TWI373452B - Hydrocarbon conversion using nanocrystalline zeolite y - Google Patents
Hydrocarbon conversion using nanocrystalline zeolite y Download PDFInfo
- Publication number
- TWI373452B TWI373452B TW094104075A TW94104075A TWI373452B TW I373452 B TWI373452 B TW I373452B TW 094104075 A TW094104075 A TW 094104075A TW 94104075 A TW94104075 A TW 94104075A TW I373452 B TWI373452 B TW I373452B
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- TW
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- Prior art keywords
- zeolite
- catalyst
- oxide
- alkylation
- product
- Prior art date
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- 239000010457 zeolite Substances 0.000 title claims description 65
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims description 58
- 229910021536 Zeolite Inorganic materials 0.000 title claims description 55
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 10
- 238000006243 chemical reaction Methods 0.000 title description 15
- 229930195733 hydrocarbon Natural products 0.000 title description 7
- 239000004215 Carbon black (E152) Substances 0.000 title description 6
- 238000000034 method Methods 0.000 claims description 41
- 239000003054 catalyst Substances 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000005804 alkylation reaction Methods 0.000 claims description 29
- 230000029936 alkylation Effects 0.000 claims description 21
- 239000013078 crystal Substances 0.000 claims description 14
- -1 octane oxime Chemical class 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 150000001336 alkenes Chemical class 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 9
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 8
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 8
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical group CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 5
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 5
- 239000012188 paraffin wax Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 230000002152 alkylating effect Effects 0.000 claims description 3
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000001282 iso-butane Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- 238000010555 transalkylation reaction Methods 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 239000006193 liquid solution Substances 0.000 claims 4
- 229910052707 ruthenium Inorganic materials 0.000 claims 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims 2
- 150000002910 rare earth metals Chemical class 0.000 claims 2
- DFVOXRAAHOJJBN-UHFFFAOYSA-N 6-methylhept-1-ene Chemical compound CC(C)CCCC=C DFVOXRAAHOJJBN-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 229910052804 chromium Inorganic materials 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 229910052741 iridium Inorganic materials 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 229910052746 lanthanum Inorganic materials 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 229910052758 niobium Inorganic materials 0.000 claims 1
- 229910052762 osmium Inorganic materials 0.000 claims 1
- 229910052763 palladium Inorganic materials 0.000 claims 1
- 229910052697 platinum Inorganic materials 0.000 claims 1
- 229910052703 rhodium Inorganic materials 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- 229910052715 tantalum Inorganic materials 0.000 claims 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 229910052721 tungsten Inorganic materials 0.000 claims 1
- 229910052720 vanadium Inorganic materials 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 229910052684 Cerium Inorganic materials 0.000 description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 150000001491 aromatic compounds Chemical class 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000002168 alkylating agent Substances 0.000 description 4
- 229940100198 alkylating agent Drugs 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 4
- 235000015097 nutrients Nutrition 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- JLHNIVALIRMXTJ-UHFFFAOYSA-N [B+]=O.[O-2].[Ce+3].[O-2] Chemical compound [B+]=O.[O-2].[Ce+3].[O-2] JLHNIVALIRMXTJ-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 1
- 238000006172 aromatic nitration reaction Methods 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052663 cancrinite Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006199 nebulizer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
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- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
-
- 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
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- 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
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/24—Type Y
-
- 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
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
- C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
- C07C6/126—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of more than one hydrocarbon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C9/00—Aliphatic saturated hydrocarbons
- C07C9/14—Aliphatic saturated hydrocarbons with five to fifteen carbon atoms
- C07C9/16—Branched-chain hydrocarbons
-
- 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
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/40—Special temperature treatment, i.e. other than just for template removal
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
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Description
1373452 ! · t (1) 九、發明說明 有關申請之交互對照 本申請案爲2002年2月5日提出申請的美國申請序號 1 0/067,7 1 9的部份追加案’其以引用方式倂於本文,且對 其主張優先權。 【發明所屬之技術領域】
本發明係有關一種烴化合物的轉化方法,且特別是有 關沸石觸媒對於烯烴/石蠟烷基化或芳族化合物烷基化之 用途。 【先前技術】 烷基化係有關將烷基化學添加到另一分子以形成更大 分子之製程。商業烷基化程序典型地可爲芳族烷基化或烯 烴/鏈烷烴烷基化。芳族烷基化典型地包括經由思(如 φφ ,乙烯,丙烯,等)將芳族化合物(如,苯)烷基化/製造 烷基芳族化合物)如,乙基苯,異丙苯,等)。烯烴/鏈烷烴 烷基化係屬在飽和烴與烯烴之間的反應以製造具有更高分 子量的高度分支飽和烴,例如,用2-丁烯將異丁烷予以烷 基化以製造具有高辛烷値之汽油產品。 - 與經由將高分子量石油餾份例如汽體油或石油殘渣予 以裂解產生汽油不相同者,烷基化可產生沒有硫或氮雜質 的更淸潔之汽油產品。再者,烷基化汽油具有很少或沒有 芳族化合物含量,其更具環境效益。 (2) 1373452 有多種烷基化方法係已知且用於整個石油工業者。例 如’於商業中經由使用液體酸觸媒例如硫酸或氫氟酸例常 地進行烷基化。或者,也有使用固體沸石觸媒者。沸石的 ' 使用可避免使用高腐蝕性和毒性液體酸之缺點。不過,沸 石可能患有被煉焦造成抑活化之缺點。多種使用含沸石觸 媒界烴-予\<烷基化之方法經揭示於美國專利第3,549,5 5 7和 1 5 之中。一種使用—用到沸石型或非沸石型材料 | 的一酸性固體觸媒之烷基化方法經揭示於美國專利第 • ^ 5,986,1>8/^,其以引用方式倂於本文。 . 沸石爲多孔型結晶型材料,其特徵在於具有特別尺寸 ' 及/或組態之次微觀通道。沸石典型地包括鋁矽酸鹽,不 ' 過沸石材料可用廣範圍的其他組成。後者常稱爲微孔型材 料。通道,或乙隙都經有序化且,因此之故,提供獨特性 質,使得沸石可用爲工業程序中的觸媒或吸收劑。例如, 可以用沸石來濾掉較小的分子,使小分子埋陷在沸石的孔 9φ隙中。此外,沸石可作爲形狀選擇性觸媒,有助於根據分 子反應物或產物的形狀或尺寸而在孔隙內進行的某些化學 轉化。沸石也被用於離子交換,例如用於水的軟化及重金 屬的選擇性回收。 合成型沸石傳流上係從氧化矽和鋁等來源(氧化砂和 - 氧化鋁a養分〃),在確保高等鹼性條件的材料,例如水 和0H·,之存在下,彼此反應。其他沸石可爲硼矽酸鹽, 鐵矽酸鹽,和類似者。許多結晶化步驟都在無機導引劑 (directing agent),或有機模板的存在中進行,彼等可誘 -6- (3) 1373452 f »
導出在沒有導引劑或模板存在中不能容易形成的特殊沸石 構造。許多有機模板都是季錢鹽,不過也可爲線型胺,醇 ,與多種其他化合物。如氫氧化物,某些導引劑可將經基 離子導到反應系統中;不過,鹼性常由氫氧化鈉(NaOH) ,氫氧化鉀(KOH),等的量所定。該反應典型地包括一液 體凝膠相,於其中發生重排和轉變,使得在氧化銘養分與 氧化矽養分之間發生重分布,且形成對應於特定沸石的分 子構造。也可以包括其他金屬氧化物,例如氧化鈦、氧化 矽、氧化硼-氧化矽,等。某些沸石只能用有機模板製成 。其他沸石只能利用無機導引劑製成。還有其他沸石可利 用親水性(如無機)導引劑或疏水性(有機基)模板任一者製 成。 有許多今日的烴加工技術係以沸石觸媒爲基礎者。有 多種沸石觸媒在技藝中爲已知者且擁有具一致孔隙尺寸的 排列良好之孔隙系統。術語A中間孔隙"係用於常指稱具 g^有4-6埃單位(A)的孔隙尺寸之沸石構造。^大孔隙〃沸石 ' 包括具有高於6至約1 2A的孔隙尺寸之構造。 由於以工業相關(亦即,高)轉化速率進行的許多烴加 工反應卻受限於質傳(特別者,粒子內擴散),因此具有理 想孔隙結構的觸媒粒子有助於反應物運送到粒子內的活性 - 觸媒部位及將產物從觸媒粒子運送出來,又仍可達到合意 的形狀選擇性催化作用。沸石形態學,亦即晶體尺寸’爲 擴散限制反應中的另一項參數。 觸媒具有有限的壽命,例如因爲煉焦所致•觸媒抑活 (4) 1373452 化常需要將反應器停機及將觸媒再生。雖然使用兩個反應 器以π擺動方式〃操作(亦即,兩反應器交錯使用,其中 一個操作烷基化,而另一個停機進行再生)可促成連續生 產,不過較佳者仍爲使用有長壽命的沸石觸媒實施烷基化 反應以使反應器停機與觸媒再生所致經濟損失減至最少。 【發明內容】
本發明提供一種用於將烴化合物烷基化之方法。該方 法包括提供一包括具有不小於1 00奈米的晶體尺寸的沸石 之觸媒:及將可烷基化的烴與烷化試劑在該觸媒存在中於 烷基化反應條件下反應以提供烷基化產物。 本文所述方法可有利地提供具有高硏究辛烷値(1 RON 〃)的烷基化產物以及有更長運轉時間的烷基化反應 【實施方式】 , 較佳具體實例之詳細說明 本文所述烷基化方法採用有超小,或奈米結晶,的晶 體尺寸,亦即不超過約100奈米("nm〃)的晶體尺寸,之 沸石。該奈米結晶型沸石擁有與某些烴轉化方法相關的數 - 項優點。例如,許多種反應物和產物的有效擴散率都可增 加。 第二’對於某些程序,尤其是依序性反應,於需要中 間產物者,可增進產物選擇率。例如,超小晶體尺寸可減 -8- (5) 1373452 低(1)過度裂解的量(例如,真空氣體油裂解所得(:3/(:4輕 質氣體產物的生產,於其中蒸餾物和石腦油產物都是所欲 產物)及(2)於芳族烷基化程序中的非所欲多烷基化之量。 • 此外,煉焦,及相體的觸媒抑活化,也會因奈米晶體沸石 使得進行中的逆行縮合反應之前促成焦油先質離開觸媒而 獲得減低。 第三,奈米晶型沸石觸媒的活性高於較大沸石晶體觸 ^ 媒,係因爲擴散限制使後述情況中的內部活性部份之可進 入者受到限制,導致奈米晶型沸石觸媒有較高有效數目的 . 活性部位每重量觸媒之故。 ' 下面要主要地關聯於以共有擁有,申請中的美國申請 - 序號10/067,719中所述方法製成的沸石Y對於烷基化催化 作用之用途來說明本發明方法。根據該申請序號 1 0/067,7 1 9所述方法製成的奈米晶型沸石Y具有立方體八 面沸石構造,具有約7至8A的有效孔隙直徑及小於25A的 φφ 單位晶胞尺寸。剛合成的沸石Υ也較佳地具有低於約1 0 ,常低於約7的氧化矽對氫化鋁莫耳比。奈米晶型沸石Υ 的晶體尺寸不超過約100奈米,較佳者不超過約50奈米, 且更佳者不超過約25奈米。 雖然奈米晶型沸石Υ的合成可在有機模板的存在中 . 進行’不過,以觸媒生產成本而論,較佳方式爲使用無機 導引劑。 奈米晶型沸石Υ可用於多種烴轉化程序中,例如乙 苯或異丙苯製造中的芳族烷基化和轉烷基化;生產高辛烷 -9- (6) 1373452 汽油所用的用烯烴將鏈烷烴烷基化;真空汽體油的加氫裂 解以生產運輪燃料:製造潤滑油基質儲料用的加氫處理, 線型烷基苯或烷基萘的製備:選擇性氫化:芳族硝化;等 製備奈米晶型沸石Y的方法包括將固體,多孔型氧 化矽-氧化鋁粒子或結構體與無機微孔隙形成性導引劑的 濃水溶液透過初起濕式浸漬予以浸漬。該多孔型氧化矽/ % 氧化鋁材料可爲非晶態或結晶型。液體的量爲比可能造成 ' 對肉眼可視察出的表面膠凝之量數爲少的量。提供給固體 ’多孔型氧化矽-氧化鋁粒子或構造體的液體會被後者的 內部空隙(voids)所吸收入且潤濕,但不會與彼等形成糊狀 材料。液體包括水,無機微孔隙形成性導引劑以及,需要 時,有機模板。
有機模板係根據合意產物而選擇的。可用於沸石合成 中的典型有機模板包括季銨鹽,線型胺和二胺,與醇。更 特定言之,特別的有機模板包括氫氧化四甲銨或其鹽,氫 氧化四乙銨或其鹽;氫氧化四丙銨或其鹽,吡咯烷,己 烷-1,6-二胺,己烷-1,6 -二醇,六氫吼畊,和18 -冠-6-
無機微孔隙形成性導引劑可提供氫氧離子且可爲鹼金 屬鹼或鹼土金屬鹼。不過,針對本發明沸石Y的製備而’ 言,較佳的微孔隙形成性導引機爲無機鹸金屬氫氧化物, 且較佳者爲氫氧化鈉(NaOH)。沒有使用有機模板。由於 高pH値對沸石Y形成比對其他晶相較有利’且有利於快 -10- (7) 1373452 速成核及結晶化,因此需要高濃度的苛性導引劑。例如, 在使用20重量%或更低濃度的NaOH時,可能會形成其他 晶相例如cancrinite或沸石p,不可能發生轉化,可能形 成太大的沸石Y晶體,或轉化可能要花一段不可接受的 長時間。
令人訝異地發現較高濃度的無機導引劑可明顯地減短 所需的反應時間。水溶液中較佳NaOH濃度範圍爲21重量 %至約60重量%,更佳者爲25重量%至約60重量%的NaOH 濃度。由於更高的NaOH濃度會導致極高黏度和不完全的 內部濕潤,此中間濃度範圍表一最佳含量》 爲維持^乾〃材料,該無機導引劑溶液的量不可超過 該多孔無機氧化物材料所具孔隙體積的1 00%,且較佳者 爲該孔隙體積的從約80%至約1 〇〇%。 浸漬均一度對於沸石Y的成功結晶化具有重要性。 局部化的不均勻性可能導致非一沸石Y副產物之形成。 爲了在小規模上提供適當的混合(例如,數克到1 0 0克範圍 內者),可以使用鉢將氧化矽-氧化鋁與微孔隙形成性導引 劑的溶液混合。於更大規模上,可以使用混合器與噴霧器 之組合。 然後將合倂的多孔型/非晶態氧化矽-氧化鋁與導引劑 (NaOH)的合成混合物置於一加熱介質中且加熱到從約50 °C至約1 5 0 °C,更佳者從約7 至約1 1 〇 °C的增溫。加成混 合物的均勻加熱係排列大沸石晶體的形成所需者。 將合成混合物將保持在合成濃度下一段足以將一充分 -11 - (8) 1373452 量的氧化矽-氧化鋁轉化爲沸石γ之時間。於結晶化後的 最後框架結構包含一實質的晶體含量(以重量計),典型地 爲至少15%,較佳者至少50%且最佳者從約75%至100%之 沸石。合成時期可決定於合成溫度,較低的合成溫度需要 較長的合成時間。合成時間可從5分至1 50小時,但更典型 者爲從10分鐘至48小時,且較佳者爲從約15分鐘至約30小 時。
於所需的合成時間之後,較佳者經由有效冷卻驟止合 成混合物。隨後,必須從產物移除微孔隙形成性導引劑以 防止於後面的處理步驟中或貯存中進一步反應。之後,必 須從沸石架構移除鈉。例如,經由與銨交換,使用諳於此 技者熟知的離子交換技術。 視需要地,可將沸石與一基質,黏合劑,或觸媒承載 體材料等摻合。此等材料包括氧化矽,氧化鋁,氧化矽鋁 ’氧化鈦,氧化锆和類似者。較佳者,本發明觸媒包括奈 米晶型沸石Υ和約5重量%至40重量%的耐火性氧化物黏合 劑例如氧化鋁,氧化矽,氧化矽-氧化鋁,氧化鈦,氧化 鉻,等。 離子交換沸石較佳者具有不超過約0.2重量%,更佳者 不超過0.1重量%,且又更佳者不超過約0.05重量%之鈉含 根據本發明方法製成的奈米晶型沸石Υ具有從約0.2 至約6.0的中孔隙至微孔隙體積比例,至少約275平方米/ 克的BET表面積和從約24.6Α至約24.9Α之單位晶胞尺寸 -12- (10) 1373452 烴予以烷基化。用丁烯或丁烯類混合物將異丁烷烷基化構 成本發明方法的一吸引性具體實例。 於另一具體實例中,本發明觸媒可用來將芳族化合物 • ,例如苯,用烯烴(如,乙烯,丙烯,1-丁烯,2-丁烯, 異丁烯,等)烷基化以製成對應的烷基芳族化合物(如,乙 苯,異丙苯,二-異丙基苯,等)。此外,該觸媒可用來用 裸環狀芳族化合物(如,苯)將多烷基化芳族化合物轉烷基 ^ 化以提供單烷基化芳族化合物。 如熟諳者所明顯知悉者,本發明方法可應用於任何適 當形式中,包括流體床方法,漿液法及固定床法。該方法 ' 可在多個床中進行,各床都分別給予烯烴添加。於此種情 - 況中,本發明方法可在每一分開的床中進行。 該烯烴-鏈烷烴烷基化法係在使將至少一部份烷化試 劑和可烷基化化合物處於液相或超臨界相中的條件下實作 。一般而言,本發明方法係在約-40 °C至約250 °C範圍內, φφ 較佳者在約5〇°C至約150°C範圍內,更佳者約75°C至約95 °C範圍內的溫度,及從1至1 00巴(bar),較佳者從1 0至40巴 ,更佳者從15至30巴的壓力下實作。反應器總進料中,可 烷基化性化合物對烷化試劑的莫耳比例較佳者爲高於5 : 1 ,更佳者高於50 : 1。烷化試劑的進料比例(WHSV)通常係 . 在〇.〇〗至5份範圍內,較佳者在0.05至0.5份範圍內,更佳 .者在0.1至0.4份範圍內的烷化試劑每份觸媒每小時。可烷 基化的飽和烴之WHSV較佳者係在0.1至SOOhr·1範圍內。 另一較佳方法爲芳族烷基化例如用乙烯將苯烷基化以 -14 -
Claims (1)
1375452 - ιοί 公告本 i___ ' 附件3A :第094104075號申請專利範圍修正本 民國101年7月9曰修正 十、申請專利範圍 1. 一種使烴化合物烷化之方法’其包括: a) 提供一包含具有不超過1〇〇奈米晶體尺寸的沸石Y 之觸媒; b) 使鏈烷烴與烯在該觸媒存在中於烷化反應條件下反
應而得烷化物產物, 其中該觸媒具有在WHS V爲0.26、至少6小時的烯失 效時所界定的壽命,且烷化物產物包括汽油產物,其中在 該觸媒壽命結束時所產收的該汽油產物具有至少100.0之 硏究法辛烷値,和其中該提供觸媒的步驟包括: a)提供一多孔型無機氧化物 b)用含有可提供氫氧根離子的無機微孔隙形成性導引 劑的液體溶液浸潰該多孔型無機氧化物,其中該液體溶液 的量不超過該無機氧化物的孔隙體積之100%,且該微孔 隙形成性導引劑在該液體溶液中的濃度爲從25重量%至60 Ο使該浸過的多孔型無機氧化物在高合成溫度下受熱 —段足以形成含沸石產物之持續時間》 2·如申請專利範圍第1項之方法,其中該鏈烷烴爲異 丁烷,且該烯爲丁烯。 3.如申請專利範圍第2項之方法,其中該烷化物產物 包括具有至少99.5的硏究法辛烷値之汽油。 1373452ιαι. 7. 9 4·如申請專利範圍第1項之方法’其中該烯爲選自乙 烯、丙烯、1-丁烯、2-丁烯、和異辛烯。 5. 如申請專利範圍第1項之方法,其中該烷化方法包 括轉烷化作用。 6. 如申請專利範圍第1項之方法,其中該無機微孔隙 形成性導引劑的液體溶液爲氫氧化鈉水溶液。 7. 如申請專利範圍第1項之方法,其中該沸石γ具有 不超過50奈米之晶體尺寸。 8. 如申請專利範圍第1項之方法,其中該沸石γ具有 不超過25奈米之晶體尺寸。 9. 如申請專利範圍第1項之方法,其中該沸石γ具有 不超過0.2重量%之鈉含量。 10. 如申請專利範圍第1項之方法,其中該沸石Υ具有 不超過0.1重量%之鈉含量。 11. 如申請專利範圍第1項之方法,其中該沸石Υ具有 不超過0.05重量%之鈉含量。 12. 如申請專利範圍第1項之方法,其中該觸媒包括— 耐火性氧化物黏合劑。 13·如申請專利範圍第12項之方法,其中該耐火性氧 化物黏合劑包括一或多種選自氧化矽、氧化鋁、氧化砂_ 氧化銘、氧化鈦和氧化锆之氧化物。 it如申請專利範圍第丨項之方法,其中該沸石γ包 括 或多種選自 Pt、Pd、Ir、Ru、Rh、Os' Fe、Co、Ni 、La' ce、pr、Ti、zr' Hf、V、Nb、Ta、Cr、Mo、W、 Cu' Ag和Au之金屬。 -2 - 101. 7. 9 1373452 15_如申請專利範圍第1項之方法,其中該沸石γ包括 鑭,且其中該鑭對沸石的質量比爲至少0.04。 16. 如申請專利範圍第1項之方法,其中該沸石γ具有 從0.2至0.6的中孔隙對微孔隙體積比。
17. 如申請專利範圍第1項之方法,其中該觸媒具有至 少275平方米/克之BET表面積,且其中該沸石γ具有稀 土金屬元素,稀土金屬對沸石的質量比爲至少0.04,其中 該沸石具有從0.2至6.0的中孔隙對微孔隙體積比,及從 24.6A至24.9A的單位晶胞尺寸。 1 8 ·如申請專利範圍第1項之方法,其中該烷化反應條 件包括從-4〇°C至25〇t的溫度,和從1巴(bar)至100巴之壓 力。
-3-
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Families Citing this family (35)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7405336B2 (en) * | 2004-10-18 | 2008-07-29 | Fina Technology, Inc. | Promoters for controlling acidity and pore size of zeolite catalysts for use in alkylation |
MX2009004152A (es) * | 2006-10-17 | 2009-10-29 | Lummus Technology Inc | Catalizadores de alquilacion metalicos. |
US7655824B2 (en) * | 2006-10-30 | 2010-02-02 | Uop Llc | Processes for producing alkylbenzenes over solid acid catalyst at low benzene to olefin ratios and low heavies make |
US7381676B1 (en) | 2007-01-16 | 2008-06-03 | Exxonmobil Chemical Patents Inc. | Catalyst composition and its use thereof in aromatics alkylation |
FR2920423B1 (fr) * | 2007-09-04 | 2009-11-13 | Inst Francais Du Petrole | Preparation d'un materiau composite poreux a base de zeolithe eu-1 et sa mise en oeuvre en isomerisation des aromatiques en c8. |
US20090275791A1 (en) * | 2008-05-05 | 2009-11-05 | Saudi Arabian Oil Company | Ceramic foam catalyst support for gasoline alkylation |
JP5564769B2 (ja) * | 2008-08-12 | 2014-08-06 | 株式会社明電舎 | 低級炭化水素芳香族化触媒及び芳香族化合物の製造方法 |
US8395006B2 (en) * | 2009-03-13 | 2013-03-12 | Exxonmobil Research And Engineering Company | Process for making high octane gasoline with reduced benzene content by benzene alkylation at high benzene conversion |
US20110143920A1 (en) * | 2009-12-16 | 2011-06-16 | Uop Llc | Rare Earth Exchanged Catalyst for Use in Detergent Alkylation |
TW201139336A (en) * | 2010-02-05 | 2011-11-16 | Fina Technology | Styrene production processes and catalysts for use therein |
WO2011155400A1 (ja) * | 2010-06-10 | 2011-12-15 | 宇部興産株式会社 | アルキル化反応用触媒及び該触媒を用いたアルキル芳香族炭化水素化合物の製造方法 |
RU2445165C1 (ru) * | 2010-09-09 | 2012-03-20 | Учреждение Российской Академии Наук Ордена Трудового Красного Знамени Институт Нефтехимического Синтеза Им. А.В. Топчиева Ран (Инхс Ран) | Катализатор, способ его получения (варианты) и способ жидкофазного алкилирования изобутана олефинами c2-c4 в его присутствии |
US8791040B2 (en) * | 2010-11-03 | 2014-07-29 | Fina Technology, Inc. | Catalysts containing nano-materials and methods of making and using same |
DE102011101877A1 (de) * | 2011-05-18 | 2012-11-22 | Süd-Chemie AG | Niedertemperatur-Oxidationskatalysator mit besonders ausgeprägten hydrophoben Eigenschaften für die Oxidation organischer Schadstoffe |
US20130005564A1 (en) * | 2011-06-30 | 2013-01-03 | Uop Llc | Synthesis of crystalline long-ranged ordered materials from preformed amorphous solids |
RU2478429C1 (ru) * | 2011-07-28 | 2013-04-10 | Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт нефтехимического синтеза им. А.В. Топчиева Российской академии наук (ИНХС РАН) | Катализатор, способ его получения и способ трансалкилирования бензола диэтилбензолами с его использованием |
US20130064757A1 (en) * | 2011-09-09 | 2013-03-14 | Uop Llc | Methods for forming zeolites from homogeneous amorphous silica alumina |
RU2505357C2 (ru) * | 2011-10-27 | 2014-01-27 | Российская Федерация, от имени которой выступает Министерство промышленности и торговли Российской Федерации (Минпромторг России) | Разработка технологии производства катализаторов алкилирования |
US20130172649A1 (en) * | 2011-12-30 | 2013-07-04 | Sivadinarayana Chinta | Supported nano sized zeolite catalyst for alkylation reactions |
RU2482917C1 (ru) * | 2012-04-05 | 2013-05-27 | Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт нефтехимического синтеза им. А.В. Топчиева Российской академии наук (ИНХС РАН) | Способ получения гетерогенного катализатора для получения ценных и энергетически насыщенных компонентов бензинов |
CN103540340B (zh) * | 2012-07-12 | 2015-10-21 | 中国石油化工股份有限公司 | 汽油精制方法 |
CN104692412A (zh) * | 2013-12-06 | 2015-06-10 | 中国石油大学(北京) | 一种合成NaY分子筛的方法及其合成的NaY分子筛 |
EP3527644A1 (en) * | 2014-07-07 | 2019-08-21 | Albemarle Europe Sprl. | Alkylation catalyst comprising cerium rich rare earth containing zeolites and a hydrogenation metal |
RU2579512C1 (ru) * | 2014-12-30 | 2016-04-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Санкт-Петербургский государственный технологический институт (технический университет)". | Способ приготовления катализатора и катализатор алкилирования изобутана изобутеном |
KR102600083B1 (ko) | 2015-06-22 | 2023-11-07 | 엑슬루스 인크 | 개선된 촉매 알킬레이션, 알킬레이션 촉매 및 알킬레이션 촉매를 만드는 방법 |
CN107866267B (zh) * | 2016-09-26 | 2020-07-07 | 中国石油化工股份有限公司 | 用于合成环己基苯的催化剂 |
WO2018158377A1 (en) * | 2017-03-01 | 2018-09-07 | Albemarle Europe Sprl | Alkylation process with improved octane number |
RU2700792C2 (ru) * | 2017-12-25 | 2019-09-23 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Санкт-Петербургский государственный технологический институт (технический университет)" (СПбГТИ(ТУ)) | Способ получения катализатора для осуществления процесса алкилирования парафинов олефинами |
CN108722406B (zh) * | 2018-06-04 | 2020-10-23 | 山东麟丰化工科技有限公司 | 一种钨基催化剂、制备方法及其在异丁烷-丁烯烷基化反应中的用途 |
CN110562995B (zh) * | 2018-06-06 | 2021-05-28 | 中国石油化工股份有限公司 | 纳米y沸石的合成方法、合成的纳米y沸石及用途 |
CN112387301B (zh) * | 2019-08-15 | 2023-05-26 | 中国石油天然气股份有限公司 | 一种含y分子筛的碳四烷基化催化剂及其制备方法 |
US11078431B2 (en) | 2019-12-16 | 2021-08-03 | Saudi Arabian Oil Company | Modified ultra-stable Y (USY) zeolite catalyst for deolefinization of hydrocarbon streams |
US11098256B2 (en) | 2020-01-08 | 2021-08-24 | Saudi Arabian Oil Company | Modified ultra-stable Y (USY) zeolite catalyst for improving cold flow properties of distillates |
RU2751336C1 (ru) * | 2020-10-02 | 2021-07-13 | Общество с ограниченной ответственностью "Газпром нефтехим Салават" (ООО "Газпром нефтехим Салават") | Катализатор, способ его получения и способ трансалкилирования бензола диэтилбензолами с его использованием |
US11484869B2 (en) | 2020-12-09 | 2022-11-01 | Saudi Arabian Oil Company | Modified ultra-stable Y (USY) zeolite catalyst for dealkylation of aromatics |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3549557A (en) | 1968-06-26 | 1970-12-22 | Union Carbide Corp | Isoparaffin alkylation process and catalyst for use therein |
US3815004A (en) | 1973-06-06 | 1974-06-04 | Hyper Loop | Rotary motor |
US3851004A (en) | 1973-09-27 | 1974-11-26 | Union Carbide Corp | Hydrocarbon alkylation process using catalyst regeneration |
US4899008A (en) * | 1986-06-27 | 1990-02-06 | Mobil Oil Corporation | Direct catalytic alkylation of mononuclear aromatics with lower alkanes |
FR2662438B1 (fr) * | 1990-05-22 | 1993-10-29 | Institut Francais Petrole | Procede de production d'alkylbenzenes utilisant des catalyseurs a base de zeolithe y desaluminee. |
US5177284A (en) * | 1991-05-28 | 1993-01-05 | Mobil Oil Corporation | Catalysts/process to synthesize alkylated naphthalene synthetic fluids with increased alpha/beta isomers for improving product qualities |
US5601798A (en) * | 1993-09-07 | 1997-02-11 | Pq Corporation | Process for preparing zeolite Y with increased mesopore volume |
JP4278067B2 (ja) * | 1996-11-27 | 2009-06-10 | アルベマーレ ネザーランズ ビー.ブイ. | 炭化水素のアルキル化法 |
US6004527A (en) | 1997-09-29 | 1999-12-21 | Abb Lummus Global Inc. | Method for making molecular sieves and novel molecular sieve compositions |
US6057485A (en) * | 1998-11-17 | 2000-05-02 | Fina Technology, Inc. | Gas phase alkylation with split load of catalyst |
JP5074654B2 (ja) * | 2000-05-30 | 2012-11-14 | アルベマーレ ネザーランズ ビー.ブイ. | アルキル化触媒によるアルキル化方法 |
US6793911B2 (en) * | 2002-02-05 | 2004-09-21 | Abb Lummus Global Inc. | Nanocrystalline inorganic based zeolite and method for making same |
JP4541688B2 (ja) * | 2003-11-28 | 2010-09-08 | 薫 藤元 | イソパラフィン−オレフィンアルキル化法 |
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