CA1250863A - Process for the preparation of hydrocarbons and/or oxygen-containing hydrocarbon derivatives and for crude oil production - Google Patents
Process for the preparation of hydrocarbons and/or oxygen-containing hydrocarbon derivatives and for crude oil productionInfo
- Publication number
- CA1250863A CA1250863A CA000463318A CA463318A CA1250863A CA 1250863 A CA1250863 A CA 1250863A CA 000463318 A CA000463318 A CA 000463318A CA 463318 A CA463318 A CA 463318A CA 1250863 A CA1250863 A CA 1250863A
- Authority
- CA
- Canada
- Prior art keywords
- gas
- oxygen
- carbon dioxide
- formation
- hydrocarbons
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 47
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 47
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000001301 oxygen Substances 0.000 title claims abstract description 30
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 17
- 239000010779 crude oil Substances 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000007789 gas Substances 0.000 claims abstract description 46
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 40
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 39
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 37
- 230000003647 oxidation Effects 0.000 claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000003921 oil Substances 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 238000002309 gasification Methods 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- -1 iron silicates Chemical class 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/34—Arrangements for separating materials produced by the well
- E21B43/40—Separation associated with re-injection of separated materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0485—Set-up of reactors or accessories; Multi-step processes
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
- E21B43/164—Injecting CO2 or carbonated water
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mining & Mineral Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Carbon And Carbon Compounds (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A B S T R A C T
PROCESS FOR THE PREPARATION OF HYDROCARBONS AND/OR
OXYGEN-CONTAINING HYDROCARBON DERIVATIVES
AND FOR CRUDE OIL PRODUCTION
Process for the preparation of hydrocarbons and/or oxygen-containing hydrocarbon derivatives and for the production of crude oil from an underground formation, wherein a) a mixture of CO and H2 is partly converted to hydrocarbons and/or oxygen-containing hydrocarbon derivatives, carbon dioxide being formed;
b) the hydrocarbons and/or oxygen-containing hydrocarbon derivatives axe separated at least partly from the product of step a) and a carbon dioxide-containing off-gas is obtained;
c) the off-gas is subjected to an oxidation; and d) subsequently at least the carbon dioxide of the off-gas is injected at elevated pressure into the underground formation and crude oil is produced from the formation. The presence of methane in gas which is injected into the underground formation is avoided.
PROCESS FOR THE PREPARATION OF HYDROCARBONS AND/OR
OXYGEN-CONTAINING HYDROCARBON DERIVATIVES
AND FOR CRUDE OIL PRODUCTION
Process for the preparation of hydrocarbons and/or oxygen-containing hydrocarbon derivatives and for the production of crude oil from an underground formation, wherein a) a mixture of CO and H2 is partly converted to hydrocarbons and/or oxygen-containing hydrocarbon derivatives, carbon dioxide being formed;
b) the hydrocarbons and/or oxygen-containing hydrocarbon derivatives axe separated at least partly from the product of step a) and a carbon dioxide-containing off-gas is obtained;
c) the off-gas is subjected to an oxidation; and d) subsequently at least the carbon dioxide of the off-gas is injected at elevated pressure into the underground formation and crude oil is produced from the formation. The presence of methane in gas which is injected into the underground formation is avoided.
Description
~;~ r~ ~08~ 3 PROOESS FOR THE PREP~ATION OF HYDR0CARBONS AND/OR
O~YGEN-CCNTAINING HYDROC~R~ON DERIU~TIVES
AND FOR CRUDE OIL PRODUCTION
The inventlon relates to a process for the preparation of hydrocarbons and/or oxygen-containiny hydrocarbon derivatives and for the production of crude oil fram an underground formation, wherein a) a mixture of carbon mono~ide and hydrogen at elevated temperature and pressure is partly converted to hydrocarbons and/or oxygen~containing hydrocarbon derivatives, carbon dio~ide belng formed;
b) the hydrocarbons and/or oxygen-containing hydrocarbon derivatives are separated at least partly frcm the product of step a) and a carboll dioxide-containing off-gas ls obtained;
c) at least the carbon dioxide of the off-gas is injected at elevated pressure into the llnderground formation and crude oil is pro*uced from the formation.
Such a process is kncwn frcm US paten-t specification No.
4,098,339. This specification discloses a process in which natural gas with a substantial c æbon dioxide content is converted by steam into a mixture of carbon ~onoxide, hydrogen and carbon dioxide. me carbon dioxide content is raised by means of the water gas shift reaction in which carbon monoxide and steam react to form carbon dioxide and hydrogen. Carbon monoxide and hydrogen in the product are subsequently convert~d into methanol or liquid hydrocarbons.
The methanol or liquid hydrocarbons are ~eparated from the product and an off-gas with a substantial carbon dioxide content is obtained.
In addition to carbon dioxide, tha off-gas still contains scme carbon monoxide. This carbon monoxide is converted in a methanator into methane, and the mixture of carbon dloxide and ~.ethane is pumpad into an oil-bearing underground formation in order to promote the production of crude oil.
,5~ 3~i3 It is known that cæbon dioxide under pressure dissolves readily in crude oil. This lowers the oil's viscosity and increases the volume of the oil/carbon dioxide mixture so that the now less viscous oil flcws more easily out of the pores of the formation.
This effect is intensified by the surface tension reduction which is caused by the presence of cæbon dioxide and which reduces the cohesion be-tween the oil and the formation.
Oil production techniques using carbon dioxide are known in the art. For example, cæbon dioxide injection can be realized via an injection well, p æt of the cæbon dioxide dissolving in the oil while another part, functioning as displacing medi~n, drives the oil to a production well. Other examples of a displacing medium are water and nitrogen. It is also possible to lower the pressure in the well after the carbon dioxide injection so that the now less viscous oil can be produced through the same well.
It will ~e clear from the above that the solubility of cæbon dioxide in oil is very important. According to the abcve-mentioned US patent specification, however, the solubility of carbon dio~ide in oil is decreased by the presence of methane. The viscosity reduction of the crude oil is therefore not ideal in the known process. In the process according to the present invention the presence of methane is avoided.
The invention therefore relates to a process for the prep æ -ation of hydrocarbons and/or o~ygen-containing hydrocarbon deriva-tives and for the production of crude oil fron an underground formation, the process ccmprising the above-mentioned steps a) to c), chæ acterized in that the off-gas is subjected to oxidation to increase the carbon dioxide content before at least the cæbon dioxide of the off-gas is injected into the formation.
me mixture of carbon monoxide and hydrogen can be obtained in many ways, for example as described in the above-mentioned US
patent specification, with the aid of steam re-forming of methane.
The mixture is, however, preferably obtained from the gasification of a carbon-containing fuel with the aid of an oxygen-containing gas and/or steam. Suitable fuels include many liquid hydrocarbon i5~ i3 fractions, as well as tar, oil from tar sands, shale oil, etc.
Solid fuels, such as coal, lignite, peat, etc., can also be employed. Possibilities for the oxygen-containing gas include air, oxygen-enriched air, or almost pure oxygen. The p~lre oxygen required is usually prepared in an air separation plant.
Gasification is generally carried out at a pressure of 5-100 bar and at a temperature of 900-1900 C.
Depending on the sulphur content of the fuel emplcyed, it is sG~etimes desirable to subject the gasification product to desul-phurization. q~lis is to prevent poisoning of the catalyst in thesynthesis stepO In addition, a carbon dio.xidP-rich gas is obtained which contains no hydrogen sulphideO This is desirable, since the transport of H2S-containing gases by pipeline to the oil field is subject to stringent safety requirements, or even prohibited.
The molar ratio of carbon monoxide to hydrogen in the miYture depænds on the gasification process emplcyed. In general, the H2 : CO ratio is betwe2n 0.25 and 2. If it is desirable to raise the hydrogen content in the mixture in order to obtain good con-version of the mixture to hydrocarbons and/or oxygen-containing hydrocarbon deriva-tives, the mixture can be subjected to a water gas shift reaction in which carbon moncxide and steam react to form carbon dioxide and hydrogen.
In the synthesis step the mixture of carbon monoxide and hydrogen is converted to hydroc æbons and/or oxygen-containing hydrocar~on derivatives. Methanol is the most important exponent of the latter group. A suitable catalyst will be necessary if it is intended to synthesize methanol. qhe st preferred catalysts contain either copper and zinc, or zinc ~xide and chrc~ium oxide.
Custcm~y pressures and temperatures for methanol synthesis are in the ran~e of 50 to 300 bar and 230 to 350 C, respectively.
Preferably, hcwever, hydrocarbons are prepared. Since hydrocarbons contain no oxygen, in contrast to methanol, an oxygen-containing byproduct is obtained from the synthesis which contains the oxygen originally present in the carbon monoxide. m is is water or carbon dioxide, depending on the catalyst chosen. Preferably, catalysts i3 are chosen which form hydrocarbons and carbon dioxide as almost the only oxygen-containing products, sueh as the catalysts mention d below. Arcmatic or paraffinic hydrocarbons can be prepared, depend-ing on the catalyst used.
If it is wished to prepare arcmatic hydrocarbons, it is advantageous to use particular crystalline metal silicates.
Particularly advantageous for the preparation of arcmatic hydro-carbons together with carbon dioxide is the use of speeial iron silicates or iron aluminium silicates which are described in British patent specification No 1,555,928 in cambinatlon with a catalyst for the synthesis of methanol or dimethyl ether. It is advantageous to employ a mixture of such a silicate and a catalyst for methanol synthesis, such as a ZnO/Cr2O3 ccmposition, as is disclosed in British patent specification No. 2,009,778. The reaction conditions under whieh the conversion is carried aut are usually a pressure of 5 to 100 b æ and a temperature of 200 to 500 C and a space velocity of 300 to 3000 Nl gas/l catalyst/hour.
If it is wished to prepare predcminantly paraffmic hydro-carbons, Fiseher-Tropsch catalysts are often used. Particularly suitable catalysts for the preparation of paraffinic hydrocarbons together with carbon dio~ide are the iron/magnesiumlalumina catalysts described in British patent specification No. 2,053,713~ and the iron/chroMium/silicate catalysts described in British patent specification No. 2,053,016. The conversion is usually conduct~d at a temperature of 200 to 450 C, a pressure of 10 to 7Q bar and a space velocity of 500 to 5000 Nl gas/l catalyst/hour.
Th~ conversion is preferably performed such that more than 90%
of the hydrogen present is converted in a single step. In this way a considerable quantity of hydrocarbon products are obtained from the available mixture of carbon monoxide and hydrogen. Moreover, after the separation of the hydrocarbons, the off-gas has a fairly high carbon dioxide cont~nt. The carbon dioxide content is then usually above 70 vol.%.
The desired hydrocarbons and/or oxygen-containing hydrocarbon derivatives are separated in a separating plant. The hydrocarbvns ~'~S~i3 in question will often be -the liquid ones; these are hydrw arbons with 5 or more carbon atGms per molecule (C5 ). Any C3 and C4 hydrocarbons formed can also be separated. mey can be used as, for example, LEG. Methane and the C2 hydrocarbons are usually discharged in the off~gas. In addition to C02, H20 and auantities of unconvexted hydrogen and carbon monoxide, the off-gas can therefore also contain cG~bustible constituents, such as ~ethane and C2 hydrocarbons. In the process according to the invention these ccn~ustible hydrocarbons, together with the unconverted lo quantities of carbon monoxide and hydrogen, are oxidized to form carbon dioxide and water vapour.
The oxidation can be performed with or without a catalyst. If there æe only small amounts of ca~bustible constituPnts present in the off-gas, the oxidation is preferably perormed with the aid of a catalyst. A variety of after-burnLng catalysts are suitable.
Preferred catalysts are copper oxide, whether or not on a vanadium pentoxide carrier, or platinum on a carrier such as asbestosO The oxidation is preferably performed at a pressure of 10 to 100 bar and at a temperature in the ra~ge of 300 to 1000 C. After the oxidation, the temperature of the gas can be lowered in a known way to any desired level, recovering usable heat at the same time.
Part of the oxidation products, e.g. water vapour, can be seFarated frGm the rest after the oxidation. This can be simply done by cooling until condensation takes place. The rest of the axidation products, consisting mainly of carbon dioxide, is then injected into the undergroNnd formation.
Preferably, hcwever, the entire oxidation product of the off-gas is injected into the formation. me presence of water can be advantageous. The carbon dio~ide dissolves in the water that is also injected into the formation. This solution has a weakly acidic effect and can thereby pramote the opening of oil-containing pores in the formation. This eases the flow of the oil, rendered less viscous by the carbon dioxide dissolved in it, and thereby also its production. Moreover, the oxidation products do not need to be cooled until the water vapour condenses. me gas can therefore be injected into the formation at a high temperature, which helps in reducing the viscosity of the crude oil in the formation and thereby eases its production.
I'he entire oxidation product, or at least the carbon dioxide of the off-gas, is injected into the formation preferably at a pressure of 50 to 400 bar and at a temperature of 20 to 500 C. In the process according to the invention, carbon dioxide is therefore obtained that has a favourable temperature and has already been brough-t to an attractively high pressure, which, if desired, can be raised further by compression. me o~timum conditions are determined in accordance with the natuîe of the formation and o~ the crude oil. The location of the field where the crude oil is produced determines the distance over which the car~on dioxide-containing gas has to be transpor~ed. This is a contributory factor in deter-mining the tempel^ature and pressure at which the gas is transportedto the field.
In addition to water vapour, the oxidation prcduct of the off^^gas can also contain some nitrogen. This occurs if air is used for the oxidation. The solubility of nitrogen in crude oil is, however, much less than that of carb~n dioxide. Nitrogen therefore only lo~ers the viscosity of the oil to a small extent. It can, however, be used as a displacing gas. Preferably, the presence of nitrogen is avoided and the off-gas is oxidized with almost pure oxygen. If the concentration of combustible materials in the off-gas is low, it is highly desirable to use pure oxygen for the oxidation, since o~idation with air proceeds far less readily, and in the absence of a catalyst sc~etimes dcies not proceed at all. The o~ygen preferably originates from the alr separating plant which also supplies the oxygen for the gasification of a carbon-containing fuel with the formation of a mixture of carbon monoxide and hydrogen, said mixture being partially converted into hydrocarbons and/or oxygen-containing hydrocarbon derivatives in step a) of the process.
The oxidation is preferably carried out wi-th a stoichiometric quantity of oxygen. It is, hcwever, not disadvantageous to use a small excess of oxygen. The oxygen is then injected with the carbon dioxide into the formation. A cc~bustion reaction can there take place between oxygen and oil in which heat is released. This heat lcwers the viscosity of the oil.
me gas injected into the formation can therefore con-tain relatively small amounts of water vapour, nitrogen and oxygen.
Preferably, hcwever, it contains no more than 10 vol.% impurities, so that a carbon dioxide-rich gas with at least 90 vol.% carbon dioxide is injected into the formation. The sas contains no harmful impurities, such as methane or hydrogen sulphide.
From an econcmical point of view, it is desirable to separate the carbon dioxide frc~ the produced oil and to re-use it. me carbon dioxide recovered from the oil already produced is preferably brcught to an elevated pressure and added to the off-gas. This addition to the off-gas can ~e done either before or after the oxidation. It is advantageous to add the carbon dioxide frc;m the oil after the oxidation, since in this case the oxidation does not need to be carried out with an off-gas having an extra high carbon dioxide content.
O~YGEN-CCNTAINING HYDROC~R~ON DERIU~TIVES
AND FOR CRUDE OIL PRODUCTION
The inventlon relates to a process for the preparation of hydrocarbons and/or oxygen-containiny hydrocarbon derivatives and for the production of crude oil fram an underground formation, wherein a) a mixture of carbon mono~ide and hydrogen at elevated temperature and pressure is partly converted to hydrocarbons and/or oxygen~containing hydrocarbon derivatives, carbon dio~ide belng formed;
b) the hydrocarbons and/or oxygen-containing hydrocarbon derivatives are separated at least partly frcm the product of step a) and a carboll dioxide-containing off-gas ls obtained;
c) at least the carbon dioxide of the off-gas is injected at elevated pressure into the llnderground formation and crude oil is pro*uced from the formation.
Such a process is kncwn frcm US paten-t specification No.
4,098,339. This specification discloses a process in which natural gas with a substantial c æbon dioxide content is converted by steam into a mixture of carbon ~onoxide, hydrogen and carbon dioxide. me carbon dioxide content is raised by means of the water gas shift reaction in which carbon monoxide and steam react to form carbon dioxide and hydrogen. Carbon monoxide and hydrogen in the product are subsequently convert~d into methanol or liquid hydrocarbons.
The methanol or liquid hydrocarbons are ~eparated from the product and an off-gas with a substantial carbon dioxide content is obtained.
In addition to carbon dioxide, tha off-gas still contains scme carbon monoxide. This carbon monoxide is converted in a methanator into methane, and the mixture of carbon dloxide and ~.ethane is pumpad into an oil-bearing underground formation in order to promote the production of crude oil.
,5~ 3~i3 It is known that cæbon dioxide under pressure dissolves readily in crude oil. This lowers the oil's viscosity and increases the volume of the oil/carbon dioxide mixture so that the now less viscous oil flcws more easily out of the pores of the formation.
This effect is intensified by the surface tension reduction which is caused by the presence of cæbon dioxide and which reduces the cohesion be-tween the oil and the formation.
Oil production techniques using carbon dioxide are known in the art. For example, cæbon dioxide injection can be realized via an injection well, p æt of the cæbon dioxide dissolving in the oil while another part, functioning as displacing medi~n, drives the oil to a production well. Other examples of a displacing medium are water and nitrogen. It is also possible to lower the pressure in the well after the carbon dioxide injection so that the now less viscous oil can be produced through the same well.
It will ~e clear from the above that the solubility of cæbon dioxide in oil is very important. According to the abcve-mentioned US patent specification, however, the solubility of carbon dio~ide in oil is decreased by the presence of methane. The viscosity reduction of the crude oil is therefore not ideal in the known process. In the process according to the present invention the presence of methane is avoided.
The invention therefore relates to a process for the prep æ -ation of hydrocarbons and/or o~ygen-containing hydrocarbon deriva-tives and for the production of crude oil fron an underground formation, the process ccmprising the above-mentioned steps a) to c), chæ acterized in that the off-gas is subjected to oxidation to increase the carbon dioxide content before at least the cæbon dioxide of the off-gas is injected into the formation.
me mixture of carbon monoxide and hydrogen can be obtained in many ways, for example as described in the above-mentioned US
patent specification, with the aid of steam re-forming of methane.
The mixture is, however, preferably obtained from the gasification of a carbon-containing fuel with the aid of an oxygen-containing gas and/or steam. Suitable fuels include many liquid hydrocarbon i5~ i3 fractions, as well as tar, oil from tar sands, shale oil, etc.
Solid fuels, such as coal, lignite, peat, etc., can also be employed. Possibilities for the oxygen-containing gas include air, oxygen-enriched air, or almost pure oxygen. The p~lre oxygen required is usually prepared in an air separation plant.
Gasification is generally carried out at a pressure of 5-100 bar and at a temperature of 900-1900 C.
Depending on the sulphur content of the fuel emplcyed, it is sG~etimes desirable to subject the gasification product to desul-phurization. q~lis is to prevent poisoning of the catalyst in thesynthesis stepO In addition, a carbon dio.xidP-rich gas is obtained which contains no hydrogen sulphideO This is desirable, since the transport of H2S-containing gases by pipeline to the oil field is subject to stringent safety requirements, or even prohibited.
The molar ratio of carbon monoxide to hydrogen in the miYture depænds on the gasification process emplcyed. In general, the H2 : CO ratio is betwe2n 0.25 and 2. If it is desirable to raise the hydrogen content in the mixture in order to obtain good con-version of the mixture to hydrocarbons and/or oxygen-containing hydrocarbon deriva-tives, the mixture can be subjected to a water gas shift reaction in which carbon moncxide and steam react to form carbon dioxide and hydrogen.
In the synthesis step the mixture of carbon monoxide and hydrogen is converted to hydroc æbons and/or oxygen-containing hydrocar~on derivatives. Methanol is the most important exponent of the latter group. A suitable catalyst will be necessary if it is intended to synthesize methanol. qhe st preferred catalysts contain either copper and zinc, or zinc ~xide and chrc~ium oxide.
Custcm~y pressures and temperatures for methanol synthesis are in the ran~e of 50 to 300 bar and 230 to 350 C, respectively.
Preferably, hcwever, hydrocarbons are prepared. Since hydrocarbons contain no oxygen, in contrast to methanol, an oxygen-containing byproduct is obtained from the synthesis which contains the oxygen originally present in the carbon monoxide. m is is water or carbon dioxide, depending on the catalyst chosen. Preferably, catalysts i3 are chosen which form hydrocarbons and carbon dioxide as almost the only oxygen-containing products, sueh as the catalysts mention d below. Arcmatic or paraffinic hydrocarbons can be prepared, depend-ing on the catalyst used.
If it is wished to prepare arcmatic hydrocarbons, it is advantageous to use particular crystalline metal silicates.
Particularly advantageous for the preparation of arcmatic hydro-carbons together with carbon dioxide is the use of speeial iron silicates or iron aluminium silicates which are described in British patent specification No 1,555,928 in cambinatlon with a catalyst for the synthesis of methanol or dimethyl ether. It is advantageous to employ a mixture of such a silicate and a catalyst for methanol synthesis, such as a ZnO/Cr2O3 ccmposition, as is disclosed in British patent specification No. 2,009,778. The reaction conditions under whieh the conversion is carried aut are usually a pressure of 5 to 100 b æ and a temperature of 200 to 500 C and a space velocity of 300 to 3000 Nl gas/l catalyst/hour.
If it is wished to prepare predcminantly paraffmic hydro-carbons, Fiseher-Tropsch catalysts are often used. Particularly suitable catalysts for the preparation of paraffinic hydrocarbons together with carbon dio~ide are the iron/magnesiumlalumina catalysts described in British patent specification No. 2,053,713~ and the iron/chroMium/silicate catalysts described in British patent specification No. 2,053,016. The conversion is usually conduct~d at a temperature of 200 to 450 C, a pressure of 10 to 7Q bar and a space velocity of 500 to 5000 Nl gas/l catalyst/hour.
Th~ conversion is preferably performed such that more than 90%
of the hydrogen present is converted in a single step. In this way a considerable quantity of hydrocarbon products are obtained from the available mixture of carbon monoxide and hydrogen. Moreover, after the separation of the hydrocarbons, the off-gas has a fairly high carbon dioxide cont~nt. The carbon dioxide content is then usually above 70 vol.%.
The desired hydrocarbons and/or oxygen-containing hydrocarbon derivatives are separated in a separating plant. The hydrocarbvns ~'~S~i3 in question will often be -the liquid ones; these are hydrw arbons with 5 or more carbon atGms per molecule (C5 ). Any C3 and C4 hydrocarbons formed can also be separated. mey can be used as, for example, LEG. Methane and the C2 hydrocarbons are usually discharged in the off~gas. In addition to C02, H20 and auantities of unconvexted hydrogen and carbon monoxide, the off-gas can therefore also contain cG~bustible constituents, such as ~ethane and C2 hydrocarbons. In the process according to the invention these ccn~ustible hydrocarbons, together with the unconverted lo quantities of carbon monoxide and hydrogen, are oxidized to form carbon dioxide and water vapour.
The oxidation can be performed with or without a catalyst. If there æe only small amounts of ca~bustible constituPnts present in the off-gas, the oxidation is preferably perormed with the aid of a catalyst. A variety of after-burnLng catalysts are suitable.
Preferred catalysts are copper oxide, whether or not on a vanadium pentoxide carrier, or platinum on a carrier such as asbestosO The oxidation is preferably performed at a pressure of 10 to 100 bar and at a temperature in the ra~ge of 300 to 1000 C. After the oxidation, the temperature of the gas can be lowered in a known way to any desired level, recovering usable heat at the same time.
Part of the oxidation products, e.g. water vapour, can be seFarated frGm the rest after the oxidation. This can be simply done by cooling until condensation takes place. The rest of the axidation products, consisting mainly of carbon dioxide, is then injected into the undergroNnd formation.
Preferably, hcwever, the entire oxidation product of the off-gas is injected into the formation. me presence of water can be advantageous. The carbon dio~ide dissolves in the water that is also injected into the formation. This solution has a weakly acidic effect and can thereby pramote the opening of oil-containing pores in the formation. This eases the flow of the oil, rendered less viscous by the carbon dioxide dissolved in it, and thereby also its production. Moreover, the oxidation products do not need to be cooled until the water vapour condenses. me gas can therefore be injected into the formation at a high temperature, which helps in reducing the viscosity of the crude oil in the formation and thereby eases its production.
I'he entire oxidation product, or at least the carbon dioxide of the off-gas, is injected into the formation preferably at a pressure of 50 to 400 bar and at a temperature of 20 to 500 C. In the process according to the invention, carbon dioxide is therefore obtained that has a favourable temperature and has already been brough-t to an attractively high pressure, which, if desired, can be raised further by compression. me o~timum conditions are determined in accordance with the natuîe of the formation and o~ the crude oil. The location of the field where the crude oil is produced determines the distance over which the car~on dioxide-containing gas has to be transpor~ed. This is a contributory factor in deter-mining the tempel^ature and pressure at which the gas is transportedto the field.
In addition to water vapour, the oxidation prcduct of the off^^gas can also contain some nitrogen. This occurs if air is used for the oxidation. The solubility of nitrogen in crude oil is, however, much less than that of carb~n dioxide. Nitrogen therefore only lo~ers the viscosity of the oil to a small extent. It can, however, be used as a displacing gas. Preferably, the presence of nitrogen is avoided and the off-gas is oxidized with almost pure oxygen. If the concentration of combustible materials in the off-gas is low, it is highly desirable to use pure oxygen for the oxidation, since o~idation with air proceeds far less readily, and in the absence of a catalyst sc~etimes dcies not proceed at all. The o~ygen preferably originates from the alr separating plant which also supplies the oxygen for the gasification of a carbon-containing fuel with the formation of a mixture of carbon monoxide and hydrogen, said mixture being partially converted into hydrocarbons and/or oxygen-containing hydrocarbon derivatives in step a) of the process.
The oxidation is preferably carried out wi-th a stoichiometric quantity of oxygen. It is, hcwever, not disadvantageous to use a small excess of oxygen. The oxygen is then injected with the carbon dioxide into the formation. A cc~bustion reaction can there take place between oxygen and oil in which heat is released. This heat lcwers the viscosity of the oil.
me gas injected into the formation can therefore con-tain relatively small amounts of water vapour, nitrogen and oxygen.
Preferably, hcwever, it contains no more than 10 vol.% impurities, so that a carbon dioxide-rich gas with at least 90 vol.% carbon dioxide is injected into the formation. The sas contains no harmful impurities, such as methane or hydrogen sulphide.
From an econcmical point of view, it is desirable to separate the carbon dioxide frc~ the produced oil and to re-use it. me carbon dioxide recovered from the oil already produced is preferably brcught to an elevated pressure and added to the off-gas. This addition to the off-gas can ~e done either before or after the oxidation. It is advantageous to add the carbon dioxide frc;m the oil after the oxidation, since in this case the oxidation does not need to be carried out with an off-gas having an extra high carbon dioxide content.
Claims (10)
1. Process for the preparation of hydrocarbons and/or oxygen-containing hydrocarbon derivatives and for the production of crude oil from an underground formation, wherein a) a mixture of carbon monoxide and hydrogen at elevated temperature and pressure is partly converted to hydrocarbons and/or oxygen-containing hydrocarbon derivatives, carbon dioxide being formed;
b) the hydrocarbons and/or oxygen-containing hydrocarbon derivatives are separated at least partly from the product of step a) and a carbon dioxide-containing off-gas is obtained;
c) at least the carbon dioxide of the off-gas is injected at elevated pressure into the underground formation and crude oil is produced from the formation, characterized in that the off-gas is subjected to an oxidation in order to raise its carbon dioxide content, before at least the carbon dioxide of the off-gas is injected into the formation.
b) the hydrocarbons and/or oxygen-containing hydrocarbon derivatives are separated at least partly from the product of step a) and a carbon dioxide-containing off-gas is obtained;
c) at least the carbon dioxide of the off-gas is injected at elevated pressure into the underground formation and crude oil is produced from the formation, characterized in that the off-gas is subjected to an oxidation in order to raise its carbon dioxide content, before at least the carbon dioxide of the off-gas is injected into the formation.
2. Process as claimed in claim 1, characterized in that the entire oxidation product of the off-gas is injected into the formation.
3. Process as claimed in claim 1 or 2, characterized in that the oxidation of the off-gas is carried out at a pressure of 10 to 100 bar and at a temperature in the range of 300 to 1000 °C.
4. Process as claimed in claim 1 or 2, characterized in that the oxidation is carried out in the presence of a catalyst.
5. Process as claimed in claim 1 or 2, characterized in that at least the carbon dioxide of the entire oxidation product of the off-gas is injected into the formation at a temperature of 20 to 500 °C and at a pressure of 50 to 400 bar.
6. Process as claimed in claim 1, characterized in that the off-gas is oxidized with almost pure oxygen.
7. Process as claimed in claim 6, characterized in that the oxygen is obtained from an air separating plant which also supplies the oxygen for the gasification of a carbon-containing fuel with the formation of a mixture of carbon monoxide and hydrogen, said mixture being partially converted in step a).
8. Process as claimed in claim 1 or 2, characterized in that the oxidation is carried out with a stoichiometric quantity of oxygen.
9. Process as claimed in claim 1 or 2, characterized in that the gas injected into the formation contains at least 90 vol.% carbon dioxide.
10. Process as claimed in claim 1 or 2, characterized in that carbon dioxide recovered from oil already produced is added to the off-gas.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL8303318 | 1983-09-28 | ||
| NL8303318A NL8303318A (en) | 1983-09-28 | 1983-09-28 | Synthesis using synthesis gas coupled with crude oil recovery - by gas drive, using co-produced carbon di:oxide after oxidising impurities |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1250863A true CA1250863A (en) | 1989-03-07 |
Family
ID=19842461
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000463318A Expired CA1250863A (en) | 1983-09-28 | 1984-09-17 | Process for the preparation of hydrocarbons and/or oxygen-containing hydrocarbon derivatives and for crude oil production |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA1250863A (en) |
| NL (1) | NL8303318A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003018958A1 (en) * | 2001-08-31 | 2003-03-06 | Statoil Asa | Method and plant for enhanced oil recovery and simultaneous synthesis of hydrocarbons from natural gas |
| US7481275B2 (en) | 2002-12-13 | 2009-01-27 | Statoil Asa | Plant and a method for increased oil recovery |
| US7673685B2 (en) | 2002-12-13 | 2010-03-09 | Statoil Asa | Method for oil recovery from an oil field |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003016676A1 (en) * | 2001-08-15 | 2003-02-27 | Shell Internationale Research Maatschappij B.V. | Tertiary oil recovery combined with gas conversion process |
-
1983
- 1983-09-28 NL NL8303318A patent/NL8303318A/en not_active Application Discontinuation
-
1984
- 1984-09-17 CA CA000463318A patent/CA1250863A/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003018958A1 (en) * | 2001-08-31 | 2003-03-06 | Statoil Asa | Method and plant for enhanced oil recovery and simultaneous synthesis of hydrocarbons from natural gas |
| US7481275B2 (en) | 2002-12-13 | 2009-01-27 | Statoil Asa | Plant and a method for increased oil recovery |
| US7673685B2 (en) | 2002-12-13 | 2010-03-09 | Statoil Asa | Method for oil recovery from an oil field |
| US7677309B2 (en) | 2002-12-13 | 2010-03-16 | Statoil Asa | Method for increased oil recovery from an oil field |
Also Published As
| Publication number | Publication date |
|---|---|
| NL8303318A (en) | 1985-04-16 |
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