WO2012087383A1 - Processes for ionic liquid catalyzed upgrading of oxygenate containing hydrocarbon feedstocks - Google Patents
Processes for ionic liquid catalyzed upgrading of oxygenate containing hydrocarbon feedstocks Download PDFInfo
- Publication number
- WO2012087383A1 WO2012087383A1 PCT/US2011/046369 US2011046369W WO2012087383A1 WO 2012087383 A1 WO2012087383 A1 WO 2012087383A1 US 2011046369 W US2011046369 W US 2011046369W WO 2012087383 A1 WO2012087383 A1 WO 2012087383A1
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- Prior art keywords
- hydrocarbon stream
- hydrocarbon
- catalyst
- ionic liquid
- process according
- Prior art date
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- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 238
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 237
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 235
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 58
- 150000001336 alkenes Chemical class 0.000 claims abstract description 107
- 239000003054 catalyst Substances 0.000 claims abstract description 81
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 79
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- 230000018044 dehydration Effects 0.000 claims description 37
- 238000006297 dehydration reaction Methods 0.000 claims description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 18
- 238000005804 alkylation reaction Methods 0.000 claims description 18
- 230000029936 alkylation Effects 0.000 claims description 16
- -1 oxides Chemical class 0.000 claims description 16
- 238000006384 oligomerization reaction Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 239000003463 adsorbent Substances 0.000 claims description 7
- 230000000737 periodic effect Effects 0.000 claims description 6
- 239000011959 amorphous silica alumina Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 239000012736 aqueous medium Substances 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 150000003568 thioethers Chemical class 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002199 base oil Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 description 29
- 238000006298 dechlorination reaction Methods 0.000 description 15
- 239000000203 mixture Substances 0.000 description 11
- 239000012071 phase Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000003426 co-catalyst Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000012084 conversion product Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003518 caustics Substances 0.000 description 3
- 150000001805 chlorine compounds Chemical group 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000002051 biphasic effect Effects 0.000 description 1
- XHIHMDHAPXMAQK-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F XHIHMDHAPXMAQK-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000000382 dechlorinating effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000013386 optimize process Methods 0.000 description 1
- 125000004817 pentamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000005208 trialkylammonium group Chemical group 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Classifications
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- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
- C07C1/30—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms by splitting-off the elements of hydrogen halide from a single molecule
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- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
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- C07C2/56—Addition to acyclic hydrocarbons
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- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
- C07C2527/04—Sulfides
- C07C2527/047—Sulfides with chromium, molybdenum, tungsten or polonium
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
- C07C2527/04—Sulfides
- C07C2527/047—Sulfides with chromium, molybdenum, tungsten or polonium
- C07C2527/051—Molybdenum
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/08—Halides
- C07C2527/10—Chlorides
- C07C2527/11—Hydrogen chloride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/08—Halides
- C07C2527/12—Fluorides
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/14—Phosphorus; Compounds thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/22—Higher olefins
Definitions
- the present invention relates to ionic liquid catalyzed processes for upgrading oxygenate containing hydrocarbon feedstocks.
- Ionic liquid catalysts may find applications in a range of hydrocarbon conversion processes.
- An example of an ionic liquid catalyzed hydrocarbon conversion reaction is the alkylation of isoparaffins with olefins (see, e.g., U.S. Pat. No. 7,432,408 to Timken et al.).
- a widely used conventional process for the alkylation of isoparaffins with olefins is catalyzed by sulfuric acid or hydrofluoric acid.
- ionic liquid catalyzed hydrocarbon conversion processes offer a number of advantages over conventional processes, including: lower capital expenditure on plants, lower operating expenditure, lower catalyst inventory volume, lower catalyst make-up rate, expansion of usable feeds, and higher product yield.
- oxygenates may be defined as any oxygen-containing hydrocarbon compound.
- oxygenates include alcohols, carboxylic acids, aldehydes, esters, ketones, and the like. Even relatively trace amounts of some oxygenates may deactivate ionic liquid catalysts. As a result, some potentially useful feedstocks for ionic liquid catalyzed hydrocarbon conversion reactions may have been considered unsuitable due to the presence of oxygenates. Therefore, there is a need for the effective removal of
- oxygenates in oxygenate containing hydrocarbon streams prior to contacting the hydrocarbon stream with an ionic liquid catalyst may provide an increased level of catalytic activity, for example, as disclosed by U.S. Pat. No. 7,432,408 to Timken et al.
- anhydrous HCI or organic chloride may be added as co-catalyst to direct the ionic liquid catalyzed reactions to the desired level of activity and selectivity (see, e.g., U.S. Pat. Nos.7,495,144 to Elomari, and 7,531 ,707 to Harris et al.).
- Figure 1 represents a scheme for an ionic liquid catalyzed hydrocarbon conversion process using an oxygenate containing hydrocarbon feed, according to an embodiment of the present invention
- Figure 2 represents a scheme for an olefin enrichment process using an oxygenate containing hydrocarbon feed, according to an aspect of the process of Figure 1 .
- the present invention provides hydrocarbon conversion processes involving the treatment of oxygenate containing hydrocarbon streams to provide an olefin enriched hydrocarbon stream, which may be contacted with an ionic liquid catalyst to provide a converted hydrocarbon stream comprising organic halide (e.g., chloride) components.
- the converted hydrocarbon stream may be treated in a dechlorination zone to remove organic chloride from the converted hydrocarbon stream, e.g., by treatment with hot caustic, an adsorbent, or a hydrodechlorination catalyst, to provide a dechlorinated hydrocarbon product.
- an ionic liquid catalyzed hydrocarbon conversion process comprising treating an oxygenate containing hydrocarbon stream in an olefin enrichment zone under olefin enrichment conditions to provide an olefin enriched hydrocarbon stream, contacting the olefin enriched hydrocarbon stream with an ionic liquid catalyst in a hydrocarbon conversion zone under hydrocarbon conversion conditions to provide a converted hydrocarbon stream comprising one or more halogenated components, and removing the one or more halogenated components from the converted hydrocarbon stream to provide a
- the present invention also provides an ionic liquid catalyzed hydrocarbon conversion process comprising contacting an oxygenate containing hydrocarbon stream with a dehydration catalyst in a dehydration zone under dehydration conditions to provide an olefin enriched hydrocarbon stream, contacting the olefin enriched hydrocarbon stream with an ionic liquid catalyst in an alkylation zone under alkylation conditions to provide an alkylate product comprising one or more halogenated components, and contacting the alkylate product with a hydrodechlorination catalyst in the presence of hydrogen in a hydrodechlorination zone under
- hydrodechlorination conditions to provide a dechlorinated alkylate product.
- the present invention further provides an ionic liquid catalyzed hydrocarbon conversion process comprising contacting an oxygenate containing hydrocarbon stream with a dehydration catalyst in a dehydration zone under dehydration conditions to provide an olefin enriched hydrocarbon stream, contacting the olefin enriched hydrocarbon stream with an ionic liquid catalyst in an oligomerization zone under oligomerization conditions to provide an oligomeric product comprising one or more halogenated components, and contacting the oligomeric product with a hydrodechlorination catalyst in the presence of hydrogen in a
- hydrodechlorination zone under hydrodechlorination conditions to provide a dechlorinated oligomeric product.
- Periodic Table is the lUPAC version of the Periodic Table of the Elements dated June 22, 2007, and the numbering scheme for the Periodic Table Groups is as described in Chemical and Engineering News, 63(5), 27 (1985).
- oxygenate containing hydrocarbon streams may be upgraded to high value products using ionic liquid catalyzed processes.
- a hydrocarbon stream containing substantial quantities of both olefins and oxygenates may be pre- treated in an olefin enrichment zone under olefin enrichment conditions to provide an oxygenate depleted, olefin enriched hydrocarbon stream.
- alcohols in an oxygenate containing hydrocarbon stream may be converted, via dehydration, to olefins.
- the depletion of oxygenates in the oxygenate containing hydrocarbon stream may prevent oxygenate- mediated deactivation of the ionic liquid catalyst.
- olefin enrichment of the hydrocarbon stream increases the olefin content of the feed, thereby increasing the product yield obtained from the ionic liquid catalyzed hydrocarbon conversion process.
- the olefins in the olefin enriched hydrocarbon stream may be oligomerized by contacting the olefin enriched hydrocarbon stream with an ionic liquid catalyst under oligomehzation conditions.
- the olefin enriched hydrocarbon stream may comprise isoparaffins as well as olefins, and the olefins may be alkylated with the isoparaffins by contacting the olefin enriched hydrocarbon stream with an ionic liquid catalyst under alkylation conditions.
- an ancillary hydrocarbon stream e.g., comprising isoparaffins
- an ancillary hydrocarbon stream may be contacted with the olefin enriched hydrocarbon stream in the presence of an ionic liquid catalyst in the hydrocarbon conversion zone.
- isoparaffin containing streams include, but are not limited to, FCC naphtha, hydrocracker naphtha, coker naphtha, Fischer-Tropsch condensate, and cracked naphtha.
- hydrocarbon conversion conditions in the hydrocarbon conversion zone may be suitable for both alkylation and oligomehzation, such that both alkylation and oligomerization may take place concurrently in a single hydrocarbon conversion zone.
- Ionic liquid catalyzed processes of the present invention may be performed in the presence of a co-catalyst or promoter to provide enhanced or improved catalytic activity.
- a co-catalyst according to the present invention may comprise, for example, anhydrous HCI or organic chloride (see, e.g., U.S. Pat. Nos.7,495, 144 to Elomari, and 7,531 ,707 to Harris et al., the disclosures of which are incorporated by reference herein in their entirety).
- HCI may be formed in situ in the reactor during the hydrocarbon conversion process.
- Products and/or by-products from ionic liquid catalyzed hydrocarbon conversion processes may typically include one or more halogenated components, as disclosed in commonly assigned co-pending patent application Serial No. 12/847,313 entitled Hydrodechlorination of ionic liquid- derived hydrocarbon products, filed on July 30, 2010, the disclosure of which is incorporated by reference herein in its entirety.
- Products of ionic liquid catalyzed hydrocarbon conversion processes of the instant invention may be dechlorinated in a dechlorination zone, for example, by hot caustic treatment, adsorption of organochlorine species using a suitable adsorbent, or catalytic hydrodechlorination, to provide one or more dechlorinated product(s).
- catalytic hydrodechlorination may involve contacting the hydrocarbon conversion stream from an ionic liquid catalyzed reaction with a hydrodechlorination catalyst in a
- the chloride content of the dechlorinated products will be sufficiently low to allow the blending of such materials into refinery product streams.
- processes according to the present invention may use a catalytic composition comprising at least one metal halide and at least one quaternary ammonium halide and/or at least one amine halohydride.
- the ionic liquid catalyst can be any halogen aluminate ionic liquid catalyst, e.g., comprising an alkyi substituted quaternary amine halide, an alkyi substituted pyridinium halide, or an alkyi substituted imidazolium halide of the general formula N + R 4 X " .
- ionic liquid catalysts useful in practicing the present invention may be represented by the general formulas A and B,
- X is chloride.
- an exemplary metal halide that may be used in accordance with the present invention is aluminum chloride (AICI3).
- Quaternary ammonium halides which can be used in accordance with the present invention include those described in U.S. Pat. No. 5,750,455, the disclosure of which is incorporated by reference herein.
- the ionic liquid catalyst may be a chloroaluminate ionic liquid prepared by mixing AICI3 and an alkyl substituted pyridinium halide, an alkyl substituted imidazolium halide, a trialkylammonium hydrohalide, or a tetraalkylammonium halide, as disclosed in commonly assigned U.S. Pat. No. 7,495,144, the disclosure of which is incorporated by reference herein in its entirety.
- the ionic liquid catalyst may comprise N-butylpyridinium heptachlorodialuminate ionic liquid, which may be prepared, for example, by combining AlCls with a salt of the general formula A, supra, wherein R is n- butyl and X is chloride.
- the present invention is not limited to any particular ionic liquid catalyst composition(s).
- feeds for the present invention may comprise oxygenate- and olefin containing hydrocarbon streams, such as various streams in a petroleum refinery, a gas-to-liquid conversion plant, or a coal-to-liquid (CTL) conversion plant, including streams from Fischer-Tropsch synthesis units, naphtha crackers, middle distillate crackers or wax crackers, as well as FCC offgas, FCC light naphtha, coker offgas, coker naphtha, and the like.
- Some such streams may contain significant amounts of isoparaffin(s) in addition to olefin(s) and oxygenates.
- the oxygenate containing hydrocarbon stream may comprise a Fischer-Tropsch condensate.
- an oxygenate containing hydrocarbon stream useful in practicing the instant invention may typically comprise from about 1 to 70 wt% olefins, and from about 0.1 to 30 wt% oxygenates.
- the oxygenate components of the oxygenated olefin containing hydrocarbon stream may comprise from about 0.1 to 30 wt% C2 - C20 alkanols, together with Ci - C20 carboxylic acids.
- Such streams may be fed to an olefin enrichment unit or zone to provide an olefin enriched hydrocarbon stream.
- the olefin enriched hydrocarbon stream may typically comprise from about 1 to 90 wt% olefins, and typically less than about 0.5 wt% oxygenates.
- the olefin enriched hydrocarbon stream may be fed to a hydrocarbon conversion unit 1 10 of the present invention (see, e.g., Figure 1 ).
- the oxygenate containing hydrocarbon stream may comprise a mixture of hydrocarbons having a range of chain lengths and thus a wide boiling range.
- the oxygenate containing hydrocarbon stream may contain two or more olefins selected from ethylene, propylene, butylenes, pentenes, and up to C36 olefins.
- the oxygenate containing hydrocarbon stream may comprise alpha-olefins and/or internal olefins (i.e., having an internal double bond).
- the olefins may be either straight chain, or branched, or a mixture of the two.
- the oxygenate containing hydrocarbon stream may comprise a mixture of mostly linear olefins from C2 to about C36.
- the olefins in the oxygenate containing hydrocarbon stream may comprise at least about 10% of alpha-olefin species. In a sub-embodiment, the olefins in the oxygenate containing hydrocarbon stream may comprise predominantly alpha-olefins.
- olefins in the olefin enriched hydrocarbon stream may undergo oligomerization when contacted with an ionic liquid catalyst in hydrocarbon conversion unit 1 10 (see, e.g., Figure 1 ).
- Ionic liquid catalyzed olefin oligomerization may take place under the same or similar conditions as ionic liquid catalyzed olefin-isoparaffin alkylation.
- both olefin oligomerization and olefin/isoparaffin alkylation may take place in a single hydrocarbon conversion zone.
- a hydrocarbon conversion system 10 for processing an oxygenate containing hydrocarbon feed using an ionic liquid catalyst may include an olefin enrichment unit 100, a hydrocarbon conversion unit 1 10, and a dechlorination unit 120.
- an oxygenate containing hydrocarbon stream may be treated in olefin enrichment unit 100 under olefin enrichment conditions to provide an olefin enriched hydrocarbon stream.
- Olefin enrichment unit 100 may also be referred to herein as an olefin enrichment zone.
- the oxygenate containing hydrocarbon stream may typically comprise from about 0.1 to 30 wt% oxygenates, and often from about 0.1 to 20 wt% oxygenates.
- the oxygenate containing hydrocarbon stream may be enriched in olefins by converting the oxygenates in the stream to olefins.
- oxygenates in the oxygenate containing hydrocarbon stream may comprise alcohols, and the alcohols may be converted to olefins by dehydration of the alcohol by treatment with a dehydrating catalyst.
- the oxygenates in the oxygenate containing hydrocarbon stream may be comprised predominantly of primary alcohols.
- treating the oxygenate containing hydrocarbon stream in olefin enrichment unit 100 may further include the removal of oxygenates and/or water from the oxygenate containing hydrocarbon stream (see, for example, Figure 2).
- the olefin enriched hydrocarbon stream from unit 100 may be introduced into hydrocarbon conversion unit 1 10.
- Hydrocarbon conversion unit 1 10 may also be referred to herein as a hydrocarbon conversion zone.
- the olefin enriched hydrocarbon stream may typically comprise from about 1 to 70 wt% olefins, and often from about 10 to 60 wt% olefins.
- the olefin enriched hydrocarbon stream may typically comprise less than about 0.5 wt% oxygenates, and often less than about 0.3 wt% oxygenates.
- the olefin enriched hydrocarbon stream and the ionic liquid catalyst may be introduced into hydrocarbon conversion unit 1 10 via separate inlet ports (not shown).
- the olefin enriched hydrocarbon stream may be contacted with the ionic liquid catalyst in hydrocarbon conversion unit 1 10 under hydrocarbon conversion conditions to provide a converted hydrocarbon stream.
- the ionic liquid catalyst may comprise a
- the feeds to hydrocarbon conversion unit 1 10 may further include a catalyst promoter, such as anhydrous HCI or an alkyl halide.
- the catalyst promoter may comprise a C2 - Ce alkyl chloride, such as n-butyl chloride or i-butyl chloride.
- Hydrocarbon conversion unit 1 10 may be vigorously mixed to promote contact between reactant(s) and ionic liquid catalyst.
- Hydrocarbon conversion conditions within hydrocarbon conversion unit 1 10 may be adjusted to optimize process performance for a particular
- the hydrocarbon conversion conditions may comprise oligomerization conditions, such that olefins in the olefin enriched stream may be
- the hydrocarbon conversion conditions may comprise alkylation conditions, such that olefins in the olefin enriched stream may be alkylated with isoparaffins to provide an alkylate product.
- the hydrocarbon conversion conditions may comprise both oligomerization conditions and alkylation conditions, such that oligomerization and alkylation reactions may occur concurrently within hydrocarbon conversion unit 1 10.
- an ancillary hydrocarbon stream e.g., comprising isoparaffins, may optionally be fed to hydrocarbon conversion unit 1 10, and the ancillary hydrocarbon stream may be contacted with the olefin enriched hydrocarbon stream in the presence of ionic liquid catalyst in the hydrocarbon conversion zone.
- hydrocarbon conversion unit 1 10 may contain a mixture comprising ionic liquid catalyst and a hydrocarbon phase.
- the hydrocarbon phase may comprise at least one hydrocarbon conversion product of the ionic liquid catalyzed reaction.
- the ionic liquid catalyst may be separated from the hydrocarbon phase via a catalyst/hydrocarbon separator (not shown), wherein the hydrocarbon and ionic liquid catalyst phases may be allowed to settle under gravity, by using a coalescer, or by a combination thereof.
- a catalyst/hydrocarbon separator not shown
- the hydrocarbon phase may be fed to dechlorination unit 120, while at least a portion of the ionic liquid phase may be recycled to hydrocarbon conversion unit 1 10.
- the hydrocarbon phase fed to dechlorination unit 120 may be referred to herein as a converted hydrocarbon stream.
- the converted hydrocarbon stream provided by hydroconversion unit 1 10 may comprise a distillate enriched stream.
- the converted hydrocarbon stream provided by hydroconversion unit 1 10 may comprise a base oil (700T+) enriched stream. Reaction conditions for ionic liquid catalyzed hydrocarbon conversions
- hydrocarbon conversion reactions in ionic liquids are generally biphasic and occur at the interface in the liquid state.
- the volume of ionic liquid catalyst in the reactor may be generally in the range from about 1 to 70 vol%, and usually from about 4 to 50 vol%.
- vigorous mixing e.g., stirring or Venturi nozzle dispensing
- the reaction temperature may be generally in the range from about -40°F to +480°F, typically from about -4°F to +210°F, and often from about +40°F to +140°F.
- the reactor pressure may be in the range from atmospheric pressure to about 8000 kPa. Typically, the reactor pressure will be sufficient to keep the reactants in the liquid phase.
- Residence time of reactants in the reactor may generally be in the range from a few seconds to hours, and usually from about 0.5 min to 60 min.
- the reactants may be introduced in an isoparaffin Olefin molar ratio generally in the range from about 1 to 100, more typically from about 2 to 50, and often from about 2 to 20.
- Heat generated by the reaction may be dissipated using various means well known to the skilled artisan. With continued operation of hydrocarbon conversion unit 1 10, the ionic liquid catalyst may become partially deactivated or spent.
- At least a portion of the ionic liquid phase may be fed to a catalyst regeneration unit (not shown) for regeneration of the ionic liquid catalyst.
- a catalyst regeneration unit (not shown) for regeneration of the ionic liquid catalyst.
- the converted hydrocarbon stream obtained from hydrocarbon conversion unit 1 10 may typically comprise one or more halogenated components.
- the converted hydrocarbon stream may have an organic chloride content generally greater than about 50 ppm, typically greater than about 200 ppm, and often greater than about 1000 ppm.
- the converted hydrocarbon stream from hydrocarbon conversion unit 1 10 may have an organic chloride content generally in the range from about 50 ppm to 5000 ppm, typically from about 100 ppm to 4000 ppm, and often from about 200 ppm to 3000 ppm.
- the converted hydrocarbon stream may be fed to dechlorination unit 120 for dechlorinating the
- Dechlorination unit 120 may also be referred to herein as a dechlorination zone.
- the converted hydrocarbon stream may be dechlorinated by treatment with hot caustic.
- the converted hydrocarbon stream may be dechlorinated by adsorption of organochlorine species using an adsorbent such as zeolites, clay, alumina, silica-alumina, and the like.
- dechlorination unit 120 may comprises a hydrodechlorination unit or zone, and the converted hydrocarbon stream may be fed to dechlorination unit 120 for
- hydrodechlorinating the hydrocarbon product(s) by contacting the converted hydrocarbon stream with a hydrodechlorination catalyst in the presence of hydrogen under hydrodechlorination conditions to provide one or more dechlorinated hydrocarbon products.
- the hydrodechlorination catalyst may comprise an element selected from the group consisting of elements of Groups 6, 8, 9, 10, and 1 1 of the Periodic Table, and combinations thereof, present as metals, oxides, or sulfides. In a sub-embodiment, the
- hydrodechlorination catalyst may comprise an element selected from Pd, Pt, Au, Ni, Co, Mo, and W, and their mixtures, present as metals, oxides, or sulfides.
- the hydrodechlorination catalyst may further comprise a support.
- the support may comprise an inorganic porous material, such as a refractory oxide, or activated carbon.
- refractory oxide support materials include alumina, silica, titania, alumina-silica, and zirconia, or the like, and combinations thereof.
- the hydrodechlorination catalyst may comprise a noble metal on a refractory oxide support.
- the hydrodechlorination catalyst may comprise Pd or Pt or a mixture of Pd and Pt, e.g., in the range from about 0.05 to 3.0 wt% of Pd or Pt or a mixture thereof.
- the hydrodechlorination conditions within the hydrodechlorination zone may include a reaction temperature generally in the range from about 300°F to 750°F, and typically from about 400°F to 650°F.
- the hydrodechlorination conditions may further include a reaction pressure generally in the range from about 100 to 5000 psig, and typically from about 200 to 2000 psig.
- a liquid hourly space velocity (LHSV) feed rate to the hydrodechlorination zone may be generally in the range from about 0.1 to 50 hr "1 , and typically from about 0.2 to 10 hr "1 .
- a hydrogen supply to the hydrodechlorination zone may be generally in the range from about 50 to 8000 standard cubic feet per barrel (SCFB) of the hydrocarbon stream, and typically from about 100 to 5000 SCFB.
- SCFB standard cubic feet per barrel
- the dechlorinated hydrocarbon product obtained from dechlorination unit 120 may typically have a much lower chloride content as compared with that of the converted hydrocarbon stream fed to dechlorination unit 120.
- a first chloride content of the hydrocarbon stream fed to dechlorination unit 120 may be greater than about 50 ppm.
- the hydrocarbon stream fed to dechlorination unit 120 may have an organic chloride content generally in the range from about 50 ppm to 5000 ppm, typically from about 100 ppm to 4000 ppm, and often from about 200 ppm to 3000 ppm.
- the organic chloride content of the dechlorinated hydrocarbon product(s) obtained from hydrocarbon conversion system 10 may be greatly decreased as compared with that of the converted hydrocarbon stream.
- a second chloride content of dechlorinated hydrocarbon product(s) provided by processes of the present invention may be less than 50 ppm, typically less than about 10 ppm, and often equal to or less than about 5 ppm. Analogous results will be obtained when the present invention is practiced using ionic liquid catalyst systems based on halides other than chlorides.
- the dechlorinated hydrocarbon product(s) may comprise a dechlorinated distillate fuel, such as dechlorinated jet fuel, or dechlorinated diesel fuel, and the like.
- Figure 2 represents a scheme for an olefin enrichment process using an oxygenate containing hydrocarbon feed, according to an aspect of the process of Figure 1 .
- the oxygenate containing hydrocarbon stream may be, for example, any of various hydrocarbon streams, which contain significant or substantial amounts of oxygenates, in a petroleum refinery, a gas-to-liquid conversion plant, or a coal-to-liquid conversion plant, and the like.
- an oxygenate containing hydrocarbon stream of the present invention may comprise Fischer-Tropsch condensate.
- olefin enrichment unit 100 for treating an oxygenate containing hydrocarbon stream may include an oxygenate dehydration unit 102.
- Oxygenate dehydration unit 102 may include a dehydration catalyst.
- Oxygenate dehydration unit 102 may also be referred to herein as a dehydration zone.
- a process for treating an oxygenate containing hydrocarbon stream may comprise dehydrating oxygenates in the oxygenate containing hydrocarbon stream by contacting the oxygenate containing hydrocarbon stream with the dehydration catalyst in the dehydration zone under dehydration conditions.
- hydrocarbon stream may comprise predominantly alcohols.
- the alcohols may be converted to olefins by contacting the oxygenate containing hydrocarbon stream with the dehydration catalyst to provide an olefin enriched
- the olefin enriched hydrocarbon stream may comprise less than about 0.5 wt% oxygen. In a sub-embodiment, the olefin enriched hydrocarbon stream may comprise less than about 0.3 wt% oxygen.
- the dehydration catalyst may be selected from the group consisting of alumina and amorphous silica-alumina.
- the dehydration catalyst may comprise alumina doped with an element selected from the group consisting of phosphorus, boron, fluorine, zirconium, titanium, gallium, magnesium, and combinations thereof.
- the dehydration catalyst may comprise amorphous silica- alumina doped with an element selected from the group consisting of phosphorus, boron, fluorine, zirconium, titanium, gallium, magnesium and combinations thereof.
- the degree of acidity of the dehydration catalyst may be selected, e.g., by the judicious doping of alumina or amorphous silica-alumina, to determine not only the degree of olefin isomerization, but also the proportion of alpha-olefins to total olefins in the olefin enriched hydrocarbon stream.
- the olefin composition of the olefin enriched hydrocarbon stream may in turn determine the composition of product(s) obtained from hydrocarbon conversion system 10.
- the dehydration conditions for dehydrating oxygenates in the oxygenate containing hydrocarbon stream may include a temperature in the range from about 400°F to 800°F, a pressure in the range from about 10 to 5000 psig, and a liquid hourly space velocity (LHSV) feed rate in the range from about 0.1 to 50 hr "1 .
- olefin enrichment unit 100 may optionally still further include one or more of an oxygenate extraction unit 104, an oxygenate adsorption unit 106, and a second distillation unit 108.
- the treatment of an oxygenate containing hydrocarbon stream according to the present invention may optionally include the use of oxygenate extraction unit 104 for extracting or washing the hydrocarbon stream with an aqueous medium, whereby residual oxygenates may be removed from the hydrocarbon stream exiting dehydration unit 102.
- the aqueous medium may comprise liquid water.
- the aqueous medium may comprise water at a pH > 7.0.
- an olefin enrichment process of the present invention may optionally further include contacting the hydrocarbon stream with an adsorbent in oxygenate adsorption unit 106, whereby residual oxygenates and/or water may be removed from the hydrocarbon stream.
- the adsorbent may comprise a molecular sieve, such as zeolite 13X. Zeolites and molecular sieves are well known in the art (see, for example, Zeolites in Industrial Separation and Catalysis, By Santi
- the hydrocarbon stream may be fed to adsorption unit 106 from oxygenate extraction unit 104.
- oxygenate extraction unit 104 may be omitted or bypassed, and the hydrocarbon stream may be fed to adsorption unit 106 directly from dehydration unit 102.
- olefin enrichment unit 100 may optionally further include a second distillation unit 108.
- second distillation unit 108 may be used to remove a heavy fraction from the hydrocarbon stream prior to ionic liquid catalyzed hydrocarbon conversion of the olefin enriched hydrocarbon stream.
- the nature of the heavy fraction, if any, to be separated from the olefin enriched hydrocarbon stream may vary, for example, according to the feedstocks used and the product(s) targeted from the ionic liquid catalyzed hydrocarbon conversion processes of various embodiments of the present invention.
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Abstract
Ionic liquid catalyzed hydrocarbon conversion processes for upgrading oxygenate containing olefinic hydrocarbon feedstocks may involve treating an oxygenate containing hydrocarbon stream to provide an olefin enriched hydrocarbon stream, which may be contacted with an ionic liquid catalyst under hydrocarbon conversion conditions to provide a converted hydrocarbon stream containing one or more halogenated components; such components may be removed from the converted hydrocarbon stream to provide one or more dechlorinated hydrocarbon products.
Description
PROCESSES FOR IONIC LIQUID CATALYZED UPGRADING OF
OXYGENATE CONTAINING HYDROCARBON FEEDSTOCKS
TECHNICAL FIELD
The present invention relates to ionic liquid catalyzed processes for upgrading oxygenate containing hydrocarbon feedstocks.
BACKGROUND
Ionic liquid catalysts may find applications in a range of hydrocarbon conversion processes. An example of an ionic liquid catalyzed hydrocarbon conversion reaction is the alkylation of isoparaffins with olefins (see, e.g., U.S. Pat. No. 7,432,408 to Timken et al.). In contrast, a widely used conventional process for the alkylation of isoparaffins with olefins is catalyzed by sulfuric acid or hydrofluoric acid. Apart from environmental, health and safety concerns related to the use of large volumes of H2SO4 or HF, ionic liquid catalyzed hydrocarbon conversion processes offer a number of advantages over conventional processes, including: lower capital expenditure on plants, lower operating expenditure, lower catalyst inventory volume, lower catalyst make-up rate, expansion of usable feeds, and higher product yield.
Many hydrocarbon streams may contain substantial amounts of oxygenates. An "oxygenate" may be defined as any oxygen-containing hydrocarbon compound. Examples of oxygenates include alcohols, carboxylic acids, aldehydes, esters, ketones, and the like. Even relatively trace amounts of some oxygenates may deactivate ionic liquid catalysts. As a result, some potentially useful feedstocks for ionic liquid catalyzed hydrocarbon conversion reactions may have been considered unsuitable due to the presence of oxygenates. Therefore, there is a need for the effective removal of
oxygenates in oxygenate containing hydrocarbon streams prior to contacting the hydrocarbon stream with an ionic liquid catalyst.
The presence of a catalyst promoter or co-catalyst with an ionic liquid catalyst may provide an increased level of catalytic activity, for example, as disclosed by U.S. Pat. No. 7,432,408 to Timken et al. Typically, anhydrous HCI or organic chloride may be added as co-catalyst to direct the ionic liquid catalyzed reactions to the desired level of activity and selectivity (see, e.g., U.S. Pat. Nos.7,495,144 to Elomari, and 7,531 ,707 to Harris et al.). However, the presence of chloride in the reactor may result in hydrocarbon conversion products having an unacceptably high organic chloride content. As an example, the removal of organic chloride components from liquid fuels may be desirable to prevent the formation of unwanted by-products during combustion (see, for example, U.S. Pat. No. 7,538,256 to Driver et al.). Accordingly, there is a further need for the effective removal of halogenated components from ionic liquid catalyzed hydrocarbon conversion products.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 represents a scheme for an ionic liquid catalyzed hydrocarbon conversion process using an oxygenate containing hydrocarbon feed, according to an embodiment of the present invention; and
Figure 2 represents a scheme for an olefin enrichment process using an oxygenate containing hydrocarbon feed, according to an aspect of the process of Figure 1 .
SUMMARY
The present invention provides hydrocarbon conversion processes involving the treatment of oxygenate containing hydrocarbon streams to provide an olefin enriched hydrocarbon stream, which may be contacted with an ionic liquid catalyst to provide a converted hydrocarbon stream comprising organic halide (e.g., chloride) components. The converted hydrocarbon stream may
be treated in a dechlorination zone to remove organic chloride from the converted hydrocarbon stream, e.g., by treatment with hot caustic, an adsorbent, or a hydrodechlorination catalyst, to provide a dechlorinated hydrocarbon product.
According to one aspect of the present invention there is provided an ionic liquid catalyzed hydrocarbon conversion process comprising treating an oxygenate containing hydrocarbon stream in an olefin enrichment zone under olefin enrichment conditions to provide an olefin enriched hydrocarbon stream, contacting the olefin enriched hydrocarbon stream with an ionic liquid catalyst in a hydrocarbon conversion zone under hydrocarbon conversion conditions to provide a converted hydrocarbon stream comprising one or more halogenated components, and removing the one or more halogenated components from the converted hydrocarbon stream to provide a
dechlorinated hydrocarbon product.
In an embodiment, the present invention also provides an ionic liquid catalyzed hydrocarbon conversion process comprising contacting an oxygenate containing hydrocarbon stream with a dehydration catalyst in a dehydration zone under dehydration conditions to provide an olefin enriched hydrocarbon stream, contacting the olefin enriched hydrocarbon stream with an ionic liquid catalyst in an alkylation zone under alkylation conditions to provide an alkylate product comprising one or more halogenated components, and contacting the alkylate product with a hydrodechlorination catalyst in the presence of hydrogen in a hydrodechlorination zone under
hydrodechlorination conditions to provide a dechlorinated alkylate product.
In another embodiment, the present invention further provides an ionic liquid catalyzed hydrocarbon conversion process comprising contacting an oxygenate containing hydrocarbon stream with a dehydration catalyst in a dehydration zone under dehydration conditions to provide an olefin enriched hydrocarbon stream, contacting the olefin enriched hydrocarbon stream with an ionic liquid catalyst in an oligomerization zone under oligomerization
conditions to provide an oligomeric product comprising one or more halogenated components, and contacting the oligomeric product with a hydrodechlorination catalyst in the presence of hydrogen in a
hydrodechlorination zone under hydrodechlorination conditions to provide a dechlorinated oligomeric product.
As used herein, the terms "comprising" and "comprises" mean the inclusion of named elements or steps that are identified following those terms, but not necessarily excluding other unnamed elements or steps.
The term "Periodic Table" as referred to herein is the lUPAC version of the Periodic Table of the Elements dated June 22, 2007, and the numbering scheme for the Periodic Table Groups is as described in Chemical and Engineering News, 63(5), 27 (1985).
DETAILED DESCRIPTION
According to one aspect of the present invention, oxygenate containing hydrocarbon streams may be upgraded to high value products using ionic liquid catalyzed processes. In an embodiment, a hydrocarbon stream containing substantial quantities of both olefins and oxygenates may be pre- treated in an olefin enrichment zone under olefin enrichment conditions to provide an oxygenate depleted, olefin enriched hydrocarbon stream. In a sub-embodiment, alcohols in an oxygenate containing hydrocarbon stream may be converted, via dehydration, to olefins. The depletion of oxygenates in the oxygenate containing hydrocarbon stream may prevent oxygenate- mediated deactivation of the ionic liquid catalyst. Furthermore, olefin enrichment of the hydrocarbon stream increases the olefin content of the feed, thereby increasing the product yield obtained from the ionic liquid catalyzed hydrocarbon conversion process.
In an embodiment, the olefins in the olefin enriched hydrocarbon stream may be oligomerized by contacting the olefin enriched hydrocarbon stream with an
ionic liquid catalyst under oligomehzation conditions. In another embodiment, the olefin enriched hydrocarbon stream may comprise isoparaffins as well as olefins, and the olefins may be alkylated with the isoparaffins by contacting the olefin enriched hydrocarbon stream with an ionic liquid catalyst under alkylation conditions.
In a sub-embodiment, an ancillary hydrocarbon stream, e.g., comprising isoparaffins, may be contacted with the olefin enriched hydrocarbon stream in the presence of an ionic liquid catalyst in the hydrocarbon conversion zone. Examples of isoparaffin containing streams include, but are not limited to, FCC naphtha, hydrocracker naphtha, coker naphtha, Fischer-Tropsch condensate, and cracked naphtha. In yet another embodiment, the
hydrocarbon conversion conditions in the hydrocarbon conversion zone may be suitable for both alkylation and oligomehzation, such that both alkylation and oligomerization may take place concurrently in a single hydrocarbon conversion zone.
Ionic liquid catalyzed processes of the present invention may be performed in the presence of a co-catalyst or promoter to provide enhanced or improved catalytic activity. A co-catalyst according to the present invention may comprise, for example, anhydrous HCI or organic chloride (see, e.g., U.S. Pat. Nos.7,495, 144 to Elomari, and 7,531 ,707 to Harris et al., the disclosures of which are incorporated by reference herein in their entirety). When organic chloride is used as the co-catalyst with the ionic liquid, HCI may be formed in situ in the reactor during the hydrocarbon conversion process.
Products and/or by-products from ionic liquid catalyzed hydrocarbon conversion processes may typically include one or more halogenated components, as disclosed in commonly assigned co-pending patent application Serial No. 12/847,313 entitled Hydrodechlorination of ionic liquid- derived hydrocarbon products, filed on July 30, 2010, the disclosure of which is incorporated by reference herein in its entirety.
Products of ionic liquid catalyzed hydrocarbon conversion processes of the instant invention may be dechlorinated in a dechlorination zone, for example, by hot caustic treatment, adsorption of organochlorine species using a suitable adsorbent, or catalytic hydrodechlorination, to provide one or more dechlorinated product(s). In an embodiment, catalytic hydrodechlorination may involve contacting the hydrocarbon conversion stream from an ionic liquid catalyzed reaction with a hydrodechlorination catalyst in a
hydrodechlorination zone in the presence of hydrogen at relatively low pressure. According to one aspect of the present invention, the chloride content of the dechlorinated products will be sufficiently low to allow the blending of such materials into refinery product streams.
Ionic liquid catalysts In an embodiment, processes according to the present invention may use a catalytic composition comprising at least one metal halide and at least one quaternary ammonium halide and/or at least one amine halohydride. The ionic liquid catalyst can be any halogen aluminate ionic liquid catalyst, e.g., comprising an alkyi substituted quaternary amine halide, an alkyi substituted pyridinium halide, or an alkyi substituted imidazolium halide of the general formula N+R4X".
As an example, ionic liquid catalysts useful in practicing the present invention may be represented by the general formulas A and B,
A B
wherein R=H, methyl, ethyl, propyl, butyl, pentyl or hexyl, and X is a halide, and Ri and R2=H, methyl, ethyl, propyl, butyl, pentyl or hexyl, wherein Ri and R2 may or may not be the same. In an embodiment, X is chloride.
An exemplary metal halide that may be used in accordance with the present invention is aluminum chloride (AICI3). Quaternary ammonium halides which can be used in accordance with the present invention include those described in U.S. Pat. No. 5,750,455, the disclosure of which is incorporated by reference herein. In an embodiment, the ionic liquid catalyst may be a chloroaluminate ionic liquid prepared by mixing AICI3 and an alkyl substituted pyridinium halide, an alkyl substituted imidazolium halide, a trialkylammonium hydrohalide, or a tetraalkylammonium halide, as disclosed in commonly assigned U.S. Pat. No. 7,495,144, the disclosure of which is incorporated by reference herein in its entirety.
In a sub-embodiment, the ionic liquid catalyst may comprise N-butylpyridinium heptachlorodialuminate ionic liquid, which may be prepared, for example, by combining AlCls with a salt of the general formula A, supra, wherein R is n- butyl and X is chloride. The present invention is not limited to any particular ionic liquid catalyst composition(s).
Oxygenate containing feedstocks for ionic liquid catalyzed processes In an embodiment, feeds for the present invention may comprise oxygenate- and olefin containing hydrocarbon streams, such as various streams in a petroleum refinery, a gas-to-liquid conversion plant, or a coal-to-liquid (CTL) conversion plant, including streams from Fischer-Tropsch synthesis units, naphtha crackers, middle distillate crackers or wax crackers, as well as FCC offgas, FCC light naphtha, coker offgas, coker naphtha, and the like. Some such streams may contain significant amounts of isoparaffin(s) in addition to olefin(s) and oxygenates. In a sub-embodiment, the oxygenate containing hydrocarbon stream may comprise a Fischer-Tropsch condensate.
As a non-limiting example, an oxygenate containing hydrocarbon stream useful in practicing the instant invention may typically comprise from about 1 to 70 wt% olefins, and from about 0.1 to 30 wt% oxygenates. The oxygenate components of the oxygenated olefin containing hydrocarbon stream may comprise from about 0.1 to 30 wt% C2 - C20 alkanols, together with Ci - C20 carboxylic acids. Such streams may be fed to an olefin enrichment unit or zone to provide an olefin enriched hydrocarbon stream. The olefin enriched hydrocarbon stream may typically comprise from about 1 to 90 wt% olefins, and typically less than about 0.5 wt% oxygenates. The olefin enriched hydrocarbon stream may be fed to a hydrocarbon conversion unit 1 10 of the present invention (see, e.g., Figure 1 ).
The oxygenate containing hydrocarbon stream may comprise a mixture of hydrocarbons having a range of chain lengths and thus a wide boiling range. In an embodiment, the oxygenate containing hydrocarbon stream may contain two or more olefins selected from ethylene, propylene, butylenes, pentenes, and up to C36 olefins. The oxygenate containing hydrocarbon stream may comprise alpha-olefins and/or internal olefins (i.e., having an internal double bond). The olefins may be either straight chain, or branched, or a mixture of the two. In an embodiment of the present invention, the oxygenate containing hydrocarbon stream may comprise a mixture of mostly linear olefins from C2 to about C36. In another embodiment, the olefins in the oxygenate containing hydrocarbon stream may comprise at least about 10% of alpha-olefin species. In a sub-embodiment, the olefins in the oxygenate containing hydrocarbon stream may comprise predominantly alpha-olefins.
In an embodiment, olefins in the olefin enriched hydrocarbon stream may undergo oligomerization when contacted with an ionic liquid catalyst in hydrocarbon conversion unit 1 10 (see, e.g., Figure 1 ). Ionic liquid catalyzed olefin oligomerization may take place under the same or similar conditions as ionic liquid catalyzed olefin-isoparaffin alkylation. As a result, in an
embodiment of the present invention, both olefin oligomerization and
olefin/isoparaffin alkylation may take place in a single hydrocarbon conversion zone.
Ionic liquid catalyzed hydrocarbon conversion systems and processes
With reference to Figure 1 , a hydrocarbon conversion system 10 for processing an oxygenate containing hydrocarbon feed using an ionic liquid catalyst, according to an embodiment of the present invention, may include an olefin enrichment unit 100, a hydrocarbon conversion unit 1 10, and a dechlorination unit 120.
During an ionic liquid catalyzed hydrocarbon conversion process of the instant invention, an oxygenate containing hydrocarbon stream may be treated in olefin enrichment unit 100 under olefin enrichment conditions to provide an olefin enriched hydrocarbon stream. Olefin enrichment unit 100 may also be referred to herein as an olefin enrichment zone. In an embodiment, the oxygenate containing hydrocarbon stream may typically comprise from about 0.1 to 30 wt% oxygenates, and often from about 0.1 to 20 wt% oxygenates. In an embodiment, the oxygenate containing hydrocarbon stream may be enriched in olefins by converting the oxygenates in the stream to olefins. In an embodiment, oxygenates in the oxygenate containing hydrocarbon stream may comprise alcohols, and the alcohols may be converted to olefins by dehydration of the alcohol by treatment with a dehydrating catalyst. In a sub- embodiment, the oxygenates in the oxygenate containing hydrocarbon stream may be comprised predominantly of primary alcohols.
In an embodiment, treating the oxygenate containing hydrocarbon stream in olefin enrichment unit 100 may further include the removal of oxygenates and/or water from the oxygenate containing hydrocarbon stream (see, for example, Figure 2). Various methods and techniques for removing
oxygenates from hydrocarbon streams are disclosed in U.S. Pat. No.
6,743,962 to O'Rear et al., the disclosure of which is incorporated by reference herein in its entirety.
During an ionic liquid catalyzed hydrocarbon conversion process of the instant invention, the olefin enriched hydrocarbon stream from unit 100 may be introduced into hydrocarbon conversion unit 1 10. Hydrocarbon conversion unit 1 10 may also be referred to herein as a hydrocarbon conversion zone. In an embodiment, the olefin enriched hydrocarbon stream may typically comprise from about 1 to 70 wt% olefins, and often from about 10 to 60 wt% olefins. In an embodiment, the olefin enriched hydrocarbon stream may typically comprise less than about 0.5 wt% oxygenates, and often less than about 0.3 wt% oxygenates.
In an embodiment, the olefin enriched hydrocarbon stream and the ionic liquid catalyst may be introduced into hydrocarbon conversion unit 1 10 via separate inlet ports (not shown). The olefin enriched hydrocarbon stream may be contacted with the ionic liquid catalyst in hydrocarbon conversion unit 1 10 under hydrocarbon conversion conditions to provide a converted hydrocarbon stream. In an embodiment, the ionic liquid catalyst may comprise a
chloroaluminate ionic liquid. The feeds to hydrocarbon conversion unit 1 10 may further include a catalyst promoter, such as anhydrous HCI or an alkyl halide. In an embodiment, the catalyst promoter may comprise a C2 - Ce alkyl chloride, such as n-butyl chloride or i-butyl chloride. Hydrocarbon conversion unit 1 10 may be vigorously mixed to promote contact between reactant(s) and ionic liquid catalyst.
Hydrocarbon conversion conditions within hydrocarbon conversion unit 1 10 may be adjusted to optimize process performance for a particular
hydrocarbon conversion process of the present invention. In an embodiment, the hydrocarbon conversion conditions may comprise oligomerization conditions, such that olefins in the olefin enriched stream may be
oligomerized to provide one or more oligomeric products. In another embodiment, the hydrocarbon conversion conditions may comprise alkylation
conditions, such that olefins in the olefin enriched stream may be alkylated with isoparaffins to provide an alkylate product. In yet another embodiment, the hydrocarbon conversion conditions may comprise both oligomerization conditions and alkylation conditions, such that oligomerization and alkylation reactions may occur concurrently within hydrocarbon conversion unit 1 10.
In an embodiment, an ancillary hydrocarbon stream, e.g., comprising isoparaffins, may optionally be fed to hydrocarbon conversion unit 1 10, and the ancillary hydrocarbon stream may be contacted with the olefin enriched hydrocarbon stream in the presence of ionic liquid catalyst in the hydrocarbon conversion zone.
During hydrocarbon conversion processes of the invention, hydrocarbon conversion unit 1 10 may contain a mixture comprising ionic liquid catalyst and a hydrocarbon phase. The hydrocarbon phase may comprise at least one hydrocarbon conversion product of the ionic liquid catalyzed reaction. In an embodiment, the ionic liquid catalyst may be separated from the hydrocarbon phase via a catalyst/hydrocarbon separator (not shown), wherein the hydrocarbon and ionic liquid catalyst phases may be allowed to settle under gravity, by using a coalescer, or by a combination thereof. The use of coalescers for liquid-liquid separations is described in commonly assigned US Pub. No. 20100130800A1 , the disclosure of which is incorporated by reference herein in its entirety. The hydrocarbon phase may be fed to dechlorination unit 120, while at least a portion of the ionic liquid phase may be recycled to hydrocarbon conversion unit 1 10. The hydrocarbon phase fed to dechlorination unit 120 may be referred to herein as a converted hydrocarbon stream. According to one aspect of the present invention, the converted hydrocarbon stream provided by hydroconversion unit 1 10 may comprise a distillate enriched stream.
According to another aspect of the present invention, the converted hydrocarbon stream provided by hydroconversion unit 1 10 may comprise a base oil (700T+) enriched stream.
Reaction conditions for ionic liquid catalyzed hydrocarbon conversions
Due to the low solubility of hydrocarbons in ionic liquids, hydrocarbon conversion reactions in ionic liquids (including olefin oligomerization and isoparaffin-olefin alkylation reactions) are generally biphasic and occur at the interface in the liquid state. The volume of ionic liquid catalyst in the reactor may be generally in the range from about 1 to 70 vol%, and usually from about 4 to 50 vol%. Generally, vigorous mixing (e.g., stirring or Venturi nozzle dispensing) is used to ensure good contact between the reactants and the ionic liquid catalyst. The reaction temperature may be generally in the range from about -40°F to +480°F, typically from about -4°F to +210°F, and often from about +40°F to +140°F. The reactor pressure may be in the range from atmospheric pressure to about 8000 kPa. Typically, the reactor pressure will be sufficient to keep the reactants in the liquid phase.
Residence time of reactants in the reactor may generally be in the range from a few seconds to hours, and usually from about 0.5 min to 60 min. In the case of ionic liquid catalyzed isoparaffin-olefin alkylation, the reactants may be introduced in an isoparaffin Olefin molar ratio generally in the range from about 1 to 100, more typically from about 2 to 50, and often from about 2 to 20. Heat generated by the reaction may be dissipated using various means well known to the skilled artisan. With continued operation of hydrocarbon conversion unit 1 10, the ionic liquid catalyst may become partially deactivated or spent. In order to maintain the catalytic activity, at least a portion of the ionic liquid phase may be fed to a catalyst regeneration unit (not shown) for regeneration of the ionic liquid catalyst. Processes for the regeneration of ionic liquid catalyst to provide steady state catalytic activity are disclosed in the patent literature (see, for example, U.S. Pat. Nos. 7,732,364 and 7,674,739, the disclosures of which are incorporated by reference herein in their entirety).
Dechlorination of ionic liquid catalyzed hydrocarbon conversion products
In an embodiment of the present invention, the converted hydrocarbon stream obtained from hydrocarbon conversion unit 1 10 may typically comprise one or more halogenated components. As an example only, the converted hydrocarbon stream may have an organic chloride content generally greater than about 50 ppm, typically greater than about 200 ppm, and often greater than about 1000 ppm. In an embodiment, the converted hydrocarbon stream from hydrocarbon conversion unit 1 10 may have an organic chloride content generally in the range from about 50 ppm to 5000 ppm, typically from about 100 ppm to 4000 ppm, and often from about 200 ppm to 3000 ppm.
According to an aspect of the instant invention, the converted hydrocarbon stream may be fed to dechlorination unit 120 for dechlorinating the
hydrocarbon product(s) to provide one or more dechlorinated hydrocarbon products. Dechlorination unit 120 may also be referred to herein as a dechlorination zone. In an embodiment, the converted hydrocarbon stream may be dechlorinated by treatment with hot caustic. In another embodiment, the converted hydrocarbon stream may be dechlorinated by adsorption of organochlorine species using an adsorbent such as zeolites, clay, alumina, silica-alumina, and the like.
According to another embodiment of the instant invention, dechlorination unit 120 may comprises a hydrodechlorination unit or zone, and the converted hydrocarbon stream may be fed to dechlorination unit 120 for
hydrodechlorinating the hydrocarbon product(s) by contacting the converted hydrocarbon stream with a hydrodechlorination catalyst in the presence of hydrogen under hydrodechlorination conditions to provide one or more dechlorinated hydrocarbon products. The hydrodechlorination catalyst may comprise an element selected from the group consisting of elements of Groups 6, 8, 9, 10, and 1 1 of the Periodic Table, and combinations thereof, present as metals, oxides, or sulfides. In a sub-embodiment, the
hydrodechlorination catalyst may comprise an element selected from Pd, Pt,
Au, Ni, Co, Mo, and W, and their mixtures, present as metals, oxides, or sulfides.
The hydrodechlorination catalyst may further comprise a support. The support may comprise an inorganic porous material, such as a refractory oxide, or activated carbon. Examples of refractory oxide support materials include alumina, silica, titania, alumina-silica, and zirconia, or the like, and combinations thereof. In an embodiment, the hydrodechlorination catalyst may comprise a noble metal on a refractory oxide support. In a sub- embodiment, the hydrodechlorination catalyst may comprise Pd or Pt or a mixture of Pd and Pt, e.g., in the range from about 0.05 to 3.0 wt% of Pd or Pt or a mixture thereof.
The hydrodechlorination conditions within the hydrodechlorination zone may include a reaction temperature generally in the range from about 300°F to 750°F, and typically from about 400°F to 650°F. The hydrodechlorination conditions may further include a reaction pressure generally in the range from about 100 to 5000 psig, and typically from about 200 to 2000 psig. A liquid hourly space velocity (LHSV) feed rate to the hydrodechlorination zone may be generally in the range from about 0.1 to 50 hr"1 , and typically from about 0.2 to 10 hr"1. A hydrogen supply to the hydrodechlorination zone may be generally in the range from about 50 to 8000 standard cubic feet per barrel (SCFB) of the hydrocarbon stream, and typically from about 100 to 5000 SCFB.
The dechlorinated hydrocarbon product obtained from dechlorination unit 120 may typically have a much lower chloride content as compared with that of the converted hydrocarbon stream fed to dechlorination unit 120. In an
embodiment, a first chloride content of the hydrocarbon stream fed to dechlorination unit 120 may be greater than about 50 ppm. In an
embodiment, the hydrocarbon stream fed to dechlorination unit 120 may have an organic chloride content generally in the range from about 50 ppm to 5000
ppm, typically from about 100 ppm to 4000 ppm, and often from about 200 ppm to 3000 ppm.
In contrast, the organic chloride content of the dechlorinated hydrocarbon product(s) obtained from hydrocarbon conversion system 10 may be greatly decreased as compared with that of the converted hydrocarbon stream.
Typically, a second chloride content of dechlorinated hydrocarbon product(s) provided by processes of the present invention may be less than 50 ppm, typically less than about 10 ppm, and often equal to or less than about 5 ppm. Analogous results will be obtained when the present invention is practiced using ionic liquid catalyst systems based on halides other than chlorides. In an embodiment, the dechlorinated hydrocarbon product(s) may comprise a dechlorinated distillate fuel, such as dechlorinated jet fuel, or dechlorinated diesel fuel, and the like.
Olefin enrichment of oxygenate containing hydrocarbon streams
Figure 2 represents a scheme for an olefin enrichment process using an oxygenate containing hydrocarbon feed, according to an aspect of the process of Figure 1 . The oxygenate containing hydrocarbon stream may be, for example, any of various hydrocarbon streams, which contain significant or substantial amounts of oxygenates, in a petroleum refinery, a gas-to-liquid conversion plant, or a coal-to-liquid conversion plant, and the like. In an embodiment, an oxygenate containing hydrocarbon stream of the present invention may comprise Fischer-Tropsch condensate.
With further reference to Figure 2, olefin enrichment unit 100 for treating an oxygenate containing hydrocarbon stream may include an oxygenate dehydration unit 102. Oxygenate dehydration unit 102 may include a dehydration catalyst. Oxygenate dehydration unit 102 may also be referred to herein as a dehydration zone. In an embodiment, a process for treating an oxygenate containing hydrocarbon stream may comprise dehydrating oxygenates in the oxygenate containing hydrocarbon stream by contacting the
oxygenate containing hydrocarbon stream with the dehydration catalyst in the dehydration zone under dehydration conditions.
In an embodiment, oxygenates present in the oxygenate containing
hydrocarbon stream may comprise predominantly alcohols. The alcohols may be converted to olefins by contacting the oxygenate containing hydrocarbon stream with the dehydration catalyst to provide an olefin enriched
hydrocarbon stream. Carboxylic acids in the hydrocarbon stream may be decarboxylated by contacting the hydrocarbon stream with the dehydration catalyst. In an embodiment, the olefin enriched hydrocarbon stream may comprise less than about 0.5 wt% oxygen. In a sub-embodiment, the olefin enriched hydrocarbon stream may comprise less than about 0.3 wt% oxygen.
In an embodiment, the dehydration catalyst may be selected from the group consisting of alumina and amorphous silica-alumina. In a sub-embodiment, the dehydration catalyst may comprise alumina doped with an element selected from the group consisting of phosphorus, boron, fluorine, zirconium, titanium, gallium, magnesium, and combinations thereof. In another sub- embodiment, the dehydration catalyst may comprise amorphous silica- alumina doped with an element selected from the group consisting of phosphorus, boron, fluorine, zirconium, titanium, gallium, magnesium and combinations thereof.
According to one aspect of the present invention, the degree of acidity of the dehydration catalyst may be selected, e.g., by the judicious doping of alumina or amorphous silica-alumina, to determine not only the degree of olefin isomerization, but also the proportion of alpha-olefins to total olefins in the olefin enriched hydrocarbon stream. The olefin composition of the olefin enriched hydrocarbon stream may in turn determine the composition of product(s) obtained from hydrocarbon conversion system 10.
The dehydration conditions for dehydrating oxygenates in the oxygenate containing hydrocarbon stream may include a temperature in the range from
about 400°F to 800°F, a pressure in the range from about 10 to 5000 psig, and a liquid hourly space velocity (LHSV) feed rate in the range from about 0.1 to 50 hr"1. With still further reference to Figure 2, olefin enrichment unit 100 may optionally still further include one or more of an oxygenate extraction unit 104, an oxygenate adsorption unit 106, and a second distillation unit 108. In an embodiment, the treatment of an oxygenate containing hydrocarbon stream according to the present invention may optionally include the use of oxygenate extraction unit 104 for extracting or washing the hydrocarbon stream with an aqueous medium, whereby residual oxygenates may be removed from the hydrocarbon stream exiting dehydration unit 102. In a sub- embodiment, the aqueous medium may comprise liquid water. In a further sub-embodiment, the aqueous medium may comprise water at a pH > 7.0.
In an embodiment, an olefin enrichment process of the present invention may optionally further include contacting the hydrocarbon stream with an adsorbent in oxygenate adsorption unit 106, whereby residual oxygenates and/or water may be removed from the hydrocarbon stream. In a sub- embodiment, the adsorbent may comprise a molecular sieve, such as zeolite 13X. Zeolites and molecular sieves are well known in the art (see, for example, Zeolites in Industrial Separation and Catalysis, By Santi
Kulprathipanja, Pub. Wiley-VCH, 2010). In an embodiment, the hydrocarbon stream may be fed to adsorption unit 106 from oxygenate extraction unit 104. Alternatively, oxygenate extraction unit 104 may be omitted or bypassed, and the hydrocarbon stream may be fed to adsorption unit 106 directly from dehydration unit 102.
In yet another embodiment of the present invention, olefin enrichment unit 100 may optionally further include a second distillation unit 108. As a non-limiting example, second distillation unit 108 may be used to remove a heavy fraction from the hydrocarbon stream prior to ionic liquid catalyzed hydrocarbon conversion of the olefin enriched hydrocarbon stream. The nature of the
heavy fraction, if any, to be separated from the olefin enriched hydrocarbon stream may vary, for example, according to the feedstocks used and the product(s) targeted from the ionic liquid catalyzed hydrocarbon conversion processes of various embodiments of the present invention.
Certain features of the various embodiments may be combined with features of other embodiments to provide further embodiments of the present invention in addition to those embodiments specifically described or shown as such. There are numerous variations on the present invention which are possible in light of the teachings herein. It is therefore understood that within the scope of the following claims, the invention may be practiced otherwise than as specifically described or exemplified herein.
Claims
1 . An ionic liquid catalyzed hydrocarbon conversion process, comprising:
a) treating an oxygenate containing hydrocarbon stream in an olefin enrichment zone under olefin enrichment conditions to provide an olefin enriched hydrocarbon stream comprising olefins;
b) contacting the olefin enriched hydrocarbon stream with an ionic liquid catalyst in a hydrocarbon conversion zone under hydrocarbon conversion conditions to provide a converted hydrocarbon stream comprising one or more halogenated components; and
c) removing the halogenated components from the converted hydrocarbon stream to provide a dechlorinated hydrocarbon product.
2. The process according to claim 1 , wherein step c) comprises contacting the converted hydrocarbon stream with a hydrodechlorination catalyst in the presence of hydrogen in a hydrodechlorination zone under hydrodechlorination conditions.
3. The process according to claim 1 , wherein step a) comprises contacting the oxygenate containing hydrocarbon stream with a dehydration catalyst in a
dehydration zone under dehydration conditions.
4. The process according to claim 1 , further comprising:
d) prior to step b), washing the olefin enriched hydrocarbon stream with an aqueous medium, whereby residual oxygenates are removed from the olefin enriched hydrocarbon stream.
5. The process according to claim 1 , further comprising:
e) prior to step b), contacting the olefin enriched hydrocarbon stream with an adsorbent, whereby residual oxygenates and water are removed from the olefin enriched hydrocarbon stream.
6. The process according to claim 5, wherein the adsorbent comprises a molecular sieve.
7. The process according to claim 3, wherein the dehydration catalyst is selected from the group consisting of alumina and amorphous silica-alumina.
8. The process according to claim 3, wherein the dehydration catalyst comprises alumina doped with an element selected from the group consisting of phosphorus, boron, fluorine, zirconium, titanium, gallium, magnesium, and combinations thereof.
9. The process according to claim 3, wherein the dehydration catalyst comprises amorphous silica-alumina doped with an element selected from the group consisting of phosphorus, boron, fluorine, zirconium, titanium, gallium, magnesium, and combinations thereof.
10. The process according to claim 1 , wherein the hydrocarbon conversion conditions comprise oligomerization conditions, and wherein olefins in the olefin enriched hydrocarbon stream are oligomerized.
1 1 . The process according to claim 1 , wherein the olefin enriched hydrocarbon stream further comprises isoparaffins, and the hydrocarbon conversion conditions comprise alkylation conditions, wherein olefins in the olefin enriched hydrocarbon stream are alkylated with the isoparaffins.
12. The process according to claim 1 , wherein the hydrocarbon conversion conditions comprise oligomerization conditions and alkylation conditions.
13. The process according to claim 1 , wherein the oxygenate containing hydrocarbon stream comprises a Fischer-Tropsch condensate.
14. The process according to claim 2, wherein a first chloride content of the converted hydrocarbon stream is greater than 50 ppm, and a second chloride content of the dechlorinated hydrocarbon product is less than 50 ppm.
15. The process according to claim 1 , wherein the converted hydrocarbon stream comprises a distillate enriched stream.
16. The process according to claim 1 , wherein the converted hydrocarbon stream comprises a base oil (700°F+) enriched stream.
17. The process according to claim 1 , wherein the ionic liquid catalyst comprises a chloroaluminate ionic liquid.
18. An ionic liquid catalyzed hydrocarbon conversion process, comprising:
a) contacting an oxygenate containing hydrocarbon stream with a dehydration catalyst in a dehydration zone under dehydration conditions to provide an olefin enriched hydrocarbon stream;
b) contacting the olefin enriched hydrocarbon stream with an ionic liquid catalyst in an alkylation zone under alkylation conditions to provide an alkylate product comprising one or more halogenated components; and
c) contacting the alkylate product with a hydrodechlorination catalyst in the presence of hydrogen in a hydrodechlorination zone under hydrodechlorination conditions to provide a dechlorinated alkylate product.
19. The process according to claim 18, wherein:
the hydrodechlorination catalyst comprises an element selected from the group consisting of elements of Groups 6, 8, 9, 10, and 1 1 of the Periodic Table, and combinations thereof, present as metals, oxides, or sulfides; and
step c) comprises contacting the alkylate product with the hydrodechlorination catalyst at a temperature in the range from about 300°F to 750°F, a pressure in the range from about 100 to 5000 psig, a liquid hourly space velocity (LHSV) feed rate in the range from about 0.1 to 50, and a hydrogen supply in the range from about 200 to 8000 standard cubic feet per barrel (SCFB) of the alkylate product.
20. An ionic liquid catalyzed hydrocarbon conversion process, comprising: a) contacting an oxygenate containing hydrocarbon stream with a dehydration catalyst in a dehydration zone under dehydration conditions to provide an olefin enriched hydrocarbon stream;
b) contacting the olefin enriched hydrocarbon stream with an ionic liquid catalyst in an oligomerization zone under oligomerization conditions to provide an oligomeric product comprising one or more halogenated components; and
c) contacting the oligomeric product with a hydrodechlorination catalyst in the presence of hydrogen in a hydrodechlorination zone under hydrodechlorination conditions to provide a dechlorinated oligomeric product.
21 . The process according to claim 20, wherein:
the hydrodechlorination catalyst comprises an element selected from the group consisting of elements of Groups 6, 8, 9, 10, and 1 1 of the Periodic Table, and combinations thereof, present as metals, oxides, or sulfides; and
step c) comprises contacting the oligomeric product with the
hydrodechlorination catalyst at a temperature in the range from about 300°F to 750°F, a pressure in the range from about 100 to 5000 psig, a liquid hourly space velocity (LHSV) feed rate in the range from about 0.1 to 50, and a hydrogen supply in the range from about 200 to 8000 standard cubic feet per barrel (SCFB) of the oligomeric product.
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US12/975,759 US20120160740A1 (en) | 2010-12-22 | 2010-12-22 | Processes for ionic liquid catalyzed upgrading of oxygenate containing hydrocarbon feedstocks |
US12/975,759 | 2010-12-22 |
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US9776877B2 (en) * | 2014-12-11 | 2017-10-03 | Uop Llc | Separation of conjunct polymer from volatile regenerant for ionic liquid regeneration |
US9914675B2 (en) | 2015-03-31 | 2018-03-13 | Uop Llc | Process for alkylation using ionic liquid catalysts |
US9914674B2 (en) | 2015-03-31 | 2018-03-13 | Uop Llc | Process for alkylation using low ionic liquid volume fraction |
US9822046B1 (en) | 2016-05-19 | 2017-11-21 | Chevron U.S.A. Inc. | Farnesane alkylation |
US10093594B2 (en) | 2016-05-19 | 2018-10-09 | Chevron U.S.A. Inc. | High viscosity index lubricants by isoalkane alkylation |
CN109694736B (en) * | 2017-10-20 | 2021-02-05 | 中国石油化工股份有限公司 | Hydrodechlorination method for ionic liquid alkylate |
CN109694735B (en) * | 2017-10-20 | 2020-11-10 | 中国石油化工股份有限公司 | Hydrogenation dechlorination method for alkylate oil |
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US20060149107A1 (en) * | 2003-06-30 | 2006-07-06 | Chevron U.S. A. Inc. | Process for the oligomerization of olefins in fischer-tropsch derived condensate feed |
US20090163759A1 (en) * | 2007-12-19 | 2009-06-25 | Chevron U.S.A. Inc. | Reduction of organic halide contamination in hydrocarbon products |
US20090264694A1 (en) * | 2006-12-12 | 2009-10-22 | Chevron U.S.A., Inc. | Reduction of organic halides in alkylate gasoline |
US20100147746A1 (en) * | 2008-12-16 | 2010-06-17 | Chevron U.S.A. Inc | Reduction of organic halide contamination in hydrocarbon products |
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US6605206B1 (en) * | 2002-02-08 | 2003-08-12 | Chevron U.S.A. Inc. | Process for increasing the yield of lubricating base oil from a Fischer-Tropsch plant |
US6933323B2 (en) * | 2003-01-31 | 2005-08-23 | Chevron U.S.A. Inc. | Production of stable olefinic fischer tropsch fuels with minimum hydrogen consumption |
US7576252B2 (en) * | 2005-12-20 | 2009-08-18 | Chevron U.S.A. Inc. | Process for the formation of a superior lubricant or fuel blendstock by ionic liquid oligomerization of olefins in the presence of isoparaffins |
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2010
- 2010-12-22 US US12/975,759 patent/US20120160740A1/en not_active Abandoned
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US20060149107A1 (en) * | 2003-06-30 | 2006-07-06 | Chevron U.S. A. Inc. | Process for the oligomerization of olefins in fischer-tropsch derived condensate feed |
US20090264694A1 (en) * | 2006-12-12 | 2009-10-22 | Chevron U.S.A., Inc. | Reduction of organic halides in alkylate gasoline |
US20090163759A1 (en) * | 2007-12-19 | 2009-06-25 | Chevron U.S.A. Inc. | Reduction of organic halide contamination in hydrocarbon products |
US20100147746A1 (en) * | 2008-12-16 | 2010-06-17 | Chevron U.S.A. Inc | Reduction of organic halide contamination in hydrocarbon products |
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