013277275 A1 US2013277275 A1 US 2013277275A1
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- hco
- solvent
- deasphalting
- oil
- solvent mixture
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- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000000295 fuel oil Substances 0.000 title description 12
- 239000002904 solvent Substances 0.000 claims abstract description 71
- 239000010779 crude oil Substances 0.000 claims abstract description 23
- 239000011877 solvent mixture Substances 0.000 claims abstract description 23
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000003921 oil Substances 0.000 claims description 51
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 8
- 102000004190 Enzymes Human genes 0.000 claims description 6
- 108090000790 Enzymes Proteins 0.000 claims description 6
- 235000010469 Glycine max Nutrition 0.000 claims description 6
- 244000068988 Glycine max Species 0.000 claims description 6
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 6
- 102000003992 Peroxidases Human genes 0.000 claims description 6
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000010903 husk Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 108040007629 peroxidase activity proteins Proteins 0.000 claims description 2
- 230000031018 biological processes and functions Effects 0.000 claims 2
- 238000000527 sonication Methods 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- 239000003153 chemical reaction reagent Substances 0.000 description 19
- 239000003054 catalyst Substances 0.000 description 18
- 239000008186 active pharmaceutical agent Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000012530 fluid Substances 0.000 description 12
- 239000010426 asphalt Substances 0.000 description 11
- 229910052759 nickel Inorganic materials 0.000 description 10
- 229910052720 vanadium Inorganic materials 0.000 description 10
- 230000005484 gravity Effects 0.000 description 9
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000003463 adsorbent Substances 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 238000003828 vacuum filtration Methods 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical class CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 150000003464 sulfur compounds Chemical class 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- -1 nickel organometallic compounds Chemical class 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- 150000004032 porphyrins Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- AYVGBNGTBQLJBG-UHFFFAOYSA-N [3-(hydroxymethyl)cyclopentyl]methanol Chemical compound OCC1CCC(CO)C1 AYVGBNGTBQLJBG-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000005608 naphthenic acid group Chemical group 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009291 secondary effect Effects 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
Images
Classifications
-
- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/003—Solvent de-asphalting
-
- 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
- C10G32/00—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms
- C10G32/02—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms by electric or magnetic means
Definitions
- the present invention relates to a method for deasphalting oils containing asphaltenes (such as heavy crude oil (HCO), bitumen, and oil refinery residues) using solvents and acoustic sound energy resulting in an upgraded higher value synthetic crude oil which may be further upgraded by chemical or biological/chemical processes.
- asphaltenes such as heavy crude oil (HCO), bitumen, and oil refinery residues
- solvents and acoustic sound energy resulting in an upgraded higher value synthetic crude oil which may be further upgraded by chemical or biological/chemical processes.
- solvent deasphalting can be used to upgrade heavy crude oil (HCO), including bitumen, to a synthetic crude oil (SCO) via enhancement of its chemical and physical properties such as:
- API gravities above 19 and viscosities below 350 centistokes are particularly desirable for purposes of product pipelining.
- Nickel contamination in oil refineries can come from two (2) sources: corrosion of stainless steel (e.g. via the presence of hydrogen chloride or naphthenic acids) or nickel organometallic compounds (e.g. porphyrins) in the asphaltene portion of bitumen.
- Nickel a hydrogen scavenger, causes catalyst fouling via coke formation due to dehydrogenation of alkanes to olefins in refinery catalytic crackers. Therefore SCO containing less nickel is more valuable.
- Vanadium contamination in oil refineries can come from vanadium organometallic compounds (e.g. porphyrins) in the asphaltene portion of bitumen. Vanadium destroys catalytic cracker catalysts by altering their crystal structure to non-catalytic forms. Therefore SCO containing less vanadium is more valuable.
- vanadium organometallic compounds e.g. porphyrins
- Canadian patent 2,549,358 (Boakye) describes a chemical and biological upgrading process for heavy oils which includes solvent deasphalting as a primary step. Although the process achieves high quality SCO output, the deasphalting step is prohibitively expensive and therefore not commercially viable due to excessive solvent requirements e.g. 10:1 preferred solvent to oil volume ratio (see page 5 section [0016]) and deasphalter processing times e.g. 2 to 3 hours (see page 2 section [0005]).
- the process of deasphalting has two purposes: to initiate upgrading of the HCO, by an average quantity of 4-5 API, as per prior technical evaluation as well as to remove a substantial quantity of sulphur from the HCO to the precipitated, insoluble asphaltene fraction.
- Deasphalting involves the solubilization of non-asphaltenes and the precipitation of asphaltenes, i.e. molecules insoluble in the deasphalting solvent.
- Deasphalting was high for non-cyclic alkanes and improved as the molecular weight of the alkane was reduced. Deasphalting was efficient based on the low solvent:bitumen ratio, however, deasphalting was extremely slow (i.e. 8 hours).
- the present invention is a method for converting heavy crude oil (HCO), such as bitumen, or oil refinery residues to a higher grade synthetic crude oil (SCO) or refinery output via separation of the SCO from asphaltenes.
- HCO heavy crude oil
- SCO synthetic crude oil
- Asphaltenes are defined as the part of the HCO or refinery residue precipitated by addition of a low-boiling paraffin solvent such as n-pentane.
- the SCO can be used as is or further upgraded via chemical and/or biological processing e.g. Canadian patent 2,549,358.
- a method for treating heavy crude oil which includes the steps of combining the HCO with an alkane containing non-polar solvent to form an HCO/solvent mixture, sonicating this mixture at audio frequency to precipitate asphaltenes from the HCO/solvent mixture, and separating the precipitated asphaltenes from the HCO/solvent mixture.
- vacuum filtration is used to remove. precipitated asphaltenes from the HCO/solvent mixture.
- Distillation may be used to remove solvent from the HCO/solvent mixture after removal of precipitated asphaltenes so as to create a deasphalted and solvent free synthetic crude oil (SCO).
- SCO deasphalted and solvent free synthetic crude oil
- the alkane containing solvent may include pentane, hexane or iso-octane.
- the deasphalted HCO/solvent mixture may advantageously be used as the feedstock for a chemical and/or biological oil upgrading process.
- the chemical and/or biological, process uses enzyme sources and one or more oxidants in the presence of an acid.
- the enzyme source may be soyabean husk and the enzyme, peroxidase.
- the acid may be acetic acid.
- the oxidant may be hydrogen peroxide combined with iron oxide.
- the deasphalting time is preferably 2 minutes (120 seconds) or less.
- the deasphalting time may be 60 seconds.
- the deasphalting solvent:HCO weight ratio may be less than or equal to 3.5.
- the deasphalting solvent:HCO weight ratio may be 1.16 or less.
- the deasphalting solvent:HCO weight ratio may be 0.91.
- the method exhibits improved solvent deasphalting, without excessive blending and dilution, by virtue of much faster deasphalting at low solvent to oil ratios, including separation of asphaltenes from deasphalted oil (in contrast to prior art methods). More particularly, this improved deasphalting is achieved by applying low-frequency, high amplitude acoustic energy to the HCO-solvent process stream (referred to as “sonication” of the HCO-solvent mixture) followed by separation of precipitated solvent insolubles (asphaltenes) via filtration, centrifugation, settling, or other appropriate technique. The method results in a SCO product that meets pipeline specifications in terms of API gravity and viscosity.
- the current invention is a method for simplified, accelerated deasphalting of HCO's with non-polar solvents, under low frequency acoustic sonication at an audio frequency that is well below the ultrasonic range (ultrasound frequency range commences at approximately 20,000 Hertz (Hz)).
- “Audio frequency” refers to a range of 16 Hz to 20,000 Hz, however, in the preferred embodiment of the invention the sonic mixing takes place at a frequency range of 30 Hz-5,000 Hz, or more preferably, in a range of 100 Hz-1,000 Hz.
- Such sonication devices come in two preferred types: sonicating probes in direct contact with fluids; and fluid containing vessels where the sonication is applied indirectly to the fluids via the vessel(e.g. component #44 on U.S. Pat. No. 5,005,773).
- Sonication devices can be of any type which can generate the desired acoustic frequency, high amplitude and sufficient energy density to the process fluids at an industrial scale.
- the preferred sonication device would achieve a high energy efficiency by using a balanced dynamic system operating at its natural resonance frequency to sonicate the fluid containing vessel (e.g. see Nyberg U.S. Pat. Nos. 4,941,134 and 5,005,773 component #44 where such vessel is mounted axially to the resonating member but in the absence of grinding media).
- non-polar, non-cyclic, low molecular weight alkane solvents and their associated analogs such as propane, pentane, hexane, heptane and iso-octane are used.
- “Sonication” and “low frequency acoustic sonication” refer to methods whereby a material is subjected to low frequency acoustic vibration.
- Devices for producing such vibration, “sonicators”, are disclosed in, for example, U.S. Pat. Nos. 4,941,134 and 5,005,773 (Nyberg et al.).
- these low frequency sonic reactors are reducible to large scale commercial practice (e.g. 20 kilowatt sonicator modules) and can achieve HCO deasphalting at low solvent:HCO doses (with ultra-low residence times in the sonicator (e.g. less than 120 seconds).
- FIG. 1 is a Heavy Oil Deasphalting Process Flow Diagram
- FIG. 2 is a Heavy Oil Upgrading Process Flow Diagram
- FIG. 3 is a SIMDIST graph for Upgraded and Raw oil showing boiling point temperature versus percentage of oil distilled at that temperature for heavy oil from South Western Texas;
- FIG. 4 is a SIMDIST graph for heavy oil from Lloydminster
- FIG. 5 is a SIMDIST graph for heavy oil from Bulgaria.
- FIG. 6 is a SIMDIST graph for American Oil Refinery Residue.
- the process is comprised of the following key unit operations:
- the sonication device reactor typically involves the conversion of electric power, via sequentially activated magnets, to produce vibrational energy.
- one sonication device used an electro-magnetic drive system to resonate a three tonne solid steel bar. Vibrational energy from the bar is transmitted to the attached to the fluid containing sonic reaction chambers (vessels containing the HCO-solvent mixture) and through which fluid materials can be pumped and be subjected to very intense audio frequency agitation (“sonication”).
- sonication very intense audio frequency agitation
- the vigorous sonication is used in the current process to enhance solvent extraction of the non-asphaltene fraction from the HCO through enhanced mass transfer as a result of the sonication and secondary effects such as cavitation.
- the sonic reactors are large (beyond bench and lab scale) low frequency sonication reactors that have sufficient processing capacity for commercial applications.
- the sonic reactors are readily transportable and require no anchoring once on site.
- Heat generation testwork indicates specific energy inputs for the 20 kW to 50 kW sonic reactor ranging up to 90 kW/m 3 of reactor volume (450 Horsepower/1,000 US gallons). This range of power input is at least one to two orders of magnitude (10 to 100 times) greater than is achieved by energy intensive industrial mixing systems such as flotation cells or standard agitation systems.
- the energy and fluid dynamic conditions and energy intensity produced by sonication devices, and in particular by the sonic reactors, is advantageous for chemical process operations. Sonication enhances process reactions by causing intense mixing and other fluid dynamic effects such that sonication improves the selectivity or efficiency of the desired chemical or physical reaction.
- the oil came from a heavy oil field located in Southwestern Texas. Fifty grams of the Southeastern Texas HCO was blended with 175 grams of iso-octane solvent (225 grams total) for sonic deasphalting in a baffled 1.7 litre stainless steel reaction chamber. The deasphalting occurred at 25 kW power applied continuously for 120 seconds in batch mode in a 1.7 fire sonic reaction chamber. Subsequently the deasphalted material was separated through direct vacuum filtration. Optionally, the subsequent deasphalted oil was oxidized via the prior art described by Boakye (Canadian patent #2,549,358) utilizing acetic acid, hydrogen peroxide, peroxidase enzyme source (i.e.
- soyabean husk soyabean husk
- iron oxide The oxidation reaction was quenched through absorption of generated polar compounds and sulfur compounds by passing the deasphalted HCO/solvent/reagent reaction product through a natural clay and activated carbon mixture that removes excess and/or unconsumed oxidation reagents.
- the solvent is recovered by atmospheric distillation at temperatures sufficient to evaporate the solvent. Any solvent recovery system may be used and persons skilled in the art may specify equipment based on recovery and cost considerations.
- the SIMDIST shows the simulated distillation via gas chromatography of upgraded and raw oil from Southeastern, Texas.
- the upper curve corresponds to raw-crude and the lower one to upgraded crude. This is the same for FIGS. 4 to 6 . If one arbitrarily chooses a value of 20 on the x-axis then 20% of the upgraded oil is distilled at 260° C. while 20% of the raw oil is distilled at 310° C. Oil value tends to increase as the boiling points of its components decrease.
- this SIMDIST graph corresponds to Example 2.
- the oxidation reaction was quenched through absorption of generated polar compounds and sulfur compounds by passing the deasphalted HCO/solvent/reagent reaction product through a natural clay and activated carbon mixture that remove all excess and/or unconsumed oxidation reagents.
- the next test sample was Processed American oil refinery residue.
- the oil refinery residue (“asphalt extender tank bottoms”) came from an oil refinery manufacturing refinery gas fuels, fuel additives, lubricants and anticorrosive materials.
- the oxidation reaction was quenched through absorption of generated polar compounds and sulfur compounds by passing the deasphalted HCO/solvent/reagent reaction product through a natural clay and activated carbon mixture that remove all excess and/or unconsumed oxidation reagents.
- the methodology involved mixing 619.4 g heavy crude oil (HCO) from Alberta with 716.7 g of solvent (n-pentane)(1,336 grams total), and therefore a solvent:oil weight ratio of 1.16, in a baffled 1.7 litre stainless steel reaction chamber. Acoustic energy was applied for 60 seconds at 40 kW continuously in batch mode followed by direct insoluble asphaltenes fraction filtration and atmospheric pressure distillation for solvent removal. The mass yield on the deasphalted oil was 85.3% of the HCO feedstock.
- the methodology involved mixing to a solvent: oil ratio of 1.09 by adding 690.9 g heavy crude oil (HCO) from Alberta with 631.6 g of solvent(n-hexane)(1,323 grams total) and therefore a solvent:oil weight ratio of 0.91, in a baffled 1.7 litre stainless steel reaction chamber. Acoustic energy was applied for 60 seconds at 40 kW continuously in batch mode followed by direct insoluble asphaltenes fraction filtration and atmospheric pressure distillation for solvent removal. The mass yield on deasphalted oil was 95.5% of the HCO feedstock.
- HCO heavy crude oil
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Abstract
According to the invention, there is provided a method for treating heavy crude oil (HCO) which includes the steps of combining the HCO with an alkane containing solvent to form an HCO/solvent mixture, sonicating this mixture at audio frequency to precipitate asphaltenes from the HCO/solvent mixture, and separating the precipitated asphaltenes from the HCO/solvent mixture.
Description
- The present invention relates to a method for deasphalting oils containing asphaltenes (such as heavy crude oil (HCO), bitumen, and oil refinery residues) using solvents and acoustic sound energy resulting in an upgraded higher value synthetic crude oil which may be further upgraded by chemical or biological/chemical processes.
- It is well known that solvent deasphalting can be used to upgrade heavy crude oil (HCO), including bitumen, to a synthetic crude oil (SCO) via enhancement of its chemical and physical properties such as:
-
- increased API gravity
- decreased viscosity
- decreased nickel content
- decreased vanadium content
- decreased sulphur content
- API gravities above 19 and viscosities below 350 centistokes are particularly desirable for purposes of product pipelining.
- Nickel contamination in oil refineries can come from two (2) sources: corrosion of stainless steel (e.g. via the presence of hydrogen chloride or naphthenic acids) or nickel organometallic compounds (e.g. porphyrins) in the asphaltene portion of bitumen. Nickel, a hydrogen scavenger, causes catalyst fouling via coke formation due to dehydrogenation of alkanes to olefins in refinery catalytic crackers. Therefore SCO containing less nickel is more valuable.
- Vanadium contamination in oil refineries can come from vanadium organometallic compounds (e.g. porphyrins) in the asphaltene portion of bitumen. Vanadium destroys catalytic cracker catalysts by altering their crystal structure to non-catalytic forms. Therefore SCO containing less vanadium is more valuable.
- U.S. Pat. Nos. 4,941,134 and 5,005,773 issued to Nyberg et al. describe a sonic reactor for the transmission of energy into fluid mediums using a “resonating bar” or probe.
- U.S. Pat. No. 6,357,526 (Abdel-Halim and Subramanian) describes “flashing” of light ends from HCO followed by solvent deasphalting of the flasher residue.
- Canadian patent 2,549,358 (Boakye) describes a chemical and biological upgrading process for heavy oils which includes solvent deasphalting as a primary step. Although the process achieves high quality SCO output, the deasphalting step is prohibitively expensive and therefore not commercially viable due to excessive solvent requirements e.g. 10:1 preferred solvent to oil volume ratio (see page 5 section [0016]) and deasphalter processing times e.g. 2 to 3 hours (see
page 2 section [0005]). - The process of deasphalting has two purposes: to initiate upgrading of the HCO, by an average quantity of 4-5 API, as per prior technical evaluation as well as to remove a substantial quantity of sulphur from the HCO to the precipitated, insoluble asphaltene fraction. Deasphalting involves the solubilization of non-asphaltenes and the precipitation of asphaltenes, i.e. molecules insoluble in the deasphalting solvent.
- U.S. Pat. No. 3,779,902 (Mitchell and Speight) shows, in Example 1, the relative deasphalting capability of a series of non-polar alkane solvents on Athabasca bitumen at 1:1 solvent to bitumen weight ratio. The solvent-bitumen mixtures were shaken vigorously for 5-10 minutes at 0.5 hour intervals for approximately 8 hours. At the end of the 8 hour reaction period, the fractions were separated by decantation followed by filtration, with light suction of the solvent-bitumen solution. The following Table 1 shows degree of asphaltene precipitation in weight % for each of the solvents:
-
TABLE 1 Solvent Asphaltenes precipitated (weight %) propane 100 butane 100 n- pentane 100 Hexane isomers 75 Heptane isomers 67 Pentane/hexane 83 Pentane/heptane 75 cyclopentane 1 cyclohexane 0 - Deasphalting was high for non-cyclic alkanes and improved as the molecular weight of the alkane was reduced. Deasphalting was efficient based on the low solvent:bitumen ratio, however, deasphalting was extremely slow (i.e. 8 hours).
- Prior art deasphalting of heavy crude oil and refinery residues suffers from the following problems alone or in combination:
-
- excessive solvent to heavy crude oil/residue ratios
- excessive processing times
- The present invention is a method for converting heavy crude oil (HCO), such as bitumen, or oil refinery residues to a higher grade synthetic crude oil (SCO) or refinery output via separation of the SCO from asphaltenes. Asphaltenes are defined as the part of the HCO or refinery residue precipitated by addition of a low-boiling paraffin solvent such as n-pentane. The SCO can be used as is or further upgraded via chemical and/or biological processing e.g. Canadian patent 2,549,358.
- According to the invention, there is provided a method for treating heavy crude oil (HCO) which includes the steps of combining the HCO with an alkane containing non-polar solvent to form an HCO/solvent mixture, sonicating this mixture at audio frequency to precipitate asphaltenes from the HCO/solvent mixture, and separating the precipitated asphaltenes from the HCO/solvent mixture.
- Preferably, vacuum filtration is used to remove. precipitated asphaltenes from the HCO/solvent mixture.
- Distillation may be used to remove solvent from the HCO/solvent mixture after removal of precipitated asphaltenes so as to create a deasphalted and solvent free synthetic crude oil (SCO).
- The alkane containing solvent may include pentane, hexane or iso-octane.
- The deasphalted HCO/solvent mixture may advantageously be used as the feedstock for a chemical and/or biological oil upgrading process.
- The chemical and/or biological, process uses enzyme sources and one or more oxidants in the presence of an acid.
- The enzyme source may be soyabean husk and the enzyme, peroxidase.
- The acid may be acetic acid.
- The oxidant may be hydrogen peroxide combined with iron oxide.
- The deasphalting time is preferably 2 minutes (120 seconds) or less.
- The deasphalting time may be 60 seconds.
- The deasphalting solvent:HCO weight ratio may be less than or equal to 3.5.
- The deasphalting solvent:HCO weight ratio may be 1.16 or less.
- The deasphalting solvent:HCO weight ratio may be 0.91.
- The method exhibits improved solvent deasphalting, without excessive blending and dilution, by virtue of much faster deasphalting at low solvent to oil ratios, including separation of asphaltenes from deasphalted oil (in contrast to prior art methods). More particularly, this improved deasphalting is achieved by applying low-frequency, high amplitude acoustic energy to the HCO-solvent process stream (referred to as “sonication” of the HCO-solvent mixture) followed by separation of precipitated solvent insolubles (asphaltenes) via filtration, centrifugation, settling, or other appropriate technique. The method results in a SCO product that meets pipeline specifications in terms of API gravity and viscosity.
- The current invention is a method for simplified, accelerated deasphalting of HCO's with non-polar solvents, under low frequency acoustic sonication at an audio frequency that is well below the ultrasonic range (ultrasound frequency range commences at approximately 20,000 Hertz (Hz)).
- “Audio frequency” refers to a range of 16 Hz to 20,000 Hz, however, in the preferred embodiment of the invention the sonic mixing takes place at a frequency range of 30 Hz-5,000 Hz, or more preferably, in a range of 100 Hz-1,000 Hz.
- Such sonication devices come in two preferred types: sonicating probes in direct contact with fluids; and fluid containing vessels where the sonication is applied indirectly to the fluids via the vessel(
e.g. component # 44 on U.S. Pat. No. 5,005,773). Sonication devices can be of any type which can generate the desired acoustic frequency, high amplitude and sufficient energy density to the process fluids at an industrial scale. The preferred sonication device would achieve a high energy efficiency by using a balanced dynamic system operating at its natural resonance frequency to sonicate the fluid containing vessel (e.g. see Nyberg U.S. Pat. Nos. 4,941,134 and 5,005,773component # 44 where such vessel is mounted axially to the resonating member but in the absence of grinding media). - In particular, non-polar, non-cyclic, low molecular weight alkane solvents and their associated analogs such as propane, pentane, hexane, heptane and iso-octane are used.
- “Sonication” and “low frequency acoustic sonication” refer to methods whereby a material is subjected to low frequency acoustic vibration. Devices for producing such vibration, “sonicators”, are disclosed in, for example, U.S. Pat. Nos. 4,941,134 and 5,005,773 (Nyberg et al.). Unlike ultrasonic devices, these low frequency sonic reactors are reducible to large scale commercial practice (e.g. 20 kilowatt sonicator modules) and can achieve HCO deasphalting at low solvent:HCO doses (with ultra-low residence times in the sonicator (e.g. less than 120 seconds).
- Further features and advantages will be apparent from the following detailed description, given by way of example, of a preferred embodiment taken in conjunction with the accompanying drawings, wherein:
-
FIG. 1 is a Heavy Oil Deasphalting Process Flow Diagram; -
FIG. 2 is a Heavy Oil Upgrading Process Flow Diagram; -
FIG. 3 is a SIMDIST graph for Upgraded and Raw oil showing boiling point temperature versus percentage of oil distilled at that temperature for heavy oil from South Western Texas; -
FIG. 4 is a SIMDIST graph for heavy oil from Lloydminster; -
FIG. 5 is a SIMDIST graph for heavy oil from Albania; and -
FIG. 6 is a SIMDIST graph for American Oil Refinery Residue. - The process is comprised of the following key unit operations:
-
- Intense agitation of the HCO/solvent mixture using audio frequency sonic energy “sonication”, resulting in efficient separation of asphaltenes from the HCO/solvent mixture. Such sonication devices come in two preferred types: sonicating probes in direct contact with fluids; and sonication of fluid containing vessels;
- Separation of the HCO from the asphaltene solids via physical separation e.g. decantation, filtration, centrifugation, etc.
- Optional biological and/or chemical oxidation of asphaltene stripped HCO/solvent mixture to create and SCO/solvent mixture.
- Removal of solvent from the asphaltene stripped HCO/solvent mixture to create a solvent free SCO.
- Recycling of the solvent for further processing of raw HCO.
- The sonication device reactor typically involves the conversion of electric power, via sequentially activated magnets, to produce vibrational energy. As an example one sonication device used an electro-magnetic drive system to resonate a three tonne solid steel bar. Vibrational energy from the bar is transmitted to the attached to the fluid containing sonic reaction chambers (vessels containing the HCO-solvent mixture) and through which fluid materials can be pumped and be subjected to very intense audio frequency agitation (“sonication”). The vigorous sonication is used in the current process to enhance solvent extraction of the non-asphaltene fraction from the HCO through enhanced mass transfer as a result of the sonication and secondary effects such as cavitation.
- The sonic reactors are large (beyond bench and lab scale) low frequency sonication reactors that have sufficient processing capacity for commercial applications. The sonic reactors are readily transportable and require no anchoring once on site.
- Heat generation testwork indicates specific energy inputs for the 20 kW to 50 kW sonic reactor ranging up to 90 kW/m3 of reactor volume (450 Horsepower/1,000 US gallons). This range of power input is at least one to two orders of magnitude (10 to 100 times) greater than is achieved by energy intensive industrial mixing systems such as flotation cells or standard agitation systems.
- The energy and fluid dynamic conditions and energy intensity produced by sonication devices, and in particular by the sonic reactors, is advantageous for chemical process operations. Sonication enhances process reactions by causing intense mixing and other fluid dynamic effects such that sonication improves the selectivity or efficiency of the desired chemical or physical reaction.
- The following non-limiting examples illustrate the effectiveness of the invention:
- Upgrading Oil from a Texas Oil Source
- The oil came from a heavy oil field located in Southwestern Texas. Fifty grams of the Southwestern Texas HCO was blended with 175 grams of iso-octane solvent (225 grams total) for sonic deasphalting in a baffled 1.7 litre stainless steel reaction chamber. The deasphalting occurred at 25 kW power applied continuously for 120 seconds in batch mode in a 1.7 lire sonic reaction chamber. Subsequently the deasphalted material was separated through direct vacuum filtration. Optionally, the subsequent deasphalted oil was oxidized via the prior art described by Boakye (Canadian patent #2,549,358) utilizing acetic acid, hydrogen peroxide, peroxidase enzyme source (i.e. soyabean husk) and iron oxide. The oxidation reaction was quenched through absorption of generated polar compounds and sulfur compounds by passing the deasphalted HCO/solvent/reagent reaction product through a natural clay and activated carbon mixture that removes excess and/or unconsumed oxidation reagents.
- The solvent is recovered by atmospheric distillation at temperatures sufficient to evaporate the solvent. Any solvent recovery system may be used and persons skilled in the art may specify equipment based on recovery and cost considerations.
-
TABLE 2 Sample Candidate Oil Balance (Run 081018E- 1), normalized to 1 barrel of oil: Inputs Mass (kg) Outputs Mass (kg) Crude Oil 154 Upgraded Oil 146 Solvent 539 Asphaltenes 6 Biological Catalyst 9 Solvent 512 Oxidizing Reagents 18 Solvent Loss 27 Chemical Catalyst 9 Reagent + Catalyst 19 Adsorbent Agents 40 Reagent + Catalyst 19 Loss Adsorbent Agents 40 TOTAL 769 TOTAL 769 Crude Oil Volume 1 bbl Upgraded Oil Volume 1.05 bbl -
TABLE 3 Analytical Change Parameters Raw Upgraded (%) Method Total Acid 0.59 0.99 67.8 ASTM D664 Number (TAN) (mg KOH/g) API gravity 17.4 27.9 71.8 ASTM D4052 (° API, @15° C.) Density 949.9 887.2 −6.6 ASTM D4052 (kg/m3, @15° C.) Nickel (μg/g) 5.4 1.9 −64.8 ASTM D5185 Vanadium (μg/g) 12 4.2 −65.0 ASTM D5185 Sulfur (mass %) 3.73 2.78 −25.5 ASTM D4294 SIMDIST IBP = 129.6 IBP = 90.0 — ASTM D7169 (by GC) See plot See plot (IBP1-720° C.) 1IBP = Initial Boiling Point (° C.) - Referring to
FIG. 3 , the SIMDIST shows the simulated distillation via gas chromatography of upgraded and raw oil from Southwestern, Texas. The upper curve corresponds to raw-crude and the lower one to upgraded crude. This is the same forFIGS. 4 to 6 . If one arbitrarily chooses a value of 20 on the x-axis then 20% of the upgraded oil is distilled at 260° C. while 20% of the raw oil is distilled at 310° C. Oil value tends to increase as the boiling points of its components decrease. - Upgrading Oil from a Canadian Oil Source
- Oil from a heavy oil field located near Lloydminster, Alberta, Canada was tested.
- Fifty grams of Lloydminster HCO was blended with 175 grams of iso-octane solvent (225 grams total) for sonic deasphalting in a baffled 1.7 litre stainless steel reaction chamber. The deasphalting occurred at 25 kW power applied continuously for 120 seconds in batch mode. After the deasphalted material was separated through direct vacuum filtration, the subsequent deasphalted oil was oxidized via the prior art described by Boakye (Canadian patent #2,549,358) utilizing acetic acid, hydrogen peroxide, peroxidase enzyme source (i.e. soyabean husk) and iron oxide. The oxidation reaction was quenched through absorption of generated polar compounds and sulfur compounds by passing the deasphalted HCO/solvent/reagent reaction product through a natural clay and activated carbon mixture.
-
TABLE 4 Sample Candidate Oil Balance (Run 081017E-1): Inputs Mass (kg) Outputs Mass (kg) Crude Oil 154 Upgraded Oil 127 Solvent 539 Asphaltenes 27 Biological Catalyst 9 Solvent 512 Oxidizing Reagents 18 Solvent Loss 27 Chemical Catalyst 9 Reagent + Catalyst 18 Adsorbent Agents 40 Reagent + Catalyst Loss 18 Adsorbent Agents 40 TOTAL 769 TOTAL 769 Crude Oil Volume 1 bbl Upgraded Oil Volume 0.95 bbl -
TABLE 5 Analytical Change Parameters Raw Upgraded (%) Method Total Acid 1.24 0.78 −37.1 ASTM D664 Number (TAN) (mg KOH/g) API gravity 14.4 30.8 +113.9 ASTM D4052 (° API, @15° C.) Density 969.0 871.5 −10.1 ASTM D4052 (kg/m3, @15° C.) Nickel (μg/g) 46 7.4 −83.9 ASTM D5185 Vanadium (μg/g) 95 20 −79.0 ASTM D5185 Sulfur (mass %) 3.62 2.15 −40.6 ASTM D4294 SIMDIST IBP = 112.8 IBP = 88.4 — ASTM D7169 (by GC) See plot See plot (IBP1-720° C.) 1IBP = Initial Boiling Point (° C.) - Referring to
FIG. 4 , this SIMDIST graph corresponds to Example 2. - Upgrading Oil from an Albanian Oil Source
- The oil from a heavy oil field located in Albania was tested next.
- Fifty grams of Albanian HCO was blended with 175 grams of iso-octane solvent (225 grams total) for sonic deasphalting in a baffled 1.7 litre stainless steel reaction chamber. The deasphalting occurred at 25 kW power applied continuously for 120 seconds in batch mode. After the deasphalted material was separated through direct vacuum filtration, the subsequent deasphalted oil was oxidized through the prior art described by Boakye (Canadian patent #2,549,358) utilizing acetic acid, hydrogen peroxide, peroxidase enzyme source (i.e. soyabean husk) and iron oxide. The oxidation reaction was quenched through absorption of generated polar compounds and sulfur compounds by passing the deasphalted HCO/solvent/reagent reaction product through a natural clay and activated carbon mixture that remove all excess and/or unconsumed oxidation reagents.
-
TABLE 6 Sample Candidate Oil Balance (Run 081119E-1): Inputs Mass (kg) Outputs Mass (kg) Crude Oil 158 Upgraded Oil 118 Solvent 474 Asphaltenes 41 Biological Catalyst 9 Solvent (Recovered) 450 Oxidizing Reagents 18 Solvent Loss 23 Chemical Catalyst 9 Reagent + Catalyst 18 Adsorbent Agents 40 Reagent + Catalyst Loss 18 Adsorbent Agents 40 TOTAL 708 TOTAL 708 Crude Oil Volume 1 bbl Upgraded Oil Volume 0.83 bbl -
TABLE 7 Analytical Change Parameters Raw Upgraded (%) Method Total Acid 0.56 0.30 −46.4 ASTM D664 Number (TAN) (mg KOH/g) API gravity 10.8 25.1 +132.4 ASTM D4052 ° API, @15° C.) Density 994 903 −9.2 ASTM D4052 (kg/m3, @15° C.) Nickel (μg/g) 68.5 8.6 −87.5 ASTM D5185 Vanadium (μg/g) 348.4 56 −83.9 ASTM D5185 Sulfur (mass %) 5.96 2.78 −53.4 ASTM D4294 SIMDIST IBP = 110.6 IBP = 93.9 — ASTM D7169 (by GC) See plot See plot (IBP1-720° C.) 1IBP = Initial Boiling Point (° C.) Referring to FIG. 5 this SIMDIST refers to the heavy oil from Albania - The next test sample was Processed American oil refinery residue. The oil refinery residue (“asphalt extender tank bottoms”) came from an oil refinery manufacturing refinery gas fuels, fuel additives, lubricants and anticorrosive materials.
- Fifty grams of refinery residue was blended with 175 grams of n-pentane solvent for sonic deasphalting in a baffled 1.7 litre stainless steel reaction chamber. The methodology involved the addition of 50 grams of the selected heavy oil indicated for each example to 175 grams of solvent (225 grams total) for sonic deasphalting. The deasphalting occurred at kW power applied continuously for 120 seconds in batch mode. After the deasphalted material was separated through direct vacuum filtration, the subsequent deasphalted oil was oxidized via the prior art described by Boakye (Canadian patent #2,549,358) utilizing acetic acid, hydrogen peroxide, peroxidase enzyme source (i.e. soyabean husk) and iron oxide. The oxidation reaction was quenched through absorption of generated polar compounds and sulfur compounds by passing the deasphalted HCO/solvent/reagent reaction product through a natural clay and activated carbon mixture that remove all excess and/or unconsumed oxidation reagents.
-
TABLE 8 Sample Candidate Oil Balance (Run 080829V-1): Inputs Mass (kg) Outputs Mass (kg) Crude Oil 154 Upgraded Oil 120 Solvent 620 Asphaltenes 34 Biological Catalyst 9 Solvent 589 Oxidizing Reagents 18 Solvent Loss 31 Chemical Catalyst 9 Reagent + Catalyst 18 Adsorbent Agents 40 Reagent + Catalyst Loss 18 Adsorbent Agents 40 TOTAL 850 TOTAL 769 Crude Oil Volume 1 bbl Upgraded Oil Volume 0.87 bbl -
TABLE 9 Analytical Change Parameters Raw Upgraded (%) Method Total Acid 3.19 0.26 −91.8 ASTM D664 Number (TAN) (mg KOH/g) API gravity 14.5 32.5 +124.1 ASTM D4052 (° API, @15° C.) Density 969.0 862.5 −11.0 ASTM D4052 (kg/m3, @15° C.) Nickel (μg/g) 12.2 <1.0 −91.8 ASTM D5185 Vanadium (μg/g) 23.8 1.7 −92.9 ASTM D5185 Sulfur (mass %) 1.18 0.62 −47.5 ASTM D4294 SIMDIST IBP = 130.8 IBP = 85.5 — ASTM D7169 (by GC) See plot See plot (IBP1 to 720° C.) 1IBP = Initial Boiling Point (° C.) Referring to FIG. 6, this SIMDIST corresponds to Example 4. - The methodology involved mixing 619.4 g heavy crude oil (HCO) from Alberta with 716.7 g of solvent (n-pentane)(1,336 grams total), and therefore a solvent:oil weight ratio of 1.16, in a baffled 1.7 litre stainless steel reaction chamber. Acoustic energy was applied for 60 seconds at 40 kW continuously in batch mode followed by direct insoluble asphaltenes fraction filtration and atmospheric pressure distillation for solvent removal. The mass yield on the deasphalted oil was 85.3% of the HCO feedstock.
-
TABLE 10 Change Analytical Parameters Raw Upgraded (%) Method API gravity 10.7 20.8 +94.4 ASTM D4052 (° API, @15° C.) Density 994.5 928.2 −6.7 ASTM D4052 (kg/m3, @15° C.) Viscosity (cSt) 25460 253.9 −99.0 Nickel (μg/g) 69 50 −27.5 ASTM D5185 Vanadium (μg/g) 159 118 −24.5 ASTM D5185 Sulfur (mass %) 4.34 3.74 −13.8 ASTM D4294 SIMDIST (by GC) IBP = 175 IBP = 31 — ASTM D7169 (IBP1-720° C.) - The methodology involved mixing to a solvent: oil ratio of 1.09 by adding 690.9 g heavy crude oil (HCO) from Alberta with 631.6 g of solvent(n-hexane)(1,323 grams total) and therefore a solvent:oil weight ratio of 0.91, in a baffled 1.7 litre stainless steel reaction chamber. Acoustic energy was applied for 60 seconds at 40 kW continuously in batch mode followed by direct insoluble asphaltenes fraction filtration and atmospheric pressure distillation for solvent removal. The mass yield on deasphalted oil was 95.5% of the HCO feedstock.
-
TABLE 11 Change Analytical Parameters Raw Upgraded (%) Method API gravity 10.7 15.0 +40.1 ASTM D4052 (° API, @15° C.) Density 994.5 965.9 −2.9 ASTM D4052 (kg/m3, @15° C) - Accordingly, while this invention has been described with reference to illustrative embodiments, this description is not intended to be construed in a limiting sense, for instance longer residence times and higher solvent ratios could be used. Various modifications of the illustrative embodiments, as well as other embodiments of the invention, will be apparent to persons skilled in the art upon reference to this description. It is therefore contemplated that the appended claims will cover any such modifications or embodiments as fall within the scope of the invention.
Claims (16)
1. A method for treating heavy crude oil (HCO) comprising the steps of:
a) combining said HCO with an alkane containing solvent to form an HCO/solvent mixture;
b) sonicating said mixture at audio frequency to precipitate asphaltenes from the HCO/solvent mixture; and
c) separating the precipitated asphaltenes from the HCO/solvent mixture.
2. A method as in claim 1 , vacuum filtering the HCO/solvent mixture to remove precipitated asphaltenes.
3. A method as in claim 1 , distilling the HCO-solvent mixture to remove solvent from the HCO/solvent mixture after removal of precipitated asphaltenes so as to create a deasphalted and solvent free synthetic crude oil (SCO).
4. A method as in claim 1 , wherein the alkane contains solvent selected from the group consisting of pentane, hexane and iso-octane.
5. A method as in claim 1 , wherein the deasphalted HCO/solvent mixture is used as the feedstock for a chemical and/or biological oil upgrading process.
6. A method as in claim 5 , wherein the chemical and/or biological process uses enzyme sources.
7. A method as in claim 5 , wherein the chemical and/or biological process uses one or more oxidants in the presence of an acid.
8. A claim as in claim 6 , wherein the enzyme source is soyabean husk.
9. A claim as in claim 8 , wherein the enzyme is peroxidase.
10. A claim as in claim 7 , wherein the acid is acetic acid.
11. A claim as in claim 7 , wherein the oxidant is hydrogen peroxide combined with iron oxide.
12. A method as in claim 1 , wherein the deasphalting time is 2 minutes (120 seconds) or less.
13. A method as in claim 13 , wherein the deasphalting time is 60 seconds.
14. A method as in claim 1 , wherein the deasphalting solvent:HCO weight ratio is less than or equal to 3.5.
15. A method as in claim 15 , wherein the deasphalting solvent:HCO weight ratio is 1.16 or less.
16. A method as in claim 16 , wherein the deasphalting solvent:HCO weight ratio is 0.91.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| US3569008P | 2008-03-11 | 2008-03-11 | |
| CAPCT/CA2009/000289 | 2009-03-11 | ||
| PCT/CA2009/000289 WO2009111871A1 (en) | 2008-03-11 | 2009-03-11 | Method for treating heavy crude oil |
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| US (1) | US20130277275A1 (en) |
| EP (1) | EP2260089A4 (en) |
| EA (2) | EA021729B1 (en) |
| WO (1) | WO2009111871A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140259883A1 (en) * | 2013-03-15 | 2014-09-18 | Petrosonic Energy Inc. | Emulsion fuel from sonication-generated asphaltenes |
| US10358610B2 (en) | 2016-04-25 | 2019-07-23 | Sherritt International Corporation | Process for partial upgrading of heavy oil |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US8475652B2 (en) * | 2009-10-19 | 2013-07-02 | Jan A. K. Paul | Method for purification of uncatalyzed natural fuels from metal ions by means of at least one hemeprotein and use of the at least on hemeprotein |
| CN101798523A (en) * | 2010-03-16 | 2010-08-11 | 李守春 | Auxiliary filtering method of heavy oil |
| EP2404983A1 (en) * | 2010-07-06 | 2012-01-11 | Total Raffinage Marketing | Hydroconversion process for heavy hydrocarbonaceous feedstock |
| CA2729457C (en) | 2011-01-27 | 2013-08-06 | Fort Hills Energy L.P. | Process for integration of paraffinic froth treatment hub and a bitumen ore mining and extraction facility |
| CA2733332C (en) | 2011-02-25 | 2014-08-19 | Fort Hills Energy L.P. | Process for treating high paraffin diluted bitumen |
| CA2931815C (en) | 2011-03-01 | 2020-10-27 | Fort Hills Energy L.P. | Process and unit for solvent recovery from solvent diluted tailings derived from bitumen froth treatment |
| CA2806891C (en) | 2011-03-04 | 2014-12-09 | Fort Hills Energy L.P. | A solvent treatment process for treating bitumen froth with axi-symmetric distribution of separator feed |
| CA2735311C (en) | 2011-03-22 | 2013-09-24 | Fort Hills Energy L.P. | Process for direct steam injection heating of oil sands bitumen froth |
| CA2815785C (en) | 2011-04-15 | 2014-10-21 | Fort Hills Energy L.P. | Heat recovery for bitumen froth treatment plant integration with temperature circulation loop circuits |
| CA2848254C (en) | 2011-04-28 | 2020-08-25 | Fort Hills Energy L.P. | Recovery of solvent from diluted tailings by feeding a desegregated flow to nozzles |
| CA2740935C (en) | 2011-05-18 | 2013-12-31 | Fort Hills Energy L.P. | Enhanced temperature control of bitumen froth treatment process |
| US9650312B2 (en) | 2013-03-14 | 2017-05-16 | Lummus Technology Inc. | Integration of residue hydrocracking and hydrotreating |
| US20140262961A1 (en) * | 2013-03-15 | 2014-09-18 | Petrosonic Energy Inc. | Solvent selection process |
| US20140262962A1 (en) * | 2013-03-15 | 2014-09-18 | Petrosonic Energy Inc. | Hydrocarbons recovery with sonic treatment |
| CN103450920A (en) * | 2013-09-13 | 2013-12-18 | 中国农业大学 | Method for increasing heavy oil yield by treating biological crude oil with ultrasonic wave |
| RU2628611C1 (en) * | 2016-10-03 | 2017-08-21 | федеральное государственное бюджетное образовательное учреждение высшего образования "Санкт-Петербургский горный университет" | Method for heavy oil feedstock processing |
| CN111575055B (en) * | 2020-05-22 | 2021-11-19 | 中国石油化工股份有限公司 | Residual oil hydrogenation raw material pretreatment method and device thereof and residual oil hydrogenation process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5547563A (en) * | 1993-10-14 | 1996-08-20 | Stowe; Lawrence R. | Method of conversion of heavy hydrocarbon feedstocks |
| US20070267327A1 (en) * | 2006-05-17 | 2007-11-22 | Boakye Frederick K | Heavy Oil Upgrading Process |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2504934A1 (en) * | 1981-04-30 | 1982-11-05 | Inst Francais Du Petrole | IMPROVED METHOD FOR SOLVENT DESASPHALTING OF HEAVY FRACTIONS OF HYDROCARBONS |
| US5017281A (en) * | 1984-12-21 | 1991-05-21 | Tar Sands Energy Ltd. | Treatment of carbonaceous materials |
-
2009
- 2009-03-11 US US13/822,818 patent/US20130277275A1/en not_active Abandoned
- 2009-03-11 EA EA201071060A patent/EA021729B1/en not_active IP Right Cessation
- 2009-03-11 EA EA201401282A patent/EA201401282A1/en unknown
- 2009-03-11 EP EP09719531A patent/EP2260089A4/en not_active Withdrawn
- 2009-03-11 WO PCT/CA2009/000289 patent/WO2009111871A1/en not_active Ceased
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5547563A (en) * | 1993-10-14 | 1996-08-20 | Stowe; Lawrence R. | Method of conversion of heavy hydrocarbon feedstocks |
| US20070267327A1 (en) * | 2006-05-17 | 2007-11-22 | Boakye Frederick K | Heavy Oil Upgrading Process |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140259883A1 (en) * | 2013-03-15 | 2014-09-18 | Petrosonic Energy Inc. | Emulsion fuel from sonication-generated asphaltenes |
| US10358610B2 (en) | 2016-04-25 | 2019-07-23 | Sherritt International Corporation | Process for partial upgrading of heavy oil |
Also Published As
| Publication number | Publication date |
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| EA201401282A1 (en) | 2015-03-31 |
| EA021729B1 (en) | 2015-08-31 |
| EA201071060A1 (en) | 2011-04-29 |
| EP2260089A1 (en) | 2010-12-15 |
| EP2260089A4 (en) | 2011-10-05 |
| WO2009111871A1 (en) | 2009-09-17 |
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