CN1660967A - Catalytic and thermal cracking catalyst for increasing production of ethane and propylene - Google Patents
Catalytic and thermal cracking catalyst for increasing production of ethane and propylene Download PDFInfo
- Publication number
- CN1660967A CN1660967A CN 200410004477 CN200410004477A CN1660967A CN 1660967 A CN1660967 A CN 1660967A CN 200410004477 CN200410004477 CN 200410004477 CN 200410004477 A CN200410004477 A CN 200410004477A CN 1660967 A CN1660967 A CN 1660967A
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- China
- Prior art keywords
- catalyzer
- zeolite
- transition metal
- sio
- ammonium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 title claims description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims description 10
- 238000004523 catalytic cracking Methods 0.000 title description 5
- 238000004227 thermal cracking Methods 0.000 title description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 title description 2
- 238000004519 manufacturing process Methods 0.000 title 1
- 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 56
- 239000010457 zeolite Substances 0.000 claims abstract description 56
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 55
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004927 clay Substances 0.000 claims abstract description 6
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 22
- 229910052723 transition metal Inorganic materials 0.000 claims description 22
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 21
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 20
- 150000003624 transition metals Chemical class 0.000 claims description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- 239000004411 aluminium Substances 0.000 claims description 18
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 18
- 150000002910 rare earth metals Chemical class 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 18
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 14
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 13
- 238000005336 cracking Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 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 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 10
- 229910052621 halloysite Inorganic materials 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 150000003863 ammonium salts Chemical class 0.000 claims description 7
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical group [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000005995 Aluminium silicate Substances 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 235000012211 aluminium silicate Nutrition 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 4
- 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 4
- 239000003513 alkali Substances 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 238000001311 chemical methods and process Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 238000000053 physical method Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 150000003623 transition metal compounds Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- 239000003921 oil Substances 0.000 description 19
- 235000010210 aluminium Nutrition 0.000 description 18
- 239000012065 filter cake Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000003756 stirring Methods 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 239000002002 slurry Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 238000010009 beating Methods 0.000 description 13
- 229930195733 hydrocarbon Natural products 0.000 description 13
- 239000002994 raw material Substances 0.000 description 12
- 239000004215 Carbon black (E152) Substances 0.000 description 11
- 241000196324 Embryophyta Species 0.000 description 11
- 150000002430 hydrocarbons Chemical class 0.000 description 11
- 239000004480 active ingredient Substances 0.000 description 9
- 238000001354 calcination Methods 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 239000003209 petroleum derivative Substances 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 238000001802 infusion Methods 0.000 description 7
- 238000012423 maintenance Methods 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 238000001694 spray drying Methods 0.000 description 7
- 239000002872 contrast media Substances 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- 239000000571 coke Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000003502 gasoline Substances 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000007233 catalytic pyrolysis Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 3
- 229910001038 basic metal oxide Inorganic materials 0.000 description 3
- 150000003818 basic metals Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- -1 for example Chemical compound 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000006276 transfer reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009415 formwork Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 208000019901 Anxiety disease Diseases 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 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
- 238000004458 analytical method Methods 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 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
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A thermocracking catalyst for increasing the output of ethene and propene is proportionally prepared from clay, meso-porous SiAl material, inorganic oxide and the zeolite with MFI structure.
Description
Technical field
The invention relates to the catalytic thermal cracking catalyst of a kind of increasing output of ethylene and propylene.
Background technology
The traditional method of producing ethene from petroleum hydrocarbon is to adopt pyrolysis in tubular furnace, and the raw material of employing is light petroleum hydrocarbons such as ethane, propane, butane, Sweet natural gas, petroleum naphtha or solar oil.Along with the anxiety of crude resources supply, the source of light petroleum hydrocarbon is restricted, so people come diversion to the technology of producing ethene from heavy petroleum hydrocarbon.As adopt quartz sand and coke as the heavy petroleum hydrocarbon pyrolysis method of thermal barrier, adopt basic metal or alkaline earth metal oxide catalyzer heavy petroleum hydrocarbon pyrolysis method as thermal barrier.
With the petroleum hydrocarbon be raw material when adopting cracking or cleavage method to produce low-carbon alkene employed catalyzer three classes are roughly arranged: a class is to be the metal load type catalyst of carrier with the oxide compound, and their carrier can be SiO
2, Al
2O
3Or other oxide compound, mostly the metallic element of institute's load is to belong to IIB, VB, VIIB and VIIIB family element (USP3,541,179; USP3,647,682; DD225,135; SU1,214,726).Require to use lightweight material (boiling range is for＜220 ℃) when adopting this type of catalyzer.
The employed second class catalyzer is composite oxides.As with ZrO
2And/or HfO
2Be main component, be aided with Al
2O
3, Cr
2O
3, MnO and/or Fe
2O
3And basic metal or alkaline earth metal oxide (USP3,725,495; USP3,839,485).Composite oxides commonly used are amorphous Si O
2Al
2O
3, DD152 has disclosed with amorphous Si O in 356
2Al
2O
3Being catalyzer, is raw material with liquid hydrocarbon or various hydrocarbon-fraction (comprising gasoline, kerosene, gas oil or vacuum distillate), produces low-carbon alkene under 600-800 ℃ temperature of reaction, C
2 =-C
4 =Productive rate can reach 40-55m% (accounting for raw material).
A large amount of reported in literature the 3rd class catalyzer, promptly contain the catalyzer of zeolite, particularly contain have the MFI structural zeolite catalyzer of (five-ring supersiliceous zeolite).As JP60-224, having disclosed with the ZSM-5 zeolite in 428 is active ingredient, Al
2O
3Be the catalyzer of carrier, under 600-750 ℃ to C
5-C
25The paraffinic hydrocarbon raw material carry out catalytic cracking, C
2 =-C
4 =Productive rate is about 30m%.
The mixture that has disclosed among the CN1004878B with ZSM-5 zeolite and y-type zeolite is the catalyzer of active ingredient, under 500-650 ℃ temperature of reaction, can improve C when improving the product gasoline octane rating
2 =-C
4 =Productive rate, and wherein with C
3 =And C
4 =Be primary product.
Disclosed a kind of method of producing ethene among the CN1069016A, the chemical constitution of the contact substance that it adopts is 30～90%SiO
2, 20～70%Al
2O
3, 0.5～30% basic metal or alkaline earth metal oxide, 1～30% faujusite, under 650～900 ℃ with the cracking of heavy crude hydro carbons, C
2 =Productive rate reaches 17～27%, C
2 =～C
4 =Productive rate reach 30～40%.
USP5,380,690 or CN1093101A to have disclosed with phosphorous and five-ring supersiliceous zeolite and y-type zeolite mixture rare earth be the catalyzer of active ingredient.This catalyzer hydro-thermal activity stability height under 580 ℃ reaction conditions, is the high 4-7 of a catalyzer transformation efficiency unit of active ingredient with the HZSM-5 zeolite, C
2 =-C
4 =The high 4-5 of a productive rate unit.
Disclose a kind of combination of molecular sieve that is used for voluminous ethene and propylene among CN1211469A and the CN1211470A, said composition is made up of penta-basic cyclic molecular sieve, 2～10% heavy phosphorus (in oxide compound), (in oxide compound) a kind of alkaline-earth metal of 0.3～5 heavy % and/or (in oxide compound) a kind of transition metal of 0.3～5 heavy % of 85～95 heavy %.
It is the catalyzer of active ingredient that CN1222558A has disclosed with phosphorous five-ring supersiliceous zeolite and y-type zeolite with aluminium or magnesium or calcium.This catalyzer has the excellent hydrothermal activity stability and improves the productive rate of low-carbon alkene (especially ethene).
The micro-pore zeolite catalytic material is owing to have very high catalytic activity and good catalysis shape selectivity energy, thereby is widely used in petrochemical industry.But along with the change of the oil that processes raw material is heavy, traditional micropore catalytic material is because the restriction in duct can not be used for macromolecular catalyzed reaction.Therefore the synthetic attention that more and more obtains people of mesopore catalytic material.The mesoporous silicon aluminum shows good medium molecule and macromole cracking performance in catalytic cracking reaction, help improving the raw material reaction transformation efficiency, reduces the heavy oil yield.
US5,951,962 disclose a kind of mesopore silica material, and organic formwork agent has been used in the preparation of this mesopore silica material, is generated by the silicon oxide presoma under hydrothermal condition, and the surface-area of this material is greater than 500m
2/ g, pore volume can be used as the accessibility that carrier improves the macromolecular reaction thing greater than 1.0ml/g.
Summary of the invention
The purpose of this invention is to provide the catalyzer of a kind of petroleum hydrocarbon catalytic pyrolysis fecund ethene and propylene, and make this catalyzer have the ability of good cracking macromole hydrocarbon, thereby improve the throughput that hydrocarbon cracking is produced ethene and propylene.
It is the clay of the 7-70% of benchmark, the mesoporous silicon aluminum of 3-70%, the inorganic oxide of 5-80% and the zeolite with MFI structure of 5-60% that the catalyzer of catalytic thermocracking of bydrocarbon increasing output of ethylene provided by the present invention and propylene contains with the catalyst weight.
Said clay can be natural or synthetic, through or the various clays that are used as cracking catalyst carrier usually handled without various chemistry and/or physical method, as kaolin and/or halloysite etc.
Said inorganic oxide is selected from Al
2O
3Or/and SiO
2
Said MFI structural zeolite is phosphorous, rare earth and transition metal M, and its anhydrous chemical expression is counted (0～0.3) Na with the weight of oxide compound
2O (0.3～7) Al
2O
3(1.0～10) P
2O
5(0.7～15) M
xO
y(0～10) RE
2O
3(70～98) SiO
2, wherein, M is selected from one or both transition metal among Fe, Co, Ni, Cu, Zn, Mo or the Mn, RE represents rare earth, and x is the valency of oxygen, and y is the valency of transition metal, wherein when if the valency of transition metal is even number, x is 1, and y is that the transition metal compound valency is divided by 2.
Phosphorous in the said MFI structural zeolite, rare earth and transition metal M, its anhydrous chemical expression, the weight in oxide compound is preferably (0～0.2) Na
2O (0.9～7) Al
2O
3(1.5～7) P
2O
5(0.9～10) M
xO
y(0.5～10) RE
2O
3(82～92) SiO
2Transition metal M wherein has dehydrogenation functionality, is selected from one or both metals among Fe, Co, Ni, Cu, Zn, Mo or the Mn, one or both among preferred Fe, Co or the Ni, more preferably Fe and/or Ni.
Described mesoporous silicon aluminum has the phase structure of pseudo-boehmite; In the weight of oxide compound, its anhydrous chemical expression is: (0-0.3) Na
2O (40-90) Al
2O
3(10-60) SiO
2Its specific surface area is 200-400m
2/ g; Pore volume is 0.5～2.0ml/g, preferred 1.0～2.0ml/g; Mean pore size is 8～20nm, preferred 10～20nm; The most probable aperture is 5～15nm, preferred 10～15nm.
Described zeolite with MFI structure, its preparation process comprises ammonium exchange, phosphorus modification, metal-modified and calcination process step usually.
The exchange of described ammonium be with the na-pretreated zeolite that contains rare earth of conventional crystallization gained with MFI structure according to zeolite: ammonium salt: H
2O=1: (0.1～1): the weight ratio of (5～10) is at room temperature to 100 ℃ 0.3～1 hour after-filtration of exchange down, and na-pretreated zeolite wherein is if adopt organic formwork agent synthetic words, at first removed template method.Described ammonium salt can be selected from one of ammonium chloride, ammonium sulfate or ammonium nitrate or their mixture for inorganic ammonium salt commonly used.
Described phosphorus modification and metal-modified be to adopt the mode of dipping or ion-exchange to carry out.Wherein said dipping can adopt following three kinds of modes again:
A. the filter cake after ammonium being exchanged and the P contained compound aqueous solution of calculated amount are in even, the oven dry of room temperature to 95 ℃ making beating, after roasting under 400～800 ℃ of conditions, ℃ mix, dry, roasting under 400～700 ℃ of conditions in room temperature to 95 with the compound water solution that contains transition metal M of calculated amount again.
B. the filter cake after ammonium being exchanged and the P contained compound aqueous solution of calculated amount are in even, the oven dry of room temperature to 95 ℃ making beating, ℃ mix, dry in room temperature to 95 with the compound water solution that contains transition metal M of calculated amount again, wherein reversed order that also can the above-mentioned two kinds of solution of dipping.Roasting under 400～700 ℃ of conditions again.
C. the mixed aqueous solution of the P contained compound of the filter cake after the ammonium exchange and calculated amount and the compound of transition metal M ℃ is mixed afterwards in room temperature to 95 and dry.Roasting under 400～700 ℃ of conditions again.Wherein said ion-exchange is: the filter cake after ammonium is exchanged and the P contained compound aqueous solution of calculated amount are in even, the oven dry of room temperature to 95 ℃ making beating, after roasting under 400～800 ℃ of conditions, again with the compound water solution that contains transition metal M of calculated amount by 1: after the solid-to-liquid ratio of (5～20) mixes, at 80～95 ℃, pH=4～7 time 2～3 hours after-filtration of stirring, but repeated exchanged is repeatedly, and the gained samples with water washing of exchange back is repeatedly, oven dry, roasting under 400～700 ℃ of conditions.
Described P contained compound is selected from one of phosphoric acid, aluminum phosphate, ammonium hydrogen phosphate, primary ammonium phosphate or ammonium phosphate or its mixture.The compound of described transition metal M is selected from their water-soluble salt, said water-soluble salt is selected from muriate, nitrate, vitriol or carbonate, for example, ferric sulfate, ferrous sulfate, iron nitrate, iron(ic) chloride, iron protochloride, rose vitriol, Xiao Suangu, cobalt chloride, single nickel salt, nickelous nitrate or nickelous chloride.
The preparation method of described mesoporous silicon aluminum is: aluminium source and alkaline solution are neutralized into glue under room temperature to 85 ℃, becoming glue terminal point pH is 7～11; Then according to SiO
2: Al
2O
3=1: weight ratio (0.6-9) adds the silicon source, room temperature to 90 ℃ following wearing out 1～10 hour; The gained solid sediment is carried out the ammonium exchange remove foreign ion; Again 100 ℃～150 ℃ down dry, 350 ℃～650 ℃ following roastings 1～20 hour.
Wherein, employed aluminium source is selected from any in aluminum nitrate, Tai-Ace S 150 or the aluminum chloride; Employed alkali is selected from any in ammoniacal liquor, potassium hydroxide, sodium hydroxide or the sodium metaaluminate; Employed silicon source is selected from any in water glass, water glass, tetraethyl silicane or the silicon oxide.
Wherein, the exchange of described ammonium be with the solid sediment after burin-in process by throw out (butt): ammonium salt: H
2O=1: (0.1-1): weight ratio (10-30) exchanges 0.3～1 hour room temperature to 100 ℃ following exchange 1-3 time at every turn, and sodium content is lower than 0.2% in solid sediment.The ammonium salt that the clearing house is used is selected from any in ammonium chloride, ammonium nitrate, volatile salt, the bicarbonate of ammonia.
Mesoporous silicon aluminum of the present invention can be the method preparation described in 03147975.8 according to application number.
Preparation of catalysts method of the present invention is as follows: with the precursor of decationized Y sieve water with inorganic oxide, as pseudo-boehmite, aluminium colloidal sol, silicon sol or its mixture and silicon-aluminum sol or gel, being mixed with solid content is the slurries of 10～50 heavy %, stir, use the mineral acid example hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid transfer to 2～4 with slurries PH, then, with the solid content that halloysite and mesoporous silicon aluminum are prepared by predetermined proportion is that 10～50 slurries that weigh % mix, stir, after leaving standstill aging 0-2 hour under 20-80 ℃, add aluminium colloidal sol or do not add, stirred 0.5-1.5 hour, the MFI structural zeolite that adds predetermined amount, homogeneous, spraying drying, the flush away free sodium ion, drying.
Catalyzer of the present invention contacts with petroleum hydrocarbon raw material in riser reactor, can react under following condition, temperature of reaction is 550-700 ℃, and reaction pressure is 0.05-0.3MPa, and agent-oil ratio is 10-40, water-oil ratio is 0.3-1.0: 1.0, and the reaction times is 0.2-5 second.
Because carrying out the raw material of catalytic cracking reaction is macromole hydrocarbon such as wax oil and residual oil, therefore, catalytic pyrolysis chain transfer reaction at first is the cracking from macromolecule hydrocarbon: a) become the medium molecule hydrocarbon by the macromole hydrocarbon pyrolysis.B) further be cracked into small molecule hydrocarbon by the medium molecule hydrocarbon.C) be cracked into products such as ethene and propylene by small molecule hydrocarbon.For guaranteeing carrying out smoothly of catalytic pyrolysis chain transfer reaction, the activity of catalytic material and aperture must distribution gradient, promptly by the mesopore material of more weak active wide aperture carrier, medium catalytic activity relatively with have the active micro-pore zeolite material of fine melt and constitute by proper ratio.
The feature of catalyzer of the present invention is: the zeolite that a) contains the MFI structure of transition metal not only has good shape selective catalysis ability, and the existence of transition metal improved its ability to small molecules cracking and dehydrogenation reaction, thereby helps the generation of low-carbon alkenes such as ethene and propylene.B) mesoporous silicon aluminum has kept the central hole structure feature of aluminum oxide, middle pore distribution concentration; Sial oxygen provides the cracking reaction activity of medium tenacity in conjunction with forming the acid site.In the catalytic cracking reaction process, this catalytic material can substitute y-type zeolite cracking medium molecule, and its aperture helps the diffusion of reaction product greater than y-type zeolite, can reduce the formation of coke.C) macropore carrier with weaker acid that is combined and formed by aluminium stone, aluminium colloidal sol and kaolin provides good place for macromole carries out cracking reaction.Therefore, the selected catalytic material of catalyzer of the present invention has the feature of catalytic activity and aperture distribution gradient, helps carrying out smoothly of catalytic pyrolysis chain transfer reaction.
Embodiment
Following example will give further instruction to the present invention.
In each example and Comparative Examples, Na in the zeolite
2O, Fe
2O
3, NiO, Al
2O
3, SiO
2Content measure (referring to " petrochemical complex analytical procedure (RIPP experimental technique) ", volumes such as Yang Cuiding, Science Press, nineteen ninety publishes) with x-ray fluorescence method.
Example 1～7 explanation is phosphorous, the preparation process of the MFI structural zeolite of rare earth and transition metal M.
The preparation process of example 8 explanation mesoporous silicon aluminums.
Example 1
With 20gNH
4Cl is dissolved in the 1000g water, and (the Qilu Petrochemical catalyst plant is produced, SiO to add 100g (butt) crystallization product ZRP zeolite in this solution
2/ Al
2O
3=30, content of rare earth RE
2O
3=2.0 heavy %), behind 90 ℃ of exchange 0.5h, filter filter cake; Add 4.2gH
3PO
4(concentration 85%) and 4.8gFe (NO
3)
3Be dissolved in the 90g water, dry with the filter cake hybrid infusion; The gained sample was 550 ℃ of calcination process 2 hours.Its elementary analytical chemistry consists of
0.1Na
2O·5.0Al
2O
3·2.4P
2O
5·1.5Fe
2O
3·1.9RE
2O
3·89.1SiO
2。
Example 2
With 50gNH
4Cl is dissolved in the 1000g water, and (the Qilu Petrochemical catalyst plant is produced, SiO to add 100g (butt) crystallization product ZRP zeolite in this solution
2/ Al
2O
3=30, content of rare earth RE
2O
3=2.0 heavy %), behind 85 ℃ of exchange 0.5h, filter filter cake; With 8.0gNH
4H
2PO
4Be dissolved in the 60g water, with filter cake hybrid infusion oven dry, through 550 ℃ of calcination process 2 hours; S' 5% Fe (NO with above-mentioned sample in 1: 5 ratio of solid-to-liquid ratio and concentration
3)
3Solution filters 80～90 ℃ of down exchanges 2 hours, exchanges several times again, until reaching aim parameter, again 550 ℃ of calcination process 2 hours.Elementary analytical chemistry consists of
0.03Na
2O·4.8Al
2O
3·4.5P
2O
5·3.0Fe
2O
3·1.8RE
2O
3·85.9SiO
2。
Example 3
With 20gNH
4Cl is dissolved in the 1000g water, and (the Qilu Petrochemical catalyst plant is produced, SiO to add 100g (butt) crystallization product ZRP zeolite in this solution
2/ Al
2O
3=50, content of rare earth RE
2O
3=2.0 heavy %), behind 90 ℃ of exchange 0.5h, filter filter cake; Add 3.8gH
3PO
4(concentration 85%) and 34.2gFe (NO
3)
3Be dissolved in the 90g water, dry with the filter cake hybrid infusion; The gained sample was 550 ℃ of calcination process 2 hours.Elementary analytical chemistry consists of
0.07Na
2O·2.8Al
2O
3·2.0P
2O
5·10Fe
2O
3·1.7RE
2O
3·83.4SiO
2。
Example 4
With 80gNH
4Cl is dissolved in the 1000g water, and (the Qilu Petrochemical catalyst plant is produced, SiO to add 100g (butt) crystallization product ZRP zeolite in this solution
2/ Al
2O
3=50, content of rare earth RE
2O
3=2.0 heavy %), behind 85 ℃ of exchange 0.5h, filter filter cake; With 9.0g (NH
4)
2HPO
4Be dissolved in the 60g water, dry with the filter cake hybrid infusion; Add 8.3gNi (NO again
3)
26H
2O is dissolved in the 90g water, with the oven dry of above-mentioned sample mix dipping; The gained sample was 600 ℃ of calcination process 2 hours.Its elementary analytical chemistry consists of
0.08Na
2O·3.0Al
2O
3·4.5P
2O
5·2.0NiO·1.9RE
2O
3·88.5SiO
2。
Example 5
With 80gNH
4Cl is dissolved in the 1000g water, and (the Qilu Petrochemical catalyst plant is produced, SiO to add 100g (butt) crystallization product ZRP zeolite in this solution
2/ Al
2O
3=30, content of rare earth RE
2O
3=2.0 heavy %), behind 85 ℃ of exchange 0.5h, filter filter cake; With 8.4g (NH
4)
2HPO
4Be dissolved in the 60g water, dry with the filter cake hybrid infusion; Add 4.2gNi (NO again
3)
26H
2O is dissolved in the 90g water, with the oven dry of above-mentioned sample mix dipping; The gained sample was 600 ℃ of calcination process 2 hours.Elementary analytical chemistry consists of
0.1Na
2O·5.0Al
2O
3·4.2P
2O
5·1.0NiO·1.9RE
2O
3·87.8SiO
2。
Example 6
With 80gNH
4Cl is dissolved in the 1000g water, and (the Qilu Petrochemical catalyst plant is produced, SiO to add 100g (butt) crystallization product ZRP zeolite in this solution
2/ Al
2O
3=30, content of rare earth RE
2O
3=2.0 heavy %), behind 85 ℃ of exchange 0.5h, filter filter cake; With 8.8g (NH
4)
2HPO
4Be dissolved in the 60g water, dry with the filter cake hybrid infusion; Add 4.2gNi (NO again
3)
26H
2O and 3.3gFe (NO
3)
3Be dissolved in the 90g water, with the oven dry of above-mentioned sample mix dipping; The gained sample was 600 ℃ of calcination process 2 hours.Elementary analytical chemistry consists of 0.08Na
2O4.8Al
2O
34.4P
2O
51.0NiO1.0Fe
2O
31.9RE
2O
386.8SiO
2
Example 7
With 20gNH
4Cl is dissolved in the 1000g water, and (the Qilu Petrochemical catalyst plant is produced, SiO to add 100g (butt) crystallization product ZRP zeolite in this solution
2/ Al
2O
3=22, content of rare earth RE
2O
3=4.0 heavy %), behind 90 ℃ of exchange 0.5h, filter filter cake; Add 6.0gH
3PO
4(concentration 85%) and 3.3gFe (NO
3)
3Be dissolved in the 90g water, dry with the filter cake hybrid infusion; The gained sample was 550 ℃ of calcination process 2 hours.Its elementary analytical chemistry consists of
0.1Na
2O·6.5Al
2O
3·3.5P
2O
5·1.0Fe
2O
3·3.8RE
2O
3·85.1SiO
2。
Example 8
Get 100mlAl
2(SO
4)
3Solution (90gAl
2O
3/ L) place beaker, under agitation condition, ammoniacal liquor is dropwise added, until system PH=8, become 55 ℃ of glue temperature; Under agitation condition, add 50ml water glass (60gSiO
2/ L), be warming up to 80 ℃ and wore out 4 hours; Use NH
4Cl solution carries out ion-exchange so that remove sodium ion in the sial throw out under 60 ℃, this process is general to repeat twice, then washing filtering; Dried 15 hours down at 120 ℃; Got product in 3 hours 600 ℃ of following roastings at last.Elementary analytical chemistry consists of: 0.12Na
2O7
3.7Al
2O
326.2SiO
2
Example 9
This example explanation: the MFI structural zeolite that has with phosphorous, rare earth and iron is an active ingredient, contains the Preparation of Catalyst and the cracking performance thereof of mesoporous silicon aluminum in the carrier.
With 11.9Kg pseudo-boehmite (Shandong Aluminum Plant's Industrial products, solid content 63m%) making beating, its PH is transferred to 2-4 with 20Kg decationized Y sieve water with hydrochloric acid.With of mesoporous silicon aluminum (butt the be 2.5Kg) making beating of 72.6Kg decationized Y sieve water with 38.7Kg halloysite (Suzhou china clay company Industrial products, solid content 72.3m%) and example 8 preparations.Above-mentioned two kinds of slurries are mixed, stir, left standstill under 60-70 ℃ aging 1 hour, maintenance PH is 2-4, cools the temperature to below 60 ℃, adds 13.8Kg aluminium colloidal sol (Qilu Petrochemical catalyst plant product, Al
2O
3Content is 21.7m%), stirred 40 minutes, what add example 1 preparation has MFI structural zeolite (butt is a 9.0Kg) slurries 32.1Kg.Stir spray drying forming, the flush away Na that dissociates
+, be drying to obtain catalyst sample A.
Example 10
Preparation process is identical with example 9, and difference is to adopt the MFI structural zeolite of example 2 preparations.Catalyzer is numbered B.
Example 11
Preparation process is identical with example 9, and difference is to adopt the MFI structural zeolite of example 5 preparations.Catalyzer is numbered C.
Example 12
Preparation process is identical with example 9, and difference is to adopt the MFI structural zeolite of example 6 preparations.Catalyzer is numbered D.
Comparative Examples 1
This Comparative Examples is an active ingredient for the zeolite in the contrast medium 1 that adopts the CN1222558A description.
With the making beating of 38.7Kg halloysite, add the 15.9Kg pseudo-boehmite with 92.6Kg decationized Y sieve water again, its PH is transferred to 2-4 with hydrochloric acid, stir, left standstill under 60-70 ℃ aging 1 hour, maintenance PH is 2-4, cool the temperature to below 60 ℃, add 13.8Kg aluminium colloidal sol, stirred 40 minutes.(the Qilu Petrochemical catalyst plant is produced, SiO to add the ZRP zeolite
2/ Al
2O
3=30, content of rare earth RE
2O
3=2.0 heavy %, P
2O
5Content is 4.0m%, and butt is 9Kg) slurries 32.1Kg, stir spray drying forming, the flush away Na that dissociates
+, be drying to obtain Comparative Examples agent DB-1.
Table 1 is listed the composition of catalyst A, B, C, D and DB-1.
On the small fixed flowing bed device, be that raw material is estimated catalyst sample with 30m% residual oil+70m% wax oil (character sees Table 2), temperature of reaction is 680 ℃, and agent-oil ratio is 10, and water-oil ratio is 0.8: 1, and weight hourly space velocity is 10h
-1Catalyst sample is in advance through 800 ℃, and 100% steam-treated 17 hours, loading amount are 180 grams, and evaluation result sees Table 3.
Table 1
| Catalyzer | ????A | ????B | ????C | ????D | ????DB-1 |
| Form heavy % kaolin pseudo-boehmite mesoporous silicon aluminum aluminium colloidal sol MFI structural zeolite | ? ????56 ????15 ????5 ????6 ????18 | ? ????56 ????15 ????5 ????6 ????18 | ? ????56 ????15 ????5 ????6 ????18 | ? ????56 ????15 ????5 ????6 ????18 | ? ????56 ????20 ? ????6 ????18 |
| Fe 2O 3 | ????1.5 | ????3.0 | ????1.0 | ||
| NiO | ????1.0 | ????1.0 |
Table 2
| Density (20 ℃), g/cm 3Carbon residue, m% alkali nitrogen, ppm boiling range, ℃ characterization factor | ????0.8658 ????2.47 ????630 ????＞293 ????12.3 |
Table 3
| Catalyzer | ????A | ????B | ????C | ????D | ????DB-1 |
| Transformation efficiency, the m% product distributes, the m% reacted gas wherein, olefins yield, m% C 2 ＝C 3 ＝C 4 ＝C 2 ＝+C 3 ＝+C 4 ＝Gasoline (C 5-221 ℃) diesel oil (221-330 ℃) heavy oil (＞330 ℃) coke | ????90.01 ? ????68.75 ? ????22.32 ????23.54 ????8.15 ????54.01 ????15.05 ????5.32 ????4.67 ????6.21 | ????89.83 ? ????68.76 ? ????21.08 ????23.32 ????8.56 ????52.96 ????14.89 ????5.34 ????4.83 ????6.18 | ????89.62 ? ????67.95 ? ????22.12 ????22.93 ????9.25 ????54.3 ????15.43 ????5.97 ????4.41 ????6.24 | ????90.34 ? ????68.69 ? ????21.14 ????22.85 ????8.89 ????52.88 ????15.12 ????5.64 ????4.02 ????6.53 | ????87.71 ? ????64.25 ? ????17.83 ????22.05 ????10.64 ????50.52 ????15.64 ????6.93 ????5.36 ????7.82 |
As can be seen from Table 3, catalyzer of the present invention can voluminous C than contrast medium
2 =About 3.2～4.5 centivals can voluminous C
3 =About 1～1.5 centival.
Example 13
With the making beating of 14.4Kg pseudo-boehmite, its PH is transferred to 2-4 with 24.3Kg decationized Y sieve water with hydrochloric acid.With of mesoporous silicon aluminum (butt the be 2.5Kg) making beating of 65Kg decationized Y sieve water with 36Kg halloysite and example 8 preparations.Above-mentioned two kinds of slurries are mixed, stir, at room temperature left standstill aging 1 hour, maintenance PH is 2-4, cools the temperature to below 60 ℃, adds 18.4Kg aluminium colloidal sol, stirs 40 minutes.Add zeolite (butt is 7.5Kg) the slurries 26.8Kg of example 3 preparations, stir, spray drying forming, the flush away Na that dissociates
+, be drying to obtain catalyst sample E.
Example 14
Preparation process is identical with example 13, and difference is to adopt the MFI structural zeolite of example 4 preparations.Catalyzer is numbered F.
Comparative Examples 2
The zeolite that adopts commodity PZRP by name to have the MFI structure is an active ingredient.
With the making beating of 36Kg halloysite, add the 18.4Kg pseudo-boehmite with 89.3Kg decationized Y sieve water again, its PH is transferred to 2-4 with hydrochloric acid, stir, at room temperature left standstill aging 1 hour, maintenance PH is 2-4, cool the temperature to below 60 ℃, add 23Kg aluminium colloidal sol, stirred 40 minutes.Add PZRP zeolite (Qilu Petrochemical catalyst plant product, SiO
2/ Al
2O
3=50, P
2O
5Content is 4.0m%, and butt is 7.5Kg) slurries 26.8Kg, stir spray drying forming, the flush away Na that dissociates
+, being drying to obtain contrast medium, sample number into spectrum is DB-2.
Table 4 is listed the composition of catalyzer E, F and DB-2.
On the small fixed flowing bed device, be that raw material is estimated catalyst sample with 30m% residual oil+70m% wax oil (character sees Table 2), temperature of reaction is 650 ℃, and agent-oil ratio is 12, and water-oil ratio is 0.8: 1, and weight space velocity is 10h
-1.Catalyst sample is in advance through 800 ℃, and 100% steam-treated 17 hours, loading amount are 180 grams, and evaluation result sees Table 5.
Table 4
| Catalyzer | ????E | ????F | ????DB-2 |
| Form heavy % kaolin pseudo-boehmite mesoporous silicon aluminum aluminium colloidal sol MFI structural zeolite | ? ????52 ????18 ????5 ????10 ????15 | ? ????52 ????18 ????5 ????10 ????15 | ? ????52 ????23 ? ????10 ????15 |
| Fe 2O 3 | ????10 | ||
| NiO | ????2.0 |
Table 5
| Catalyzer | ??E | ????F | ????DB-2 |
| Transformation efficiency, the m% product distributes, the m% reacted gas wherein, olefins yield, m% C 2 ＝C 3 ＝C 4 ＝C 2 ＝+C 3 ＝+C 4 ＝Gasoline (C 5-221 ℃) diesel oil (221-330 ℃) heavy oil (＞330 ℃) coke | ??83.04 ? ??58.93 ? ??14.94 ??18.72 ??11.85 ??45.51 ??18.26 ??9.53 ??7.43 ??5.85 | ????82.08 ? ????58.92 ? ????15.38 ????20.13 ????10.54 ????46.05 ????17.74 ????9.90 ????8.02 ????5.42 | ????78.32 ? ????52.26 ? ????12.24 ????18.07 ????11.28 ????41.59 ????20.12 ????12.23 ????9.45 ????5.94 |
As can be seen from Table 5, the C of catalyzer of the present invention
2 =+ C
3 =Productive rate improves about 3～5 centivals than contrast medium, and the zeolite (containing rare earth) of the MFI structure of high silica alumina ratio is described, after phosphorus and transition metal modified processing, adds mesoporous silicon aluminum carrier simultaneously, can improve C
2 =And C
3 =Productive rate.
Example 15
With the making beating of 40.5Kg pseudo-boehmite, its PH is transferred to 2-4 with 80Kg decationized Y sieve water with hydrochloric acid.With of mesoporous silicon aluminum (butt the be 75Kg) making beating of 210Kg decationized Y sieve water with 20.8Kg halloysite and example 8 preparations, above-mentioned two kinds of slurries are mixed, stir, at room temperature left standstill aging 30 minutes, maintenance PH is 2-4, add 20.7Kg aluminium colloidal sol, stirred 40 minutes, add MFI structural zeolite (butt is 30Kg) the slurries 105Kg of example 7 preparations, stir, spray drying forming, with ammonium dihydrogen phosphate (phosphorus content is 1m%) washing, the flush away Na that dissociates
+, be drying to obtain catalyst sample G.
Example 16
With the making beating of 60.7Kg pseudo-boehmite, its PH is transferred to 2-4 with 105Kg decationized Y sieve water with hydrochloric acid.With of mesoporous silicon aluminum (butt the be 22.5Kg) making beating of 190Kg decationized Y sieve water with 20.8Kg halloysite and example 8 preparations.Above-mentioned two kinds of slurries are mixed, stir, at room temperature left standstill aging 30 minutes, maintenance PH is 2-4, adds 20.7Kg aluminium colloidal sol, stirred 40 minutes, add MFI structural zeolite (butt is 30Kg) the slurries 105Kg of example 7 preparations, stir spray drying forming, with ammonium dihydrogen phosphate (phosphorus content is 1m%) washing, the flush away Na that dissociates
+, be drying to obtain catalyst sample H.
Example 17
Preparation process is identical with example 15, and difference is that adopting the MFI structural zeolite of example 5 preparations is active ingredient.Catalyzer is numbered I.
Comparative Examples 3
This Comparative Examples is to be contrast medium 3 according to the example 13 that CN1222558A describes.
With 292.5Kg decationized Y sieve water the 106.8Kg halloysite is pulled an oar, add the 59.5Kg pseudo-boehmite again, with 11.0Kg hydrochloric acid, stir, under 75 ℃, left standstill aging 1 hour, maintenance PH is 2-4, cool the temperature to below 60 ℃, add through phosphorus and magnesium-modified zeolite with MFI structure (butt is 30Kg) and SRY zeolite (butt is 5.3Kg) mix slurry 125.3Kg, homogeneous, spray drying forming, the flush away Na that dissociates
+, be drying to obtain Comparative Examples agent DB-3.
Table 6 is listed the composition of catalyzer G, H, I and DB-3.
On medium-sized riser tube reaction unit, be that raw material is estimated catalyst sample with the vacuum gas oil, feedstock property and appreciation condition see Table 7, and catalyst sample is in advance through 800 ℃, 100% steam-treated 17 hours, evaluation result sees Table 8.
Table 6
| Catalyzer | ????G | ????H | ????I | ????DB-3 |
| Form heavy % kaolin pseudo-boehmite mesoporous silicon aluminum aluminium colloidal sol MFI structural zeolite SRY | ? ????10 ????17 ????50 ????3 ????20 | ? ????36.5 ????25.5 ????15 ????3 ????20 ? | ? ? ??10 ????17 ????50 ????3 ????20 ? | ? ????51.5 ????25 ? ? ????20 ????3.5 |
| Fe 2O 3NiO | ????1.0 ? | ????1.0 ? | ? ????1.0 |
Table 7
| Stock oil character: density (20 ℃), g/cm 3Carbon residue, m% alkali nitrogen, ppm boiling range, ℃ characterization factor | ? ????0.8658 ????2.47 ????6?30 ????＞293 ????12.3 |
| Operational condition: temperature of reaction, ℃ reaction pressure (gauge pressure), the MPa agent-oil ratio water-oil ratio residence time, the s regeneration temperature, ℃ | ? ????620 ????0.07 ????25 ????0.8∶1 ????1.0 ????700 |
Table 8
| Catalyzer | ??G | ??H | ??I | ??DB-3 |
| Transformation efficiency, the m% product distributes, the m% reacted gas wherein, olefins yield, m% C 2 ＝C 3 ＝C 4 ＝C 2 ＝+C 3 ＝+C 4 ＝Gasoline+diesel oil+heavy oil, the m% coke | ??84.61 ? ??62.37 ? ??16.95 ??19.22 ??8.66 ??44.83 ??30.11 ??7.52 | ??83.04 ? ??61.34 ? ??15.89 ??18.44 ??9.12 ??43.45 ??30.43 ??8.23 | ??83.52 ? ??61.77 ? ??16.47 ??18.12 ??8.87 ??43.46 ??30.28 ??7.95 | ??80.69 ? ??57.81 ? ??15.21 ??17.53 ??9.08 ??41.82 ??33.41 ??8.78 |
As can be seen from Table 8, DB-3 compares with contrast medium, the C of catalyst sample G of the present invention, H and I
2 =Productive rate has improved 0.7～1.7, C
3 =Productive rate has improved 0.6～1.8 centival.
Claims (16)
1, the catalyzer of a kind of catalytic thermocracking of bydrocarbon increasing output of ethylene and propylene is characterized in that it is the clay of the 7-70% of benchmark, the mesoporous silicon aluminum of 3-70%, the inorganic oxide of 5-80% and the zeolite with MFI structure of 5-60% that this catalyzer contains with the catalyst weight.
2,, it is characterized in that described inorganic oxide is selected from Al according to the described catalyzer of claim 1
2O
3Or/and SiO
2
3,, it is characterized in that described clay is selected from according to the described catalyzer of claim 1: natural or synthetic, through or the various clays that are used as cracking catalyst carrier usually handled without various chemistry and/or physical method.
4, according to the described catalyzer of claim 1, it is characterized in that the zeolite of the described MFI of having structure is phosphorous, rare earth and transition metal M, its anhydrous chemical expression is counted (0～0.3) Na with the weight of oxide compound
2O (0.3～7) Al
2O
3(1.0～10) P
2O
5(0.7～15) M
xO
y(0～10) RE
2O
3(70～98) SiO
2, wherein, M is selected from one or both transition metal among Fe, Co, Ni, Cu, Zn, Mo or the Mn, RE represents rare earth, and x is the valency of oxygen, and y is the valency of transition metal, wherein when if the valency of transition metal is even number, x is 1, and y is that the transition metal compound valency is divided by 2.
5, according to the described catalyzer of claim 4, it is characterized in that the anhydrous chemical expression of the described MFI of having structural zeolite, count (0～0.2) Na with the weight of oxide compound
2O (0.9～7) Al
2O
3(1.5～7) P
2O
5(0.9～10) M
xO
y(0.5～10) RE
2O
3(82～92) SiO
2Transition metal M wherein is selected from one or both among Fe, Co or the Ni.
6,, it is characterized in that described transition metal M is selected from Fe and/or Ni according to the described catalyzer of claim 5.
7, according to the described catalyzer of claim 1, it is characterized in that described mesoporous silicon aluminum has the phase structure of pseudo-boehmite, in the anhydrous chemical expression of oxide weight be: (0-0.3) Na
2O (40-90) Al
2O
3(10-60) SiO
2, its specific surface area is 200-400m
2/ g, pore volume are 0.5～2.0ml/g, and mean pore size is 8～20nm, and the most probable aperture is 5～15nm.
8, according to the described catalyzer of claim 7, the pore volume that it is characterized in that described mesoporous silicon aluminum is 1.0～2.0ml/g, and mean pore size is 10～20nm, and the most probable aperture is 10～15nm.
9, according to the described catalyzer of claim 7, it is characterized in that the preparation method of described mesoporous silicon aluminum is: aluminium source and alkaline solution are neutralized into glue under room temperature to 85 ℃, becoming glue terminal point pH is 7～11; Then according to SiO
2: Al
2O
3=1: weight ratio (0.6-9) adds the silicon source, room temperature to 90 ℃ following wearing out 1～10 hour; The gained solid sediment is carried out the ammonium exchange remove foreign ion; Again 100 ℃～150 ℃ down dry, 350 ℃～650 ℃ following roastings 1～20 hour.
10, according to the said catalyzer of claim 9, wherein employed aluminium source is selected from any in aluminum nitrate, Tai-Ace S 150 or the aluminum chloride.
11, according to the said catalyzer of claim 9, wherein employed alkali is selected from any in ammoniacal liquor, potassium hydroxide, sodium hydroxide or the sodium metaaluminate.
12, according to the said catalyzer of claim 9, wherein employed silicon source is selected from any in water glass, water glass, tetraethyl silicane or the silicon oxide.
13, according to the said catalyzer of claim 9, the ammonium that is wherein adopted exchange be with the solid sediment after burin-in process by throw out (butt): ammonium salt: H
2O=1: (0.1-1): weight ratio (10-30) exchanges 0.3～1 hour room temperature to 100 ℃ following exchange 1-3 time at every turn, and sodium content is lower than 0.2% in solid sediment.
14, according to the said catalyzer of claim 13, wherein the ammonium salt used of clearing house is selected from any in ammonium chloride, ammonium nitrate, volatile salt, the bicarbonate of ammonia.
15, according to the said catalyzer of claim 9, wherein said drying process can be carried out in baking oven 10-24 hour, also can adopt the mode of spraying drying or expansion drying to carry out.
16,, it is characterized in that described clay is selected from: kaolin and/or halloysite according to the described catalyzer of claim 3.
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