US20110000823A1 - Membrane desulfurization of liquid hydrocarbons using an extractive liquid membrane contactor system and method - Google Patents
Membrane desulfurization of liquid hydrocarbons using an extractive liquid membrane contactor system and method Download PDFInfo
- Publication number
- US20110000823A1 US20110000823A1 US12/826,019 US82601910A US2011000823A1 US 20110000823 A1 US20110000823 A1 US 20110000823A1 US 82601910 A US82601910 A US 82601910A US 2011000823 A1 US2011000823 A1 US 2011000823A1
- Authority
- US
- United States
- Prior art keywords
- sulfur
- methylimidazolium
- membrane
- extractive liquid
- ethyl
- 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.)
- Abandoned
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 111
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 85
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 84
- 239000007788 liquid Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 66
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 31
- 230000023556 desulfurization Effects 0.000 title claims abstract description 31
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 72
- 239000011593 sulfur Substances 0.000 claims abstract description 72
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 70
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 67
- 150000003464 sulfur compounds Chemical class 0.000 claims abstract description 28
- 239000012466 permeate Substances 0.000 claims abstract description 19
- 239000012465 retentate Substances 0.000 claims abstract description 15
- 238000011084 recovery Methods 0.000 claims abstract description 3
- -1 1-ethyl Chemical group 0.000 claims description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 37
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- 238000000926 separation method Methods 0.000 claims description 29
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 24
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 22
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 22
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- CEIPQQODRKXDSB-UHFFFAOYSA-N ethyl 3-(6-hydroxynaphthalen-2-yl)-1H-indazole-5-carboximidate dihydrochloride Chemical compound Cl.Cl.C1=C(O)C=CC2=CC(C3=NNC4=CC=C(C=C43)C(=N)OCC)=CC=C21 CEIPQQODRKXDSB-UHFFFAOYSA-N 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 12
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
- OUDFNZMQXZILJD-UHFFFAOYSA-N 5-methyl-2-furaldehyde Chemical compound CC1=CC=C(C=O)O1 OUDFNZMQXZILJD-UHFFFAOYSA-N 0.000 claims description 9
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 8
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 8
- MCTWTZJPVLRJOU-UHFFFAOYSA-O 1-methylimidazole Chemical compound CN1C=C[NH+]=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-O 0.000 claims description 6
- XSISYLHWKIXNBN-UHFFFAOYSA-N 3-methyl-1h-imidazol-3-ium;methyl sulfate Chemical compound COS([O-])(=O)=O.C[N+]=1C=CNC=1 XSISYLHWKIXNBN-UHFFFAOYSA-N 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 6
- IPXNUECGLTYKNJ-UHFFFAOYSA-N ethyl sulfate;1-methyl-1h-imidazol-1-ium Chemical compound C[NH+]1C=CN=C1.CCOS([O-])(=O)=O IPXNUECGLTYKNJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 239000004310 lactic acid Substances 0.000 claims description 5
- 235000014655 lactic acid Nutrition 0.000 claims description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 5
- 229940032159 propylene carbonate Drugs 0.000 claims description 5
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical class C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 4
- WVDDUSFOSWWJJH-UHFFFAOYSA-N 1-methyl-3-propylimidazol-1-ium Chemical compound CCCN1C=C[N+](C)=C1 WVDDUSFOSWWJJH-UHFFFAOYSA-N 0.000 claims description 4
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 claims description 4
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- ZJRCIQAMTAINCB-UHFFFAOYSA-N benzoylacetonitrile Chemical compound N#CCC(=O)C1=CC=CC=C1 ZJRCIQAMTAINCB-UHFFFAOYSA-N 0.000 claims description 4
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 claims description 4
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical class C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 4
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 claims description 4
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 claims description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 229930192474 thiophene Natural products 0.000 claims description 4
- 150000003577 thiophenes Chemical class 0.000 claims description 4
- MYAQZIAVOLKEGW-UHFFFAOYSA-N 4,6-dimethyldibenzothiophene Chemical class S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 238000005194 fractionation Methods 0.000 claims description 3
- POCJOGNVFHPZNS-ZJUUUORDSA-N (6S,7R)-2-azaspiro[5.5]undecan-7-ol Chemical compound O[C@@H]1CCCC[C@]11CNCCC1 POCJOGNVFHPZNS-ZJUUUORDSA-N 0.000 claims description 2
- KYPOHTVBFVELTG-OWOJBTEDSA-N (e)-but-2-enedinitrile Chemical compound N#C\C=C\C#N KYPOHTVBFVELTG-OWOJBTEDSA-N 0.000 claims description 2
- KYPOHTVBFVELTG-UPHRSURJSA-N (z)-but-2-enedinitrile Chemical compound N#C\C=C/C#N KYPOHTVBFVELTG-UPHRSURJSA-N 0.000 claims description 2
- LDVVBLGHGCHZBJ-UHFFFAOYSA-N 1-decyl-3-methylimidazolium Chemical compound CCCCCCCCCCN1C=C[N+](C)=C1 LDVVBLGHGCHZBJ-UHFFFAOYSA-N 0.000 claims description 2
- RVEJOWGVUQQIIZ-UHFFFAOYSA-N 1-hexyl-3-methylimidazolium Chemical compound CCCCCCN1C=C[N+](C)=C1 RVEJOWGVUQQIIZ-UHFFFAOYSA-N 0.000 claims description 2
- WHNAMGUAXHGCHH-UHFFFAOYSA-N 1-nitro-3-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC=CC(C(F)(F)F)=C1 WHNAMGUAXHGCHH-UHFFFAOYSA-N 0.000 claims description 2
- FUBFWTUFPGFHOJ-UHFFFAOYSA-N 2-nitrofuran Chemical compound [O-][N+](=O)C1=CC=CO1 FUBFWTUFPGFHOJ-UHFFFAOYSA-N 0.000 claims description 2
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 claims description 2
- GZPHSAQLYPIAIN-UHFFFAOYSA-N 3-pyridinecarbonitrile Chemical compound N#CC1=CC=CN=C1 GZPHSAQLYPIAIN-UHFFFAOYSA-N 0.000 claims description 2
- BSPUVYFGURDFHE-UHFFFAOYSA-N Nitramine Natural products CC1C(O)CCC2CCCNC12 BSPUVYFGURDFHE-UHFFFAOYSA-N 0.000 claims description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 229940015043 glyoxal Drugs 0.000 claims description 2
- POCJOGNVFHPZNS-UHFFFAOYSA-N isonitramine Natural products OC1CCCCC11CNCCC1 POCJOGNVFHPZNS-UHFFFAOYSA-N 0.000 claims description 2
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 claims description 2
- OVWYEQOVUDKZNU-UHFFFAOYSA-N m-tolualdehyde Chemical compound CC1=CC=CC(C=O)=C1 OVWYEQOVUDKZNU-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- BTFQKIATRPGRBS-UHFFFAOYSA-N o-tolualdehyde Chemical compound CC1=CC=CC=C1C=O BTFQKIATRPGRBS-UHFFFAOYSA-N 0.000 claims description 2
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 claims description 2
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 2
- 230000008961 swelling Effects 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 44
- 150000002898 organic sulfur compounds Chemical class 0.000 abstract description 7
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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
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
- C10G31/11—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by dialysis
-
- 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
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
Definitions
- the invention relates to processes for desulfurization of a hydrocarbon feed using membrane separation, and more particularly to a process and system for desulfurization of a hydrocarbon feed using an extractive liquid membrane separation contactor.
- compositions of natural petroleum or crude oils vary significantly, generally based upon the source. However, virtually all crude oils contain some level of sulfur compounds, including inorganically combined sulfur and organically combined sulfur, i.e., organosulfur compounds.
- Whole crude oil that contains a substantial concentration of sulfur compounds, such as hydrogen sulfide, and organosulfur compounds such as mercaptans, thiophenes, benzothiophenes, and dibenzothiophenes is referred to as “sour,” whereas whole crude oil that does not contain a substantial concentration of sulfur compounds is referred to as “sweet.”
- Crude oil is generally converted in refineries by distillation, followed by cracking and/or hydroconversion processes, to produce various fuels, lubricating oil products, chemicals, and chemical feedstocks.
- Fuels for transportation are generally produced by processing and blending distilled fractions from crude oil to meet the particular product specifications.
- distilled fractions are subject to various hydrocarbon desulfurization processes to make sulfur-containing hydrocarbons more marketable, attractive to customers and environmentally acceptable.
- sweet crude oil commands a higher price than sour crude oil because it has fewer environmental problems and requires less refining to meet sulfur standards imposed on end product fuels.
- Hydrocarbon desulfurization processes are required to reduce the sulfur content.
- most desulfurization processing occurs after varying levels of refining of the crude oil.
- hydrocarbon desulfurization process is hydrotreating, in particular, hydrodesulfurization.
- oil and hydrogen are introduced to a fixed bed reactor that is packed with a hydrodesulfurization catalyst, commonly under elevated operating conditions, including temperatures of about 300 to 400° C. and pressures of about 30 to 200 atmospheres.
- the temperatures and pressures in hydrotreating processes must be further elevated to achieve the low and ultra low sulfur content requirements.
- hydrocarbons are typically converted to less desirable intermediates or products.
- membrane separation One alternate desulfurization process that has been proposed for treating various refined fractions of hydrocarbons is membrane separation.
- membrane separation technology involves selective transport of a material through the membrane, a permeate, leaving behind a retentate on the feed side of the membrane. Permeated components of the mixture are removed by various driving forces. Membrane processes that rely upon pressure driving forces are known as pervaporation processes, and membrane processes that rely upon concentration gradients across the membrane are known as perstraction processes. Membrane separation often relies on the affinity of a specific compound or class of compounds for the membrane. Components in a mixture having affinity for the membrane will permeate the membrane. Membrane separation has been used for desulfurization of refined hydrocarbon fractions.
- Balko U.S. Pat. No. 7,267,761 also assigned to W.R. Grace & Co., describes another process for treating naphtha streams from an FCC unit, where the feedstream is treated in a fractionation zone to produce a low boiling point fraction and a second fraction, both containing sulfur.
- the low boiling point fraction is treated in a membrane separation zone, where the sulfur-enriched permeate is combined with the second fraction for treatment in a hydrodesulfurization zone.
- Plummer et al. U.S. Pat. No. 6,736,961 assigned to Marathon Oil Company, discloses a process employing a solid membrane process containing a transport facilitating liquid, identified as amines, hydroxyamines, and alcohols.
- the feed is described as a refinery hydrocarbon product such as naphtha or diesel.
- hydrocarbon feed streams in all of the above-mentioned references are products of upstream distillation and cracking processes and/or other refining operations.
- unrefined petroleum products e.g., crude oil
- membrane desulfurization processes require material to be transformed into a gaseous phase in order to increase the permeate transport rate.
- the material is transformed by heating and/or vacuum, also increasing the energy requirements.
- Other membrane desulfurization processes require the use of a transport agent to enhance the transport rate of sulfur compounds in dense layer of polymeric membrane. Transport agents generally cause plasticizing of the selective membrane and has a deleterious impact on its selectively to sulfur compounds.
- dispersed phase contactors require high solvent holdup, which is often associated with other problems such as emulsion formation, foaming, unloading and flooding.
- conventional extraction techniques such as liquid-liquid extraction, in which the two liquids are intermixed, suffers from many drawbacks, including slow phase separation and production of stable emulsions, resulting in the need to produce high surface area for mass transfer.
- the present invention utilizes an extractive liquid membrane contactor to desulfurize a hydrocarbon stream.
- a sulfur-containing liquid hydrocarbon is passed in contact with the retentate side of a porous membrane, while an extractive liquid is passed along the permeate side of the porous membrane.
- the membrane provides a controlled interface to allow the extractive liquid to draw sulfur-containing compounds from the hydrocarbon liquid.
- the proposed membrane contactor relies on extractive liquids to solubilize and transfer the sulfur compounds though pores of the membrane, so that the transfer rate of the sulfur compounds is not hindered.
- the membrane contactor brings the extractive liquid and the liquid feedstream into controlled contact without intermixing.
- the requirements for creating a vacuum or to convert the permeate in a gaseous phase in order to enhance the transport of the sulfur compounds are obviated, and the operating costs associated with the use of vacuum and energy of vaporization are eliminated.
- a process of the present invention is directed to desulfurization of a sulfur-containing hydrocarbon stream with a membrane separation apparatus in which sulfur compounds are concentrated in a sulfur-rich stream on a permeate side of the membrane and a sulfur-lean stream is recovered as a retentate.
- the sulfur-rich stream which has a small volume relative to the original hydrocarbon stream, is subsequently conveyed to a desulfurization apparatus or system, such as a hydrotreating system, to recover the hydrocarbons associated with the organosulfur compounds.
- the stream desulfurized by conventional processes, such as hydrotreating, and the hydrocarbon stream desulfurized by the membrane separation apparatus can be combined to provide a low sulfur hydrocarbon effluent with minimal or no significant loss of the original volume of hydrocarbons.
- FIG. 1 is a schematic diagram of a combined membrane separation desulfurization process and an alternate desulfurization process according to embodiments of the invention.
- FIG. 2 is a schematic diagram of a combined membrane separation desulfurization process and an alternate desulfurization process according to embodiments of the invention using extractive liquid as a sweep stream and including an extractive liquid regeneration/recovery zone.
- unrefined hydrocarbon is to be understood to mean crude oil and a distillate product of crude oil (including impurities such as sulfur) that has not been subjected to hydroprocessing, hydrodesulfurization, hydrodenitrogenation, catalytic processing, or cracking, and includes unrefined diesel, unrefined naphtha, unrefined gas oil, or unrefined vacuum gas oil.
- crude oil is to be understood to include a mixture of petroleum liquids and gases (including impurities such as sulfur) as distinguished from refined fractions of hydrocarbons.
- a hydrocarbon feedstream 12 such as a hydrocarbon feedstream containing organosulfur compounds is introduced into a membrane separation unit 14 where the feedstream 12 is separated into streams 16 , 18 .
- Sulfur-containing hydrocarbon compounds permeate a membrane of the membrane separation unit 14 by transfer to an extractive liquid stream on the permeate side of the membrane.
- the sulfur-containing hydrocarbons thus are concentrated into a sulfur-rich hydrocarbon stream 16 .
- the portion of the feedstream remaining on the feed side of the membrane, the retentate, is conveyed as a sulfur-lean hydrocarbon stream 18 .
- the sulfur-lean hydrocarbon stream 18 has a substantially reduced concentration of sulfur-containing compounds as compared to the feedstream 12 .
- the sulfur-rich stream 16 is transferred to a second stage desulfurization system 20 , such as a hydrotreating unit, after a post treatment step to remove at least a portion of the extractive liquid, to recover useful hydrocarbons associated with the organosulfur compounds.
- Effluent from the second stage desulfurization system 20 , a second stage sulfur-lean stream 22 , and the membrane desulfurized hydrocarbon stream 18 can be combined to provide a low sulfur hydrocarbon stream 24 with minimal or no loss in hydrocarbon product volume.
- the second stage sulfur-lean stream 22 that may be rich in aromatics is transferred to one or more subsequent processing steps.
- the combined membrane separation system 10 described herein advantageously is conducted as a liquid separation process.
- the hydrocarbon feedstream 12 , the sulfur-rich hydrocarbon stream 16 and the sulfur-lean hydrocarbon stream 18 are all maintained in the liquid phase.
- the feedstream 12 which can be a crude oil feedstream, a diesel feedstream, a naphtha feedstream, a gas oil feedstream, or a vacuum gas oil feedstream, is generally in the liquid phase initially, and the permeate and retentate remain in the liquid phase, without conversion into vapors and subsequent condensation, thereby conserving energy.
- the sequence of a membrane separation zone followed by second stage desulfurization zone is also conducive to integration with existing commercial hydrotreating units.
- This sequence realizes substantial economic savings, since the cost of operating a hydrotreating unit is proportional to the feed volume and is generally not sensitive to the sulfur content of the feed.
- the cost of a membrane separation unit is generally much less than the cost of a hydrotreating unit; therefore, technically mature hydrodesulphurization units can be employed with the attendant economic savings.
- the use of common and well understood processing units in combination will facilitate the capability for rapid scale-up or development of hydrocarbon feedstream desulfurization.
- the overall performance of the integrated process and system generally depends on the performance of the membrane separation unit, which in turn is enhanced by the selectivity and permeability of the membrane used. Accordingly, the membrane material is selected based on the permeation rate and selectivity for the range of sulfur compounds that are present in the hydrocarbon stream. The selection of the type of membrane can also increase efficiency and reliability of the separation unit, and hence increase efficiency and reliability of the overall process.
- the membrane is generally formed of a porous material, which provides sites for controlled interface between liquid hydrocarbon feed and extractive liquid.
- the transport of sulfur compounds mainly occurs between the liquids in the membrane pores.
- the porous membrane provides a non-dispersive contact interface between the extractive liquid and the hydrocarbon feedstream.
- the non-dispersive contact via the porous membrane contactor improves performance as compared to conventional dispersed-phase contactors, such as liquid-liquid extraction.
- solvent holdup is low, which is advantageous especially in embodiments in which expensive extractive liquid solvents are used.
- the membrane contactor of the present invention also avoids problems often encountered in conventional contactors, such as formation of emulsions, foaming, unloading and flooding.
- the porous membrane is formed of a material which has good wetability properties and is insoluble in the hydrocarbon and the extractive liquid. Further, the material for the membrane is selected so as to minimize swelling in the presence of the hydrocarbon and the extractive liquids.
- Membrane materials include those conventionally used for ultrafiltration and microfiltration membranes, for instance, formed of polymeric materials such as polyethersulfone (PES), polycarbonate, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), including hydrophilic PVDF, polyester, fluorinated polyimide, polyethyl-oxazoline, Nafion®, nylon and polyether terephthalate (PET). Other non-polymer materials can also be used.
- polymeric materials such as polyethersulfone (PES), polycarbonate, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), including hydrophilic PVDF, polyester, fluorinated polyimide, polyethyl-oxazoline, Nafion®, nylon and polyether terephthalate (PET).
- PET polyether terephthalate
- Other non-polymer materials can also be used.
- the membrane contactor provides a contact interface between the hydrocarbon feed and the extractive liquid.
- the selectivity of the membrane system to sulfur compounds is generally impacted by the choice of extractive liquid.
- much higher flux and permeability are obtainable when compared to nonporous (solid) membranes, such as those used in pervaporation membrane processes.
- the extractive liquid comprises a compound or mixture selected from the group consisting of fumaronitrile; maleonitrile; glyoxal; 2-nitrofuran; acetonitrile; acrylonitrile; nitramine; isoxazole; furfural; 5-methylfurfural; benzoylacetonitrile; vinyl formate; methyl formate; oxazole; sulfuric acid; diketene; benzonitrile; acrolein; dimethyl-oxalate; furan; benzaldehyde; acetic anhydride; methacrylonitrile; dimethyl sulfide; lactic acid; acetic acid; dimethyl formamide; dimethyl sulfoxide; aqueous potassium hydroxide; furfuryl alcohol; vinylacetylene; nicotinonitrile; pyridazine; methylmaleic anhydride; acetaldehyde; cis-crotonitrie; 3-nitro
- Table 1 summarizes the performance of certain extractive solvents for sulfur removal from diesel having a 1.4% w/w sulfur content, based on equilibrium partitioning of sulfur compounds between the hydrocarbon phase and extractive liquid phase:
- the extractive liquid is selected from the group consisting of acetonitrile; dimethyl sulfoxide; acrylonitrile; benzonitrile; dimethyl formamide; aqueous sodium hydroxide; aqueous potassium hydroxide; furfuryl alcohol; vinylacetylene; sulfuric acid; dimethylsulfoxide and methanol; furfural; and 5-methylfurfural.
- the target sulfur compounds comprise aromatic sulfur compounds including thiophenes, benzothiophenes and dibenzothiophenes
- the extractive liquid is selected from the group consisting of acetonitrile; furfural; benzonitrile; dimethyl sulfide; dimethyl formamide; methanol; lactic acid; propylene-carbonate; 5-methylfurfural; methyl formate; 1-ethyl, 3-methylimidazolium ethyl sulfate; 1-ethyl, 3-methylimidazolium methyl sulfate; 1-ethyl, 3-methylimidazolium hexafluorophosphate; 1-butyl, 3-methylimidazolium tetrafluoroborate; 1-ethyl, 3-methylimidazolium bis(trifluoromethanesulfonyl)imidate; 1-n-propyl-3-methylimidazolium bis(trifluoromethanesulfony
- the extractive liquid is selected from the group consisting of acetonitrile; acrylonitrile; furfural; 5-methylfurfural; benzoylacetonitrile; vinyl formate; diketene; benzonitrile; acrolein; dimethyl-oxalate; benzaldehyde; acetic anhydride; methacrylonitrile; acetic acid; dimethyl formamide; dimethyl sulfoxide; aqueous potassium hydroxide; furfuryl alcohol; 1-ethyl, 3-methylimidazolium ethyl sulfate; 1-ethyl, 3-methylimidazolium methyl sulfate; 1-ethyl, 3-methylimidazolium hexafluorophosphate; 1-butyl, 3-methylimidazolium tetrafluoroborate
- the membrane separation system for separating sulfur compounds from hydrocarbon feeds of the present invention operates at temperatures and pressures that maintain the feedstream in liquid phase.
- the membrane unit can be in any suitable configuration.
- the membrane unit can be in a spirally wound configuration, a hollow fiber configuration, a plate and frame configuration, or a tubular configuration.
- the membrane unit is in a spirally wound or a hollow fiber configuration.
- a plurality of membrane units can optionally be operated in parallel or series. In the parallel configuration, one or more membrane units can be decommissioned for maintenance without disrupting the continuity of the desulfurization process.
- the membrane unit is configured and dimensioned to allow maximum contact between the liquid hydrocarbon feedstream and the porous membrane on the retentate side, and to allow maximum contact between the extractive liquid and the porous membrane on the permeate side.
- the configuration and dimensions are provided to allow substantially all of the liquid hydrocarbon feedstream to come into contact with the porous membrane, and hence with the extractive liquid maintained in the pores of the membrane.
- the stream desulfurized by conventional processes, such as hydrotreating, and the hydrocarbons desulfurized by the membrane separation apparatus, can be combined to provide a low sulfur hydrocarbon system effluent with minimal or no loss of the original hydrocarbon volume.
- This low sulfur hydrocarbon effluent can serve as a feedstream for subsequent fractionating in a downstream process.
- the low sulfur hydrocarbon effluent may be sold as sweet crude oil, thereby taking advantage of the favorable price differential between sweet and sour crude oils.
- a configuration of a system 100 of the present invention is schematically depicted.
- Crude oil or other hydrocarbons are conveyed from a feed tank 108 in a stream 112 to a retentate side 136 of the membrane contactor 114 .
- Extractive liquid is introduced via a sweep stream 140 to the permeate side of the membrane contactor from an extractive liquid vessel 142 .
- controlled contact is provided between the feedstream and the extractive liquid so as to minimize intermixing of the liquids.
- the membrane contactor 114 provides the required surface area to meet the requisite degree of sulfur removal.
- the extractive liquids are selected to draw the sulfur-containing compounds out of the hydrocarbon feedstream, such as aliphatic sulfur molecules (including but not limited to sulfides, disulfides and mercaptans) and/or aromatic molecules (including but not limited to thiophenes, benzothiophenes, dibenzothiophenes and alkyl derivatives of aromatic sulfur molecules such as 4,6-dimethyl-dibenzothiophenes).
- the sulfur-lean stream 118 can be used as is, or combined with the sulfur-rich stream 116 after it has been subjected to further desulfurization.
- the sulfur-rich stream 116 including a high concentration of sulfur compounds and extractive liquids, are passed to a suitable regeneration zone, such as a flash tank 144 , within which solvents (extractive liquid) is recovered/regenerated via a recycle line 145 , and sulfur rich oil is discharged.
- a suitable regeneration zone such as a flash tank 144
- solvents extentractive liquid
- the sulfur-rich hydrocarbon stream is passed to a conventional desulfurization process 120 such as a hydrodesulfurization unit.
- the hydrodesulfurized hydrocarbons 122 and the retentate hydrocarbons 118 can be used as separate product streams or combined as a single product stream.
- PVDF polyvinylidene fluoride
Abstract
The process of the present invention is directed to the desulfurization of a sulfur-containing hydrocarbon stream with a membrane contactor, where sulfur compounds are concentrated in a sulfur-rich stream on a permeate side of the membrane using an extractive liquid, and a sulfur-lean stream is recovered as a retentate. The sulfur-rich stream, which has a small volume relative to the original hydrocarbon stream, is conveyed to a recovery zone to recover extractive liquid, and the remaining hydrocarbon stream having an increased concentration of sulfur compounds is passed to a downstream desulfurization apparatus or system, such as a hydrotreating system, to recover the hydrocarbons associated with the organosulfur compounds.
Description
- This applications claims priority to U.S. Provisional Patent Application Ser. No. 61/222,411, which is incorporated by reference in its entirety herein.
- The invention relates to processes for desulfurization of a hydrocarbon feed using membrane separation, and more particularly to a process and system for desulfurization of a hydrocarbon feed using an extractive liquid membrane separation contactor.
- Compositions of natural petroleum or crude oils vary significantly, generally based upon the source. However, virtually all crude oils contain some level of sulfur compounds, including inorganically combined sulfur and organically combined sulfur, i.e., organosulfur compounds. Whole crude oil that contains a substantial concentration of sulfur compounds, such as hydrogen sulfide, and organosulfur compounds such as mercaptans, thiophenes, benzothiophenes, and dibenzothiophenes is referred to as “sour,” whereas whole crude oil that does not contain a substantial concentration of sulfur compounds is referred to as “sweet.”
- Crude oil is generally converted in refineries by distillation, followed by cracking and/or hydroconversion processes, to produce various fuels, lubricating oil products, chemicals, and chemical feedstocks. Fuels for transportation are generally produced by processing and blending distilled fractions from crude oil to meet the particular product specifications. Conventionally, distilled fractions are subject to various hydrocarbon desulfurization processes to make sulfur-containing hydrocarbons more marketable, attractive to customers and environmentally acceptable.
- The evolution of sulfur compounds during processing and end-use of the petroleum products derived from sour crude oil poses safety and environmental problems. Laws have been enacted to reduce sulfur content of fuels, including diesel and gasoline. For instance, in 2007 the United States Environmental Protection Agency required sulfur content of highway diesel fuel to be reduced 97%, from 500 parts per million (low sulfur diesel) to 15 parts per million (ultra low sulfur diesel). The European Union has enacted even more stringent standards, requiring diesel and gasoline fuels sold in 2009 to contain less than 10 parts per million of sulfur.
- Furthermore, the price differential between sour crude oil and sweet crude oil (crude oil having relatively low level of sulfur compounds) favors sweet crude oil. Sweet crude oil commands a higher price than sour crude oil because it has fewer environmental problems and requires less refining to meet sulfur standards imposed on end product fuels. Hydrocarbon desulfurization processes are required to reduce the sulfur content. However, most desulfurization processing occurs after varying levels of refining of the crude oil.
- The most common hydrocarbon desulfurization process is hydrotreating, in particular, hydrodesulfurization. In typical hydrodesulfurization processes, oil and hydrogen are introduced to a fixed bed reactor that is packed with a hydrodesulfurization catalyst, commonly under elevated operating conditions, including temperatures of about 300 to 400° C. and pressures of about 30 to 200 atmospheres. The temperatures and pressures in hydrotreating processes must be further elevated to achieve the low and ultra low sulfur content requirements. However, under these more severe conditions, hydrocarbons are typically converted to less desirable intermediates or products.
- Typical advances in the industry for minimizing these undesirable effects include development of more robust hydrotreating catalysts and advanced hydrodesulfurization reactor designs. Alternative processes are also being developed to meet the requirements of decreased sulfur levels in fuels and other petrochemical products.
- One alternate desulfurization process that has been proposed for treating various refined fractions of hydrocarbons is membrane separation. In general, membrane separation technology involves selective transport of a material through the membrane, a permeate, leaving behind a retentate on the feed side of the membrane. Permeated components of the mixture are removed by various driving forces. Membrane processes that rely upon pressure driving forces are known as pervaporation processes, and membrane processes that rely upon concentration gradients across the membrane are known as perstraction processes. Membrane separation often relies on the affinity of a specific compound or class of compounds for the membrane. Components in a mixture having affinity for the membrane will permeate the membrane. Membrane separation has been used for desulfurization of refined hydrocarbon fractions.
- Saxton et al. U.S. Pat. No. 6,702,945 and Minhas et al. U.S. Pat. No. 6,649,061, both assigned to ExxonMobil, disclose reducing the sulfur content in a hydrocarbon fraction, particularly light cracked naphtha. The membrane system is operated under pervaporation conditions in the examples. In addition, the process discloses a transport agent (such as methanol) as an additive to the hydrocarbon mixture to enhance the permeate flux through the membrane.
- White et al. U.S. Pat. No. 6,896,796, and related U.S. Pat. Nos. 7,018,527, 7,041,212 and 7,048,846, all assigned to W.R. Grace & Co., disclose a method for lowering the sulfur content of an FCC light cut naphtha feed under pervaporation conditions. The processes propose to minimize olefin and naphthene hydrogenation during hydrotreating, particularly problematic in hydrotreating FCC naphtha since the high olefin content is again prone to hydrogenation.
- Balko U.S. Pat. No. 7,267,761, also assigned to W.R. Grace & Co., describes another process for treating naphtha streams from an FCC unit, where the feedstream is treated in a fractionation zone to produce a low boiling point fraction and a second fraction, both containing sulfur. The low boiling point fraction is treated in a membrane separation zone, where the sulfur-enriched permeate is combined with the second fraction for treatment in a hydrodesulfurization zone.
- Plummer et al. U.S. Pat. No. 6,736,961, assigned to Marathon Oil Company, discloses a process employing a solid membrane process containing a transport facilitating liquid, identified as amines, hydroxyamines, and alcohols. The feed is described as a refinery hydrocarbon product such as naphtha or diesel.
- Importantly, the hydrocarbon feed streams in all of the above-mentioned references are products of upstream distillation and cracking processes and/or other refining operations. However, the use of unrefined petroleum products (e.g., crude oil) as a feedstream to a membrane separation process remains heretofore unknown to the inventors.
- Another desulfurization process is described in Schoonover U.S. Pat. No. 7,001,504, where hydrocarbon materials are contacted with an ionic liquid to extract organosulfur compounds into the ionic liquid. The ionic liquid is regenerated by various methods including heating, gas stripping, oxidation, or extraction with another solvent or supercritical carbon dioxide. However, this process does not utilize membrane separation units to provide relatively compact and efficient separation.
- Various problems exist with the above-described existing membrane desulfurization processes. In some processes, dense layer of polymeric membrane are relied upon to enhance the selectivity of the membrane to sulfur compounds. However, this required extensive energy consumption to pass the materials through the membrane, and also limits the feed stream.
- In addition, some existing membrane desulfurization processes require material to be transformed into a gaseous phase in order to increase the permeate transport rate. The material is transformed by heating and/or vacuum, also increasing the energy requirements. Other membrane desulfurization processes require the use of a transport agent to enhance the transport rate of sulfur compounds in dense layer of polymeric membrane. Transport agents generally cause plasticizing of the selective membrane and has a deleterious impact on its selectively to sulfur compounds.
- Another approach to reducing the sulfur content in hydrocarbons uses dispersed phase contactors. However, dispersed phase contactors require high solvent holdup, which is often associated with other problems such as emulsion formation, foaming, unloading and flooding. Further, conventional extraction techniques such as liquid-liquid extraction, in which the two liquids are intermixed, suffers from many drawbacks, including slow phase separation and production of stable emulsions, resulting in the need to produce high surface area for mass transfer.
- Therefore, it is an object of the present invention to provide a membrane separation process and apparatus to desulfurize liquid hydrocarbon streams without the above-described problems associated with conventional membrane desulfurization processes.
- It is a further object of the present invention to provide a liquid extraction process and system to desulfurize liquid hydrocarbon streams without the above-described problems associated with dispersed phase contactors.
- It would therefore be desirable to provide a system and method that reduces the sulfur content of hydrocarbon streams using an extractive liquid membrane contactor.
- The present invention utilizes an extractive liquid membrane contactor to desulfurize a hydrocarbon stream. A sulfur-containing liquid hydrocarbon is passed in contact with the retentate side of a porous membrane, while an extractive liquid is passed along the permeate side of the porous membrane. The membrane provides a controlled interface to allow the extractive liquid to draw sulfur-containing compounds from the hydrocarbon liquid.
- In particular, the proposed membrane contactor relies on extractive liquids to solubilize and transfer the sulfur compounds though pores of the membrane, so that the transfer rate of the sulfur compounds is not hindered. The membrane contactor brings the extractive liquid and the liquid feedstream into controlled contact without intermixing. The requirements for creating a vacuum or to convert the permeate in a gaseous phase in order to enhance the transport of the sulfur compounds are obviated, and the operating costs associated with the use of vacuum and energy of vaporization are eliminated.
- In one aspect, a process of the present invention is directed to desulfurization of a sulfur-containing hydrocarbon stream with a membrane separation apparatus in which sulfur compounds are concentrated in a sulfur-rich stream on a permeate side of the membrane and a sulfur-lean stream is recovered as a retentate. The sulfur-rich stream, which has a small volume relative to the original hydrocarbon stream, is subsequently conveyed to a desulfurization apparatus or system, such as a hydrotreating system, to recover the hydrocarbons associated with the organosulfur compounds. The stream desulfurized by conventional processes, such as hydrotreating, and the hydrocarbon stream desulfurized by the membrane separation apparatus can be combined to provide a low sulfur hydrocarbon effluent with minimal or no significant loss of the original volume of hydrocarbons.
- Further advantages and features of the present invention will become apparent from the detailed description of a preferred embodiment of the invention that follows and reference to the accompanying drawings, in which:
-
FIG. 1 is a schematic diagram of a combined membrane separation desulfurization process and an alternate desulfurization process according to embodiments of the invention; and -
FIG. 2 is a schematic diagram of a combined membrane separation desulfurization process and an alternate desulfurization process according to embodiments of the invention using extractive liquid as a sweep stream and including an extractive liquid regeneration/recovery zone. - As used herein, the term “unrefined hydrocarbon” is to be understood to mean crude oil and a distillate product of crude oil (including impurities such as sulfur) that has not been subjected to hydroprocessing, hydrodesulfurization, hydrodenitrogenation, catalytic processing, or cracking, and includes unrefined diesel, unrefined naphtha, unrefined gas oil, or unrefined vacuum gas oil. Additionally, as used herein, the term “crude oil” is to be understood to include a mixture of petroleum liquids and gases (including impurities such as sulfur) as distinguished from refined fractions of hydrocarbons.
- With reference to
FIG. 1 , a schematic overview of adesulfurization system 10 is described. Ahydrocarbon feedstream 12, such as a hydrocarbon feedstream containing organosulfur compounds is introduced into amembrane separation unit 14 where thefeedstream 12 is separated intostreams membrane separation unit 14 by transfer to an extractive liquid stream on the permeate side of the membrane. The sulfur-containing hydrocarbons thus are concentrated into a sulfur-rich hydrocarbon stream 16. The portion of the feedstream remaining on the feed side of the membrane, the retentate, is conveyed as a sulfur-lean hydrocarbon stream 18. The sulfur-lean hydrocarbon stream 18 has a substantially reduced concentration of sulfur-containing compounds as compared to thefeedstream 12. The sulfur-rich stream 16, typically a small volume as compared to the volume of theoriginal feedstream 12, is transferred to a secondstage desulfurization system 20, such as a hydrotreating unit, after a post treatment step to remove at least a portion of the extractive liquid, to recover useful hydrocarbons associated with the organosulfur compounds. Effluent from the secondstage desulfurization system 20, a second stage sulfur-lean stream 22, and the membrane desulfurizedhydrocarbon stream 18, can be combined to provide a lowsulfur hydrocarbon stream 24 with minimal or no loss in hydrocarbon product volume. In an alternative embodiment of the process, the second stage sulfur-lean stream 22 that may be rich in aromatics is transferred to one or more subsequent processing steps. - The combined
membrane separation system 10 described herein advantageously is conducted as a liquid separation process. Thehydrocarbon feedstream 12, the sulfur-rich hydrocarbon stream 16 and the sulfur-lean hydrocarbon stream 18 are all maintained in the liquid phase. Thefeedstream 12, which can be a crude oil feedstream, a diesel feedstream, a naphtha feedstream, a gas oil feedstream, or a vacuum gas oil feedstream, is generally in the liquid phase initially, and the permeate and retentate remain in the liquid phase, without conversion into vapors and subsequent condensation, thereby conserving energy. A majority of hydrocarbon gases that are in the feedstream, in particular a crude oil feedstream, are generally dissolved in the liquid and do not pass through the membrane, and thus remain in the sulfur-lean hydrocarbon stream 18. Accordingly, the prior art pervaporation operations described above relating to processes for separation of particular fractions using sulfur-selective membranes and which consume large amounts of energy due to vaporization and vacuum maintenance, are not required. - The sequence of a membrane separation zone followed by second stage desulfurization zone is also conducive to integration with existing commercial hydrotreating units. This sequence realizes substantial economic savings, since the cost of operating a hydrotreating unit is proportional to the feed volume and is generally not sensitive to the sulfur content of the feed. The cost of a membrane separation unit is generally much less than the cost of a hydrotreating unit; therefore, technically mature hydrodesulphurization units can be employed with the attendant economic savings. The use of common and well understood processing units in combination will facilitate the capability for rapid scale-up or development of hydrocarbon feedstream desulfurization.
- The overall performance of the integrated process and system generally depends on the performance of the membrane separation unit, which in turn is enhanced by the selectivity and permeability of the membrane used. Accordingly, the membrane material is selected based on the permeation rate and selectivity for the range of sulfur compounds that are present in the hydrocarbon stream. The selection of the type of membrane can also increase efficiency and reliability of the separation unit, and hence increase efficiency and reliability of the overall process.
- The membrane is generally formed of a porous material, which provides sites for controlled interface between liquid hydrocarbon feed and extractive liquid. The transport of sulfur compounds mainly occurs between the liquids in the membrane pores. In certain embodiments, the porous membrane provides a non-dispersive contact interface between the extractive liquid and the hydrocarbon feedstream. The non-dispersive contact via the porous membrane contactor improves performance as compared to conventional dispersed-phase contactors, such as liquid-liquid extraction. In addition, solvent holdup is low, which is advantageous especially in embodiments in which expensive extractive liquid solvents are used. The membrane contactor of the present invention also avoids problems often encountered in conventional contactors, such as formation of emulsions, foaming, unloading and flooding.
- Preferably, the porous membrane is formed of a material which has good wetability properties and is insoluble in the hydrocarbon and the extractive liquid. Further, the material for the membrane is selected so as to minimize swelling in the presence of the hydrocarbon and the extractive liquids.
- Membrane materials include those conventionally used for ultrafiltration and microfiltration membranes, for instance, formed of polymeric materials such as polyethersulfone (PES), polycarbonate, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), including hydrophilic PVDF, polyester, fluorinated polyimide, polyethyl-oxazoline, Nafion®, nylon and polyether terephthalate (PET). Other non-polymer materials can also be used.
- The membrane contactor provides a contact interface between the hydrocarbon feed and the extractive liquid. The selectivity of the membrane system to sulfur compounds is generally impacted by the choice of extractive liquid. In addition, because of the porous nature of the membrane, much higher flux and permeability are obtainable when compared to nonporous (solid) membranes, such as those used in pervaporation membrane processes.
- In certain embodiments, the extractive liquid comprises a compound or mixture selected from the group consisting of fumaronitrile; maleonitrile; glyoxal; 2-nitrofuran; acetonitrile; acrylonitrile; nitramine; isoxazole; furfural; 5-methylfurfural; benzoylacetonitrile; vinyl formate; methyl formate; oxazole; sulfuric acid; diketene; benzonitrile; acrolein; dimethyl-oxalate; furan; benzaldehyde; acetic anhydride; methacrylonitrile; dimethyl sulfide; lactic acid; acetic acid; dimethyl formamide; dimethyl sulfoxide; aqueous potassium hydroxide; furfuryl alcohol; vinylacetylene; nicotinonitrile; pyridazine; methylmaleic anhydride; acetaldehyde; cis-crotonitrie; 3-nitrobenzotrifluoride; methyl phenyl ketone; vinyl acetate; p-tolualdehyde; m-tolualdehyde; o-tolualdehyde; propylene-carbonate; methanol; methanol and aqueous sodium hydroxide; dimethylsulfoxide and methanol; 1-ethyl, 3−-methylimidazolium ethyl sulfate; 1-ethyl, 3-methylimidazolium methyl sulfate; 1-ethyl, 3-methylimidazolium hexafluorophosphate; 1-butyl, 3-methylimidazolium tetrafluoroborate; 1-ethyl, 3-methylimidazolium bis(trifluoromethanesulfonyl)imidate; 1-n-propyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imidate; 1-n-butyl-3-methylimidazolium; 1-n-butyl-3-methylimidazolium trifluorotris(pentafluoroethyl)phosphate; 1-n-hexyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imidate; and 1-n-decyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imidate.
- The following Table 1 summarizes the performance of certain extractive solvents for sulfur removal from diesel having a 1.4% w/w sulfur content, based on equilibrium partitioning of sulfur compounds between the hydrocarbon phase and extractive liquid phase:
-
TABLE 1 Solvent Weight % Sulfur removal Furfural 28.6 Acetonitrile 26.2 Methanol 16.1 5-Methyl furfural 47.3 Propylene carbonate 16.0 Dimethyl sulfoxide 10.5 Acetone/water (50/50) 3.7 Furfuryl alcohol 18.8 Acetic acid 22.6 Lactic acid 2.0 Dimethylformamide 40.8 - The following Table 2 summarizes the performance of certain extractive solvents for sulfur removal from Arab Light crude oil having a 1.9% w/w sulfur content, based on equilibrium partitioning of sulfur compounds between the hydrocarbon phase and extractive liquid phase:
-
TABLE 2 Solvent Weight % Sulfur removal Furfural 13.6 Acetonitrile 3.9 Methanol 1.5 - In certain embodiments in which the target sulfur compounds comprise aliphatic sulfur molecules, the extractive liquid is selected from the group consisting of acetonitrile; dimethyl sulfoxide; acrylonitrile; benzonitrile; dimethyl formamide; aqueous sodium hydroxide; aqueous potassium hydroxide; furfuryl alcohol; vinylacetylene; sulfuric acid; dimethylsulfoxide and methanol; furfural; and 5-methylfurfural.
- In additional embodiments in which the target sulfur compounds comprise aromatic sulfur compounds including thiophenes, benzothiophenes and dibenzothiophenes, and the extractive liquid is selected from the group consisting of acetonitrile; furfural; benzonitrile; dimethyl sulfide; dimethyl formamide; methanol; lactic acid; propylene-carbonate; 5-methylfurfural; methyl formate; 1-ethyl, 3-methylimidazolium ethyl sulfate; 1-ethyl, 3-methylimidazolium methyl sulfate; 1-ethyl, 3-methylimidazolium hexafluorophosphate; 1-butyl, 3-methylimidazolium tetrafluoroborate; 1-ethyl, 3-methylimidazolium bis(trifluoromethanesulfonyl)imidate; 1-n-propyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imidate; 1-n-butyl-3-methylimidazolium trifluorotris(pentafluoroethyl)phosphate; and 1-n-butyl-3-methylimidazolium.
- In further embodiments in which the target sulfur compounds comprise alkyl derivatives of aromatic sulfur molecules including 4,6-dimethyl-dibenzothiophenes, the extractive liquid is selected from the group consisting of acetonitrile; acrylonitrile; furfural; 5-methylfurfural; benzoylacetonitrile; vinyl formate; diketene; benzonitrile; acrolein; dimethyl-oxalate; benzaldehyde; acetic anhydride; methacrylonitrile; acetic acid; dimethyl formamide; dimethyl sulfoxide; aqueous potassium hydroxide; furfuryl alcohol; 1-ethyl, 3-methylimidazolium ethyl sulfate; 1-ethyl, 3-methylimidazolium methyl sulfate; 1-ethyl, 3-methylimidazolium hexafluorophosphate; 1-butyl, 3-methylimidazolium tetrafluoroborate; and 1-ethyl, 3-methylimidazolium bis(trifluoromethane sulfonyl)imidate.
- In contrast to pervaporation techniques commonly known in the art, the membrane separation system for separating sulfur compounds from hydrocarbon feeds of the present invention operates at temperatures and pressures that maintain the feedstream in liquid phase.
- The membrane unit can be in any suitable configuration. For instance, the membrane unit can be in a spirally wound configuration, a hollow fiber configuration, a plate and frame configuration, or a tubular configuration. In certain preferred embodiments, the membrane unit is in a spirally wound or a hollow fiber configuration. In addition, a plurality of membrane units can optionally be operated in parallel or series. In the parallel configuration, one or more membrane units can be decommissioned for maintenance without disrupting the continuity of the desulfurization process.
- In a preferred embodiment, the membrane unit is configured and dimensioned to allow maximum contact between the liquid hydrocarbon feedstream and the porous membrane on the retentate side, and to allow maximum contact between the extractive liquid and the porous membrane on the permeate side. The configuration and dimensions are provided to allow substantially all of the liquid hydrocarbon feedstream to come into contact with the porous membrane, and hence with the extractive liquid maintained in the pores of the membrane.
- The stream desulfurized by conventional processes, such as hydrotreating, and the hydrocarbons desulfurized by the membrane separation apparatus, can be combined to provide a low sulfur hydrocarbon system effluent with minimal or no loss of the original hydrocarbon volume. This low sulfur hydrocarbon effluent can serve as a feedstream for subsequent fractionating in a downstream process. Alternatively, the low sulfur hydrocarbon effluent may be sold as sweet crude oil, thereby taking advantage of the favorable price differential between sweet and sour crude oils.
- Referring to
FIG. 2 , a configuration of asystem 100 of the present invention is schematically depicted. Crude oil or other hydrocarbons are conveyed from afeed tank 108 in astream 112 to aretentate side 136 of themembrane contactor 114. Extractive liquid is introduced via asweep stream 140 to the permeate side of the membrane contactor from an extractiveliquid vessel 142. At themembrane 114 interface, controlled contact is provided between the feedstream and the extractive liquid so as to minimize intermixing of the liquids. Themembrane contactor 114 provides the required surface area to meet the requisite degree of sulfur removal. - The extractive liquids are selected to draw the sulfur-containing compounds out of the hydrocarbon feedstream, such as aliphatic sulfur molecules (including but not limited to sulfides, disulfides and mercaptans) and/or aromatic molecules (including but not limited to thiophenes, benzothiophenes, dibenzothiophenes and alkyl derivatives of aromatic sulfur molecules such as 4,6-dimethyl-dibenzothiophenes). The sulfur-
lean stream 118 can be used as is, or combined with the sulfur-rich stream 116 after it has been subjected to further desulfurization. - The sulfur-
rich stream 116, including a high concentration of sulfur compounds and extractive liquids, are passed to a suitable regeneration zone, such as aflash tank 144, within which solvents (extractive liquid) is recovered/regenerated via arecycle line 145, and sulfur rich oil is discharged. The sulfur-rich hydrocarbon stream is passed to aconventional desulfurization process 120 such as a hydrodesulfurization unit. Thehydrodesulfurized hydrocarbons 122 and theretentate hydrocarbons 118 can be used as separate product streams or combined as a single product stream. - Membrane contactors using polyvinylidene fluoride (PVDF) flat sheet ultrafiltration membranes were constructed and tested in accordance with the present invention. The membranes were about 125 μm in thickness, had pores of 0.1 μm or 0.2 μm, and a porosity of 70%, 75% or 80%. Furfural was used as the extractive solvent. The flow rate of both the extractive solvent and the hydrocarbon streams was set at 10 milliliters per minute. Table 3 provides the results indicating effective mass transfer coefficients (in centimeters per hour).
-
TABLE 3 Mass Transfer Hydrocarbon stream Membrane Contactor Coefficient Arab light crude 0.1 μm pore, 70% porosity 0.25 (1.9% w/w sulfur) Diesel (1.5% w/w sulfur) 0.1 μm pore, 70% porosity 0.19 Diesel (1.5% w/w sulfur) 0.1 μm pore, 75% porosity 0.28 Diesel (1.5% w/w sulfur) 0.2 μm pore, 80% porosity 0.37 - The process of the invention has been described and explained with reference to the schematic process drawings and examples. Additional variations and modifications will be apparent to those of ordinary skill in the art based on the above description and the scope of the invention is to be determined by the claims that follow.
Claims (14)
1. A method of reducing the sulfur content of a sulfur-containing hydrocarbon feedstream comprising:
passing the feedstream in contact with a membrane on a retentate side of a membrane separation unit;
passing an extractive liquid in contact with the membrane on a permeate side of the membrane separation unit under conditions in which the extractive liquid contacts the feedstream;
concentrating sulfur compounds in the extractive liquid in a permeate stream of the membrane separation unit;
recovering as a retentate stream a first hydrocarbon product stream of reduced sulfur content;
recovering and subjecting the permeate stream to a fractionation process step for recovery of at least a portion of the extractive liquid; and
recovering a resulting sulfur-rich hydrocarbon stream from the fractionation process step.
2. The method of claim 1 , wherein the sulfur-rich hydrocarbon stream is subjected to a hydrodesulfurization process step, and recovering a second hydrocarbon product stream of reduced sulfur content.
3. The method of claim 1 , further comprising mixing the first and second hydrocarbon product streams to provide a final product stream of reduced sulfur content.
4. The method of claim 1 , wherein the feedstream contains a plurality of different sulfur-containing compounds and at least certain of the sulfur-containing compounds are soluble in the extractive liquid.
5. The method of claim 4 , wherein the extractive liquid is selected from the group consisting of fumaronitrile; maleonitrile; glyoxal; 2-nitrofuran; acetonitrile; acrylonitrile; nitramine; isoxazole; furfural; 5-methylfurfural; benzoylacetonitrile; vinyl formate; methyl formate; oxazole; sulfuric acid; diketene; benzonitrile; acrolein; dimethyl-oxalate; furan; benzaldehyde; acetic anhydride; methacrylonitrile; dimethyl sulfide; lactic acid; acetic acid; dimethyl formamide; dimethyl sulfoxide; aqueous potassium hydroxide; furfuryl alcohol; vinylacetylene; nicotinonitrile; pyridazine; methylmaleic anhydride; acetaldehyde; cis-crotonitrie; 3-nitrobenzotrifluoride; methyl phenyl ketone; vinyl acetate; p-tolualdehyde; m-tolualdehyde; o-tolualdehyde; propylene-carbonate; methanol; methanol and aqueous sodium hydroxide; dimethylsulfoxide and methanol; 1-ethyl, 3-methylimidazolium ethyl sulfate; 1-ethyl, 3-methylimidazolium methyl sulfate; 1-ethyl, 3-methylimidazolium hexafluorophosphate; 1-butyl, 3-methylimidazolium tetrafluoroborate; 1-ethyl, 3-methylimidazolium bis(trifluoromethanesulfonyl)imidate; 1-n-propyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imidate; 1-n-butyl-3-methylimidazolium; 1-n-butyl-3-methylimidazolium trifluorotris(pentafluoroethyl)phosphate; 1-n-hexyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imidate; and 1-n-decyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imidate.
6. The method of claim 1 , wherein target sulfur compounds comprise aliphatic sulfur molecules, and the extractive liquid is selected from the group consisting of acetonitrile; dimethyl sulfoxide; acrylonitrile; benzonitrile; dimethyl formamide; aqueous sodium hydroxide; aqueous potassium hydroxide; furfuryl alcohol; vinylacetylene; sulfuric acid; dimethylsulfoxide and methanol; furfural; and 5-methylfurfural.
7. The method of claim 1 , wherein target sulfur compounds comprise aromatic sulfur compounds including thiophenes, benzothiophenes and dibenzothiophenes, and the extractive liquid is selected from the group consisting of acetonitrile; furfural; benzonitrile; dimethyl sulfide; dimethyl formamide; methanol; lactic acid; propylene-carbonate; 5-methylfurfural; methyl formate; 1-ethyl, 3-methylimidazolium ethyl sulfate; 1-ethyl, 3-methylimidazolium methyl sulfate; 1-ethyl, 3-methylimidazolium hexafluorophosphate; 1-butyl, 3-methylimidazolium tetrafluoroborate; 1-ethyl, 3-methylimidazolium bis(trifluoromethanesulfonyl)imidate; 1-n-propyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imidate; 1-n-butyl-3-methylimidazolium trifluorotris(pentafluoroethyl)phosphate; and 1-n-butyl-3-methylimidazolium.
8. The method of claim 1 , wherein target sulfur compounds comprise alkyl derivatives of aromatic sulfur molecules including 4,6-dimethyl-dibenzothiophenes, and the extractive liquid is selected from the group consisting of acetonitrile; acrylonitrile; furfural; 5-methylfurfural; benzoylacetonitrile; vinyl formate; diketene; benzonitrile; acrolein; dimethyl-oxalate; benzaldehyde; acetic anhydride; methacrylonitrile; acetic acid; dimethyl formamide; dimethyl sulfoxide; aqueous potassium hydroxide; furfuryl alcohol; 1-ethyl, 3-methylimidazolium ethyl sulfate; 1-ethyl, 3-methylimidazolium methyl sulfate; 1-ethyl, 3-methylimidazolium hexafluorophosphate; 1-butyl, 3-methylimidazolium tetrafluoroborate; and 1-ethyl, 3-methylimidazolium bis(trifluoromethanesulfonyl)imidate.
9. The method of claim 1 , wherein the membrane is a porous membrane.
10. The method of claim 9 , wherein the porous membrane constitutes a controlled interface for contact between the hydrocarbon feedstream and the extractive liquid.
11. The method of claim 9 , wherein the porous membrane constitutes a non-dispersive contact interface between the extractive liquid and the hydrocarbon feedstream.
12. The method of claim 9 , wherein the porous membrane comprises a material which is insoluble in the hydrocarbon and the extractive liquid.
13. The method of claim 9 , wherein the porous membrane comprises a material which undergoes minimal swelling in the hydrocarbon and the extractive liquid.
14. A liquid hydrocarbon desulfurization system comprising:
a source of extractive liquid;
a membrane housing including
a porous membrane having a retentate side and a permeate side,
a retentate portion configured and dimensioned for maximizing contact between a liquid hydrocarbon feedstream and the retentate side of the membrane, and
a permeate portion configured and dimensioned for maximizing contact between the extractive liquid and the retentate side of the membrane.
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Citations (53)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2137206A (en) * | 1937-01-28 | 1938-11-15 | Indian Refining Co | Solvent refining hydrocarbon oil |
US2522065A (en) * | 1947-10-27 | 1950-09-12 | Phillips Petroleum Co | Catalytic desulfurization and reforming process |
US3410794A (en) * | 1966-01-20 | 1968-11-12 | Exxon Research Engineering Co | Separating hydrocarbons with liquid membranes |
US3666660A (en) * | 1970-04-30 | 1972-05-30 | Exxon Research Engineering Co | PURIFICATION OF A HYDROCARBON STREAM WITH Cr{115 {115 {115 {11 IONS IN SOLUTION |
US3719590A (en) * | 1970-12-17 | 1973-03-06 | Exxon Research Engineering Co | Liquid membrane system for separation of components of liquid mixtures |
US4359596A (en) * | 1981-08-03 | 1982-11-16 | Exxon Research And Engineering Co. | Liquid salt extraction of aromatics from process feed streams |
US4411790A (en) * | 1980-05-22 | 1983-10-25 | Commissariat A L'energie Atomique | Process for the treatment of a hydrocarbon charge by high temperature ultrafiltration |
US4816140A (en) * | 1986-04-02 | 1989-03-28 | Institut Francais Du Petrole | Process for deasphalting a hydrocarbon oil |
US4831207A (en) * | 1987-03-05 | 1989-05-16 | Uop | Chemical processing with an operational step sensitive to a feedstream component |
US4831208A (en) * | 1987-03-05 | 1989-05-16 | Uop | Chemical processing with an operational step sensitive to a feedstream component |
US4929358A (en) * | 1989-08-09 | 1990-05-29 | Exxon Research And Engineering Company | Polyurethane-imide membranes and their use for the separation of aromatics from non-aromatics |
US5039418A (en) * | 1990-12-06 | 1991-08-13 | Exxon Research And Engineering Company | Membrane made from a multi-block polymer comprising an oxazolidone prepolymer chain extended with a compatible second prepolymer and its use in separations |
US5045206A (en) * | 1990-12-05 | 1991-09-03 | Exxon Research & Engineering Company | Selective multi-ring aromatics extraction using a porous, non-selective partition membrane barrier |
US5063186A (en) * | 1987-10-14 | 1991-11-05 | Exxon Research & Engineering Company | Highly aromatic polyurea/urethane membranes and their use of the separation of aromatics from non-aromatics |
US5075006A (en) * | 1989-08-09 | 1991-12-24 | Exxon Research And Engineering Company | Isocyanurate crosslinked polyurethane membranes and their use for the separation of aromatics from non-aromatics |
US5107056A (en) * | 1990-12-05 | 1992-04-21 | Exxon Research And Engineering Company | Selective separation of naphthenes from paraffins by membrane extraction |
US5220106A (en) * | 1992-03-27 | 1993-06-15 | Exxon Research And Engineering Company | Organic non-quaternary clathrate salts for petroleum separation |
US5221481A (en) * | 1990-12-06 | 1993-06-22 | Exxon Research And Engineering Company | Multi-block polymer comprising an ester prepolymer, made by combining epoxy with polyester, chain extended with a compatible second prepolymer, the membrane made therefrom and its use for separations |
US5241039A (en) * | 1992-08-14 | 1993-08-31 | Exxon Research & Engineering Company | Polyimide/aliphatic polyester copolymers without pendent carboxylic acid groups (C-2662) |
US5320816A (en) * | 1992-10-21 | 1994-06-14 | The Dow Chemical Company | Process for absorption of sulfur dioxide and nitric oxide from flue gas |
US5366634A (en) * | 1992-08-26 | 1994-11-22 | The United States Of America As Represented By The United States Department Of Energy | Waste treatment process for removal of contaminants from aqueous, mixed-waste solutions using sequential chemical treatment and crossflow microfiltration, followed by dewatering |
US5512179A (en) * | 1994-03-24 | 1996-04-30 | Deutsche Carbone Ag | Membrane process for separation of fluid mixtures |
US5643442A (en) * | 1994-07-19 | 1997-07-01 | Exxon Research And Engineering Company | Membrane process for enhanced distillate or hydrotreated distillate aromatics reduction |
US5905182A (en) * | 1996-09-24 | 1999-05-18 | Institut Francais Du Petrole | Process for the purification of benzene that comprises two permeation stages |
US5914435A (en) * | 1996-09-24 | 1999-06-22 | Institut Francais Du Petrole | Process for reducing the benzene content in a hydrocarbon fraction |
US5928518A (en) * | 1996-05-03 | 1999-07-27 | Degussa Aktiengesellschaft | Cross-flow filtration process for separating organic compound by adsorption on inorganic solids |
US6024880A (en) * | 1996-02-26 | 2000-02-15 | Ciora, Jr.; Richard J. | Refining of used oils using membrane- and adsorption-based processes |
US6180008B1 (en) * | 1998-07-30 | 2001-01-30 | W. R. Grace & Co.-Conn. | Polyimide membranes for hyperfiltration recovery of aromatic solvents |
US6187987B1 (en) * | 1998-07-30 | 2001-02-13 | Exxon Mobil Corporation | Recovery of aromatic hydrocarbons using lubricating oil conditioned membranes |
US6273937B1 (en) * | 2000-03-29 | 2001-08-14 | Trans Ionics Corporation | Membrane pervaporation and vapor permeation system |
US6358402B1 (en) * | 1999-12-28 | 2002-03-19 | Exxonmobil Research And Engineering Company | Extractive distillation process for the reduction of sulfur species in hydrocarbons streams |
US20020111524A1 (en) * | 2000-12-28 | 2002-08-15 | Minhas Bhupender S. | Membrane process for separating sulfur compounds from FCC light naphtha |
US20020139719A1 (en) * | 2000-12-28 | 2002-10-03 | Minhas Bhupender S. | Removal of thiophenic sulfur from gasoline by membrane separation process |
US6524469B1 (en) * | 2000-05-16 | 2003-02-25 | Trans Ionics Corporation | Heavy oil upgrading process |
US20030085156A1 (en) * | 2001-11-06 | 2003-05-08 | Schoonover Roger E. | Method for extraction of organosulfur compounds from hydrocarbons using ionic liquids |
US20030094400A1 (en) * | 2001-08-10 | 2003-05-22 | Levy Robert Edward | Hydrodesulfurization of oxidized sulfur compounds in liquid hydrocarbons |
US6579343B2 (en) * | 2001-03-30 | 2003-06-17 | University Of Notre Dame Du Lac | Purification of gas with liquid ionic compounds |
US20030188992A1 (en) * | 2000-04-18 | 2003-10-09 | Halbert Thomas R. | Selective hydroprocessing and mercaptan removal |
US6638419B1 (en) * | 1999-05-05 | 2003-10-28 | Total Raffinage Distribution S.A. | Method for obtaining oil products with low sulphur content by desulfurization of extracts |
US6702945B2 (en) * | 2000-12-28 | 2004-03-09 | Exxonmobil Research And Engineering Company | Ionic membranes for organic sulfur separation from liquid hydrocarbon solutions |
US6736961B2 (en) * | 2001-01-30 | 2004-05-18 | Marathon Oil Company | Removal of sulfur from a hydrocarbon through a selective membrane |
US7018527B2 (en) * | 2001-02-16 | 2006-03-28 | W.R. Grace & Co.-Conn. | Membrane separation for sulfur reduction |
US7267761B2 (en) * | 2003-09-26 | 2007-09-11 | W.R. Grace & Co.-Conn. | Method of reducing sulfur in hydrocarbon feedstock using a membrane separation zone |
US7314565B2 (en) * | 2003-11-18 | 2008-01-01 | Exxonmobil Research And Engineering Company | Method and apparatus for separating aromatic hydrocarbons in an isothermal system |
US7318898B2 (en) * | 2003-11-18 | 2008-01-15 | Exxonmobil Research And Engineering Company | Polymeric membrane wafer assembly and method |
US20080011680A1 (en) * | 2006-07-14 | 2008-01-17 | Partridge Randall D | Membrane separation process using mixed vapor-liquid feed |
US20080035574A1 (en) * | 2006-08-08 | 2008-02-14 | Sabottke Craig Y | Membrane Barrier films and method of use |
US7341663B2 (en) * | 2004-12-16 | 2008-03-11 | The United States Of America As Represented By The Secretary Of Agriculture | Spiral-wound liquid membrane module for separation of fluids and gases |
US7452405B2 (en) * | 2005-02-02 | 2008-11-18 | Intelligent Energy, Inc. | Multi stage sulfur removal system and process for an auxiliary fuel system |
US7459072B2 (en) * | 2003-02-07 | 2008-12-02 | Basf Aktiengesellschaft | Method for processing naphtha |
US7575621B2 (en) * | 2005-01-14 | 2009-08-18 | Cabot Corporation | Separation of metal nanoparticles |
US7619129B2 (en) * | 2003-12-22 | 2009-11-17 | Shell Oil Company | Process for the separation of olefins and paraffins |
US20100270211A1 (en) * | 2009-04-27 | 2010-10-28 | Saudi Arabian Oil Company | Desulfurization and denitrogenation with ionic liquids and metal ion systems |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5107059A (en) * | 1990-12-05 | 1992-04-21 | Exxon Research & Engineering Company | Iso/normal paraffin separation by membrane extraction |
US8343336B2 (en) * | 2007-10-30 | 2013-01-01 | Saudi Arabian Oil Company | Desulfurization of whole crude oil by solvent extraction and hydrotreating |
-
2010
- 2010-06-29 WO PCT/US2010/040335 patent/WO2011002745A1/en active Application Filing
- 2010-06-29 US US12/826,019 patent/US20110000823A1/en not_active Abandoned
Patent Citations (57)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2137206A (en) * | 1937-01-28 | 1938-11-15 | Indian Refining Co | Solvent refining hydrocarbon oil |
US2522065A (en) * | 1947-10-27 | 1950-09-12 | Phillips Petroleum Co | Catalytic desulfurization and reforming process |
US3410794A (en) * | 1966-01-20 | 1968-11-12 | Exxon Research Engineering Co | Separating hydrocarbons with liquid membranes |
US3666660A (en) * | 1970-04-30 | 1972-05-30 | Exxon Research Engineering Co | PURIFICATION OF A HYDROCARBON STREAM WITH Cr{115 {115 {115 {11 IONS IN SOLUTION |
US3719590A (en) * | 1970-12-17 | 1973-03-06 | Exxon Research Engineering Co | Liquid membrane system for separation of components of liquid mixtures |
US4411790A (en) * | 1980-05-22 | 1983-10-25 | Commissariat A L'energie Atomique | Process for the treatment of a hydrocarbon charge by high temperature ultrafiltration |
US4359596A (en) * | 1981-08-03 | 1982-11-16 | Exxon Research And Engineering Co. | Liquid salt extraction of aromatics from process feed streams |
US4816140A (en) * | 1986-04-02 | 1989-03-28 | Institut Francais Du Petrole | Process for deasphalting a hydrocarbon oil |
US4831207A (en) * | 1987-03-05 | 1989-05-16 | Uop | Chemical processing with an operational step sensitive to a feedstream component |
US4831208A (en) * | 1987-03-05 | 1989-05-16 | Uop | Chemical processing with an operational step sensitive to a feedstream component |
US5063186A (en) * | 1987-10-14 | 1991-11-05 | Exxon Research & Engineering Company | Highly aromatic polyurea/urethane membranes and their use of the separation of aromatics from non-aromatics |
US4929358A (en) * | 1989-08-09 | 1990-05-29 | Exxon Research And Engineering Company | Polyurethane-imide membranes and their use for the separation of aromatics from non-aromatics |
US5075006A (en) * | 1989-08-09 | 1991-12-24 | Exxon Research And Engineering Company | Isocyanurate crosslinked polyurethane membranes and their use for the separation of aromatics from non-aromatics |
US5045206A (en) * | 1990-12-05 | 1991-09-03 | Exxon Research & Engineering Company | Selective multi-ring aromatics extraction using a porous, non-selective partition membrane barrier |
US5107056A (en) * | 1990-12-05 | 1992-04-21 | Exxon Research And Engineering Company | Selective separation of naphthenes from paraffins by membrane extraction |
US5039418A (en) * | 1990-12-06 | 1991-08-13 | Exxon Research And Engineering Company | Membrane made from a multi-block polymer comprising an oxazolidone prepolymer chain extended with a compatible second prepolymer and its use in separations |
US5221481A (en) * | 1990-12-06 | 1993-06-22 | Exxon Research And Engineering Company | Multi-block polymer comprising an ester prepolymer, made by combining epoxy with polyester, chain extended with a compatible second prepolymer, the membrane made therefrom and its use for separations |
US5220106A (en) * | 1992-03-27 | 1993-06-15 | Exxon Research And Engineering Company | Organic non-quaternary clathrate salts for petroleum separation |
US5241039A (en) * | 1992-08-14 | 1993-08-31 | Exxon Research & Engineering Company | Polyimide/aliphatic polyester copolymers without pendent carboxylic acid groups (C-2662) |
US5366634A (en) * | 1992-08-26 | 1994-11-22 | The United States Of America As Represented By The United States Department Of Energy | Waste treatment process for removal of contaminants from aqueous, mixed-waste solutions using sequential chemical treatment and crossflow microfiltration, followed by dewatering |
US5320816A (en) * | 1992-10-21 | 1994-06-14 | The Dow Chemical Company | Process for absorption of sulfur dioxide and nitric oxide from flue gas |
US5512179A (en) * | 1994-03-24 | 1996-04-30 | Deutsche Carbone Ag | Membrane process for separation of fluid mixtures |
US5643442A (en) * | 1994-07-19 | 1997-07-01 | Exxon Research And Engineering Company | Membrane process for enhanced distillate or hydrotreated distillate aromatics reduction |
US6024880A (en) * | 1996-02-26 | 2000-02-15 | Ciora, Jr.; Richard J. | Refining of used oils using membrane- and adsorption-based processes |
US5928518A (en) * | 1996-05-03 | 1999-07-27 | Degussa Aktiengesellschaft | Cross-flow filtration process for separating organic compound by adsorption on inorganic solids |
US5905182A (en) * | 1996-09-24 | 1999-05-18 | Institut Francais Du Petrole | Process for the purification of benzene that comprises two permeation stages |
US5914435A (en) * | 1996-09-24 | 1999-06-22 | Institut Francais Du Petrole | Process for reducing the benzene content in a hydrocarbon fraction |
US6187987B1 (en) * | 1998-07-30 | 2001-02-13 | Exxon Mobil Corporation | Recovery of aromatic hydrocarbons using lubricating oil conditioned membranes |
US6180008B1 (en) * | 1998-07-30 | 2001-01-30 | W. R. Grace & Co.-Conn. | Polyimide membranes for hyperfiltration recovery of aromatic solvents |
US6638419B1 (en) * | 1999-05-05 | 2003-10-28 | Total Raffinage Distribution S.A. | Method for obtaining oil products with low sulphur content by desulfurization of extracts |
US6358402B1 (en) * | 1999-12-28 | 2002-03-19 | Exxonmobil Research And Engineering Company | Extractive distillation process for the reduction of sulfur species in hydrocarbons streams |
US6273937B1 (en) * | 2000-03-29 | 2001-08-14 | Trans Ionics Corporation | Membrane pervaporation and vapor permeation system |
US20030188992A1 (en) * | 2000-04-18 | 2003-10-09 | Halbert Thomas R. | Selective hydroprocessing and mercaptan removal |
US6524469B1 (en) * | 2000-05-16 | 2003-02-25 | Trans Ionics Corporation | Heavy oil upgrading process |
US6702945B2 (en) * | 2000-12-28 | 2004-03-09 | Exxonmobil Research And Engineering Company | Ionic membranes for organic sulfur separation from liquid hydrocarbon solutions |
US20020139719A1 (en) * | 2000-12-28 | 2002-10-03 | Minhas Bhupender S. | Removal of thiophenic sulfur from gasoline by membrane separation process |
US6649061B2 (en) * | 2000-12-28 | 2003-11-18 | Exxonmobil Research And Engineering Company | Membrane process for separating sulfur compounds from FCC light naphtha |
US20020111524A1 (en) * | 2000-12-28 | 2002-08-15 | Minhas Bhupender S. | Membrane process for separating sulfur compounds from FCC light naphtha |
US6736961B2 (en) * | 2001-01-30 | 2004-05-18 | Marathon Oil Company | Removal of sulfur from a hydrocarbon through a selective membrane |
US7048846B2 (en) * | 2001-02-16 | 2006-05-23 | W.R. Grace & Co.-Conn. | Membrane separation for sulfur reduction |
US7041212B2 (en) * | 2001-02-16 | 2006-05-09 | W.R. Grace & Co. - Conn. | Membrane separation for sulfur reduction |
US7018527B2 (en) * | 2001-02-16 | 2006-03-28 | W.R. Grace & Co.-Conn. | Membrane separation for sulfur reduction |
US6579343B2 (en) * | 2001-03-30 | 2003-06-17 | University Of Notre Dame Du Lac | Purification of gas with liquid ionic compounds |
US20030094400A1 (en) * | 2001-08-10 | 2003-05-22 | Levy Robert Edward | Hydrodesulfurization of oxidized sulfur compounds in liquid hydrocarbons |
US7001504B2 (en) * | 2001-11-06 | 2006-02-21 | Extractica, Llc. | Method for extraction of organosulfur compounds from hydrocarbons using ionic liquids |
US20030085156A1 (en) * | 2001-11-06 | 2003-05-08 | Schoonover Roger E. | Method for extraction of organosulfur compounds from hydrocarbons using ionic liquids |
US7459072B2 (en) * | 2003-02-07 | 2008-12-02 | Basf Aktiengesellschaft | Method for processing naphtha |
US7267761B2 (en) * | 2003-09-26 | 2007-09-11 | W.R. Grace & Co.-Conn. | Method of reducing sulfur in hydrocarbon feedstock using a membrane separation zone |
US7314565B2 (en) * | 2003-11-18 | 2008-01-01 | Exxonmobil Research And Engineering Company | Method and apparatus for separating aromatic hydrocarbons in an isothermal system |
US7318898B2 (en) * | 2003-11-18 | 2008-01-15 | Exxonmobil Research And Engineering Company | Polymeric membrane wafer assembly and method |
US7619129B2 (en) * | 2003-12-22 | 2009-11-17 | Shell Oil Company | Process for the separation of olefins and paraffins |
US7341663B2 (en) * | 2004-12-16 | 2008-03-11 | The United States Of America As Represented By The Secretary Of Agriculture | Spiral-wound liquid membrane module for separation of fluids and gases |
US7575621B2 (en) * | 2005-01-14 | 2009-08-18 | Cabot Corporation | Separation of metal nanoparticles |
US7452405B2 (en) * | 2005-02-02 | 2008-11-18 | Intelligent Energy, Inc. | Multi stage sulfur removal system and process for an auxiliary fuel system |
US20080011680A1 (en) * | 2006-07-14 | 2008-01-17 | Partridge Randall D | Membrane separation process using mixed vapor-liquid feed |
US20080035574A1 (en) * | 2006-08-08 | 2008-02-14 | Sabottke Craig Y | Membrane Barrier films and method of use |
US20100270211A1 (en) * | 2009-04-27 | 2010-10-28 | Saudi Arabian Oil Company | Desulfurization and denitrogenation with ionic liquids and metal ion systems |
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