CN103168088A - 由乙烯和异丁烷生产高辛烷值烷基化物 - Google Patents
由乙烯和异丁烷生产高辛烷值烷基化物 Download PDFInfo
- Publication number
- CN103168088A CN103168088A CN2011800483726A CN201180048372A CN103168088A CN 103168088 A CN103168088 A CN 103168088A CN 2011800483726 A CN2011800483726 A CN 2011800483726A CN 201180048372 A CN201180048372 A CN 201180048372A CN 103168088 A CN103168088 A CN 103168088A
- Authority
- CN
- China
- Prior art keywords
- catalytic material
- ethene
- trimethylmethane
- catalyst
- bead
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 title claims abstract description 106
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000005977 Ethylene Substances 0.000 title abstract description 38
- 239000001282 iso-butane Substances 0.000 title abstract description 10
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 title abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 108
- 230000003197 catalytic effect Effects 0.000 claims abstract description 99
- 239000003054 catalyst Substances 0.000 claims abstract description 76
- 238000000034 method Methods 0.000 claims abstract description 45
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 42
- 230000029936 alkylation Effects 0.000 claims abstract description 41
- 238000006471 dimerization reaction Methods 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000010457 zeolite Substances 0.000 claims description 40
- 229910021536 Zeolite Inorganic materials 0.000 claims description 39
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 33
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 31
- 239000011324 bead Substances 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 21
- 230000008929 regeneration Effects 0.000 claims description 17
- 238000011069 regeneration method Methods 0.000 claims description 17
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 15
- 238000005984 hydrogenation reaction Methods 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 229960001866 silicon dioxide Drugs 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- -1 chlorinated aluminas Chemical compound 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- GHTGICGKYCGOSY-UHFFFAOYSA-K aluminum silicon(4+) phosphate Chemical compound [Al+3].P(=O)([O-])([O-])[O-].[Si+4] GHTGICGKYCGOSY-UHFFFAOYSA-K 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 230000000447 dimerizing effect Effects 0.000 abstract 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 16
- 150000001336 alkenes Chemical class 0.000 description 11
- 239000000571 coke Substances 0.000 description 9
- 238000007598 dipping method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 239000003502 gasoline Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 238000004231 fluid catalytic cracking Methods 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000002152 alkylating effect Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 150000007517 lewis acids Chemical group 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 101150101537 Olah gene Proteins 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- GIXWDMTZECRIJT-UHFFFAOYSA-N aurintricarboxylic acid Chemical compound C1=CC(=O)C(C(=O)O)=CC1=C(C=1C=C(C(O)=CC=1)C(O)=O)C1=CC=C(O)C(C(O)=O)=C1 GIXWDMTZECRIJT-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical group 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Images
Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7415—Zeolite Beta
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/90—Regeneration or reactivation
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- B01J35/19—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- 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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
- C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
-
- 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
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Abstract
一种通过使乙烯和异丁烷在催化转化条件下反应由乙烯和异丁烷来生产高辛烷值烷基化物的方法。使该乙烯和异丁烷与包含二聚催化剂(即,用于二聚乙烯)的第一催化材料和包含烷基化催化剂的第二催化材料接触。该第一和第二催化材料是彼此分离和不同的。作为乙烯和异丁烷在第一和第二催化材料存在下反应的结果而回收高辛烷值烷基化物。
Description
本申请要求基于2010年10月6日申请的临时申请61/404597的优选权,其内容全部引入作为参考。
本发明涉及由包含乙烯和异丁烷的进料来生产高辛烷值烷基化物。更具体地,本发明涉及由乙烯和异丁烷,通过乙烯和异丁烷在催化转化条件下反应来生产高辛烷值烷基化物,该反应是在第一催化材料(其包括二聚催化剂和促进了二聚催化剂再生的材料)和第二催化材料(其包括烷基化催化剂)存在下进行的,其中该第一和第二催化材料是彼此分离和不同的。
流化催化裂化(FCC)是每个现代化精炼厂的心脏,由此将重质石油组分转化成高价值燃料。FCC操作以及其他通常的裂化方法总是产生从轻质气体到重质燃油的一系列产物。在这个系列中,包括C2(乙烷、乙烯)到C4(丁烷、异丁烷、丁烯、异丁烯)范围的轻质链烷烃和烯烃。典型地,精炼厂将在被称作烷基化的方法中,将C4 烯烃(以及可能的C3和C5烯烃)与异丁烷化学结合。来自这种方法的产物被称作烷基化物。
烷基化物是精炼厂中生产的最清洁的汽油混合流,并且是一种理想的清洁燃料组分,这是因为它具有高辛烷值、低蒸气压和低毒性。数十年以来,烷基化物已经被混入到汽油中来提高汽油的辛烷值和由此改进抗爆特性。另外,州和联邦对于汽油配方和物理性能的严格限制使得烷基化物成为汽油调合用组分中最重要和最有价值的调和组分油(blendstock)之一。
目前,烷基化物的大规模生产是通过被称作异链烷烃烷基化的方法来进行的。商业上,异链烷烃烷基化是一种液体酸催化的反应,其将异丁烷与烯烃(如丙烯、丁烯和戊烯(C3-C5烯烃))相结合。对于这种方法来说,精炼厂使用了氢氟酸(HF)或硫酸(H2SO4)作为液体烷基化催化剂。
乙烯(C2烯烃)是FCC装置中产生的另外一种主要组分。虽然所有商业烷基化装置中所使用的液体酸催化剂在活化C3-C5烯烃方面是相当有效的,但是它们不能活化乙烯。相反,乙烯与所述酸在这些装置中形成稳定的乙基醚,由此提供惰性的和无用的混合物。(Nivarty等人,Microporous and Mesoporous,第35-36卷,第75-87页(2000))。因此,市售的烷基化装置不能进行乙烯的烷基化。
在烷基化中,烯烃的质子化是一个关键的引发步骤(Corma等人,Trends Catal.Rev.-Sci.Eng.,第35卷第483页(1993)),由此烯烃的活化主要取决于所产生的碳阳离子的稳定性。乙烯的反应性天生比丁烯弱;乙烯中任一碳原子的质子化导致形成不稳定的伯碳阳离子,而丁烯的质子化形成更稳定的仲碳阳离子。
丁烯可以在常规的烷基化过程中,通过布朗斯台德酸(如常规的液体酸催化剂)来容易的质子化。相反,活化乙烯以进行烷基化需要Friedel-Crafts类型的催化剂,如BF3和氯化氧化铝(Goupil等人,Catalysis Letters,第31卷,第121-131页(1995);Hoffman,US专利No.3873634)。用于异链烷烃与乙烯的烷基化的最有活性的催化剂是路易斯酸与质子无机酸的混合物,如HCl和AlCl3,因为这样的混合物具有能够活化乙烯的路易斯中心和促进随后的杂化迁移反应所必需的布朗斯台德中心(Olah等人,Hydrocarbon Chemistry,第2版,Wiley Interscience,第632页(1995))。在US专利7432408中使用了相关的催化剂、具有氯化铝阴离子的离子液体来用乙烯烷基化异戊烷。
但是,这些催化剂对于痕量水是敏感的,容易失活和腐蚀装置。因此,它们不适于成本有效的精炼方法,并且在商业上没有用于这个用途。
沸石同时具有布朗斯台德和路易斯酸中心;但是,这些催化剂不表现对乙烯烷基化的高活性。例如,据报道沸石β仅仅表现出10小时的40%的稳定乙烯转化率,而在相同条件下对丁烯却实现了完全转化(Nivarthy等人)。还计算了其他沸石系统,乙烯质子化的活化能垒会相当高(23-30kcal/mol)(Namuangruk等人,Chemphys.Chem.,第6卷,第1333-1339页(2005);Svelle等人,J.Physical Chemistry.第108卷,第2953-2962页(2004))。作为这种低活性的结果,已知的固体酸催化剂也不适于在商业方法中直接用乙烯烷基化,因为它们需要不切实际的大量的催化剂。
乙烯可以通过二聚转化成丁烯,由此两个乙烯分子结合成单个丁烯分子。乙烯二聚成丁烯是在例如Axens Alphabutol方法中商业实施的。这样的商业方法需要高选择性均相催化剂,例如US专利5162595中所公开的那些,并且限于相对纯的乙烯流。用于乙烯低聚的非均相催化剂对于丁烯不是选择性的,允许产生不太期望的高级烯烃。
用于解决低乙烯反应性问题的一种已知的可选方案(http://www.icis.com/Articles/1999/05/31/81473/the-ethalk-route-to-high-octane-alkylate.html)是向烷基化催化剂中并入乙烯二聚功能。使用这种催化剂,乙烯首先被二聚成丁烯,其然后经历与异丁烷的常规烷基化。丁烯具有比乙烯大得多的烷基化反应性,导致了更高的整体反应速率。但是,这仍然需要合适的烷基化催化剂,并且将二聚功能加入到烷基化催化剂中妨碍了组合的催化剂再生,这归因于形成了难以去除的乙烯低聚物和焦炭。
与这个方案有关的一个问题是烷基化催化剂中的二聚中心随着使用被一种焦炭变得失活,所述焦炭只有在非常苛刻的再生条件下才能被除去。适于再生这样的催化剂上的二聚中心的唯一方法是首先用含氧流体如空气来氧化该焦炭,然后使用含氢的流体来氢化任何剩余的焦炭。两个步骤都在高温(250℃)下进行。这样的再生方案在工业操作中不实用,这是因为将氧气引入到烃工艺中的危险性和当它从烃基的变成氧基的时需要频繁的净化所述系统。
本发明涉及由浓缩的或稀释的乙烯流来生产高辛烷值的烷基化物,这与仅仅能够使用浓缩的乙烯流的常规方法形成了对比。
根据本发明的一方面,提供了一种由乙烯和异丁烷来生产高辛烷值烷基化物的方法。该方法包括使乙烯和异丁烷在催化转化条件下反应。该乙烯和异丁烷与第一催化材料和第二催化材料接触。该第一催化材料包含二聚催化剂和促进该二聚催化剂再生的材料。该第二催化材料包含烷基化催化剂。该第一催化材料和第二催化材料是彼此分离和不同的。在乙烯和异丁烷反应后,回收了高辛烷值烷基化物。
作为此处使用的,与第一和第二催化材料有关的术语“彼此分离和不同的”表示第一和第二催化材料是两种独立的和物理分开的材料。然而在本发明的非限定性实施方案中,该第一和第二催化材料可以彼此物理混合,例如,其中第一催化材料的颗粒或小球和第二催化材料的颗粒或小球被容纳在同一催化剂床中,或者该第一和第二催化材料可以包含在同一颗粒或小球中,但该第一和第二催化材料保留它们单独的特性。
如上文所述,该第一催化材料包含二聚催化剂和促进该二聚催化剂再生的材料。该二聚催化剂催化乙烯向丁烯的二聚,其然后与异丁烷反应来产生高辛烷值烷基化物。在一种非限定性实施方案中,该二聚催化剂包含金属和用于该金属的载体。可用于该二聚催化剂中的金属包括但不限于镍,钯,铬,钒,铁,钴,钌,铑,铜,银,铼,钼,钨和锰。可用的载体包括但不限于沸石,氧化铝,二氧化硅,碳,二氧化钛,氧化锆,二氧化硅/氧化铝和介孔二氧化硅。
在一种非限定性实施方案中,该二聚催化剂是通过将金属的盐沉积或浸渍到载体上来制造的。在一种非限定性实施方案中,基于载体的重量,金属以大约0.1wt%-大约10wt%的量沉积或浸渍到载体上。然后干燥和在空气或氮气中煅烧该催化剂,由此将金属固定到载体上。
虽然本发明的范围不限于任何的理论推理,但是据信二聚催化剂的活性是由金属和载体的相互作用产生的。在一种非限定性实施方案中,能够使用的二聚催化剂包括但不限于负载在脱铝沸石Y上的镍;负载在浸渍的二氧化硅/氧化铝上的镍;负载在铝交换的介孔沸石A1MCM-41上的镍;负载在沸石ZSM-5上的镍;负载在二氧化硅上的双(亚氨基)吡啶基铁(II);负载在硅胶上的二(亚氨基)铁(II)三齿物;具有改性的甲基铝氧烷配体的锰、铬和/或钒;负载在用改性的甲基铝氧烷配体活化的二氧化硅上的镍、钴、钯、铂或铁;和负载在具有铝试剂的硅胶上的铬。
该二聚催化剂还包含促进该二聚催化剂再生的材料。在一种非限定性的实施方案中,该促进该二聚催化剂再生的材料是氢化催化剂。可用的氢化催化剂包括但不限于铂、镍和钯。在一种非限定性实施方案中,该氢化催化剂是铂。在另一种非限定性实施方案中,该氢化催化剂是钯。在另一种非限定性实施方案中,该氢化催化剂是镍。
该烷基化催化剂通常是对用丁烯(即,作为乙烯二聚的结果而形成的)烷基化异丁烷表现出至少一些活性的催化剂。在一种非限定性实施方案中,能够使用的烷基化催化剂包括但不限于沸石、硫酸化氧化锆、钨酸化氧化锆、氯化氧化铝、氯化铝(AICI3)、磷酸硅-铝、钛硅酸盐(包括VTM沸石)、多磷酸(包括固体磷酸或SPA,催化剂,它们是通过磷酸与硅藻土反应制造的)、多钨酸和负载型液体酸,如负载在二氧化硅上的三氟甲磺酸、负载在二氧化硅上的硫酸、负载在碳上的氟化氢、负载在二氧化硅上的氟化锑和负载在氧化铝(A12O3)上的氯化铝(AICI3)。
在一种非限定性实施方案中,该烷基化催化剂是沸石。能够使用的沸石包括但不限于沸石β;BEA*沸石;MC沸石;八面沸石,其包括沸石X、沸石Y(包括稀土交换的沸石X和沸石Y)和USY沸石;LTL沸石;丝光沸石;MF1沸石,其包括ZSM-5;EMT沸石;LTA沸石;ITW沸石,ITQ沸石和SFO沸石。
如上文所述,乙烯和异丁烷在催化转化条件下反应,并且与上述第一和第二催化材料接触,产生高辛烷值烷基化物。在一种非限定性实施方案中,进料除了乙烯和异丁烷之外,还可以包含链烷烃(例如甲烷、乙烷、丙烷、丁烷等)和烯烃(例如丙烯、丁烯、戊烯等)。使进料在催化材料上反应产生烷基化物。如果该进料包含乙烯之外的烯烃,也可以使这样的烯烃反应来产生烷基化物。另外,如果存在异丁烷之外的异链烷烃(例如异戊烷),也可以使其反应来形成烷基化物。
该反应可以在液相、混合的气-液相或气相中进行。在一种非限定性实施方案中,该反应是在液相或混合相中进行的,其中含乙烯的流与含液体异丁烷的流组合产生两相进料流)。每个相的组成是由所形成的混合物在所用温度和压力下的蒸气-液体平衡决定的。
乙烯和异丁烷在产生高辛烷值烷基化物的条件下反应。在一种非限定性实施方案中,乙烯和异丁烷在大约60°-大约150℃的温度下反应。在另一种非限定性实施方案中,乙烯和异丁烷在大约75℃的温度下反应。
在另一种非限定性实施方案中,乙烯和异丁烷在高到大约500psig的压力下反应。在仍然的另一种非限定性实施方案中,乙烯和异丁烷在大约300psig-大约400psig的压力下反应。
在另外一种非限定性实施方案中,乙烯和异丁烷以异丁烷:乙烯为大约5-大约15的摩尔比反应。在另一种非限定性实施方案中,乙烯和异丁烷以大约8-大约12的摩尔比反应。
在一种非限定性实施方案中,本发明的方法进一步包括再生该第一催化材料。在另一非限定性实施方案中,该第一催化材料的再生包括使该第一催化材料与氢接触。在又一非限定性实施方案中,使该第一催化材料与氢在大约250℃大约350℃的温度下接触。
虽然本发明的这种实施方案的范围不限于任何理论推断,但是据信氢是在包含在第一催化材料中的氢化催化剂存在下,与已经在该第一催化材料上形成的乙烯低聚物(例如己烯、辛烯)反应,由此该低聚物变成饱和的,从而使得该饱和低聚物能够从第一催化材料上热解吸,由此提供包含在该第一催化材料中的二聚催化剂的再生。
如上所述,该第一和第二催化材料是彼此分离和不同的。通过将该第一和第二催化材料保持彼此分离和不同,防止了在包含于第二催化材料中的烷基化催化剂上形成硬焦炭。
更具体地,存在于该烷基化催化剂上的强酸中心不会促使在二聚催化剂和烷基化催化剂二者上形成硬焦炭。通过将该第一和第二催化材料保持彼此分离的和不同,防止了该第一和第二催化材料彼此发生不期望的相互作用,由此防止了形成焦炭,焦炭将使得该第一和第二催化材料的再生变得更困难。
该第一和第二催化材料可以结合在单个反应器中,也可以包含在分别的反应器中。在仍又一可选择的非限定性实施方案中,提供了多个(即,3个或更多个)反应器,其中含有该第一和第二催化材料的反应器以交替的次序排列。
在一种非限定性实施方案中,该第一催化材料的颗粒或小球和该第二催化材料的颗粒或小球结合在单个反应器中。在一种非限定性实施方案中,当该第一催化材料的颗粒或小球与该第二催化材料的颗粒或小球结合在单个反应器中时,该第一和第二催化材料的颗粒或小球是以第一催化材料:第二催化材料为大约1:10-大约10:1的重量比来结合的。在另一非限定性实施方案中,该第一和第二催化材料的颗粒或小球是以第一催化材料:第二催化材料为大约1:5-大约5:1的重量比来结合的。
在另一非限定性实施方案中,该第一催化材料和第二催化材料混合和物理结合成颗粒或小球,由此每个这样的颗粒或小球包括第一催化材料和第二催化材料。在这样的颗粒或小球中,第一催化材料不包含在第二催化材料中或吸附在第二催化材料的表面上,反之亦然。在一种非限定性实施方案中,当该第一和第二催化材料混合和物理结合成颗粒或小球时,该第一和第二催化材料是以第一催化材料:第二催化材料为大约1:10-大约10:1的重量比来混合和结合的。在另一非限定性实施方案中,该第一和第二催化材料是以第一催化材料:第二催化材料为大约1:5-5:1的重量比来混合和结合的。
虽然上述实施方案的范围并非意在限制于任何理论推断,但是两种催化材料的物理混合为二聚催化剂上所形成的丁烯,通过在烷基化催化剂存在下的使用所述丁烯的异丁烷烷基化,而快速消耗做好了准备。这通过使乙烯的高级低聚物(例如己烯、辛烯)的产生最小化而提高了所形成的烷基化物的品质和产率。第一和第二催化材料这种物理混合还限制了二聚活性(其是高度放热的),由此减少了催化剂床中的“热点”。另外,可以通过调整第一和第二催化材料各自的量来控制乙烯二聚活性和烷基化活性的相对量。
因此,本发明能够反应尽可能多的乙烯,产生高辛烷值烷基化物,其几乎与使用丁烯作为初始烯烃所产生的产物相同,并且使用了仅需单个再生步骤的可再生催化剂。
下面将参考附图来描述本发明,其中:
图1是反应时间(TOS)对乙烯转化百分率的图,其中乙烯与异丁烷在未处理的沸石β催化剂或用钯浸渍的沸石β催化剂存在下反应;
图2是反应时间(TOS)对乙烯转化百分率的图,其中乙烯与异丁烷在未处理的镧交换的沸石X催化剂或用钯浸渍的镧交换的沸石X催化剂存在下反应;
图3是反应时间(TOS)对乙烯转化百分率的图,其中乙烯与异丁烷在未处理的沸石β催化剂或用镍浸渍的沸石β催化剂存在下反应;
图4是反应时间(TOS)对乙烯转化百分率的图,对于第一次和第二次反应运行来说,其中乙烯与异丁烷在用镍浸渍的沸石β催化剂存在下反应;和
图5是反应时间(TOS)对烯烃转化百分率的图,其中乙烯与异丁烷在分离的二聚和烷基化催化剂存在下反应。
实施例
下面将参考下面的实施例来描述本发明。但是应当理解本发明的范围不限于此。
实施例1
这个实施例证实了当使用乙烯作为烯烃时,加入二聚催化剂到已知的烷基化催化剂中产生了性能的明显改进。
烷基化催化剂是如下来制备的:通过与0.5M硝酸铵溶液交换,将沸石β转化成它的酸形式,随后使用本领域公知的技术进行干燥和煅烧。向该材料的一个部分添加四氨合硝酸钯(II)形式的二聚催化剂,以在最终催化剂中实现0.1wt%的Pd负载量。Pd盐是经由常规的湿浸渍程序添加的,其包括将期望量的盐溶解在蒸馏水中,将该溶液添加到干燥的催化剂,使该溶液在催化剂中保持4小时的时间,通过蒸发除去溶剂(水),然后在空气中煅烧来分解所述盐。在催化剂测试之前,通过将氢送过350℃的催化剂床来在反应器中活化每个催化剂。
在相同的条件下,测试了Pd浸渍的和未处理的烷基化催化剂各2g样品的乙烯烷基化活性。使异丁烷:乙烯摩尔比为12:1的乙烯在异丁烷中的进料与所述催化剂的固定床在一次通过式连续流动反应器系统中接触。进料流速是1.2h-1重量时空速率。反应温度是80℃和压力是400psig。
该测试的结果表示在图1中。虽然未处理的催化剂失去了快速乙烯烷基化的活性,但是包含Pd二聚催化剂的催化剂在测试期间表现出完全的乙烯转化率。此外,作为令人期望的辛烷(C8)异构体存在的烷基化物的分数从未处理的催化剂的26%增加到Pd处理的催化剂的60%。通过Pd处理的催化剂所产生的烷基化物具有90的研究法辛烷值(RON)。
实施例2
重复实施例1的程序,除了将La交换的沸石X用作母体烷基化催化剂之外。在与实施例1的那些相同的条件下测试该催化剂。这个测试的结果表示在图2中。同样,含Pd的催化剂表现出比母体材料明显更高的乙烯烷基化活性。作为令人期望的辛烷(C8)异构体存在的烷基化物的分数从未处理的催化剂的70%增加到Pd处理的催化剂的90%。通过Pd处理的催化剂所产生的烷基化物具有97.5的研究法辛烷值(RON)。
实施例3
重复实施例1的程序,除了将烷基化催化剂与0.2M硝酸镍的水溶液交换,代替Pd盐的浸渍之外。将交换的催化剂用蒸馏水清洗和干燥,随后煅烧。该催化剂的镍负载量为5wt%。将该镍交换的催化剂以与实施例1相同的方式活化和测试。该测试的结果在图3中给出。
如图3所示,该含镍的催化剂表现出与含Pd的催化剂相同的活性提高,这清楚地表明任何催化乙烯二聚的金属都可以用于本发明中。使用镍或其他贱金属的益处是它们比贵金属(如钯)低得多的成本。
实施例4
虽然前面的实施例中所示的催化剂是活性的,但是它们不能在不使用不期望的氧化步骤的情况下再生。在这个实施例中,将普通再生材料Pt添加到实施例3的Ni-沸石β催化剂的新样品中。将该催化剂用于乙烯和异丁烷在75℃温度,400psig压力,0.20h-1的烯烃空速和进料异丁烷/乙烯比12mol/mol下的反应。8小时后,停止所述运行,通过在流动的氢气下加热到400℃持续3小时来再生该催化剂。然后重复该运行。如图4所示,催化剂没有恢复全部的活性。
实施例5
通过将1wt%的Ni浸渍到二氧化硅-氧化铝载体上来制造二聚催化剂。还添加了0.1wt%的Pt作为氢化催化剂。通过向沸石β添加0.1wt%的Pt来制备分离的烷基化催化剂。将两个催化剂在反应器中物理混合。将该混合的催化剂用于在与实施例4相同的条件下的使用乙烯的异丁烷烷基化。如同实施例4中那样,8小时后,停止所述运行,通过在流动的氢气下加热到400℃持续3小时来再生该催化剂。然后重复该运行两次以上。图5所示的结果证实了在每个循环后,催化剂活性完全恢复。
全部的专利和公开文献(包括公开的专利申请)的公开内容都以如同每个专利和公开文献单独引入作为参考的相同程度引入作为参考。
但是,应当理解本发明的范围不限于上述的具体实施方案。本发明可以以不同于所具体描述的,但是仍然处于附加的权利要求的范围内的方式来实施。
Claims (26)
1. 一种由乙烯和异丁烷来生产高辛烷值烷基化物的方法,其包括:
(a) 使乙烯和异丁烷在催化转化条件下反应,其中使所述乙烯和异丁烷与(i)第一催化材料和(ii)第二催化材料接触,所述第一催化材料包含二聚催化剂和促进所述二聚催化剂再生的材料,所述第二催化材料包含烷基化催化剂,其中所述第一催化材料和所述第二催化材料是彼此分离和不同的;和
(b) 回收来自步骤(a)的高辛烷值烷基化物。
2. 权利要求1的方法,其中所述促进所述二聚催化剂再生的材料是氢化催化剂。
3. 权利要求1的方法,其中所述二聚催化剂包含金属和用于所述金属的载体。
4. 权利要求3的方法,其中所述金属选自镍、钯、铂、铬、钒、铁、钴、钌、铑、铜、银、铼、钼、钨和锰。
5. 权利要求3的方法,其中所述用于所述金属的载体选自沸石、二氧化硅、氧化铝、碳、二氧化钛、氧化锆、二氧化硅/氧化铝和介孔二氧化硅。
6. 权利要求2的方法,其中所述氢化催化剂选自铂、镍和钯。
7. 权利要求6的方法,其中所述氢化催化剂是铂。
8. 权利要求6的方法,其中所述氢化催化剂是钯。
9. 权利要求6的方法,其中所述氢化催化剂是镍。
10. 权利要求1的方法,其中所述烷基化催化剂选自沸石、硫酸化氧化锆、钨酸化氧化锆、氯化氧化铝、氯化铝,磷酸硅-铝、钛硅酸盐、多磷酸、多钨酸、负载在二氧化硅上的三氟甲磺酸、负载在二氧化硅上的硫酸、负载在碳上的氟化氢、负载在二氧化硅上的氟化锑和负载在氧化铝上的氯化铝。
11. 权利要求10的方法,其中所述烷基化催化剂是沸石。
12. 权利要求1的方法,其中所述乙烯和所述异丁烷在大约60℃-大约150℃的温度下反应。
13. 权利要求12的方法,其中所述乙烯和所述异丁烷在大约75℃的温度下反应。
14. 权利要求1的方法,其中所述乙烯和所述异丁烷在最高大约500psig的压力下反应。
15. 权利要求14的方法,其中所述乙烯和所述异丁烷在大约300psig-大约400psig的压力下反应。
16. 权利要求1的方法,其中所述乙烯和所述异丁烷以异丁烷:乙烯为大约5-大约15的摩尔比反应。
17. 权利要求16的方法,其中所述乙烯和所述异丁烷以异丁烷:乙烯为大约8-大约12的摩尔比反应。
18. 权利要求2的方法,其进一步包括:
(c)再生所述第一催化材料。
19. 权利要求18的方法,其中所述第一催化材料的所述再生包括使所述第一催化材料与氢接触。
20. 权利要求19的方法,其中使所述第一催化材料与氢在大约250℃-大约350℃的温度下接触。
21. 权利要求1的方法,其中所述第一催化材料和所述第二催化材料结合在单个反应器中。
22. 权利要求21的方法,其中所述第一催化材料的颗粒或小球和所述第二催化材料的颗粒或小球以所述第一催化材料:所述第二催化材料为大约1:10到大约10:1的重量比来结合。
23. 权利要求22的方法,其中所述第一催化材料的颗粒或小球和所述第二催化材料的颗粒或小球以所述第一催化材料:所述第二催化材料为大约1:5到大约5:1的重量比来结合。
24. 权利要求21的方法,其中所述第一催化材料和所述第二催化材料已经物理结合成颗粒或小球,由此每个所述颗粒或小球包含所述第一催化材料和所述第二催化材料。
25. 权利要求24的方法,其中所述第一催化材料和所述第二催化材料以所述第一催化材料:所述第二催化材料为大约1:10到大约10:1的重量比来物理结合成颗粒或小球。
26. 权利要求25的方法,其中所述第一催化材料和所述第二催化材料以所述第一催化材料:所述第二催化材料为大约1:5到大约5:1的重量比来结合成颗粒或小球。
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Application Number | Priority Date | Filing Date | Title |
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US40459710P | 2010-10-06 | 2010-10-06 | |
US61/404597 | 2010-10-06 | ||
US61/404,597 | 2010-10-06 | ||
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CA2812666A1 (en) | 2012-04-12 |
US20120088948A1 (en) | 2012-04-12 |
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HUE053372T2 (hu) | 2021-06-28 |
CA2812666C (en) | 2017-09-19 |
ES2845613T3 (es) | 2021-07-27 |
WO2012047274A2 (en) | 2012-04-12 |
PL2625251T3 (pl) | 2021-05-04 |
EP2625251A4 (en) | 2015-01-21 |
CN103168088B (zh) | 2015-10-07 |
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EP2625251A2 (en) | 2013-08-14 |
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