CN101970382A - 减少烃产物中的有机卤化物杂质 - Google Patents
减少烃产物中的有机卤化物杂质 Download PDFInfo
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- CN101970382A CN101970382A CN2008801217121A CN200880121712A CN101970382A CN 101970382 A CN101970382 A CN 101970382A CN 2008801217121 A CN2008801217121 A CN 2008801217121A CN 200880121712 A CN200880121712 A CN 200880121712A CN 101970382 A CN101970382 A CN 101970382A
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- ssz
- zeolite
- zsm
- molecular sieve
- mixture
- Prior art date
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- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 37
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 37
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 35
- 150000004820 halides Chemical class 0.000 title claims abstract 5
- 238000011109 contamination Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 47
- 239000002808 molecular sieve Substances 0.000 claims abstract description 32
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002608 ionic liquid Substances 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 16
- 150000002367 halogens Chemical class 0.000 claims abstract description 12
- 239000011831 acidic ionic liquid Substances 0.000 claims abstract description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 34
- 239000010457 zeolite Substances 0.000 claims description 34
- 229910021536 Zeolite Inorganic materials 0.000 claims description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 150000002896 organic halogen compounds Chemical class 0.000 claims description 20
- 150000002500 ions Chemical class 0.000 claims description 17
- 230000029936 alkylation Effects 0.000 claims description 15
- 238000005804 alkylation reaction Methods 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 238000001179 sorption measurement Methods 0.000 claims description 13
- 238000012216 screening Methods 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 7
- 238000003795 desorption Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 150000001721 carbon Chemical group 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 4
- 239000007848 Bronsted acid Substances 0.000 claims description 3
- 238000006471 dimerization reaction Methods 0.000 claims description 3
- 238000005649 metathesis reaction Methods 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 238000007037 hydroformylation reaction Methods 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- 238000006317 isomerization reaction Methods 0.000 claims description 2
- 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 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 description 24
- -1 sulfonium cation Chemical class 0.000 description 13
- 238000011068 loading method Methods 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 6
- 150000001348 alkyl chlorides Chemical class 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000026030 halogenation Effects 0.000 description 4
- 238000005658 halogenation reaction Methods 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 229910001507 metal halide Inorganic materials 0.000 description 4
- 150000005309 metal halides Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 229910007926 ZrCl Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 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 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000002594 sorbent Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000005504 petroleum refining Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- CDXLWOUTFCMPDM-UHFFFAOYSA-N 1-butyl-4-methyl-2h-pyridine Chemical compound CCCCN1CC=C(C)C=C1 CDXLWOUTFCMPDM-UHFFFAOYSA-N 0.000 description 1
- REACWASHYHDPSQ-UHFFFAOYSA-N 1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1 REACWASHYHDPSQ-UHFFFAOYSA-N 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000949473 Correa Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001673102 Jaya Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001347 alkyl bromides Chemical class 0.000 description 1
- 150000001351 alkyl iodides Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 231100001010 corrosive Toxicity 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000005208 trialkylammonium group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
- C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/56—Addition to acyclic hydrocarbons
- C07C2/58—Catalytic processes
- C07C2/60—Catalytic processes with halides
-
- 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
- C10G21/08—Inorganic compounds only
-
- 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
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step
-
- 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
- C10G57/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process
- C10G57/005—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process with alkylation
-
- 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
- C10G57/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process
- C10G57/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process with polymerisation
-
- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
-
- 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
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1081—Alkanes
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1088—Olefins
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1088—Olefins
- C10G2300/1092—C2-C4 olefins
-
- C—CHEMISTRY; METALLURGY
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Abstract
公开了减少有机卤化物含量为50-4000ppm的烃产物中的卤化物浓度的方法，所述烃产物是使用包含含卤素的酸性离子液体的离子液体催化剂由烃转化方法生产的，所述方法包括使至少一部分所述烃产物与孔尺寸为4-16埃的至少一种分子筛在有机卤化物吸附条件下接触，以将该烃产物中的卤素浓度减少至小于40ppm。
Description
发明领域
本发明涉及减少烃产物中的有机卤化物浓度的方法，所述烃产物是使用包含含卤素的酸性离子液体的离子液体催化剂由烃转化方法生产的。
发明背景
离子液体是完全由离子组成的液体。所谓的“低温”离子液体通常是熔点低于100℃，甚至往往低于室温的有机盐。离子液体可适合于例如在烷基化反应和聚合反应以及在二聚、低聚、乙酰化、复分解和共聚反应中用作催化剂和用作溶剂。
一类离子液体是熔融盐组合物，它们在低温下被熔融，并用作催化剂、溶剂和电解质。这种组合物是组分的混合物，该混合物在低于各组分的各自熔点的温度下为液体。
离子液体可以定义为这样的液体，该液体的组成完全由作为阳离子和阴离子的组合的离子组成。最常见的离子液体是由有机基的阳离子和无机或有机阴离子制备的那些。最常见的有机阳离子是铵阳离子，但也经常使用磷鎓阳离子和锍阳离子。吡啶鎓和咪唑鎓的离子液体也许是最常用的阳离子。阴离子包括，但不限于，BF4 -、PF6 -、卤铝酸根例如Al2Cl7 -和Al2Br7 -、[(CF3SO2)2N]-、烷基硫酸根(RSO3 -)、羧酸根(RCO2 -)和许多其它阴离子。催化上最让人感兴趣的用于酸催化的离子液体是衍生自卤化铵和路易斯酸(例如AlCl3、TiCl4、SnCl4、FeCl3…等)的那些。氯铝酸盐离子液体也许是用于酸催化的反应的最常用的离子液体催化剂体系。
这类低温离子液体或熔融盐的实例是氯铝酸盐。例如，烷基咪唑鎓或吡啶鎓氯化物可以与三氯化铝(AlCl3)混合生成熔融的氯铝酸盐。美国专利4,122,245讨论了1-烷基吡啶鎓氯化物和三氯化铝的熔融盐作为电解质的用途。
离子液体及其制备方法的其他实例也可以在美国专利5,731,101；6,797,853和在美国专利申请出版物2004/0077914和2004/0133056中找到。
在离子液体中用丁烯和乙烯来烷基化异丁烷已经在美国专利5,750,455、6,028,024和6,235,959和公开文献(Journal ofMolecular Catalysis，92(1994)，155-165)、“Ionic Liquids inSynthesis”，P.Wasserscheid和T.Welton(编辑)，Wiley-VCHVerlag，2003，275页)中有述。
分子筛作为吸附剂的用途已经在文献中有述。丁基氯与NaY沸石的相互作用已经报告于以下文献中：Suer等人；Journal of Catalysis，1996，162，320-326和Correa等人；Phys.Chem.Chem.Phys.，2002，4，4268-4274.[Jaya，请得到这些出版物的副本，我们仍需要将它们提供给PTO]。
通常，将轻质链烷烃和轻质烯烃转化成更有价值的馏分对于炼油工业来说是非常有利的。这已经通过链烷烃与烯烃的烷基化反应并通过烯烃的聚合而实现。该领域中最广泛使用的方法之一是使用硫酸和氢氟酸使异丁烷与C3-C5烯烃进行烷基化以制备具有高辛烷值的汽油馏分。这种方法自二十世纪四十年代以来一直为炼油工业所采用。该方法受到了对于高品质和清洁燃烧的高辛烷值汽油的日益增加的需求的驱动。
烷基化物汽油是高品质的且有效燃烧的汽油，其占汽油库存的约14％。烷基化物汽油一般通过用低端烯烃(主要是丁烯)来烷基化炼油厂异丁烷而产生。当前，使用HF和H2SO4作为催化剂来生产烷基化物。尽管这些催化剂已经成功地用于经济地生产最佳品质的烷基化物，但对于更安全且更环境友好的催化剂体系的需要已经成为所涉及的工业的一个课题。
发明概述
本发明涉及减少有机卤化物含量为50-4000ppm的烃产物中的有机卤化物浓度的方法，该烃产物是使用含卤素的酸性离子液体催化剂由烃转化方法生产的。所述方法包括使至少一部分该烃产物与孔尺寸为4-16埃的分子筛在有机卤化物吸附条件下接触，以将该烃产物中的卤素浓度减少至小于40ppm。
发明详述
使用含卤素的酸性离子液体催化剂的烃转化方法将产生有机卤化物杂质含量为50-4000ppm的烃产物。这类方法的实例包括链烷烃的烷基化、芳烃的烷基化、聚合、二聚、低聚、乙酰化、复分解、共聚、异构化、烯烃加氢、加氢甲酰化。有机卤化物在这样的产物中的存在可能是不希望的。本方法能用来减少这样的烃产物中的有机卤化物浓度。
在很大程度上参照使用某些具体的离子液体催化剂的烷基化方法来描述和例示本方法，但这样的描述不打算限制本发明的范围。基于本文包括的教导、说明和实施例，本领域技术人员将会理解，本文描述的减少有机卤化物的方法可用于有机卤化物含量为50-4000ppm的任何烃产物，该烃产物是使用包含含卤素的酸性离子液体的离子液体催化剂由烃转化方法生产的。
一方面，本方法涉及一种烷基化方法，该烷基化方法包括使包含至少一种具有2-6个碳原子的烯烃和至少一种具有3-6个碳原子的异链烷烃的烃混合物在烷基化条件下与含卤素的酸性离子液体催化剂接触。
通常，强酸性离子液体对于链烷烃烷基化反应例如异链烷烃烷基化反应是必需的。在这种情况下，氯化铝，它是与低浓度布朗斯台德酸组合的强路易斯酸，是离子液体催化剂方案中的优选的催化剂组分。
如上所述，所述酸性离子液体可以是任何酸性离子液体。在一个实施方案中，所述酸性离子液体是通过将三氯化铝(AlCl3)与烃基取代的吡啶鎓卤化物、烃基取代的咪唑鎓卤化物、三烷基铵氢卤化物或卤化四烷基铵混合而制备的氯铝酸盐离子液体，以制备通式分别为A、B、C和D的离子液体，
其中，R＝H、甲基、乙基、丙基、丁基、戊基或己基，和X是卤铝酸根且优选为氯铝酸根，和R1和R2＝H、甲基、乙基、丙基、丁基、戊基或己基，和其中R1和R2可以相同或不同，和R3、R4和R5和R6＝甲基、乙基、丙基、丁基、戊基或己基，和其中R3、R4、R5和R6可以相同或不同。
所述酸性离子液体优选选自1-丁基-4-甲基吡啶鎓氯铝酸盐、1-丁基-吡啶鎓氯铝酸盐、1-丁基-3-甲基咪唑鎓氯铝酸盐和1-H-吡啶鎓氯铝酸盐。在根据本发明的方法中，烷基卤可任选地用作助催化剂。
所述烷基卤被任选地添加到所述离子液体催化剂中并通过与氯化铝反应生成必备的阳离子来以与Friedel-Crafts反应相似的模式促进烷基化反应。可以使用的烷基卤包括烷基溴、烷基氯和烷基碘。优选的是异戊基卤、异丁基卤、正丁基卤、丙基卤和乙基卤。当使用氯铝酸盐离子液体作为催化剂体系时，优选这些烷基卤的烷基氯形式。也可使用具有1-8个碳原子的其它烷基氯或烷基卤。所述烷基卤可以单独或组合使用。
可采用金属卤化物来修改所述催化剂的活性和选择性。金属卤化物，其最通常在氯化铝催化的烯烃-异链烷烃烷基化反应中用作抑制剂/改性剂，包括NaCl、LiCl、KCl、BeCl2、CaCl2、BaCl2、SrCl2、MgCl2、PbCl2、CuCl、ZrCl4和AgCl，如Roebuck和Evering所述(Ind.Eng.Chem.Prod.Res.Develop.卷9，77，1970)。优选的金属卤化物是CuCl、AgCl、PbCl2、LiCl和ZrCl4。
可采用HCl或任何布朗斯台德酸作为助催化剂来通过增加所述离子液体基催化剂的整体酸度来增强所述催化剂的活性。这样的助催化剂和离子液体催化剂的使用公开于美国公布的专利申请2003/0060359和2004/0077914中。可用于增强活性的其它助催化剂包括IVB金属化合物，优选IVB金属卤化物，例如Hirschauer等人在美国专利6,028,024中描述的ZrCl4、ZrBr4、TiCl4、TiCl3、TiBr4、TiBr3、HfCl4、HfBr4。
例如，在使用卤铝酸盐离子液体催化剂生产烷基化物烃汽油的方法中，在烷基化物烃中存在痕量的有机卤化物。希望从汽油中除去有机卤化物以满足产物规格。当然，当使用含有非氯化物的卤化物的离子液体催化剂时，发生类似的结果。
在其中离子液体催化剂含有氯化物的实施方案中，污染所得产物的有机卤化物是有机氯化物。使用氯铝酸盐离子液体催化剂制备的烷基化物烃物流中的氯化物含量一般为50-4000ppm。也希望从烷基化物中除去痕量的有机氯化物，因为有机氯化物在燃烧过程中会产生腐蚀性物质或有害物质，例如HCl或二噁英。
在本方法中，使用分子筛来从烃产物中吸附有机卤化物并除去它们。用于该吸附方法的分子筛选自大孔沸石、中孔沸石和小孔沸石。
沸石是具有一维至三维结构的硅铝酸盐，该结构形成具有分子尺度的通道或笼。铝原子是四配位的，构成该结构中的负电荷，其被骨架外阳离子所平衡。沸石中的铝的量可以广泛变化，SiO2/Al2O3摩尔比可为1至10000。
孔尺寸为4-16埃的大孔分子筛、中孔分子筛或小孔分子筛可用作吸附剂以减少烷基化物中的有机卤化物含量。大孔分子筛包括沸石X、沸石Y、USY沸石、丝光沸石、ALPO-5、SAPO-5、β、ZSM-12、MCM-22、MCM-36、MCM-68、ITQ-7、ITQ-10、ITQ-14、SSZ-24、SSZ-31、SSZ-33、SSZ-48、SSZ-55、SSZ-59和SSZ-60。中孔沸石包括ZSM-5、ZSM-11、ZSM-22、ZSM-35、ALPO-11、SAPO-11、SSZ-25、SSZ-32、SSZ-35、SSZ-41和SSZ-44。小孔分子筛包括沸石A、SSZ-16、SSZ-39和SSZ-52。这些材料可具有不同的阳离子。最普通的骨架外阳离子是钠、钾、铯、钙、镁和钡。
所述大孔分子筛、中孔分子筛或小孔分子筛可单独使用或作为混合物使用。例如，有可能使用大孔沸石和小孔沸石的混合物以及不同的小孔沸石的混合物。
在本发明的一个实施方案中，将含有有机卤化物的含有机卤的烷基化物与分子筛在吸附条件下接触，该吸附条件可包括：温度32-1000华氏度、压力1-1000psi，液时空速(LHSV)在0.1h-1和40h-1之间。在一个实施方案中，将所述分子筛维持在室温和常压下。根据本发明的方法可以以间歇过程、半连续过程或连续过程来进行。
在吸附过程之后，可测量烷基化物烃产物中的有机氯化物含量。在一个实施方案中，所述烷基化物烃产物中的有机氯化物含量小于40ppm。在另一个实施方案中，所述烷基化物烃产物中的有机氯化物含量小于10ppm。
所述分子筛有效地用于除去有机氯化物直至它达到其对有机氯化物的最大吸附容量为止。不同的沸石或分子筛对于有机氯化物具有不同的吸附容量。通常优选的是具有高有机氯化物吸附容量的材料，因为高容量材料能处理含更大量的有机氯化物的汽油。
在分子筛达到其对有机氯化物吸附的最大容量且不能吸附任何更多的有机氯化物之后，该分子筛能任选地被再生或再活化以多次循环使用。活化步骤可包括停止使含烷基化物的汽油与该分子筛材料接触，然后用脱附介质的流动来升高床温。可使用的脱附介质包括氮气、氢气、空气、气体二氧化碳或超临界液体状态的二氧化碳和C1-C10轻质烃，优选不含有机氯化物。脱附条件包括温度200-1000华氏度、压力1-1000psi，气时空速(GHSV)在1h-1和10000h-1之间或液时空速(LHSV)在0.1h-1和40h-1之间。脱附完成后，分子筛得以再活化并准备用于另一轮有机卤化物吸附循环。
实施例
以下实施例是本发明的说明性的实施例，但是并不打算以任何超出含于所附的权利要求中的内容的方式限制本发明。
测试了不同组成和孔尺寸的沸石。USY沸石、NaX沸石是含直径13埃的超笼且孔直径为7.2埃的三维网络的大孔分子筛。研究了Cs交换的USY，并显示具有不同阳离子的沸石在有机卤化物去除方面都是有效的。NaA沸石是含孔通道直径为4埃的二位网络的小孔分子筛。将这些沸石的有机卤化物去除性能与二氧化硅-氧化铝进行了对比，该二氧化硅-氧化铝含有与USY相当的总孔体积，不同之处在于二氧化硅-氧化铝中的孔主要是巨孔(孔直径大于30埃)且二氧化硅-氧化铝含有非常少的微孔(孔直径小于20埃)。
购买了NaX、USY、NaA和二氧化硅-氧化铝。CsUSY通过用Cs交换USY来制备。所有这些材料在538℃下在流动的干燥空气中煅烧3小时以除去任何吸附的水份。然后这些材料在N2下冷却并在吸附实验前存储在气密性的容器中。
实施例1
使用不同的吸附材料减少烷基化物烃中的氯化物
在密闭容器中装入0.5g的吸附材料和50mL的含有机氯化物的汽油。剧烈摇动该混合物30分钟以确保均匀混合。然后使该混合物静置以将烷基化物汽油与固体吸附材料分开。对比吸附前后的汽油样品以测定吸附材料的效果。结果概括于表1中。
表1
沸石与无定形材料吸收有机氯化物的比较
| 吸附材料 | 刚烷基化的汽油中的Cl(ppm) | 汽油中的Cl(ppm)，吸收后 | Cl减少，％ | 注释 |
| 二氧化硅-氧化铝 | 1286 | 1012 | 21.3 | 基础情况 |
| USY | 1286 | 37 | 97.1 | 本发明 |
| NaX | 880 | ＜5 | 99+ | 本发明 |
以上结果表明，NaX和USY沸石给出远胜于无定形二氧化硅-氧化铝的性能。我们的结果清晰地表明，含有微孔的分子筛材料大大优于无定形材料。
实施例2
不同的吸附材料的氯化物吸附容量
表2概括了不同材料的吸附容量。在这些实施例中，将不同量的吸附材料添加到50mL的含烷基氯的汽油中。测量了该烷基化物烃汽油中的氯含量和烷基化物烃产物中的氯含量。计算了每克吸附材料吸收有机氯化物的最大容量。
表2
不同的材料的有机氯化物吸收容量
| 吸附材料 | 吸附容量，gCl/吸附剂 | 注释 |
| 二氧化硅-氧化铝 | 0.01 | 基础情况 |
| NaA | 0.06 | 本发明 |
| NaX | 0.16 | 本发明 |
| USY | 0.07 | 本发明 |
| Cs交换的USY | 0.05 | 本发明 |
以上数据表明，含微孔的沸石材料具有远远优于中孔二氧化硅-氧化铝材料的对于有机氯化物的吸附容量。
实施例3
连续的有机氯化物去除方法
将外径为3/8”的反应器管充以12cc的尺寸为-24/+40的NaX分子筛，该分子筛被6cc的粒度90的碳化硅所稀释。通过在N2流下加热至600华氏度持续最少1小时来干燥该NaX。然后使反应器冷却至室温(约70华氏度)。然后使氯化物含量在50ppm和900ppm之间的烷基化物汽油在室温下在1h-1和10h-1之间的线性小时空速(LHSV)下穿过该吸附材料。收集反应器流出物并用X-射线荧光光谱(XRF)进行分析，以测量氯化物含量。将烷基化物汽油进料到该装置中直至观察到有机氯化物的流穿，并计算吸附容量。
在该吸附期间，NaX分子筛显示了0.1g氯化物/gNaX的氯化物吸附容量。通过气相色谱对反应器流出物进行的分析显示，在该吸附过程中没有烷基化物汽油的降解。
实施例4
使用脱附气体再活化分子筛
按照以下程序将来自实施例3的被氯化物充分饱和的NaX材料再活化，以恢复吸附容量。
首先，停止含有有机氯化物的烷基化物物流的流动。然后在N2流动下将反应器加热到600华氏度一整夜。次日，将NaX冷却到室温，然后恢复按照实施例3的含有机氯化物的烷基化物物流的过程。通过这一再活化过程，NaX的容量从0恢复到0.08g氯化物/gNaX。
Claims (16)
1.减少有机卤化物含量为50-4000ppm的烃产物中的卤化物浓度的方法，所述烃产物是使用包含含卤素的酸性离子液体的离子液体催化剂由烃转化方法生产的，所述方法包括使至少一部分所述烃产物与孔尺寸为4-16埃的至少一种分子筛在有机卤化物吸附条件下接触，以将该烃产物中的卤素浓度减少至小于40ppm。
2.权利要求1的方法，其中所述烃转化方法选自烷基化、聚合、二聚、低聚、乙酰化、复分解、共聚、异构化、烯烃加氢、加氢甲酰化和它们的组合。
3.权利要求1的方法，其中所述催化剂还包含布朗斯台德酸助催化剂。
4.权利要求1的方法，其中所述分子筛选自大孔沸石、中孔沸石、小孔沸石和它们的混合物。
5.权利要求1的方法，其中所述分子筛选自沸石X、沸石Y、USY沸石、丝光沸石、ALPO-5、SAPO-5、β、ZSM-12、MCM-22、MCM-36、MCM-68、ITQ-7、ITQ-10、ITQ-14、SSZ-24、SSZ-31、SSZ-33、SSZ-48、SSZ-55、SSZ-59、SSZ-60和它们的混合物。
6.权利要求1的方法，其中所述分子筛选自ZSM-5、ZSM-11、ZSM-22、ZSM-35、ALPO-11、SAPO-11、SSZ-25、SSZ-32、SSZ-35、SSZ-41、SSZ-44和它们的混合物。
7.权利要求1的方法，其中所述分子筛选自沸石A、SSZ-16、SSZ-39、SSZ-52和它们的混合物。
8.权利要求1的方法，其中所述分子筛被再活化并再次用作所述至少一种分子筛。
9.一种烷基化方法，包括使包含至少一种具有2-6个碳原子的烯烃的第一烃原料和包含至少一种具有3-6个碳原子的异链烷烃的第二烃原料在烷基化条件下与含卤素的酸性离子液体催化剂接触，以产生有机卤化物含量为50-4000ppm的烷基化物，并使至少一部分该烷基化物与孔尺寸为4-16埃的至少一种分子筛在有机卤化物吸附条件下接触，以生产有机氯化物含量小于40ppm的烷基化物烃产物。
10.权利要求9的方法，其中所述分子筛选自大孔沸石、中孔沸石、小孔沸石和它们的混合物。
11.权利要求9的方法，其中所述分子筛选自沸石X、沸石Y、USY沸石、丝光沸石、ALPO-5、SAPO-5、β、ZSM-12、MCM-22、MCM-36、MCM-68、ITQ-7、ITQ-10、ITQ-14、SSZ-24、SSZ-31、SSZ-33、SSZ-48、SSZ-55、SSZ-59、SSZ-60和它们的混合物。
12.权利要求9的方法，其中所述分子筛选自ZSM-5、ZSM-11、ZSM-22、ZSM-35、ALPO-11、SAPO-11、SSZ-25、SSZ-32、SSZ-35、SSZ-41、SSZ-44和它们的混合物。
13.权利要求9的方法，其中所述分子筛选自沸石A、SSZ-16、SSZ-39、SSZ-52和它们的混合物。
14.权利要求9的方法，其中所使用的离子液体催化剂是N-丁基吡啶鎓氯铝酸盐。
15.权利要求9的方法，其中所述分子筛被再活化并再次用作所述至少一种分子筛。
16.权利要求15的方法，其中通过在脱附介质的流动下将所述分子筛加热至200-1000华氏度的温度来对其进行再活化。
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| US11/960,506 US8105481B2 (en) | 2007-12-19 | 2007-12-19 | Reduction of organic halide contamination in hydrocarbon products |
| PCT/US2008/082347 WO2009079107A1 (en) | 2007-12-19 | 2008-11-04 | Reduction of organic halide contamination in hydrocarbon products |
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| EP (1) | EP2231560A4 (zh) |
| KR (1) | KR20100103825A (zh) |
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| CN103328095A (zh) * | 2011-06-27 | 2013-09-25 | 雪佛龙美国公司 | 通过废吸附剂的碱性溶液处理使烷基氯吸附能力恢复 |
| CN106457207A (zh) * | 2014-06-20 | 2017-02-22 | 埃克森美孚研究工程公司 | 使用itq‑55分离和储存流体 |
| CN111068613A (zh) * | 2019-12-26 | 2020-04-28 | 四川润和催化新材料股份有限公司 | 一种有机氯脱除剂及其制备方法与应用 |
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| CN102108306B (zh) | 2009-12-28 | 2013-12-18 | 中国石油大学(北京) | 一种以离子液体为催化剂的烷基化反应方法 |
| US8237004B2 (en) * | 2009-12-31 | 2012-08-07 | Chevron U.S.A. Inc. | Process for making products with low hydrogen halide |
| WO2012038413A1 (en) * | 2010-09-23 | 2012-03-29 | Shell Internationale Research Maatschappij B.V. | Process for reducing the halogen content of a hydrocarbon product stream by mixing with an aqeous caustic solution in the presence of a phase transfer catalyst |
| WO2012038499A1 (en) | 2010-09-23 | 2012-03-29 | Shell Internationale Research Maatschappij B.V. | Process for reducing the halogen content of a hydrocarbon product stream by contacting with a metal |
| US20120160740A1 (en) * | 2010-12-22 | 2012-06-28 | Chevron U.S.A. Inc. | Processes for ionic liquid catalyzed upgrading of oxygenate containing hydrocarbon feedstocks |
| US8551328B2 (en) | 2011-01-20 | 2013-10-08 | Basf Corporation | Organic chloride adsorbent |
| US9839897B2 (en) * | 2013-05-30 | 2017-12-12 | Chevron U.S.A. Inc. | Method for reducing organic halide contamination in hydrocarbon products using a metal chloride |
| US9328037B2 (en) * | 2014-07-09 | 2016-05-03 | Uop Llc | Benzene alkylation using acidic ionic liquids |
| US9776877B2 (en) * | 2014-12-11 | 2017-10-03 | Uop Llc | Separation of conjunct polymer from volatile regenerant for ionic liquid regeneration |
| US10828625B2 (en) | 2015-06-01 | 2020-11-10 | California Institute Of Technology | Crystalline germanosilicate materials of new CIT-13 topology and methods of preparing the same |
| CN107873015B (zh) | 2015-06-01 | 2021-12-24 | 加州理工学院 | 具有新的cit-13拓扑结构的晶体锗硅酸盐材料及其制备方法 |
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| AU2008338817B2 (en) | 2012-04-05 |
| US20100320125A1 (en) | 2010-12-23 |
| EP2231560A4 (en) | 2012-02-29 |
| EP2231560A1 (en) | 2010-09-29 |
| US20090163759A1 (en) | 2009-06-25 |
| KR20100103825A (ko) | 2010-09-28 |
| BRPI0821207A2 (pt) | 2015-06-16 |
| WO2009079107A1 (en) | 2009-06-25 |
| US8105481B2 (en) | 2012-01-31 |
| AU2008338817A1 (en) | 2009-06-25 |
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