CN1292052C - Hydrocarbon conversion catalyst containing zeolite and its preparing method - Google Patents
Hydrocarbon conversion catalyst containing zeolite and its preparing method Download PDFInfo
- Publication number
- CN1292052C CN1292052C CN 200410029862 CN200410029862A CN1292052C CN 1292052 C CN1292052 C CN 1292052C CN 200410029862 CN200410029862 CN 200410029862 CN 200410029862 A CN200410029862 A CN 200410029862A CN 1292052 C CN1292052 C CN 1292052C
- Authority
- CN
- China
- Prior art keywords
- zeolite
- weight
- catalyzer
- transition metal
- content
- 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.)
- Expired - Lifetime
Links
- 239000010457 zeolite Substances 0.000 title claims abstract description 193
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 185
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 185
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims description 41
- 229930195733 hydrocarbon Natural products 0.000 title abstract description 11
- 150000002430 hydrocarbons Chemical class 0.000 title abstract description 11
- 239000004215 Carbon black (E152) Substances 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 title description 20
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 54
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 39
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 239000004927 clay Substances 0.000 claims abstract description 33
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 31
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011574 phosphorus Substances 0.000 claims abstract description 30
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 12
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 4
- 230000000737 periodic effect Effects 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 62
- 229910052723 transition metal Inorganic materials 0.000 claims description 58
- 150000003624 transition metals Chemical class 0.000 claims description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 31
- 229910052742 iron Inorganic materials 0.000 claims description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 30
- 238000002360 preparation method Methods 0.000 claims description 30
- 239000002002 slurry Substances 0.000 claims description 28
- 230000032683 aging Effects 0.000 claims description 26
- 239000002243 precursor Substances 0.000 claims description 20
- 239000011148 porous material Substances 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- 229910052621 halloysite Inorganic materials 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 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 15
- 238000010009 beating Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 229910052788 barium Inorganic materials 0.000 claims description 14
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 14
- 239000004411 aluminium Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims description 10
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 9
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 9
- -1 polynite Chemical compound 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 150000003623 transition metal compounds Chemical class 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 239000005995 Aluminium silicate Substances 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 235000012211 aluminium silicate Nutrition 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 3
- 239000010953 base metal Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 239000004113 Sepiolite Substances 0.000 claims description 2
- 229960000892 attapulgite Drugs 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
- 150000003016 phosphoric acids Chemical class 0.000 claims description 2
- 229910000275 saponite Inorganic materials 0.000 claims description 2
- 229910052624 sepiolite Inorganic materials 0.000 claims description 2
- 235000019355 sepiolite Nutrition 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 36
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 19
- 239000003209 petroleum derivative Substances 0.000 abstract description 7
- 229910001404 rare earth metal oxide Inorganic materials 0.000 abstract description 7
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 2
- 239000004615 ingredient Substances 0.000 abstract 2
- 229910016287 MxOy Inorganic materials 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 239000010970 precious metal Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 19
- 238000003756 stirring Methods 0.000 description 17
- 238000005336 cracking Methods 0.000 description 16
- 239000012065 filter cake Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 239000003502 gasoline Substances 0.000 description 12
- 239000003921 oil Substances 0.000 description 12
- 239000002808 molecular sieve Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 10
- 241000196324 Embryophyta Species 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000001694 spray drying Methods 0.000 description 7
- 102100028099 Thyroid receptor-interacting protein 6 Human genes 0.000 description 6
- 101710084345 Thyroid receptor-interacting protein 6 Proteins 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000007233 catalytic pyrolysis Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- ISNYUQWBWALXEY-OMIQOYQYSA-N tsg6xhx09r Chemical compound O([C@@H](C)C=1[C@@]23CN(C)CCO[C@]3(C3=CC[C@H]4[C@]5(C)CC[C@@](C4)(O)O[C@@]53[C@H](O)C2)CC=1)C(=O)C=1C(C)=CNC=1C ISNYUQWBWALXEY-OMIQOYQYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 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 description 4
- 230000000694 effects Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910001593 boehmite Inorganic materials 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910001723 mesolite Inorganic materials 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 239000003795 chemical substances by application 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
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-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
- 239000005977 Ethylene Substances 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-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
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910001038 basic metal oxide Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001833 catalytic reforming Methods 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
- 238000004939 coking Methods 0.000 description 1
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical group 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
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002063 nanoring Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- UKDIAJWKFXFVFG-UHFFFAOYSA-N potassium;oxido(dioxo)niobium Chemical compound [K+].[O-][Nb](=O)=O UKDIAJWKFXFVFG-UHFFFAOYSA-N 0.000 description 1
- BQFYGYJPBUKISI-UHFFFAOYSA-N potassium;oxido(dioxo)vanadium Chemical compound [K+].[O-][V](=O)=O BQFYGYJPBUKISI-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
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Abstract
The present invention relates to a hydrocarbon converting catalyst which comprises the following components: 1 wt% to 60 wt% zeolite by the reference of the total amount of the catalyst; 0.1 wt% to 10 wt% of auxiliary agent, 5 wt% to 99 wt% of heat resistant inorganic oxide, and 0 to 70 wt % of clay which are counted by the oxides, wherein the zeolite is the zeolite which contains phosphorus and bimetallic ingredients and has an MFI structure, or the mixture of the zeolite and macropore zeolite; the zeolite comprises 75 wt% to 100 wt% of zeolite with the MFI structure, and 0 wt% to 25 wt% of macropore zeolite which are counted by the total amount of the zeolite. Counted by the mass of the oxides, the zeolite which contains phosphorus and bimetallic ingredients and has the MFI structure has the following anhydrous chemical expression: (0 to 0.3) Na2O. (0.3 to 5)Al2O3. (1.0 to 10)P2O5. (0.7 to 15)MxOy. (0 to 10)RE2O3. (70 to 98)SiO2. The auxiliary agent is selected from one or a plurality of alkaline earth metals, metals in the IV B group, and the non-precious metals and the rare earth metals in the VIII group in the periodic table. The catalyst has high converting capability of petroleum hydrocarbon, and the yields of propene, ethene and light aromatic hydrocarbon are high.
Description
Technical field
The invention relates to a kind of Hydrocarban coversion catalysts that contains molecular sieve and preparation method thereof, more particularly, is about a kind of Hydrocarban coversion catalysts that contains zeolite and preparation method thereof.
Background technology
Low-carbon alkene, as ethene and propylene, and light aromatics is important petrochemical materials, its demand is increasing day by day.In the prior art, the maturation process method of production ethene and propylene has: hydro carbons is produced ethene, propylene by the thermal conversion processes of free radical reaction, as the tube furnace steam cracking process of lighter hydrocarbons; The catalytic pyrolysis or the catalytic pyrolysis technology of the heavy hydrocarbon by carbonium ion mechanism can a certain amount of propylene of by-product and ethene.In addition, also have and use the catalyzer that contains zeolite, produce the method for ethene and propylene from the hydrocarbon raw material that contains alkene by catalyzed conversion.And the production of aromatic hydrocarbons mainly is the catalytic reforming by straight-run spirit.
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.One 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 VIII family element (US3541179, US3647682, DD225135, SU1214726).When using this class catalyzer because the dehydrogenation of institute's loaded metal, the also corresponding quickening of polymerization coking reaction when carrying out cracking reaction, therefore, generally can only use boiling range when adopting this type of catalyzer is＜220 ℃ lightweight material.
The employed second class catalyzer is composite oxides.As with ZrO
2And/or HfO
2Catalyzer for main component is aided with Al
2O
3, Cr
2O
3, MnO and/or Fe
2O
3And basic metal or alkaline earth metal oxide (USP3725495, USP3839485); Be catalyzer and for example with potassium vanadate, potassium stannate or potassium niobate, low-carbon alkene that can about 56 weight % after the naphtha cracking, the therein ethylene productive rate can reach 36.5 weight %, and productivity of propylene is 12.5 weight % (SU523133, SU487927, SU410073); Contain small amount of Fe for another example
2O
3, TiO
2, CaO, MgO, Na
2O, K
2The SiO of O
2Al
2O
3Catalyzer is used for the cracking (SU550173, SU559946) of various hydrocarbon-fractions.Composite oxides commonly used are amorphous Si O
2Al
2O
3(DD152356)
Along with zeolite increasingly extensive application in petrochemical complex and refining of petroleum field, the 3rd class catalyzer has appearred, promptly contain the catalyzer of zeolite, particularly contain have the MFI structural zeolite catalyzer of (five-ring supersiliceous zeolite).
US3758403 discloses a kind of method of catalytically crack hydrocarbons raw material, this method is included under the cracking conditions, described hydro carbons is contacted with a kind of catalyzer, described catalyzer contains a kind of ZSM-5 zeolite and the aperture mixture greater than the zeolite of 7 dusts, this method can in improving product in the gasoline octane rating, make (C
3 =+ C
4 =) gain in yield.
CN1042201C discloses a kind of voluminous C
3-C
5The cracking catalyst of alkene, be the ZSM-5 zeolite that is selected from modifications such as P, RE, Ca, Mg, H, Al by y-type zeolite, the 2-40% of 10-50% lattice constant≤2.450nm, β zeolite and composition thereof, 20-80% are made up of the semi-synthetic carrier that kaolin and al binder are formed.This catalyzer can voluminous ethene and propylene, and makes gasoline yield keep higher level.
CN1055301C discloses the cracking catalyst of a kind of voluminous isomeric olefine and gasoline, it is made up of the zeolite of the clay of the composite aluminum base binding agent of 5-70%, 5-65% and 23-50%, and said zeolite is that the phosphorus content of the y-type zeolite of 15-82% and surplus is (with P
2O
5Meter) is the mixture that contains rare-earth five-membered ring supersiliceous zeolite and/or HZSM-5 zeolite of 0-10 weight %, when containing rare-earth five-membered ring supersiliceous zeolite and HZSM-5 zeolite and exist simultaneously, contains rare-earth five-membered ring supersiliceous zeolite content and be no more than 65%.This catalyzer is mainly used in the productive rate that improves isomeric olefine and gasoline.
CN1102634C discloses a kind of catalyst for catalytic thermal cracking process to prepare lower olefine, this catalyzer has the clay of following composition: 10-70%, the inorganic oxide of 5-85% and the zeolite of 1-50%, its mesolite is y-type zeolite and the phosphorous and aluminium of 75-100% or the five-membered ring structure high-silicon zeolite of magnesium or calcium of 0-25%, this supersiliceous zeolite is the ZSM-5 that contains the aluminium of the phosphorus of 2-8% and 0.3-3% or magnesium or calcium (in oxide compound) ,-8 or the zeolite of-11 types, and its silica alumina ratio is 15-60.This catalyzer is mainly used in catalytic pyrolysis and produces ethene.
CN1317543A discloses the method for a kind of petroleum hydrocarbon catalytic pyrolysis fecund ethene and propylene, this method comprises that heavy petroleum hydrocarbon with preheating is in reactor, contacting with the catalyzer that contains the ZSM-5 molecular sieve in the presence of high-temperature steam, is that 650-750 ℃, reaction pressure are 1.5-4 * 10 in temperature of reaction
5Handkerchief, reaction times are that the weight ratio of 0.2-5 second, catalyzer and stock oil is 15-40: 1, the weight ratio of water vapor and stock oil is 0.3-1: carry out the catalytic pyrolysis reaction under 1 the condition, described ZSM-5 molecular sieve contains Ag or the Cu of 0.1-8 weight %.
US 5006497 discloses a kind of multi-zeolite catalyzer, this catalyzer contains (1) at least a large pore molecular sieve, (2) a kind of restricted index (constraint index) is the shape-selective molecular sieve of 1-12, this shape-selective molecular sieve does not contain the hydrogenation/dehydrogenation component substantially, and has cracking/isomerization activity, (3) restricted index is the shape-selective molecular sieve of 1-12, and this shape-selective molecular sieve has aromatization activity and (4) a kind of matrix.Wherein, described large pore molecular sieve is selected from conventional large pore zeolite, as L zeolite, X zeolite, Y zeolite.The shape-selective molecular sieve that described restricted index is 1-12 is selected from the ZSM-5 of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-48, ZSM-57, boracic, gallium, zirconium, titanium.This catalyzer can improve gasoline octane rating, yield of gasoline.
Reported at SiO among the US 5236880
2/ Al
2O
3The paraffinic hydrocarbon cracking catalyst that adds VIIIB family metal component, preferred nickel in＞5 the zeolite with MFI or MEL structure, this catalyzer can improve the paraffinic hydrocarbon conversion of raw material, increase the aromatic component in the gasoline fraction, improve the octane value and the gasoline yield of gasoline.
CN1048428C discloses a kind of multi-zeolite catalyzer of producing low-carbon alkene, be made up of the clay of 0-70 weight %, the inorganic oxide of 5-90 weight % and the zeolite of 10-35% weight %, its mesolite is made up of the five-ring supersiliceous zeolite of the phosphorous and rare earth of 20-75 weight %, the type-Y high silicon zeolite of 20-75 weight % and the y-type zeolite that contains rare earth of 1-25 weight %.This catalyzer is mainly used in the productive rate that improves iso-butylene and isopentene.
CN1053918C discloses a kind of double zeolite catalyst of producing low-carbon alkene, be made up of the clay of 0-70 weight %, the inorganic oxide of 5-90 weight % and the zeolite of 10-40 weight %, its mesolite is made up of the type-Y high silicon zeolite of the five-ring supersiliceous zeolite of the phosphorous and rare earth of 25-75 weight % and 25-75 weight % or the y-type zeolite that contains rare earth.This catalyzer is mainly used in the productive rate that improves propylene, iso-butylene and isopentene.
CN1043520A discloses a kind of catalyst for cracking, and its carrier is the clay of 0-70 weight % and the inorganic oxide of 5-99 weight %, and its active ingredient is the ZSM-5 of 1-50 weight % and the mixture of Y zeolite.The ZSM-5 molecular sieve accounts for 75-100 weight % in the active ingredient, and the Y type divides in sieve and accounts for 0-25 weight %.This catalyst for cracking is applicable to production low-carbon alkene, particularly propylene and butylene, and double oil and the diesel oil of steaming.
CN1034223C discloses a kind of catalyst for cracking, this catalyzer is made up of the clay of 0-70%, the inorganic oxide of 5-99% and the zeolite of 1-50%, and zeolite wherein is the mixture of five-ring supersiliceous zeolite of the phosphorous and rare earth of the REY of 0-25 weight % or type-Y high silicon zeolite and 75-100 weight %.This catalyzer is applicable to that the petroleum hydrocarbon cracking produces ethene, propylene and butylene, mainly is propylene and butylene, and double oil and the diesel oil of steaming.
Summary of the invention
The purpose of this invention is to provide a kind of higher petroleum hydrocarbon conversion capability that has, propylene, ethene and the higher catalyzer of light aromatics productive rate.Another object of the present invention provides this Preparation of catalysts method.
Catalyzer provided by the invention contains zeolite, heat-resistant inorganic oxide, contain or argillaceous not, wherein, described zeolite is the zeolite with MFI structure or this zeolite with MFI structure that contains transition metal and phosphorus and the mixture of large pore zeolite that contains transition metal and phosphorus, total amount in zeolite, the content that contains the zeolite with MFI structure of transition metal and phosphorus is 75-100 weight %, and the content of large pore zeolite is 0-25 weight %; In the quality of oxide compound, the described zeolite with MFI structure that contains transition metal and phosphorus has following anhydrous chemical expression: (0-0.3) Na
2O (0.3-5) 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 a kind of transition metal that is selected among Fe, Co, Ni, Cu, Zn, Mo or the Mn, and RE represents rare earth metal, and x is 1 or 2, and when x was 1, the numerical value of y was half of transition metal compound valency, when x was 2, the numerical value of y was the transition metal compound valency; This catalyzer also contains a kind of auxiliary agent, and described auxiliary agent is selected from one or more in alkaline-earth metal in the periodic table of elements, IVB family metal, group VIII base metal and the rare earth metal; With the catalyzer total amount is benchmark, and the content of zeolite is 1-60 weight %, in oxide compound, and the content of auxiliary agent is that the content of 0.1-10 weight %, heat-resistant inorganic oxide is that the content of 5-99 weight %, clay is 0-70 weight %.
Preparation of catalysts method provided by the invention comprises all or part of heat-resistant inorganic oxide and/or its precursor and water mixing making beating, add or do not add clay, add zeolite, the slurries that drying obtains, roasting then, wherein, before adding zeolite, add before or after the clay, also add a kind of auxiliary compound, and add the pH value that a kind of acid makes slurries and be 1-5, and under 30-90 ℃ temperature aging 0.1-10 hour; Aging back adds remaining heat-resistant inorganic oxide and/or its precursor; Described zeolite is the zeolite with MFI structure or this zeolite with MFI structure that contains transition metal and phosphorus and the mixture of large pore zeolite that contains transition metal and phosphorus, total amount in zeolite, the content that contains the zeolite with MFI structure of transition metal and phosphorus is 75-100 weight %, and the content of large pore zeolite is 0-25 weight %; In the quality of oxide compound, the described zeolite with MFI structure that contains transition metal and phosphorus has following anhydrous chemical expression: (0-0.3) Na
2O (0.3-5) 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 a kind of transition metal that is selected among Fe, Co, Ni, Cu, Zn, Mo or the Mn, and RE represents rare earth metal, and x is 1 or 2, and when x was 1, the numerical value of y was half of transition metal compound valency, when x was 2, the numerical value of y was the transition metal compound valency; The consumption of each component makes in the final catalyzer and contains, and is benchmark with the catalyzer total amount, the zeolite of 1-60 weight %, in oxide compound, the heat-resistant inorganic oxide of 0.1-10 weight % auxiliary agent, 5-99 weight % and the clay of 0-70 weight %.
Maybe this contains the zeolite with MFI structure of transition metal and phosphorus and the mixture of large pore zeolite is an active ingredient because catalyzer provided by the invention adopts the zeolite with MFI structure that contains transition metal and phosphorus, contain a kind of auxiliary agent that improves catalyst catalytic performance that has simultaneously in the catalyzer, therefore, catalyzer provided by the invention has good activity stability and selectivity, show through water vapour aged catalyzer to have higher petroleum hydrocarbon conversion capability, propylene, ethene and light aromatics productive rate are higher.
Embodiment
According to catalyzer provided by the invention, be benchmark with the catalyzer total amount, the content of zeolite is that the content of 1-60 weight %, auxiliary agent is that the content of 0.1-10 weight %, heat-resistant inorganic oxide is that the content of 5-99 weight %, clay is 0-70 weight %.Under the preferable case, the content of zeolite is that the content of 10-50 weight %, auxiliary agent is that the content of 0.5-8 weight %, heat-resistant inorganic oxide is that the content of 10-70 weight %, clay is 0-60 weight %.
Under the preferable case, in the quality of oxide compound, the described zeolite with MFI structure that contains transition metal and phosphorus has following anhydrous chemical expression: (0-0.2) Na
2O (0.9-5) Al
2O
3(1.5-7) P
2O
5(0.9-10) M
xO
y(0.5-10) RE
2O
3(82-92) SiO
2
A kind of among the preferred Fe of described transition metal M, Co or the Ni, more preferably Fe or Ni.
Described rare earth metal (RE) is preferably lanthanum, cerium or contains lanthanum and/or the norium of cerium.
Described auxiliary agent is preferably one or more in barium, calcium, magnesium, zirconium, titanium, lanthanum, cerium, iron, cobalt, the nickel.Described auxiliary agent can exist with the oxide compound of above-mentioned metal and/or the form of salt, also can with heat-resistant inorganic oxide and/or clay effect, exist with the form of complex compound.Described auxiliary agent be dispersed in heat-resistant inorganic oxide and or clay in.
Described large pore zeolite is the zeolite with cavernous structure of at least 0.7 nano-rings opening, as in faujusite, L zeolite, Beta zeolite, omega zeolite, mordenite, the ZSM-18 zeolite one or more, the particularly overstable gamma zeolite of the y-type zeolite of y-type zeolite, phosphorous and/or rare earth, overstable gamma zeolite, phosphorous and/or rare earth, in the Beta zeolite one or more.
Described heat-resistant inorganic oxide is selected from as in the heat-resistant inorganic oxide of cracking catalyst matrix and binder component one or more, as in aluminum oxide, silicon oxide, the amorphous silicon aluminium one or more.These heat-resistant inorganic oxides are conventionally known to one of skill in the art.
Described clay is selected from as in the clay of active component of cracking catalyst one or more, as in kaolin, halloysite, polynite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the wilkinite one or more.Preferred clay is one or more in kaolin, halloysite, the polynite.These clays are conventionally known to one of skill in the art.
According to Preparation of catalysts method provided by the invention, before aging, heat-resistant inorganic oxide and/or its precursor all can be added or partly add, in order to make catalyzer have the better wear resistance energy, preferably before aging, add part heat-resistant inorganic oxide and/or its precursor earlier, add remaining heat-resistant inorganic oxide and/or its precursor again after aging, earlier to make the weight ratio of the heat-resistant inorganic oxide that the heat-resistant inorganic oxide that adds earlier in the catalyzer and back add be 1 to the part that adds of the part that adds and back: 0.1-10, more preferably 1: 0.1-5.
Described clay can add before aging or after aging, and the order that described clay adds is to the not influence of performance of catalyzer.
Described acid is selected from one or more in water-soluble mineral acid and the organic acid, is preferably hydrochloric acid, nitric acid, phosphoric acid, carbonatoms and is in the carboxylate salt of 1-10 one or more.The consumption of acid makes the pH value of slurries for 1-5, is preferably 1.5-4.
Described aging temperature is 30-90 ℃, is preferably 40-80 ℃, and the aged time is 0.1-10 hour, is preferably 0.5-8 hour.
The precursor of described heat-resistant inorganic oxide refers in described catalyst preparation process, can form in the material of described heat-resistant inorganic oxide one or more.Precursor as aluminum oxide can be selected from hydrated aluminum oxide and/or aluminium colloidal sol; Described hydrated aluminum oxide is selected from one or more in boehmite (boehmite), false boehmite (pseudo-boehmite), hibbsite, the amorphous hydroted alumina.The precursor of silicon oxide can be selected from silicon sol, one or more in silicon gel and the water glass.The precursor of amorphous aluminum silicide can be selected from silicon-aluminum sol, the mixture of silicon sol and aluminium colloidal sol, one or more in the silica-alumina gel.The precursor of these heat-resistant inorganic oxides is conventionally known to one of skill in the art.
Described auxiliary compound is selected from one or more in one or more in water soluble or water-fast alkaline-earth metal, IVB family metal, group VIII base metal and the rare earth compound, particularly water soluble or water-fast barium, calcium, magnesium, zirconium, titanium, lanthanum, cerium, iron, cobalt, nickel compound.As in the halogenide of barium, calcium, magnesium, zirconium, titanium, lanthanum, cerium, iron, cobalt, nickel, nitrate, vitriol, the phosphoric acid salt one or more.Wherein, the halogenide of described barium, calcium, magnesium, zirconium, titanium, lanthanum, cerium, iron, cobalt, nickel is preferably the muriate of barium, calcium, magnesium, zirconium, titanium, lanthanum, cerium, iron, cobalt, nickel.
The consumption of each component makes in the final catalyzer and contains, and is benchmark with the catalyzer total amount, the heat-resistant inorganic oxide of the zeolite of 1-60 weight %, 0.1-10 weight % auxiliary agent, 5-99 weight % and the clay of 0-70 weight %.Under the preferable case, the consumption of each component makes in the final catalyzer and contains, and is benchmark with the catalyzer total amount, the heat-resistant inorganic oxide of the zeolite of 10-50 weight %, 0.5-8 weight % auxiliary agent, 10-70 weight % and the clay of 0-60 weight %.
The drying means of slurries and condition are conventionally known to one of skill in the art, for example, the exsiccant method can be dry, oven dry, forced air drying or spraying drying, preferably spray drying.The exsiccant temperature can be a room temperature to 400 ℃, is preferably 100-350 ℃.For the ease of spraying drying, the solid content of dry preceding slurries is preferably 10-50 weight %, more preferably 20-50 weight %.
Roasting condition after the described slurry dried also is conventionally known to one of skill in the art, and in general, the maturing temperature after the described slurry dried is 400-700 ℃, be preferably 450-650 ℃, roasting time was at least 0.5 hour, was preferably 0.5-100 hour, more preferably 0.5-10 hour.
The described prepare zeolite method with MFI structure that contains transition metal and phosphorus is included in and introduces phosphorus and transition metal in the zeolite with MFI structure that contains or do not contain rare earth.
Or the mode of ion-exchange, in the zeolite that contains or do not contain rare earth, introduce phosphorus and transition metal with MFI structure.Describedly introduce phosphorus and transition metal in the process of the synthetic zeolite with MFI structure that contains or do not contain rare earth, the method that perhaps adopts the mode of dipping, mixing and/or ion-exchange to introduce phosphorus and transition metal is conventionally known to one of skill in the art.
For example, can the zeolite with MFI structure and the P contained compound aqueous solution that contain or do not contain rare earth is even in room temperature to 95 ℃ making beating, drying is after roasting under the 400-800 ℃ of condition, ℃ mix drying with the compound water solution of transition metal M in room temperature to 95 again.The compound water solution that contains or do not contain the zeolite with MFI structure of rare earth and transition metal M ℃ can be mixed in room temperature to 95, drying ℃ mixes drying with the compound water solution of transition metal M in room temperature to 95 again.Also the zeolite with MFI structure that contains or do not contain rare earth simultaneously ℃ can be mixed drying with the mixed aqueous solution of the compound of P contained compound and transition metal M in room temperature to 95.Can also the zeolite with MFI structure and the phosphorous compound aqueous solution that contain or do not contain rare earth is even in room temperature to 95 ℃ making beating, dry, after roasting under the 400-800 ℃ of condition, again with the compound water solution of transition metal M by 1: after solid-to-liquid ratio (5-20) mixes, at 80-95 ℃, pH=4-7 stirred 2-3 hour down, proceeded to few primary ions exchange, filtered also dry then.
Wherein, described drying can adopt any exsiccant method, as dry, method such as oven dry.The exsiccant temperature can be a room temperature to 350 ℃, is preferably 100-200 ℃.
Sodium content in the described zeolite with MFI structure that contains or do not contain rare earth should guarantee sodium content requirement in the anhydrous chemical expression of the zeolite with MFI structure that contains transition metal and phosphorus that finally obtains.If undesirable, the method that can adopt ammonia to exchange is removed sodium wherein.The method that the method that adopts ammonia to exchange is removed the sodium of zeolite is conventionally known to one of skill in the art.
Described P contained compound is selected from one or more in phosphoric acid, aluminum phosphate, ammonium hydrogen phosphate, primary ammonium phosphate or the ammonium phosphate.The compound of described transition metal M is selected from their water-soluble salt, as in muriate, nitrate, vitriol or the carbonate of transition metal M one or more, be preferably in ferric sulfate, ferrous sulfate, iron nitrate, iron(ic) chloride, iron protochloride, rose vitriol, Xiao Suangu, cobalt chloride, single nickel salt, nickelous nitrate and the nickelous chloride one or more.
Catalyzer provided by the invention can be applicable to existing catalytic cracking or Deep Catalytic Cracking process, be used to produce low-carbon alkene, improve the productive rate of low-carbon alkene, the productive rate of propylene and ethene particularly, increase the content of light aromatics in the gasoline simultaneously, also can be used for a kind of brand-new hydrocarbon conversion process, be about to heavy distillate and carry out catalyzed conversion, produce low-carbon alkene, particularly propylene and ethene and light aromatics.
Following example will the present invention is described further, but therefore do not limit the present invention.
Example 1-8 illustrates zeolite with MFI structure of phosphorous and transition metal M and preparation method thereof.
Example 1
With 2 kilograms of NH
4Cl is dissolved in 100 kg of water, and (zeolite with MFI structure, the Qilu Petrochemical catalyst plant is produced, SiO to add 10 kilograms of (butt) ZRP-1 zeolites in this solution
2/ Al
2O
3=30, rare earth oxide RE
2O
3Content is 4.0 weight %, and wherein, lanthanum trioxide content is 2.12 weight %, and cerium oxide content is 0.52 weight %, and other rare earth oxide content is 1.36 weight %, Na
2O content is 1.7 weight %), 90 ℃ the exchange 0.5 hour after, filter filter cake; Contain 0.34 kilogram of H with 9.88 kilograms
3PO
4With 0.48 kilogram of Fe (NO
3)
3Mixing solutions and filter cake mix, 120 ℃ of oven dry, 550 ℃ of roastings 2 hours obtain phosphorous and the zeolite Z1 with MFI structure transition metal iron.The anhydrous chemical expression of Z1 is:
0.1Na
2O·4.9Al
2O
3·2.4P
2O
5·1.5Fe
2O
3·3.8RE
2O
3·87.3SiO
2。Wherein, the anhydrous chemical expression of the zeolite with MFI structure of phosphorous and transition metal M is elementary composition with the x-ray fluorescence spectrometry zeolite, obtains through conversion again.
Example 2
With 5 kilograms of NH
4Cl is dissolved in 100 kg of water, adds 10 kilograms of (butt) ZRP-1 zeolites (with example 1) in this solution, 85 ℃ of exchanges after 0.5 hour, filter filter cake; The filter cake that obtains and 6.8 kilograms are contained 0.8 kilogram of NH
4H
2PO
4Solution mix, 120 ℃ of oven dry were 550 ℃ of roastings 2 hours; With above-mentioned sample is the Fe (NO of 5 weight % in 5: 1 ratio of solid-to-liquid ratio and concentration
3)
3Solution filters 80-90 ℃ of down exchange 2 hours, and exchange again reaches the amount of iron in the following anhydrous chemical expression until iron level, again 550 ℃ of roastings 2 hours, obtains phosphorous and the zeolite Z2 with MFI structure transition metal iron.The anhydrous chemical expression of Z2 is:
0.03Na
2O·4.7Al
2O
3·4.5P
2O
5·3.0Fe
2O
3·3.7RE
2O
3·84.1SiO
2。
Example 3
With 2 kilograms of NH
4Cl is dissolved in 100 kg of water, and (zeolite with MFI structure, the Qilu Petrochemical catalyst plant is produced, SiO to add 10 kilograms of (butt) ZRP-5 zeolites in this solution
2/ Al
2O
3=60), 90 ℃ the exchange 0.5 hour after, filter filter cake; The filter cake that obtains and 12.8 kilograms are contained 0.32 kilogram of H
3PO
4With 3.42 kilograms of Fe (NO
3)
3Mixing solutions mix, 120 ℃ of oven dry, 550 ℃ of roastings 2 hours obtain phosphorous and the zeolite Z3 with MFI structure transition metal iron.The anhydrous chemical expression of Z3 is:
0.1Na
2O·2.4Al
2O
3·2.0P
2O
5·10Fe
2O
3·85.5SiO
2。
Example 4
With 8 kilograms of NH
4Cl is dissolved in 100 kg of water, adds 10 kilograms of (butt) ZRP-5 zeolites (with example 3) in this solution, 85 ℃ of exchanges after 0.5 hour, filter filter cake; The filter cake that obtains and 6.89 kilograms are contained 0.89 kilogram of NH
4H
2PO
4Solution mix 120 ℃ of oven dry; With the oven dry after sample and 9.52 kilograms contain 0.52 kilogram of FeSO
46H
2The solution of O mixes, 120 ℃ of oven dry, and 600 ℃ of roastings 2 hours obtain phosphorous and the zeolite Z4 with MFI structure transition metal iron.Z4's.Its anhydrous chemical expression is:
0.1Na
2O·2.6Al
2O
3·5.1P
2O
5·1.5Fe
2O
3·90.7SiO
2。
Example 5
With 8 kilograms of NH
4Cl is dissolved in 100 kg of water, and (zeolite with MFI structure, the Qilu Petrochemical catalyst plant is produced, SiO to add 10 kilograms of (butt) ZRP-5 zeolites in this solution
2/ Al
2O
3=70), 85 ℃ the exchange 0.5 hour after, filter filter cake; The filter cake that obtains and 6.89 kilograms are contained 0.89 kilogram of NH
4H
2PO
4Solution mix 120 ℃ of oven dry; With the oven dry after sample and 9.35 kilograms contain 0.35 kilogram of FeSO
46H
2The solution of O mixes, 120 ℃ of oven dry, and 600 ℃ of roastings 2 hours obtain phosphorous and the zeolite Z5 with MFI structure transition metal iron.The anhydrous chemical expression of Z5 is: 0.1Na
2O2.2Al
2O
35.1P
2O
51.0Fe
2O
391.6SiO
2
Example 6
With 8 kilograms of NH
4Cl is dissolved in 100 kg of water, adds 10 kilograms of (butt) ZRP-5 zeolites (with example 3) in this solution, 85 ℃ of exchanges after 0.5 hour, filter filter cake; The filter cake that obtains and 6.9 kilograms are contained 0.9 kilogram of (NH
4)
2HPO
4Solution mix 120 ℃ of oven dry; With the oven dry after sample and 9.83 kilograms contain 0.83 kilogram of Ni (NO
3)
26H
2The solution of O mixes, 120 ℃ of oven dry, and 600 ℃ of roastings 2 hours obtain phosphorous and the zeolite Z6 with MFI structure transiting metal nickel.The anhydrous chemical expression of Z6 is:
0.1Na
2O·2.6Al
2O
3·4.5P
2O
5·2.0NiO·90.8SiO
2。
Example 7
With 8 kilograms of NH
4Cl is dissolved in 100 kg of water, adds 10 kilograms of (butt) ZRP-1 zeolites (with example 1) in this solution, 85 ℃ of exchanges after 0.5 hour, filter filter cake; The filter cake that obtains and 6.84 kilograms are contained 0.84 kilogram of (NH
4)
2HPO
4Solution mix 120 ℃ of oven dry; With the oven dry after sample and 9.39 kilograms contain 0.39 kilogram of Ni (NO
3)
26H
2The solution of O mixes, 120 ℃ of oven dry, and 600 ℃ of roastings 2 hours obtain phosphorous and the zeolite Z7 with MFI structure transiting metal nickel.The anhydrous chemical expression of Z7 is:
0.1Na
2O·4.9Al
2O
3·4.1P
2O
5·1.0NiO·3.8RE
2O
3·86.1SiO
2。
Example 8
With 8 kilograms of NH
4Cl is dissolved in 100 kg of water, adds 10 kilograms of (butt) ZRP-5 zeolites (with example 3) in this solution, 85 ℃ of exchanges after 0.5 hour, filter filter cake; The filter cake that obtains and 6.89 kilograms are contained 0.89 kilogram of NH
4H
2PO
4Solution mix 120 ℃ of oven dry; With the oven dry after sample and 10.06 kilograms contain 1.06 kilograms of FeSO
46H
2The solution of O mixes, 120 ℃ of oven dry, and 600 ℃ of roastings 2 hours obtain phosphorous and the zeolite Z8 with MFI structure transition metal iron.The anhydrous chemical expression of Z8 is:
0.07Na
2O·2.5Al
2O
3·5.0P
2O
5·3.0Fe
2O
3·89.4SiO
2。
Example 9
This example illustrates Catalysts and its preparation method provided by the invention.
With 0.34 kilogram of Ba (NO
3)
2Be dissolved in 18 kilograms of decationized Y sieve water, add 4.2 kilograms of halloysites (Suzhou china clay company Industrial products, solid content 71.6 weight %) making beating, add 3.2 kilograms of pseudo-boehmites (Shandong Aluminum Plant's Industrial products, solid content 62.0 weight %) again, its pH is transferred to 2 with hydrochloric acid, stir, under 70 ℃, left standstill aging 1 hour, and added 3.7 kilograms of aluminium colloidal sols (Qilu Petrochemical company catalyst plant product, Al
2O
3Content is 21.5 weight %, (weight ratio of the heat-resistant inorganic oxide that the heat-resistant inorganic oxide precursor that adds before and after aging adds before and after making and wearing out is 1: 0.4), stir, (the industrial trade mark is DASY2.0 to add the zeolite Z1 with MFI structure of phosphorous and transition metal iron of 3.5 kilograms of (butt) examples 1 preparation and 0.5 kilogram of (butt) overstable gamma zeolite, Qilu Petrochemical catalyst plant Industrial products, lattice constant is 2.446, rare earth oxide RE
2O
3Content is 2.0 weight %, wherein, lanthanum trioxide content is 1.06 weight %, cerium oxide content is 0.26 weight %, and other rare earth oxide content is 0.68 weight %) mixture and 11.4 kilograms of slurries obtaining of water making beating, stir, obtain the slurries that solid content is 24.5 weight %, with the slurries spray drying forming under 250 ℃ temperature that obtains is that diameter is the particle of 20-150 micron, 550 ℃ of roastings 2 hours, catalyzer C1 provided by the invention.The composition of C1 sees Table 1.
Example 10
This example illustrates Catalysts and its preparation method provided by the invention.
Method by example 9 prepares catalyzer, and different is with 0.46 kilogram of LaCl
37H
2O replaces 0.34 kilogram of Ba (NO
3)
2, replace Z1 with the zeolite Z2 with MFI structure of the phosphorous and transition metal iron of example 2 preparation of equivalent, catalyzer C2 provided by the invention.The composition of C2 sees Table 1.
Example 11
This example illustrates Catalysts and its preparation method provided by the invention.
Method by example 9 prepares catalyzer, and different is with 0.17 kilogram of Ba (NO
3)
2With 0.34 kilogram of FeCl
36H
2O replaces 0.34 kilogram of Ba (NO
3)
2, replace Z1 with the zeolite Z7 with MFI structure of the phosphorous and transiting metal nickel of example 7 preparation of equivalent, catalyzer C3 provided by the invention.The composition of C3 sees Table 1.
Comparative Examples 1
The explanation of this Comparative Examples contains the reference catalyst and the preparation thereof of the zeolite with MFI structure of not phosphorous and transition metal.
Method by example 9 prepares catalyzer, and that different is the zeolite Z1 with MFI structure that replaces the phosphorous and transition metal iron of example 1 preparation with ZRP-1 zeolite (with example 1), obtains reference catalyst CB1.The composition of CB1 sees Table 1.
Comparative Examples 2
The explanation of this Comparative Examples does not contain reference catalyst of auxiliary agent and preparation method thereof.
Method by example 1 prepares catalyzer, and different is not add Ba (NO
3)
2, the consumption of aluminium colloidal sol is 4.7 kilograms, obtains reference catalyst CB2.The composition of CB2 sees Table 1.
Comparative Examples 3
This Comparative Examples illustrates the zeolite with MFI structure of not phosphorous and transition metal, and does not contain reference catalyst of auxiliary agent and preparation method thereof.
Method by example 1 prepares catalyzer, and different is not add Ba (NO
3)
2, the consumption of aluminium colloidal sol is 4.7 kilograms, replaces the zeolite Z1 with MFI structure of the phosphorous and transition metal iron of example 1 preparation with ZRP-1 zeolite (with example 1), obtains reference catalyst CB3.The composition of CB3 sees Table 1.
Table 1
| Example number | Example 9 | Example 10 | Example 11 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 |
| Catalyzer | C1 | C2 | C3 | CB1 | CB2 | CB3 |
| The clay types clay content, weight % heat-resistant inorganic oxide kind heat-resistant inorganic oxide content, weight % auxiliary agent kind analog assistant content (in oxide compound), weight % has the zeolite content that the zeolite type of MFI structure has the MFI structure, weight % large pore zeolite kind large pore zeolite content, weight % | Halloysite 30 aluminium oxide 28 barium 2 Z1 35 DASY2.0 5 | Halloysite 30 aluminium oxide 28 lanthanums 2 Z2 35 DASY2.0 5 | Halloysite 30 aluminium oxide 28 iron+barium 2 Z7 35 DASY2.0 5 | Halloysite 30 aluminium oxide 28 barium 2 ZRP-1 35 DASY2.0 5 | Halloysite 30 aluminium oxide 30--Z1 35 DASY2.0 5 | Halloysite 30 aluminium oxide 30--ZRP-1 35 DASY2.0 5 |
Example 12
This example illustrates Catalysts and its preparation method provided by the invention.
With 0.17 kilogram of Ba (NO
3)
2Be dissolved in 12.5 kilograms of decationized Y sieve water, add 4.0 kilograms of pseudo-boehmites (with example 9), its pH is transferred to 2, stir, under 50 ℃, left standstill aging 5 hours, the product after obtaining wearing out with nitric acid.
In 2.5 kilograms of decationized Y sieve water, add 1.9 kilograms of aluminium colloidal sols (with example 9, the weight ratio of the heat-resistant inorganic oxide that the heat-resistant inorganic oxide precursor that adds before and after aging adds before and after making and wearing out is 1: 0.16), (solid content is 76 weight % to add 4.0 kilograms of kaolin again, Suzhou kaolin company produces) making beating, stir, add above-mentioned product after aging, (the industrial trade mark is USY to add have MFI structural zeolite Z3 and 1 kilogram of (butt) overstable gamma zeolite of phosphorous and transition metal iron of 3 kilograms of (butt) examples 3 preparation again, Qilu Petrochemical Zhou village catalyst plant Industrial products, lattice constant is 2.445 nanometers, sodium oxide content is 0.36 weight %) 11.4 kilograms of slurries obtaining with decationized Y sieve water making beating, stir, obtaining the slurries that solid content is 27.4 weight %, under 220 ℃, is that diameter is the particle of 20-150 micron with the slurries spray drying forming that obtains, 520 ℃ of roastings 4 hours obtain catalyzer C4 provided by the invention.The composition of C4 sees Table 2.
Example 13
This example illustrates Catalysts and its preparation method provided by the invention.
With 0.17 kilogram of Ba (NO
3)
2Be dissolved in 18 kilograms of decationized Y sieve water, (solid content is 95 weight % to add 3.0 kilograms of halloysites (with example 9) and 0.9 kilogram of polynite, Zhejiang Feng Hong clay chemical industry company limited produces) making beating, add 4.0 kilograms of pseudo-boehmites (with example 9) again, with hydrochloric acid its pH is transferred to 3.5, stir, add and Ba (NO
3)
2Equimolar sulfuric acid, make barium wherein be completed into barium sulfate precipitate, under 75 ℃, left standstill aging 0.5 hour, add 1.8 kilograms of aluminium colloidal sols (with example 9, the weight ratio of the heat-resistant inorganic oxide that the heat-resistant inorganic oxide precursor that adds before and after aging adds before and after making and wearing out is 1: 0.16), stir, have MFI structural zeolite Z4 and 1.0 kilograms (butt) that add the phosphorous and transition metal iron of 3.0 kilograms of (butt) examples 4 preparation contain rare earth hydrogen Y zeolite (the industrial trade mark are REHY, Qilu Petrochemical Zhou village catalyst plant Industrial products, lattice constant is 2.465 nanometers, sodium oxide content is 3.2 weight %, rare earth oxide content is for being 7.0 weight %, wherein, lanthanum trioxide content is 3.71 weight %, cerium oxide content is 0.91 weight %, other rare earth oxide content is 2.38 weight %) 11.4 kilograms of slurries obtaining with water making beating, stir, obtain the slurries that solid content is 25.5 weight %, under 280 ℃, with the slurries spray drying forming that obtains is that diameter is the particle of 20-150 micron, 580 ℃ of roastings 2.5 hours obtain catalyzer C5 provided by the invention.The composition of C5 sees Table 2.
Example 14
This example illustrates Catalysts and its preparation method provided by the invention.
With 0.22 kilogram of CeCl
37H
2O is dissolved in 5.0 kilograms of decationized Y sieve water, floods 7.0 kilograms of halloysites (with example 9), and 120 ℃ of oven dry obtain containing CeO
22.0 the halloysite of weight %.
In 21.8 kilograms of decationized Y sieve water, add the above-mentioned CeO that contains
2Halloysite making beating, add 3.9 kilograms of pseudo-boehmites again (with example 9, the heat-resistant inorganic oxide precursor all adds before aging), with hydrochloric acid its pH is transferred to 3, stir, under 60 ℃, left standstill aging 2 hours, add 7.2 kilograms of slurries that the zeolite Z5 with MFI structure of phosphorous and transition metal iron of 2.0 kilograms of (butt) examples 5 preparation and 0.5 kilogram of (butt) overstable gamma zeolite (with example 9) and water making beating obtain, stir, obtain the slurries that solid content is 25.2 weight %, under 250 ℃, with the slurries spray drying forming that obtains is that diameter is the particle of 20-150 micron, 600 ℃ of roastings 1 hour obtain catalyzer C6 provided by the invention.The composition of C6 sees Table 2.
Example 15
This example illustrates Catalysts and its preparation method provided by the invention.
With 1.44 kilograms of Zr (SO
4)
24H
2O is dissolved in 18 kilograms of decationized Y sieve water, add 5.6 kilograms of halloysites (with example 9) making beating, add 3.2 kilograms of pseudo-boehmites (with example 9) again, with hydrochloric acid its pH is transferred to 4, stir, under 60 ℃, left standstill aging 1 hour, add 2.3 kilograms of aluminium colloidal sols (with example 9, the weight ratio of the heat-resistant inorganic oxide that the heat-resistant inorganic oxide precursor that adds before and after aging adds before and after making and wearing out is 1: 0.25), stir, add 8.6 kilograms of slurries that the zeolite Z6 with MFI structure of phosphorous and transiting metal nickel of 2.5 kilograms of (butt) examples 6 preparation and 0.5 kilogram of (butt) overstable gamma zeolite (with example 9) and water making beating obtain, stir, obtain the slurries that solid content is 25.6 weight %, under 220 ℃, with the slurries spray drying forming that obtains is that diameter is the particle of 20-150 micron, and 550 ℃ of roastings 2 hours obtain catalyzer C7 provided by the invention.The composition of C7 sees Table 2.
Example 16
This example illustrates Catalysts and its preparation method provided by the invention.
With 0.43 kilogram of Ba (NO
3)
2With 0.57 kilogram of LaCl
37H
2O is dissolved in 12 kilograms of decationized Y sieve water, add 3.2 kilograms of pseudo-boehmites (with example 9) making beating, with hydrochloric acid its pH is transferred to 3, stir, under 55 ℃, left standstill aging 6 hours, (silica content is 16.0 weight % to add 25.0 kilograms of silicon sol again, the Beijing Chemical Plant produces), with 2.3 kilograms of aluminium colloidal sols (with example 9, the weight ratio of the heat-resistant inorganic oxide that the heat-resistant inorganic oxide precursor that adds before and after aging adds before and after making and wearing out is 1: 2.25), stir, add 8.6 kilograms of slurries that the zeolite Z8 with MFI structure and the water of the phosphorous and transition metal iron of 3.0 kilograms of (butt) examples 8 preparation are pulled an oar and obtained, stir, obtaining the slurries that solid content is 19.2 weight %, under 250 ℃, is that diameter is the particle of 20-150 micron with the slurries spray drying forming that obtains, 550 ℃ of roastings 2 hours obtain catalyzer C8 provided by the invention.The composition of C8 sees Table 2.
Table 2
| Example number | Example 12 | Example 13 | Example 14 | Example 15 | Example 16 |
| Catalyzer | C4 | C5 | C6 | C7 | C8 |
| The clay types clay content, weight % heat-resistant inorganic oxide kind heat-resistant inorganic oxide content, weight % auxiliary agent kind analog assistant content (in oxide compound), weight % has the zeolite content that the zeolite type of MFI structure has the MFI structure, weight % large pore zeolite kind large pore zeolite content, weight % | Kaolin 30 aluminium oxide 29 barium 1 Z3 30 USY 10 | Halloysite+imvite 30 aluminium oxide 29 barium 1 Z4 30 REHY 10 | Halloysite 50 aluminium oxide 24 ceriums 1 Z5 20 DASY2.0 5 | Halloysite 40 aluminium oxide 25 zirconiums 5 Z6 25 DASY2.0 5 | --aluminium oxide+silica 65 barium+lanthanum 5 Z8 30-- |
Example 17-19
Following example illustrates the catalytic performance of catalyzer provided by the invention.
With catalyzer C1-C3 at 800 ℃, with 100% steam aging 17 hours, pack in the reactor of small fixed flowing bed device, the catalyzer loading amount is 180 grams, is 580 ℃ in temperature of reaction, and agent weight of oil ratio is 10, weight hourly space velocity is under 10 hours-1 the condition, feed the mixture of vacuum gas oil shown in the table 3 and water vapor, the amount of water vapour is 25 weight % of vacuum gas oil, the results are shown in Table 4.
Comparative Examples 4-6
The catalytic performance of following Comparative Examples explanation reference catalyst.
Method by example 17 is carried out catalyzed conversion to identical stock oil, and different is that catalyst system therefor is respectively reference catalyst CB1, CB2 and CB3, the results are shown in Table in 4.
Table 3
| The stock oil title | Vacuum gas oil | Long residuum |
| Density (20 ℃), gram per centimeter 3Viscosity, millimeter 2/ second bituminous matter, weight % Conradson carbon residue, weight % boiling range, ℃ IBP 10% 30% 50% 70% 90% FBP | 0.8730 8.04 - 0.15 346 411 437 462 489 523 546 | 0.8906 24.84 0.8 4.3 282 370 482 553 - - - |
Table 4
| Example number | Example 17 | Example 18 | Example 19 | Comparative Examples 4 | Comparative Examples 5 | Comparative Examples 6 |
| Catalyzer | C1 | C2 | C3 | CB1 | CB2 | CB3 |
| Transformation efficiency | 92.0 | 91.9 | 91.0 | 86.8 | 91.5 | 88.1 |
| Product distributes, weight % reacted gas gasoline, diesel heavy oil coke | 67.3 18.7 4.8 3.2 6.0 | 66.8 18.6 4.7 3.4 6.5 | 66.7 17.9 5.5 3.5 6.4 | 63.4 18.5 8.1 5.1 4.9 | 66.7 18.2 5.1 3.4 6.6 | 63.9 19.1 6.9 5.0 5.1 |
| Wherein, third is wherein rare, ethene wherein, BTX * | 31.5 10.3 5.9 | 30.9 10.1 5.8 | 31.7 9.8 6.0 | 28.3 8.8 5.7 | 29.6 9.0 5.6 | 27.8 8.6 5.7 |
*BTX represents benzene, toluene and dimethylbenzene.
The presentation of results of table 4, with the aged zeolite content is identical under the same conditions, the catalyzer of the zeolite with MFI structure of not phosphorous and transition metal is compared, the heavy oil cracking ability of catalyzer provided by the invention significantly improves, the reacted gas productive rate is higher, and particularly propylene and ethene and BTX productive rate are higher; Identical with zeolite content and type, the catalyzer that does not contain auxiliary agent is compared, and catalyzer provided by the invention has higher propylene, ethene and BTX productive rate and lower coke yield.
Example 20-24
Following example illustrates the catalytic performance of catalyzer provided by the invention.
Method by example 1 is carried out catalyzed conversion to stock oil, and different is, uses catalyzer C4-C8 replaced C 1 respectively, and raw materials used oil is long residuum shown in the table 3, and reaction conditions and reaction result see Table 5.
Table 5
| Example number | Example 20 | Example 21 | Example 22 | Example 23 | Example 24 |
| Catalyzer | C4 | C5 | C6 | C7 | C8 |
| Transformation efficiency | 79.9 | 83.6 | 86.6 | 88.6 | 92.5 |
| Temperature of reaction, ℃ | 550 | 580 | 620 | 620 | 680 |
| Agent weight of oil ratio | 10 | 10 | 10 | 15 | 25 |
| Weight hourly space velocity, hour -1 | 10 | 10 | 15 | 15 | 20 |
| The amount of water vapour is the weight percentage of long residuum, weight % | 25 | 25 | 50 | 80 | 80 |
| Product distributes, weight % reacted gas gasoline, diesel heavy oil coke | 50.1 21.5 12.6 7.5 8.3 | 53.4 20.4 10.3 6.1 9.8 | 55.1 19.3 8.9 4.5 12.2 | 57.6 18.2 7.6 3.8 12.8 | 61.7 16.1 6.0 1.5 14.7 |
| Wherein, propylene wherein, ethene wherein, BTX | 21.5 7.7 6.0 | 23.4 10.2 6.6 | 24.2 12.4 6.7 | 25.6 12.8 7.0 | 22.9 21.8 6.7 |
Claims (15)
1. Hydrocarban coversion catalysts that contains zeolite, this catalyzer contains zeolite, heat-resistant inorganic oxide, contain or argillaceous not, it is characterized in that, described zeolite is the zeolite with MFI structure or this zeolite with MFI structure that contains transition metal and phosphorus and the mixture of large pore zeolite that contains transition metal and phosphorus, in the total amount of zeolite, the content that contains the zeolite with MFI structure of transition metal and phosphorus is 75-100 weight %, and the content of large pore zeolite is 0-25 weight %; In the quality of oxide compound, the described zeolite with MFI structure that contains transition metal and phosphorus has following anhydrous chemical expression: (0-0.3) Na
2O (0.3-5) 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 a kind of transition metal that is selected among Fe, Co, Ni, Cu, Zn, Mo or the Mn, and RE represents rare earth metal, and x is 1 or 2, and when x was 1, the numerical value of y was half of transition metal compound valency, when x was 2, the numerical value of y was the transition metal compound valency; This catalyzer also contains a kind of auxiliary agent, and described auxiliary agent is selected from one or more in alkaline-earth metal in the periodic table of elements, IVB family metal, group VIII base metal and the rare earth metal; With the catalyzer total amount is benchmark, and the content of zeolite is 1-60 weight %, in oxide compound, and the content of auxiliary agent is that the content of 0.1-10 weight %, heat-resistant inorganic oxide is that the content of 5-99 weight %, clay is 0-70 weight %.
2. catalyzer according to claim 1, it is characterized in that, with the catalyzer total amount is benchmark, and the content of zeolite is that the content of 10-50 weight %, auxiliary agent is that the content of 0.5-8 weight %, heat-resistant inorganic oxide is that the content of 10-70 weight %, clay is 0-60 weight %.
3. catalyzer according to claim 1 is characterized in that, in the quality of oxide compound, the described zeolite with MFI structure that contains transition metal and phosphorus has following anhydrous chemical expression: (0-0.2) Na
2O (0.9-5) Al
2O
3(1.5-7) P
2O
5(0.9-10) M
xO
y(0.5-10) RE
2O
3(82-92) SiO
2
4. catalyzer according to claim 1 is characterized in that, described transition metal M is selected from a kind of among Fe, Co or the Ni.
5. catalyzer according to claim 1 is characterized in that described auxiliary agent is selected from one or more in barium, calcium, magnesium, zirconium, titanium, lanthanum, cerium, iron, cobalt, the nickel.
6. catalyzer according to claim 1 is characterized in that, described large pore zeolite is selected from one or more in faujusite, L zeolite, Beta zeolite, omega zeolite, mordenite, the ZSM-18 zeolite.
7. catalyzer according to claim 6 is characterized in that, described large pore zeolite is selected from the overstable gamma zeolite of the y-type zeolite, overstable gamma zeolite of y-type zeolite, phosphorous and/or rare earth, phosphorous and/or rare earth, in the Beta zeolite one or more.
8. catalyzer according to claim 1 is characterized in that described heat-resistant inorganic oxide is selected from one or more in aluminum oxide, silicon oxide, the amorphous silicon aluminium.
9. catalyzer according to claim 1 is characterized in that described clay is selected from one or more in kaolin, halloysite, polynite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the wilkinite.
10. claim 1 Preparation of catalysts method, this method comprises all or part of heat-resistant inorganic oxide and/or its precursor and water mixing making beating, add or do not add clay, add zeolite, the slurries that drying obtains, it is characterized in that, before adding zeolite, add before or after the clay, also add a kind of auxiliary compound, add a kind of acid and make the pH value of slurries be 1-5, and under 30-90 ℃ temperature, wore out 0.1-10 hour; Aging back adds remaining heat-resistant inorganic oxide and/or its precursor; Described zeolite is the zeolite with MFI structure or this zeolite with MFI structure that contains transition metal and phosphorus and a kind of mixture of large pore zeolite that contains transition metal and phosphorus, total amount in zeolite, the content that contains the zeolite with MFI structure of transition metal and phosphorus is 75-100 weight %, and the content of large pore zeolite is 0-25 weight %; In the quality of oxide compound, the described zeolite with MFI structure that contains transition metal and phosphorus has following anhydrous chemical expression: (0-0.3) Na
2O (0.3-5) 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 a kind of transition metal that is selected among Fe, Co, Ni, Cu, Zn, Mo or the Mn, and RE represents rare earth metal, and x is 1 or 2, and when x was 1, the numerical value of y was half of transition metal compound valency, when x was 2, the numerical value of y was the transition metal compound valency; The consumption of each component makes in the final catalyzer and contains, and is benchmark with the catalyzer total amount, the zeolite of 1-60 weight %, in oxide compound, the heat-resistant inorganic oxide of 0.1-10 weight % auxiliary agent, 5-99 weight % and the clay of 0-70 weight %.
11. method according to claim 10, it is characterized in that, before aging, part heat-resistant inorganic oxide and/or its precursor that elder generation adds, add remaining heat-resistant inorganic oxide and/or its precursor again after aging, to make the weight ratio of the heat-resistant inorganic oxide that the heat-resistant inorganic oxide that adds earlier in the catalyzer and back add be 1 to the part that adds of the part that adds and back earlier: 0.1-10.
12. method according to claim 11 is characterized in that, described weight ratio is 1: 0.1-5.
13. method according to claim 10 is characterized in that, described acid is selected from one or more in the carboxylate salt that hydrochloric acid, nitric acid, phosphoric acid, carbonatoms are 1-10; The consumption of acid makes the pH value of slurries be 1.5-4.
14. method according to claim 10 is characterized in that, described aging temperature is 40-80 ℃, and the aged time is 0.5-8 hour.
15. method according to claim 10 is characterized in that, described auxiliary compound is selected from one or more in the halogenide, nitrate, vitriol, phosphoric acid salt of barium, calcium, magnesium, zirconium, titanium, lanthanum, cerium, iron, cobalt, nickel.
Priority Applications (8)
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|---|---|---|---|
| CN 200410029862 CN1292052C (en) | 2004-03-31 | 2004-03-31 | Hydrocarbon conversion catalyst containing zeolite and its preparing method |
| CA2563262A CA2563262C (en) | 2004-03-31 | 2005-03-31 | A zeolite-containing hydrocarbon-converting catalyst, the preparation process thereof, and a process for converting hydrocarbon oils with the catalyst |
| US11/547,209 US7923399B2 (en) | 2004-03-31 | 2005-03-31 | Zeolite-containing hydrocarbon-converting catalyst, the preparation process thereof, and a process for converting hydrocarbon oils with the catalyst |
| RU2006138442/04A RU2372142C2 (en) | 2004-03-31 | 2005-03-31 | Zeolite-containing catalyst for coverting hydrocarbons, method of making said catalyst and method of converting hydrocarbon petroleum products using said catalyst |
| EP05733042.5A EP1762299B1 (en) | 2004-03-31 | 2005-03-31 | A catalyst containing zeolite for hydrocarbon converting and preparation thereof, and a hydrocarbon oil converting method using said catalyst |
| JP2007505361A JP4987693B2 (en) | 2004-03-31 | 2005-03-31 | Zeolite-containing hydrocarbon conversion catalyst, method for producing the same, and method for converting hydrocarbon oil with the catalyst |
| BRPI0509507-7A BRPI0509507B1 (en) | 2004-03-31 | 2005-03-31 | hydrocarbon conversion catalyst containing zeolite, the process for preparing them, and a process for converting hydrocarbon oils with the catalyst |
| PCT/CN2005/000427 WO2005094992A1 (en) | 2004-03-31 | 2005-03-31 | A catalyst containing zeolite for hydrocarbon converting and preparation thereof, and a hydrocarbon oil converting method using said catalyst |
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| CN101733140B (en) * | 2008-11-18 | 2012-01-11 | 中国石油天然气股份有限公司 | Preparation method of shape-selective molecular sieve composition |
| CN103007987B (en) * | 2011-09-22 | 2015-04-29 | 中国石油化工股份有限公司 | Cracking assistant for improving low-carbon olefin concentration |
| CN103007992B (en) * | 2011-09-22 | 2015-04-29 | 中国石油化工股份有限公司 | Cracking assistant for improving low-carbon olefin concentration |
| CN104014359B (en) * | 2014-06-04 | 2016-03-16 | 湛江天成投资有限公司 | A kind of preparation method of cracking catalyst for petroleum hydrocarbon |
| CN107974286B (en) * | 2016-10-21 | 2020-11-13 | 中国石油化工股份有限公司 | Catalytic cracking method for producing low-carbon olefin and light aromatic hydrocarbon |
| CN112010323B (en) * | 2019-05-31 | 2022-06-24 | 中国石油化工股份有限公司 | MFI structure molecular sieve containing phosphorus and metal and preparation method thereof |
| CN114425423B (en) * | 2020-09-25 | 2023-12-12 | 中国石油化工股份有限公司 | Hydrocarbon conversion catalyst for producing low-carbon olefin and light aromatic hydrocarbon, preparation method thereof and heavy oil catalytic conversion method |
| CN114425376B (en) * | 2020-09-27 | 2024-03-12 | 中国石油化工股份有限公司 | Hydrocarbon conversion catalyst containing MFI zeolite and its preparation method |
-
2004
- 2004-03-31 CN CN 200410029862 patent/CN1292052C/en not_active Expired - Lifetime
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