CN1721505A - Catalytic conversion method for selective preparation of micromolecular olefin - Google Patents
Catalytic conversion method for selective preparation of micromolecular olefin Download PDFInfo
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- CN1721505A CN1721505A CN 200410068930 CN200410068930A CN1721505A CN 1721505 A CN1721505 A CN 1721505A CN 200410068930 CN200410068930 CN 200410068930 CN 200410068930 A CN200410068930 A CN 200410068930A CN 1721505 A CN1721505 A CN 1721505A
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- Prior art keywords
- zeolite
- heavy
- membered ring
- phosphorous
- reaction
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Links
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 38
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 35
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims description 10
- 230000003197 catalytic effect Effects 0.000 title description 2
- 239000010457 zeolite Substances 0.000 claims abstract description 87
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 86
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- 239000003921 oil Substances 0.000 claims abstract description 27
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 17
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 17
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 14
- 239000004927 clay Substances 0.000 claims abstract description 13
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 13
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- 229910052709 silver Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 36
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 31
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 30
- 150000002910 rare earth metals Chemical class 0.000 claims description 27
- 241000353097 Molva molva Species 0.000 claims description 26
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 17
- 239000011777 magnesium Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 238000004230 steam cracking Methods 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- 238000012986 modification Methods 0.000 claims description 13
- 230000004048 modification Effects 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000011701 zinc Substances 0.000 claims description 11
- 239000000571 coke Substances 0.000 claims description 10
- 238000011069 regeneration method Methods 0.000 claims description 10
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 8
- 239000013058 crude material Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 230000008929 regeneration Effects 0.000 claims description 8
- 238000005336 cracking Methods 0.000 claims description 7
- 239000003502 gasoline Substances 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 239000010944 silver (metal) Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 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 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- 238000002441 X-ray diffraction Methods 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000000084 colloidal system Substances 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 29
- 239000000047 product Substances 0.000 description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 21
- 239000002994 raw material Substances 0.000 description 20
- 238000012360 testing method Methods 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000002872 contrast media Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000004411 aluminium Substances 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012263 liquid product Substances 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000003562 lightweight material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000243 solution 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
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- MJBPUQUGJNAPAZ-UHFFFAOYSA-N Butine Natural products O1C2=CC(O)=CC=C2C(=O)CC1C1=CC=C(O)C(O)=C1 MJBPUQUGJNAPAZ-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 101000643890 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 5 Proteins 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 102100021017 Ubiquitin carboxyl-terminal hydrolase 5 Human genes 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- YIFVJYNWLCNYGB-UHFFFAOYSA-N [Si]=O.[Zr] Chemical compound [Si]=O.[Zr] YIFVJYNWLCNYGB-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000001941 cyclopentenes Chemical class 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000002010 green coke Substances 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- -1 iron modified zeolite Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- OTUXRAAQAFDEQT-UHFFFAOYSA-N magnesium oxosilicon(2+) oxygen(2-) Chemical compound [O-2].[Mg+2].[Si+2]=O.[O-2] OTUXRAAQAFDEQT-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910001723 mesolite Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The selectively small molecular weight olefin preparing process includes contacting hydrocarbon oil material with rich C4-C8 olefin with catalyst inside the catalytic cracking reactor and reaction at the conditions of temperature 550-700 deg.c, pressure 0.01-0.2 MPa, weight hourly space velocity 1-20 /hr and catalyst/oil ratio 5-30. The catalyst consists of clay 10-70 wt%, inorganic oxide 5-75 wt%, and zeolite 10-70 wt%, the zeolite is high silicon zeolite in five-element cyclic structure containing P and RE and modified with one or several of Fe, Zn, Mg and Ag, and the clay contains rectorite in 10-50 wt%.
Description
Technical field
The invention belongs to the catalysis conversion method of petroleum hydrocarbon under the situation that does not have hydrogen, more particularly, is a kind of catalysis conversion method of selective preparation of micromolecular olefin.
Background technology
The needed small-numerator olefin of chemical process as ethene, propylene etc., is mainly derived from steam cracking device at present, and rest part is from the by product of oil refining process, as catalytic cracking process.In addition, can also by hydro carbons particularly alkene contact with zeolite containing catalyst the generation scission reaction, produce small-numerator olefin.Disclosing a kind of silica alumina ratio of producing ethene and propylene by low value-added alkene as CN1414068A is the ZSM-5 type zeolite catalyst of 20-70.At least two kinds of materials that the contained zeolite utilization of catalyzer is selected from IIA family metal, thulium and the phosphorus carry out modification.
CN1149185C discloses and a kind ofly will contain C
4-C
12The hydrocarbon feed of alkene contacts with zeolite containing catalyst, produces the method for ethene and propylene.The silica alumina ratio of described zeolite is that 200-5000, aperture are 0.5-0.65nm, and this zeolite contains the metal of at least a IB of being selected from family, preferred silver, this zeolite contain every gram zeolite 0.02 mmole or proton still less during by ionic liquid phase exchange/filtrate titration measuring.
CN1284109A disclose a kind of with olefin feedstock with contain the method that the MFI type zeolite catalyst of sial atom at least about 180 contacted, produced propylene.The raw material that this method adopted is the mild cracking petroleum naphtha, from FCC apparatus or steam cracking device or produce the C of MTBE device
4Cut, C
5Cut, raw material contacts the preferred 540-580 of temperature ℃ with the initial of catalyzer, and raw material is 10-30h by the LHSV of catalyzer
-1
CN1406253A has disclosed a kind of polyacrylic method of C3 olefin production of being produced by selectivity in the fluid catalytic cracking process.This method will contain the petroleum naphtha that is lower than 40 heavy % paraffinic hydrocarbonss and the heavy % alkene of about 15-70 to be injected the FCC reaction zone, contacts with catalyzer, to form cracked product; Described catalyzer contains the zeolite of mean pore size less than 0.7nm; Temperature of reaction 500-650 ℃, hydrocarbon partial pressure 10-40psia, hydrocarbon residence time 1-10 second, agent-oil ratio 4-10; The paraffinic hydrocarbons that is no more than 20 heavy % is converted into alkene, and propylene accounts at least 90 moles of % of total C3 product.
US6222087 disclose a kind of utilize silicon-aluminum containing than greater than 300 ZSM-5 type zeolite catalyst with C
4-C
7Alkene or alkane are converted into the method for small-numerator olefin, and zeolite utilizes phosphorus and gallium to carry out modification.
CN1037327C discloses a kind of catalyst for cracking that contains supersiliceous zeolite, and this catalyzer is made up of the modification supersiliceous zeolite of the heavy % of 10-30 and the carrier of the heavy % of 70-90.Wherein, the modification supersiliceous zeolite is to contain the heavy % phosphorus of 0.01-3.0, the heavy % iron of 0.01-1.0 or the heavy % aluminium of 0.01-10, its framework si-al ratio greater than 15 ZSM zeolite, β zeolite or mordenite.Carrier is a kind of inorganic oxide or above-mentioned inorganic oxide and kaolinic mixture that comprises aluminum oxide, silicon oxide, silica-alumina, silicon oxide-magnesium oxide, silicon oxide-zirconium white.This catalyzer has stronger acidity and comparatively ideal low-carbon alkene, gasoline, diesel yield.
Above-mentioned technology changes measures such as zeolite silica alumina ratio mainly by Zeolite modifying, improves the productive rate and the selectivity of propylene in the product.Because the raw material that is adopted is a lightweight material, the contained zeolite of catalyzer is a supersiliceous zeolite, and its sour density is low, thereby coking rate is low on the catalyzer, causes above-mentioned technology to be difficult to keep the thermal equilibrium of reactive system self in process of production.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of catalysis conversion method of selective preparation of micromolecular olefin, so that keeping comparatively ideal ethene, propylene optionally simultaneously, improve the coke selectivity of catalyzer to a certain extent, make the heat of reaction-regeneration system keep balance as much as possible.
Method provided by the invention is as follows: be rich in C
4-C
8The hydrocarbon oil crude material of alkene contacts with catalyzer in catalyst cracker, and is that 550-700 ℃, reaction pressure are 0.1-2 * 10 in temperature of reaction
5Pa, weight hourly space velocity are 1-20h
-1, agent-oil ratio is to react under the condition of 5-30, described catalyzer contains with the catalyst weight clay of the heavy % of 10-70 that is benchmark, the inorganic oxide of the heavy % of 5-75 and the zeolite of the heavy % of 10-65, wherein, described zeolite is the supersiliceous zeolite with five-membered ring structure of the phosphorous and rare earth of any one or more than one metallic element modification in Fe, Zn, Mg, Ag, contains the rectorite leng of the heavy % of 10-50 in the described clay.
Compared with prior art, beneficial effect of the present invention is mainly reflected in following aspect:
Range of application of the present invention is more extensive, both can use separately, again can with the steam cracking device coupling.Utilize the C of steam cracking device by-product
4-C
8Alkene, the P/E ratio of raising steam cracking device, the while can also be utilized the tripping device of steam cracking device, produces the propylene and the ethene of polymerization-grade.The present invention can also with the catalytic cracking unit coupling, increasing the productive rate of catalytic cracking unit propylene, ethene, and when keeping the catalytically cracked gasoline octane value, reduce its olefin(e) centent.
Catalyzer of the present invention has good small-numerator olefin, and particularly propylene selectivity, good hydrothermal stability and physical strength can be produced propylene and ethene by highly selective.
Generally, by C
4-C
8When olefins to prepare propylene, ethene, coking yield is lower, and reaction-regeneration system self is difficult to the maintenance heat balance.Implement to take method replenishment system heat flexibly when of the present invention, for example, improve the preheating temperature of raw material,, improve carbon hanging rate of catalyzer or the like by catalyst modification by heat exchange.
Under normal conditions, the heating of raw material and the required heat that gasifies account for very big proportion in conversion zone institute consumption of calorie.The present invention uses the lightweight material that is rich in alkene to produce propylene and ethene, compares with conventional catalytically cracked material, and the possibility of raw material coking is less, can improve the preheating temperature of raw material largely.By with the heavy oil catalytically cracking equipment coupling, make the regenerator of raw material of the present invention and heavy oil catalytically cracking equipment carry out heat exchange and obtain heat, can also carry out heat exchange with the product logistics of device own simultaneously, the preheating temperature of raw material is improved.
Embodiment
The C that is rich in of the present invention
4-C
8The hydrocarbon oil crude material of alkene is selected from: steam cracking C
4, C
5The mixture of one or more in cut, thermo-cracking light gasoline fraction, catalytic cracking liquefied gas and the catalytic cracking light gasoline fraction.In above-mentioned hydrocarbon oil crude material, preferred C
4-C
8The content of alkene further is preferably greater than 60 heavy % greater than 50 heavy %.
Reaction conditions of the present invention is: temperature of reaction is 550-700 ℃, preferably 600-680 ℃; Reaction pressure is 0.1-2 * 10
5Pa, preferably 0.2-1 * 10
5Pa; Weight hourly space velocity is 1-20h
-1, 2-18h preferably
-1Agent-oil ratio is 5-30, preferably 6-28.
For obtaining low olefin partial pressures, raw material can dilute with water vapour and/or low-carbon alkanes.Described low-carbon alkanes can be a kind of or their mixture in methane, ethane, propane, the butane.Low-carbon alkanes does not transform in reaction process substantially, and main purpose is in order to reduce olefin partial pressures.
By the diluting effect of water vapour and low-carbon alkanes, can reduce the olefine reaction dividing potential drop, molecular balance is moved to generating the small-numerator olefin direction, can suppress gelatinous polymer simultaneously and generate, reduce green coke, improve the productive rate and the selectivity of purpose product.But, too much unsuitable as the amount of the water vapour of thinner, in order to avoid cause energy consumption excessive, and the device material requires harsh more.
Catalyst cracker of the present invention is meant the reactor that is used for catalytic cracking or catalytic conversion process, for example, fixed-bed reactor, fluidized-bed reactor, riser reactor or on above-mentioned reactor basis improved reactor all can.
Reaction oil gas that the present invention generated and mixture of catalysts preferably are separated the catalyzer of reaction oil gas and reaction back carbon deposit by fast gas-solid separator.Described reaction oil gas further is separated into various hydrocarbon ils products, for example, and ethene, propylene, gasoline, diesel oil etc.The catalyzer of described reaction back carbon deposit is delivered to revivifier, coke burning regeneration under the effect of oxygen-containing gas behind stripping.Catalyzer Returning reactor after the regeneration recycles.
Reaction oil gas of the present invention can be divided into C through initial gross separation
2Cut, C
3Cut, C
4-C
8Cut and C
8The cut that above cut etc. are different, wherein C
3Propylene content is preferably greater than 80 heavy % greater than 70 heavy % in the cut, further is preferably greater than 85 heavy %.Resulting C
4-C
8The best Returning reactor freshening of cut is to obtain maximum propylene+ethylene yield.
Inorganic oxide in the catalyzer of the present invention is selected from Al
2O
3, SiO
2, SiO
2Al
2O
3Or MgOAl
2O
3In one or more mixture.
Clay in the catalyzer of the present invention can be natural or synthetic, through or without various chemistry and/or physical treatment, usually as the various clays of cracking catalyst carrier, as rectorite leng, kaolin, halloysite etc.The weight of rectorite leng accounts for the heavy % of 10-50 of clay weight, the heavy % of preferred 15-40 in the described clay.The present invention introduces the inorganic oxide that accounts for the heavy % of rectorite leng weight 10-20 in the rectorite leng expanding layer and supports, and the structure of rectorite leng is carried out modulation.Described inorganic oxide is selected from: a kind of in aluminum oxide, silicon oxide, the zirconium white, preferred aluminum oxide.The modulating method of rectorite leng is as follows: with the precursor of rectorite leng, inorganic oxide, as aluminium colloidal sol, pseudo-boehmite, mix by predetermined proportion, and it is mixed with the slurries of solid content at the heavy % of 25-50 with decationized Y sieve water, stirred at normal temperatures 3-5 hour, the gained slurries promptly can be used for catalyst preparation process.
In the five-membered ring structure high-silicon zeolite of phosphorous and rare earth of the present invention, with molecular sieve weight is benchmark, the heavy % of iron content and/or magnesium and/or zinc and/or silver (in metal oxide) 0.5-5, the heavy % of preferred iron content and/or magnesium and/or zinc and/or silver-colored 0.75-4.5.
Phosphorous and five-membered ring structure high-silicon zeolite rare earth of the present invention carries out modification as follows: the supersiliceous zeolite of the phosphorous and rare-earth five-membered ring structure that will make is with being selected from: the nitrate of any one or more than one the metallic element among Fe, Zn, Mg, the Ag or halide salt solution flood the five-membered ring structure high-silicon zeolite of phosphorous and rare earth, and the five-ring supersiliceous zeolite behind the dipping was at 300-600 ℃ of roasting 0.5-6 hour.
Phosphorous and rare-earth five-membered ring supersiliceous zeolite of the present invention be with aluminum phosphate handle obtain contain the rare-earth five-membered ring supersiliceous zeolite, phosphorous in this zeolite (with P
2O
5Meter) the heavy % of 2-20, the preferably heavy % of 2-10.
The described five-ring supersiliceous zeolite (trade names ZRP) that contains rare earth be the applicant at USP5, the zeolite disclosed in 232,675, it has the x-ray diffraction spectra of ZSM-5 zeolite family, its anhydrous chemical constitution expression formula is: 0.01-0.30RE
2O
30.4-1.0Na
2OAl
2O
320-150SiO
2Rare earth in this composition used faujasite seeds that contains rare earth when synthetic.The duct of this zeolite is narrow than the ZSM-5 zeolite, it to the ratio of the adsorptive capacity of normal hexane and hexanaphthene be the ZSM-5 zeolite 2-4 doubly.This zeolite is to be raw material with water glass, aluminum phosphate, mineral acid, is crystal seed with REY or REHY, makes at 130-200 ℃ of following crystallization 12-60 hour.When the silica alumina ratio of zeolite at 20-150, preferably during 40-100, catalyzer mesolite content is preferably in 20-50% at 10-65%, activity of such catalysts is mated preferably with selecting performance.
The method of handling the ZRP zeolite with aluminum phosphate is as follows: zeolite is exchanged processing in advance with ammonium ion, make its sodium content (with Na
2O meter) reduces to and be not more than 0.1 heavy %, will form Al
2O
3: P
2O
5=1: the aluminum phosphate colloid of 1-3 is according to P
2O
5: zeolite (butt)=1: the weight ratio of 5-99 and this zeolite mix, in the presence of 300-600 ℃, 10-100% water vapour roasting 0.5-6 hour.
Method for preparing catalyst provided by the invention is as follows: with the precursor of inorganic oxide, as aluminium colloidal sol, pseudo-boehmite, silicon sol or its mixture and silicon-aluminum sol or gel, mix by preset blending ratio with the rectorite leng slurries behind clay and the modulation, stir, use mineral acid, example hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid transfers to 2-4 with slurries PH, keep this pH value, the zeolite slurry that after leaving standstill 0-2 hour under 20-80 ℃, adds predetermined amount, and it is mixed with the slurries of the heavy % of solid content 15-25, homogeneous, spraying drying with decationized Y sieve water, the flush away free sodium ion, drying.
The following examples will give further instruction to method provided by the invention, but not thereby limiting the invention.
Used rectorite leng is that the distinguished personages of Zhongxiang City, Hubei rectorite leng Science and Technology Co., Ltd. produces in the example, and its composition sees Table 1, represents with weight percentage.
Table 1
| F | Na 2O | MgO | Al 2O 3 | SiO 2 | P 2O 5 | SO 3 | K 2O |
| 0.17 | 1.4 | 0.55 | 39.3 | 42.5 | 0.52 | 2.5 | 1.6 |
| CaO | TiO 2 | Cr 2O 3 | Fe 2O 3 | SrO | Y 2O 3 | ZrO 2 | |
| 4.7 | 3.5 | 0.12 | 2.9 | 0.19 | 0.065 | 0.093 |
The modulating method of used rectorite leng is as follows in the example: with rectorite leng (solid content 80%), aluminium colloidal sol (Zhou village, Shandong catalyst plant product, Al
2O
311.4%, pH:2-3), by 85: 15 (butt) mixed, and with decationized Y sieve water it to be mixed with solid content be 35% slurries, stirred at normal temperatures 3-5 hour, and the gained slurries promptly can be used for follow-up Preparation of Catalyst.Part character before and after the rectorite leng modulation sees Table 2.
Table 2
| Sample | Specific surface/m 2/g | Pore volume/ml/g | |||
| S BET | S Z | S M | V micro | V pore | |
| Before the modulation | 13 | 0 | 13 | 0 | 0.03 |
| Behind the modulation | 125 | 22 | 103 | 0.01 | 0.14 |
Annotate: S
BETRepresent total specific surface area, S
ZRepresentative is corresponding to the specific surface of aperture less than 20 dusts,
S
MRepresentative is corresponding to the specific surface of aperture greater than 20 dusts, V
MicroRepresent the pore volume of aperture less than 20 dusts,
V
PoreRepresent total void volume.
Being prepared as follows of the five-ring supersiliceous zeolite of used phosphorous and rare earth in the example: get 100 gram (butt) ZRP zeolite (Zhou village, Shandong catalyst plant product, SiO
2/ Al
2O
3=60, RE
2O
3=2.0%), according to zeolite (butt): ammonium sulfate: the weight ratio of decationized Y sieve water=100: 25: 2000 is 90 ℃ of following ion-exchanges 1 hour, and exchange is once again after the filtration.Atomic absorption spectrum records in this zeolite sodium content (with Na
2The O meter) be 0.04%.With 13.8 gram pseudo-boehmite (Shandong Aluminum Plant's product, Al
2O
395%, solid content 30%), 9.0 gram industrial phosphoric acids (content 85%) and 200 gram decationized Y sieve water mix the back add above-mentioned ammonium exchange zeolite in, stir, 110 ℃ of dry backs promptly got phosphorus content (with P in aging 4 hours in 800 ℃, 100% steam atmosphere
2O
5Meter) is the five-ring supersiliceous zeolite of 5% phosphorous and rare earth.
The five-ring supersiliceous zeolite of the phosphorous and rare earth of used any one or multiple modification in Fe, Zn, Mg, Ag is according to the following steps modification in the example: prepared phosphorous and rare-earth five-membered ring supersiliceous zeolite 100 grams are restrained Fe (NO with 50
3)
3(concentration is 4.5 heavy % to solution, Fe (NO
3)
3Purity is greater than 99%) flooded 3 hours, five-ring supersiliceous zeolite behind the dipping was 120 ℃ of dryings 2 hours, 450 ℃ of roastings 2 hours, obtain containing the phosphorous and rare-earth five-membered ring supersiliceous zeolite of Fe (in metal oxide) 1.5 heavy %, below brief note is Fe-ZRP (1).By changing the kind and the consumption thereof of metal nitrate, prepare the zeolite shown in the table 3 respectively.
Prepared phosphorous the gram with 50 with rare-earth five-membered ring supersiliceous zeolite 100 restrained Fe (NO
3)
3And Mg (NO
3)
2Solution (Fe (NO
3)
3Concentration is 2.25 heavy %, Mg (NO
3)
2Concentration is 5.5 heavy %, Fe (NO
3)
3, Mg (NO
3)
2Purity greater than 99%) dipping 3 hours, five-ring supersiliceous zeolite behind the dipping was 450 ℃ of roastings 2 hours, obtain containing Fe (in metal oxide) 0.75 heavy %, contain the phosphorous and rare-earth five-membered ring supersiliceous zeolite that Mg (in metal oxide) 0.75 weighs %, below brief note is FeMg-ZRP.
Table 3
| Numbering | Modified metal | Modified metal content * |
| Fe-ZRP(1) | Fe | 1.5 |
| Fe-ZRP(2) | Fe | 0.75 |
| Fe-ZRP(3) | Fe | 4.5 |
| Ag-ZRP | Ag | 1.5 |
| Zn-ZRP | Zn | 1.5 |
| Mg-ZRP | Mg | 1.5 |
| FeMg-ZRP | Fe and Mg | 1.5 |
* in metal oxide, account for the heavy % of molecular sieve
The preparation of catalyst system therefor among the embodiment: at 175 kilograms of aluminium colloidal sols (Zhou village, Shandong catalyst plant product, Al
2O
311.4%, pH:2-3) add 50 kilograms of kaolin (Suzhou china clay company Industrial products in, solid content 80%), 15 kilograms of rectorite leng slurries (solid content is 35%) stirred 90 minutes, added 117 kilograms of Fe-ZRP (1) zeolite slurry (solid content is 30%) and 143 kilograms of decationized Y sieve water again, homogeneous, spraying drying, the gained sample is washed till pH value near 6, drying, 500 ℃ of following roastings 3 hours, promptly get catalyst sample A1-5.According to each component concentration shown in the table 4, adjust rectorite leng slurries and kaolinic amount ranges, and be respectively the catalyzer of A1-10, A1-20, A2, A3, B, C, D, E according to the method for preparing numbering.
The preparation of contrast medium: at 175 kilograms of aluminium colloidal sols (Zhou village, Shandong catalyst plant product, Al
2O
311.4%, pH:2-3) the middle 56 kilograms of kaolin (Suzhou china clay company Industrial products, solid content 80%) that add stirred 90 minutes, added 117 kilograms of ZRP zeolites (Zhou village, Shandong catalyst plant product, SiO again
2/ Al
2O
3=60, RE
2O
3=2.0%) slurries (solid content is 30%) and 152 kilograms of decationized Y sieve water, homogeneous, spraying drying promptly gets contrast medium 1.
Embodiment 1-9
Embodiment 1-9 explanation: the implementation result of method provided by the present invention.
Adopt the small fixed flowing bed device to test.Before the test, listed catalyst sample and aging 14h in 790 ℃, 100% water vapour respectively in the his-and-hers watches 4, and adopt catalyst sample A1-5, A1-10, A1-20, A2, A3, B, C, D, E to test respectively.The principal reaction condition is as follows: 620 ℃ of temperature of reaction, agent-oil ratio 15, weight space velocity 6 hours
-1, water injection rate 20%.Raw materials used composition sees Table 5.Test-results is listed in table 6.Testing sequence is as follows: raw material shown in the table 5 injects the small fixed flowing bed reactor, in the presence of water vapour, contacts with the catalyst sample of heat and reacts; Reaction product isolated obtains various products.Coke burning regeneration behind the reclaimable catalyst stripping, the catalyst recirculation after the regeneration is used.Test-results is listed in table 6-8 respectively.
By the test-results among the table 6-8 as can be seen, the present invention not only has comparatively ideal small-numerator olefin selectivity, and coke yield increases to some extent than contrast medium.This characteristics help alleviating the unbalanced problem of cat-cracker self heat, and the heat of 10-50% can be provided for reactive moieties more.In addition, the test-results among the table 6-8 shows that also compare with other several modified metals, iron has better modified effect, and the catalyzer that contains the iron modified zeolite has higher small-numerator olefin productive rate and better choice.
Comparative Examples
Adopt catalyst aging condition same as the previously described embodiments before test contrast medium to be carried out hydrothermal aging, the catalyzer after wearing out is used for this test.The raw material that is adopted in the process of the test, testing apparatus, testing sequence and operational condition are all same as the previously described embodiments.The contrast of test-results is referring to table 6-8.
Table 4
| The catalyzer code name | The molecular sieve numbering | Molecular sieve content | Modified metal | Clay | Rectorite leng | Inorganic oxide |
| A1-5 | Fe-ZRP(1) | 35 | Fe | 40 | 5 | 20 |
| A1-10 | Fe-ZRP(1) | 35 | Fe | 35 | 10 | 20 |
| A1-20 | Fe-ZRP(1) | 35 | Fe | 25 | 20 | 20 |
| A2 | Fe-ZRP(2) | 35 | Fe | 35 | 10 | 20 |
| A3 | Fe-ZRP(3) | 35 | Fe | 35 | 10 | 20 |
| B | Ag-ZRP | 35 | Ag | 35 | 10 | 20 |
| C | Zn-ZRP | 35 | Zn | 35 | 10 | 20 |
| D | Mg-ZRP | 35 | Mg | 35 | 10 | 20 |
| E | FeMg-ZRP | 35 | Fe and Mg | 35 | 10 | 20 |
| Contrast medium 1 | ZRP | 35 | / | 45 | 0 | 20 |
Table 5
| Title | Form heavy % |
| The steam cracking carbon-4 | |
| Butane | 3.67 |
| Butylene | 96.33 |
Table 6
| Example | 1 | 2 | 3 | Comparative Examples |
| Stock oil | The swallowization steam cracking is taken out surplus C 4 | |||
| Catalyzer | A1-5 | A1-10 | A1-20 | Contrast medium 1 |
| Material balance, heavy % | ||||
| Splitting gas | 82.75 | 83.94 | 84.07 | 83.21 |
| Liquid product+loss | 15.08 | 13.65 | 13.27 | 15.41 |
| Coke | 2.17 | 2.41 | 2.67 | 1.38 |
| The main products one-pass yield, heavy % | ||||
| Propylene | 28.24 | 27.58 | 28.19 | 27.67 |
| Ethene | 6.76 | 5.82 | 6.58 | 6.94 |
| Propylene, m/m | 12 | 11 | 12 | 11 |
| The main products selectivity | ||||
| Propylene | 45.5 | 46.9 | 46.5 | 46.2 |
| Ethene | 10.9 | 9.9 | 10.9 | 11.6 |
| Propylene+ethene | 56.4 | 56.8 | 57.4 | 57.8 |
Table 7
| Embodiment | 4 | 5 | 6 | Comparative Examples |
| Stock oil | The swallowization steam cracking is taken out surplus C 4 | |||
| Catalyzer | A2 | A3 | B | Contrast medium |
| Material balance, heavy % | ||||
| Splitting gas | 82.39 | 84.56 | 84.74 | 83.21 |
| Liquid product+loss | 15.4 | 12.82 | 10.64 | 15.41 |
| Coke | 2.21 | 2.62 | 4.62 | 1.38 |
| The main products one-pass yield, heavy % | ||||
| Propylene | 23.5 | 26.4 | 20.8 | 27.67 |
| Ethene | 4.90 | 7.52 | 7.38 | 6.94 |
| Propylene, m/m | 11 | 10 | 8 | 11 |
| The main products selectivity | ||||
| Propylene | 42.6 | 43.5 | 41.6 | 46.2 |
| Ethene | 8.9 | 12.4 | 14.8 | 11.6 |
| Propylene+ethene | 51.5 | 55.9 | 56.4 | 57.8 |
Table 8
| Embodiment | 7 | 8 | 9 | Comparative Examples |
| Stock oil | The swallowization steam cracking is taken out surplus C 4 | |||
| Catalyzer | C | D | E | Contrast medium |
| Material balance, heavy % | ||||
| Splitting gas | 83.83 | 83.54 | 84.67 | 83.21 |
| Liquid product+loss | 13.08 | 13.85 | 12.83 | 15.41 |
| Coke | 3.09 | 2.61 | 2.50 | 1.38 |
| The main products one-pass yield, heavy % | ||||
| Propylene | 22.1 | 22.9 | 23.1 | 27.67 |
| Ethene | 6.06 | 5.48 | 5.40 | 6.94 |
| Propylene, m/m | 12 | 13 | 13 | 11 |
| The main products selectivity | ||||
| Propylene | 41.6 | 44.3 | 45.8 | 46.2 |
| Ethene | 11.4 | 10.6 | 10.7 | 11.6 |
| Propylene+ethene | 55.7 | 56.4 | 56.4 | 57.8 |
Embodiment 10-11
This embodiment explanation: when adopting different petroleum hydrocarbon raw materials, implementation result of the present invention.
Be raw material with the FCC petroleum naphtha that is rich in C4-C8 alkene shown in C 5 fraction of steam cracking shown in the table 9 and the table 10 respectively, adopt the small fixed flowing bed device to test.The principal reaction condition is as follows: 620 ℃ of temperature of reaction, agent-oil ratio 15, weight space velocity 6 hours
-1, water injection rate 20%.Catalyst system therefor is the catalyst sample A1-10 behind the hydrothermal aging.Test-results is listed in table 11.Testing sequence is as follows: raw material injects the small fixed flowing bed reactor, in the presence of water vapour, contacts with the catalyst sample of heat and reacts; Reaction product isolated obtains various products.Coke burning regeneration behind the reclaimable catalyst stripping, the catalyst recirculation after the regeneration is used.
Table 9
| The components by weight percent of raw material, % | Steam cracking C5 |
| Butylene | 12.57 |
| 1,3-butadiene | 9.6 |
| Butane | 0.44 |
| Pentane | 5.93 |
| Amylene | 36.04 |
| Butine | 1.28 |
| Pentadiene | 21.16 |
| 1+suitable-1,3-pentadiene | 4.76 |
| Cyclopentenes | 0.19 |
| Pentamethylene | 0.01 |
| Other | 8.02 |
| Add up to | 100.00 |
Table 10
| Project | The catalytic cracking petroleum naphtha |
| Boiling range/℃ | |
| Initial boiling point | 30 |
| 10％ | 45 |
| 50％ | 76 |
| 90％ | 98 |
| Final boiling point | 102 |
| Group composition/weight % | |
| Alkane | 20.75 |
| Naphthenic hydrocarbon | 3.83 |
| Alkene | 72.52 |
| Aromatic hydrocarbons | 2.9 |
Table 11
| Embodiment | 9 | 10 |
| Catalyzer | A1-10 | A1-10 |
| Raw material | Steam cracking C 5 | The catalytic cracking petroleum naphtha |
| Product distributes, heavy % | ||
| Splitting gas | 65.92 | 70.13 |
| Liquid product+loss | 28.90 | 26.75 |
| Coke | 5.18 | 3.12 |
| Wherein, propylene | 24.73 | 25.82 |
| Ethene | 12.72 | 7.82 |
| Propylene, m/m | 11.7 | 11.3 |
Claims (22)
1, a kind of catalysis conversion method of selective preparation of micromolecular olefin is to make to be rich in C
4-C
8The hydrocarbon oil crude material of alkene contacts with catalyzer in catalyst cracker, and is that 550-700 ℃, reaction pressure are 0.1-2 * 10 in temperature of reaction
5Pa, weight hourly space velocity are 1-20h
-1, agent-oil ratio is to react under the condition of 5-30, described catalyzer contains with the catalyst weight clay of the heavy % of 10-70 that is benchmark, the inorganic oxide of the heavy % of 5-75 and the zeolite of the heavy % of 10-65, it is characterized in that the supersiliceous zeolite with five-membered ring structure of described zeolite, and contain the rectorite leng of the heavy % of 10-50 in the described clay for the phosphorous and rare earth of any one or more than one metallic element modification in Fe, Zn, Mg, Ag.
2,, it is characterized in that containing in the described clay rectorite leng of the heavy % of 15-40 according to the method for claim 1.
3, according to the method for claim 1 or 2, it is characterized in that described rectorite leng is the rectorite leng through the structure modulation, that is, introduce the inorganic oxide that accounts for the heavy % of rectorite leng weight 10-20 in the expanding layer of rectorite leng expanding layer is supported.
4, according to the method for claim 3, the modulating method that it is characterized in that described rectorite leng is as follows: the precursor of rectorite leng, inorganic oxide is mixed by predetermined proportion, and it is mixed with the slurries of solid content at the heavy % of 25-50 with decationized Y sieve water, stirred at normal temperatures 3-5 hour.
5, according to the method for claim 1, it is characterized in that the supersiliceous zeolite with five-membered ring structure of described phosphorous and rare earth, be benchmark with molecular sieve weight, in metal oxide, the heavy % of iron content and/or magnesium and/or zinc and/or silver-colored 0.5-5.
6, according to the method for claim 5, it is characterized in that the supersiliceous zeolite with five-membered ring structure of described phosphorous and rare earth, be benchmark with molecular sieve weight, in metal oxide, the heavy % of iron content and/or magnesium and/or zinc and/or silver-colored 0.75-4.5.
7,, it is characterized in that any one metallic element modification in Fe, Zn, Mg, Ag of the supersiliceous zeolite with five-membered ring structure of described phosphorous and rare earth according to the method for claim 5 or 6.
8, according to the method for claim 7, the supersiliceous zeolite with five-membered ring structure that it is characterized in that described phosphorous and rare earth is through the Fe modification.
9, according to claim 1,5,6, one of 7 or 8 method, it is characterized in that described phosphorous and five-membered ring structure high-silicon zeolite rare earth carries out modification as follows: adopt the nitrate of selected metallic element or the halide salt solution dipping is phosphorous and the supersiliceous zeolite with five-membered ring structure of rare earth, the five-ring supersiliceous zeolite behind the dipping was at 300-600 ℃ of roasting 0.5-6 hour.
10, according to the method for claim 1, it is characterized in that described phosphorous and rare-earth five-membered ring supersiliceous zeolite be with aluminum phosphate handle obtain contain the rare-earth five-membered ring supersiliceous zeolite, with P
2O
5Meter, the heavy % of phosphorous 2-20 in this zeolite.
11, according to the method for claim 10, it is characterized in that described phosphorous and rare-earth five-membered ring supersiliceous zeolite be with aluminum phosphate handle obtain contain the rare-earth five-membered ring supersiliceous zeolite, with P
2O
5Meter, the heavy % of phosphorous 2-10 in this zeolite.
12, according to the method for claim 10 or 11, it is characterized in that the described x-ray diffraction spectra that the rare-earth five-membered ring supersiliceous zeolite has ZSM-5 zeolite family that contains, its anhydrous chemical constitution expression formula is: 0.01-0.30RE
2O
30.4-1.0Na
2OAl
2O
320-150SiO
2
13,, it is characterized in that described to handle the method contain the rare-earth five-membered ring supersiliceous zeolite with aluminum phosphate as follows: zeolite is exchanged processing in advance with ammonium ion, make it with Na according to the method for claim 10 or 11
2The sodium content of O meter is reduced to and is not more than 0.1 heavy %, will form Al
2O
3: P
2O
5=1: the aluminum phosphate colloid of 1-3 is according to P
2O
5: the weight ratio of zeolite=1: 5-99 and this zeolite mix, in the presence of 300-600 ℃, 10-100% water vapour roasting 0.5-6 hour.
14, according to the method for claim 1, it is characterized in that described Preparation of catalysts method is as follows: the rectorite leng slurries behind the precursor of inorganic oxide and clay and the modulation are mixed by preset blending ratio, stir, slurries PH is transferred to 2-4, keep this pH value with mineral acid, the zeolite slurry that after leaving standstill 0-2 hour under 20-80 ℃, adds predetermined amount, and it is mixed with the slurries of the heavy % of solid content 15-25, homogeneous, spraying drying with decationized Y sieve water, the flush away free sodium ion, drying.
15,, it is characterized in that the described C of being rich in according to the method for claim 1
4-C
8The hydrocarbon oil crude material of alkene is selected from: steam cracking C
4, C
5The mixture of one or more in cut, thermo-cracking light gasoline fraction, catalytic cracking liquefied gas and the catalytic cracking light gasoline fraction, and C in the hydrocarbon oil crude material
4-C
8The content of alkene is greater than 50 heavy %.
16,, it is characterized in that C in the described hydrocarbon oil crude material according to the method for claim 15
4-C
8The content of alkene is greater than 60 heavy %.
17,, it is characterized in that described temperature of reaction is that 600-680 ℃, reaction pressure are 0.2-1 * 10 according to the method for claim 1
5Pa, weight hourly space velocity are 2-18h
-1, agent-oil ratio is 6-28.
18,, it is characterized in that described hydrocarbon oil crude material dilutes through water vapour and/or low-carbon alkanes in reaction process according to the method for claim 1.
19,, it is characterized in that described catalyst cracker is fixed-bed reactor, fluidized-bed reactor, riser reactor or improved reactor on above-mentioned reactor basis according to the method for claim 1.
20,, it is characterized in that the C that this method generates according to the method for claim 1
3Propylene content is greater than 70 heavy % in the cut.
21,, it is characterized in that the C that this method generates according to the method for claim 1
4-C
8The cut Returning reactor continues to participate in reaction.
22, according to the method for claim 1, it is characterized in that this method is further comprising the steps of: separate reaction oil gas that is generated and the catalyzer that reacts the back carbon deposit, described reaction oil gas further is separated into various hydrocarbon ils products, and the catalyzer of reaction back carbon deposit is delivered to revivifier behind stripping, coke burning regeneration under the effect of oxygen-containing gas, the catalyzer Returning reactor after the regeneration recycles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100689307A CN100351344C (en) | 2004-07-14 | 2004-07-14 | Catalytic conversion method for selective preparation of micromolecular olefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100689307A CN100351344C (en) | 2004-07-14 | 2004-07-14 | Catalytic conversion method for selective preparation of micromolecular olefin |
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| Publication Number | Publication Date |
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| CN1721505A true CN1721505A (en) | 2006-01-18 |
| CN100351344C CN100351344C (en) | 2007-11-28 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011050505A1 (en) * | 2009-10-30 | 2011-05-05 | 中国石油天然气股份有限公司 | Double-component modified molecular sieve with improved hydrothermal stability and production method thereof |
| CN102430422A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Catalytic cracking catalyst for producing low-carbon olefin and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1004878B (en) * | 1987-08-08 | 1989-07-26 | 中国石油化工总公司 | Hydrocarbon catalytic conversion method for preparing low-carbon olefin |
| CN1048427C (en) * | 1994-02-18 | 2000-01-19 | 中国石油化工总公司 | Laminar column molecular sieve catalyst of high yield olefines |
| EP1117750B1 (en) * | 1998-09-28 | 2004-06-30 | BP Corporation North America Inc. | Process for manufacturing olefins using a pentasil zeolite based catalyst |
-
2004
- 2004-07-14 CN CNB2004100689307A patent/CN100351344C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011050505A1 (en) * | 2009-10-30 | 2011-05-05 | 中国石油天然气股份有限公司 | Double-component modified molecular sieve with improved hydrothermal stability and production method thereof |
| US9895686B2 (en) | 2009-10-30 | 2018-02-20 | Petrochina Company Limited | Double-component modified molecular sieve with improved hydrothermal stability and production method thereof |
| CN102430422A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Catalytic cracking catalyst for producing low-carbon olefin and application thereof |
| CN102430422B (en) * | 2010-09-29 | 2013-07-31 | 中国石油化工股份有限公司 | Catalytic cracking catalyst for producing low-carbon olefin and application thereof |
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| Publication number | Publication date |
|---|---|
| CN100351344C (en) | 2007-11-28 |
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