CN108452838A - A kind of catalytic cracking catalyst - Google Patents
A kind of catalytic cracking catalyst Download PDFInfo
- Publication number
- CN108452838A CN108452838A CN201710097154.0A CN201710097154A CN108452838A CN 108452838 A CN108452838 A CN 108452838A CN 201710097154 A CN201710097154 A CN 201710097154A CN 108452838 A CN108452838 A CN 108452838A
- Authority
- CN
- China
- Prior art keywords
- weight
- acid
- molecular sieve
- modified zeolite
- catalytic cracking
- 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 102
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 68
- 239000002808 molecular sieve Substances 0.000 claims abstract description 197
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 196
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 180
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 109
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 94
- 229910001868 water Inorganic materials 0.000 claims abstract description 94
- 239000002253 acid Substances 0.000 claims abstract description 67
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 67
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 44
- 239000000654 additive Substances 0.000 claims abstract description 43
- 230000000996 additive effect Effects 0.000 claims abstract description 43
- 239000011148 porous material Substances 0.000 claims abstract description 42
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 38
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000002360 preparation method Methods 0.000 claims abstract description 37
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910001948 sodium oxide Inorganic materials 0.000 claims abstract description 31
- 239000004411 aluminium Substances 0.000 claims abstract description 17
- 239000004927 clay Substances 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000005049 silicon tetrachloride Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 74
- 239000007789 gas Substances 0.000 claims description 54
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 37
- 230000032683 aging Effects 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 31
- 238000005406 washing Methods 0.000 claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- 229910001593 boehmite Inorganic materials 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 25
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 25
- 239000002002 slurry Substances 0.000 claims description 23
- -1 rectorite Inorganic materials 0.000 claims description 22
- 239000000377 silicon dioxide Substances 0.000 claims description 21
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 20
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 20
- 239000005995 Aluminium silicate Substances 0.000 claims description 18
- 235000012211 aluminium silicate Nutrition 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 17
- 150000007524 organic acids Chemical class 0.000 claims description 17
- 150000007522 mineralic acids Chemical class 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 15
- 229910052593 corundum Inorganic materials 0.000 claims description 13
- 238000005342 ion exchange Methods 0.000 claims description 13
- 238000001179 sorption measurement Methods 0.000 claims description 13
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 229910052681 coesite Inorganic materials 0.000 claims description 12
- 229910052906 cristobalite Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 229910052682 stishovite Inorganic materials 0.000 claims description 12
- 229910052905 tridymite Inorganic materials 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 11
- 229910003910 SiCl4 Inorganic materials 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- 230000014759 maintenance of location Effects 0.000 claims description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 238000001694 spray drying Methods 0.000 claims description 9
- 239000004575 stone Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 239000002689 soil Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 6
- 150000002602 lanthanoids Chemical class 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 235000015165 citric acid Nutrition 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 229910001680 bayerite Inorganic materials 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 229910001679 gibbsite Inorganic materials 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- KLZYRCVPDWTZLH-UHFFFAOYSA-N 2,3-dimethylsuccinic acid Chemical compound OC(=O)C(C)C(C)C(O)=O KLZYRCVPDWTZLH-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 239000004113 Sepiolite Substances 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- 229960000892 attapulgite Drugs 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 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
- 210000000988 bone and bone Anatomy 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 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
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 229960004889 salicylic acid Drugs 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
- 210000002966 serum Anatomy 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 2
- 239000001301 oxygen Substances 0.000 claims 2
- 229910052760 oxygen Inorganic materials 0.000 claims 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims 1
- 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 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims 1
- 239000001630 malic acid Substances 0.000 claims 1
- 235000011090 malic acid Nutrition 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 22
- 239000000571 coke Substances 0.000 abstract description 13
- 239000000295 fuel oil Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 9
- 239000003502 gasoline Substances 0.000 abstract description 8
- 239000010457 zeolite Substances 0.000 description 39
- 229910021536 Zeolite Inorganic materials 0.000 description 37
- 230000000052 comparative effect Effects 0.000 description 20
- 238000005336 cracking Methods 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- 238000005360 mashing Methods 0.000 description 11
- 238000012986 modification Methods 0.000 description 11
- 230000004048 modification Effects 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 10
- 238000003483 aging Methods 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 238000000634 powder X-ray diffraction Methods 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- 239000012065 filter cake Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 239000010426 asphalt Substances 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910001415 sodium ion Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 229910052779 Neodymium Inorganic materials 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910052777 Praseodymium Inorganic materials 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 3
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000004846 x-ray emission Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 244000131522 Citrus pyriformis Species 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052622 kaolinite Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910017119 AlPO Inorganic materials 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910001122 Mischmetal Inorganic materials 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-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
- 229940001007 aluminium phosphate Drugs 0.000 description 1
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical compound O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 229940092782 bentonite Drugs 0.000 description 1
- OVYQSRKFHNKIBM-UHFFFAOYSA-N butanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCC(O)=O OVYQSRKFHNKIBM-UHFFFAOYSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 229940091250 magnesium supplement Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/12—Noble metals
- B01J29/126—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/14—After treatment, characterised by the effect to be obtained to alter the inside of the molecular sieve channels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A kind of catalytic cracking catalyst, aluminium oxide containing clay, containing additive and Modified Zeolite Y, the Modified Zeolite Y contains 5~12 weight % rare earths, no more than 0.5 weight % sodium oxide molybdenas, total pore volume is 0.36~0.48mL/g, and two level pore volume accounts for the 20~38% of total pore volume, lattice constant is 2.440~2.455nm, non-framework aluminum accounts for the 10% of total aluminium hereinafter, lattice collapse temperature is higher than 1060 DEG C, and B acid amount and the ratio of L acid amounts are not less than 3.50.Preparation method includes：The Y type molecular sieve for preparing the conventional unit cell dimension containing rare earth, roasts 4.5~7 hours under 350~520 DEG C, 30~95 volume % water vapour atmospheres, is handled with silicon tetrachloride gas haptoreaction and acid.The catalytic cracking catalyst has higher heavy oil conversion activity and lower coke selectivity, has higher yield of gasoline, yield of liquefied gas, yield of light oil and total liquid yield.
Description
Technical field
The present invention relates to a kind of catalytic cracking catalysts.
Background technology
Y type molecular sieve has been always the main work of catalytic cracking (FCC) catalyst since the sixties in last century of use for the first time
Property constituent element.However, with the aggravation of crude oil heaviness, the polycyclic compound content in FCC feedstock significantly increases, in zeolite pore
Diffusivity in road is but remarkably decreased.And the aperture of the Y type molecular sieve as chief active constituent element only has 0.74nm, directly uses
Carry out the heavy ends such as process residual oils, the accessibility of catalyst active center will be as the master of polycyclic compound cracking contained therein
Want obstacle.
Molecular Sieve Pore and cracking reaction property relationship are close, especially to residue cracking catalyst, the two of molecular sieve
Secondary aperture can increase the accessibility of residual oil macromolecular and its activated centre, and then improve the cracking ability to residual oil.
Hydrothermal dealumination method is one of industrial most widely used method, and this method is first by the water of NaY zeolite ammonium ion
Solution exchanges, and to reduce the sodium ions content in zeolite, then, roasts ammonium ion under steam atmosphere in 600-825 DEG C and hands over
Zeolite after changing makes its super stabilizing.This method is at low cost and is easy to industrialization large-scale production, obtained ultrastable tool
There is more rich second hole, but overstable gamma zeolite crystallinity loss is serious.
Currently, industrially production ultrastable is usually improvement to above-mentioned hydrothermal calcine technique, using exchanging twice
The method of double roasting, the purpose is to walk to take relatively mild roasting condition step by step, to solve the institute under harsh roasting condition
The problem of crystallinity heavy losses of generation, prepared overstable gamma zeolite also have a certain amount of second hole, still, large hole
Ratio of the second hole of diameter in total second hole is relatively low, in addition, the specific surface and crystallinity of super steady zeolite need further
It improves.
US5,069,890 and US5 disclose a kind of preparation method of the Y type molecular sieve of containing mesopore in 087,348, mainly
Process is：Using commercially available USY as raw material, in the atmosphere of 100% vapor, handled 24 hours at 760 DEG C.This method obtains
Y type molecular sieve mesopore volume 0.14ml/g is increased to by 0.02mL/g, but crystallinity drops to 70% by 100%, surface area
By 683m2/ g is reduced to 456m2/ g, sour density more drop sharply to 6% by 28.9%.
US5 in the method for 601, the 798 disclosed Y type molecular sieves for preparing containing mesopores, using HY or USY as raw material, is placed on height
Press kettle in NH4NO3Solution or NH4NO3With HNO3Mixed solution mix, at a temperature of 115~250 DEG C to be above the boiling point
Processing 2~20 hours, obtained Y type molecular sieve mesopore volume is up to 0.2~0.6ml/g, but crystallinity and surface area are all notable
Decline.
CN201310240740.8 discloses a kind of combination method of modifying of the mesoporous ultra-steady Y molecular sieve of richness, the spy of this method
Point is that in modifying process while organic acid and inorganic salts dealuminzation reagent is added, and the combination for carrying out organic acid-inorganic salts is modified, and
And optium concentration, volume proportion, reaction time and the reaction temperature of organic acid and inorganic salt solution are determined by orthogonal test
Equal optimum process conditions.The more industrial USY molecular sieve secondary pore contents of USY obtained using this method are significantly improved, while can be tieed up
Higher crystallinity is held, silica alumina ratio increases, and lattice constant reduces, which carries suitable for medium oil type hydrocracking catalyst
Body.
CN1388064 discloses a kind of method (Dong preparing the high-silicon Y-Zeolite that lattice constant is 2.420-2.440 nanometers
The soughing of the wind in the pines；Li Xuanwen；Li Dadong；Shi Jianwen；Nie Hong；Shi Yahua), this method includes by NaY zeolite or having already passed through at super stabilizing
The y-type zeolite of reason carries out one or many ammonium exchanges, hydro-thermal process and/or chemical dealuminization；It is characterized in that described ammonium exchanges
In first time ammonium at least before hydro-thermal process and/or chemical dealuminization to exchange be that use temperature be that room temperature is extremely less than 60 DEG C low
Temperature selective ammonium exchanges, remaining ammonium exchanges the either cryogenic selective ammonium for room temperature extremely less than 60 DEG C and exchanges or be 60-90
DEG C conventional ammonium exchange.High-silicon Y-Zeolite made from the patent still has higher crystal retention in smaller lattice constant,
There is more secondary pore simultaneously, be suitable as intermediate oil hydrocracking catalyst.
Although containing a certain amount of second hole, structure cell in the ultra-steady Y molecular sieve prepared by method disclosed in the above patent
Constant is small, and sial is relatively high, but these modified molecular screens are suitable for hydrogenation catalyst, are difficult to meet catalyzed cracking processing weight
The required high cracking activity requirement of oil.
CN1629258 discloses a kind of preparation method (Mu Xuhong of the Cracking catalyst containing rare earth superstable Y-type molecular sieve；
Wang Ying；Shu Xingtian；Luo Yibin；Zong Baoning；He Mingyuan；Wu Jia；Wang Xuan), it is characterised in that this method be by NaY molecular sieve with contain
The ammonium salt aqueous solution of 6~94 weight % ammonium salts normal pressure and more than 90 DEG C to be not more than ammonium salt aqueous solution boiling temperature under conditions of
It is contacted with the weight ratio of molecular sieve 0.1~24 according to ammonium salt twice or more than twice, makes Na in molecular sieve2O content is reduced to 1.5
Weight % hereinafter, then with rare earth salt content be 2~10 weight % aqueous solution contacted with molecular sieve at 70 DEG C~95 DEG C, make molecule
Rare earth in sieve is with RE2O3It is calculated as 0.5~18 heavy %, then mixed, dried with carrier.The molecular sieve needs in preparation process
It is exchanged by multiple ammonium salt, preparation process is cumbersome, ammonia and nitrogen pollution is serious, cost is higher.In addition, the super steady degree of the molecular sieve is not
Height, sial is relatively low, and second hole is less in molecular sieve.
CN1127161 discloses a kind of preparation method (Du Jun of the rich silicon ultra stabilization Y-type molecular sieve containing rare earth；Li Caiying；Lee
It is towering；Hu Lianliang；Shao Zhaonan), this method is using NaY as raw material, in solid RECl3In the presence of use SiCl4Carry out gas phase dealumination complement silicon
Reaction, a step complete the super stabilizing and rare earth ion exchanged of NaY.Its lattice constant of molecular sieve a prepared by this methodoFor
2.430~2.460 nanometers, content of rare earth is 0.15~10.0 heavy %, Na2O content is less than 1.0 heavy %.But the molecular sieve is only
It is prepared with the super steady method of gas phase, although the ultra-steady Y molecular sieve containing rare earth can be made, lack in prepared molecular sieve
Second hole.
CN1031030 discloses a kind of preparation method of low content of rare earth super-stable Y molecular sieves, and this method provides one kind
For the low content of rare earth super-stable Y molecular sieves of cracking hydrocarbon, be using NaY types molecular sieve as raw material, through ammonium ion and rare earth from
The mixed once exchange of son, stabilization processes, slough part skeleton aluminium atom, heat or hydro-thermal process and etc. be prepared into.It should
Content of rare earth (the RE of molecular sieve2O3) it is 0.5~6 heavy %, SiO2/Al2O3Up to 9~50, lattice constant a0For 2.425~
2.440nm.The silica alumina ratio of super stable molecular sieve prepared by this method is high, and lattice constant is smaller, also, containing a certain amount of dilute
Soil, still, without reference to high stability molecular sieve in the molecular sieve with second hole is prepared, activated centre accessibility is poor,
Activity is not high.
The present inventor the study found that the super-stable Y molecular sieves containing prior art preparation catalytic cracking catalyst,
It is difficult to that there is higher heavy oil catalytic cracking activity and preferable coke selectivity simultaneously.
Invention content
One of the technical problem to be solved in the present invention is to provide a kind of catalysis suitable for mink cell focus catalyzed cracking processing and splits
Change catalyst, containing Modified Zeolite Y (Y type molecular sieve is also referred to as y-type zeolite), which has higher residual oil cracking
Active and better coke selectivity.The invention solves second technical problem be to provide a kind of catalytic cracking catalyst
Preparation method.
A kind of catalytic cracking catalyst of present invention offer contains 10 weight in terms of butt on the basis of the weight of catalyst
Measure the aluminium oxide containing additive of the weight % of the Modified Zeolite Y of the weight of %~50 %, in terms of butt 2 weight~40 and with dry
The clay of the weight % of 10 weight of base meter~80；It is described containing adding in terms of butt on the basis of the alumina weight containing additive
Add the aluminium oxide containing 60 weight %-99.5 weight % in the aluminium oxide of agent, the additive of 0.5 weight %-40 weight % described
Additive is selected from one or more of the compound containing alkaline-earth metal, lanthanide series metal, silicon, gallium, boron or P elements, described to change
Property Y type molecular sieve rare earth oxide content be the 5 weight % of weight %~12, sodium oxide content (Na2O content) it is no more than 0.5
Weight % is, for example, the 0.05 weight % of weight %~0.5, and total pore volume is 0.36mL/g~0.48mL/g such as 0.38~0.45mL/
G, the percentage that the pore volume of the second hole that the aperture of the Modified Zeolite Y is 2nm~100nm accounts for total pore volume is 20%~
38%, lattice constant is 2.440nm~2.455nm, and non-framework aluminum content accounts for the percentage of total aluminium content in the Modified Zeolite Y
Than being not higher than 10%, lattice collapse temperature is not less than 1060 DEG C, also, measured at 200 DEG C with pyridine adsorption infrared method should
B acid amount and the ratio of L acid amounts are not less than 3.50 in the total acid content of Modified Zeolite Y.
Modified Zeolite Y provided by the invention, lattice collapse temperature are not less than 1060 DEG C, it is preferred that the molecular sieve is brilliant
1060 DEG C~1085 DEG C, for example, 1064~1081 DEG C of lattice collapse temperature.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y is existed with pyridine adsorption infrared method
In the Modified Zeolite Y total acid content measured at 200 DEG C the ratio of B acid amount and L acid amounts be preferably 3.5~6 be, for example, 3.6~
5.5 or 3.5~5 or 3.5~4.6.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y, lattice constant be 2.440nm~
2.455nm is, for example, 2.442~2.453nm or 2.442~2.451nm.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y is high-Si Y-type molecular sieve, bone
Frame silica alumina ratio (SiO2/Al2O3Molar ratio) it is 7~14, for example, 8.5~12.6 or 8.7~12.
In catalytic cracking catalyst provided by the invention, non-framework aluminum content accounts for total aluminium in the Modified Zeolite Y
The percentage of content is not higher than 10%, for example, 5~9.5% or 6-9.5%.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y, 800 DEG C, normal pressure, 100 bodies
Crystal retention under product % water vapour atmospheres after aging 17 hours be 38% or more be, for example, 38~65% or 46~60% or
52~60%.The normal pressure is 1atm.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y, relative crystallinity be not less than
70%, for example, 70~80% is preferred, the relative crystallinity of the Modified Zeolite Y provided by the invention be not less than
71%, for example, 71~77%.
Catalytic cracking catalyst provided by the invention, a kind of embodiment, the Modified Zeolite Y, specific surface
Product is 600~680m2/ g is, for example, 610~670m2/ g or 640~670m2/g。
In catalytic cracking catalyst provided by the invention, it is preferred that the Modified Zeolite Y total pore volume is 0.36
~0.48mL/g is, for example, 0.38~0.45mL/g or 0.38~0.42mL/g.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y, aperture is 2.0nm~100nm's
The pore volume of second hole is that 0.08~0.18mL/g is, for example, 0.10~0.16mL/g.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y, aperture (referring to diameter) be 2nm~
The percentage that the pore volume of the second hole of 100nm accounts for total pore volume is 20%~38%, preferably 28~38% or 25~38%.
Aperture is the pore volume (total volume in the holes 8nm~100nm)/total two of the second hole of 8nm~100nm in the Modified Zeolite Y
Grade hole pore volume (aperture be the total volume in the hole of 2nm~100nm) ratio be 40%~80% for example, 45~75% or
55~77%.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y contains rare earth element, modification Y
With RE in type molecular sieve2O3The rare earth oxide content of meter is that 5~12 weight % are preferably 5.5~10 weight %.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y, sodium oxide content is no more than
0.5%, can be, for example, 0.1~0.4 weight % or 0.15~0.3 weight % for 0.05~0.5 weight %.
In catalytic cracking catalyst provided by the invention, the modification Y types containing in terms of butt 10 weight of weight %~50 %
Molecular sieve, it is preferred that the content of the Modified Zeolite Y is that 15~45 weight % are, for example, 20~40 weight % or 25~35
Weight %.
Clay can also be contained in catalytic cracking catalyst provided by the present invention, with the weight of the catalytic cracking catalyst
On the basis of, the content of the clay is no more than 70 weight %, preferably 10 weight %-70 weight %.The clay, which is selected from, to be used as
One or more of clay of cracking catalyst component, such as kaolin, halloysite, montmorillonite, diatomite, Ai Luo
One or more of stone, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, bentonite.These clays are that this field is general
Well known to logical technical staff.The content of clay described in catalytic cracking catalyst provided by the invention can be 20~55 in terms of butt
Weight % or 30~50 weight %.
In catalytic cracking catalyst of the present invention, contain the aluminium oxide containing additive, with the weight of catalytic cracking catalyst
On the basis of amount, the content of the aluminium oxide containing additive is calculated as 2 weight %-40 weight %, preferably 2 weight %- with butt
20 weight %.The aluminium oxide containing additive can be according to described in patent CN1915486A, CN1915485A, CN1916116A
It is prepared by method.It is preferred that on the basis of the aluminium oxide dry weight containing additive, contain in the aluminium oxide containing additive
The aluminium oxide of 70 weight %-95 weight %, the additive of in terms of butt 5 weight %-30 weight %.Wherein the additive is excellent
It is selected as phosphorous and/or magnesium compound.
The dry weight is that substance roasts 1 hour obtained solid product weight at 800 DEG C.
Preferably, the preparation method of the aluminium oxide containing additive includes the following steps：
(1) boehmite is mixed under stiring with being enough to make the water of its pulp and acid, wherein the dosage of acid make it is described
The weight ratio of acid and aluminium oxide in boehmite is 0.01-0.5；
(2) by the mixed serum of step (1) at a temperature of -90 DEG C of room temperature aging 0-24 hours；
(3) product of step (2) is mixed with additive, optionally drying and optionally roasting.
In the preparation method of the aluminium oxide containing additive, it is preferred that sour dosage makes institute in the wherein described step (1)
The weight ratio for stating acid and aluminium oxide in boehmite is 0.05-0.3.Step (1) described pulp makes boehmite and water
The solid content of the slurries of formation is 10~50 weight %, preferably 15~30 weight %.The acid is in inorganic acid, organic acid
One or more, for example, the inorganic acid can be hydrochloric acid, nitric acid, sulfuric acid, one or more of phosphoric acid, the organic acid
Can be one or more of formic acid, acetic acid, oxalic acid or stubborn rubber acid, hydrochloric acid preferably wherein or nitric acid.
In the preparation method of the aluminium oxide containing additive, it is preferred that the aging temperature in the wherein described step (2) is
Room temperature~80 DEG C, the room temperature are, for example, 15~40 DEG C, and ageing time is 0.5-4 hours.By the production of step (2) in step (3)
The mixture that object is formed with additive, is used directly for preparing catalytic cracking catalyst, i.e., will be formed by mixture and shape
It is mixed at other components of catalytic cracking catalyst, can also dry and be used to prepare catalyst after roasting.The drying example
As dried, being spray-dried.
In the preparation method of the aluminium oxide containing additive, the temperature of a kind of embodiment, step (3) described roasting is
350~800 DEG C such as 400~600 DEG C, roasting time such as 0.5~8 hour.The additive is selected from alkaline including earth metal, group of the lanthanides
One or more of the compound of metal, silicon, gallium, canopy or P elements, it is described containing alkaline-earth metal, copper system metal, silicon, transfer,
The compound of canopy or P elements can be oxide, the hydrous oxide of these elements, such as magnesia, the hydrogen in alkaline-earth metal
Magnesia, the oxidation rare earth in lanthanide series metal, silica, Ludox, one or more of phosphorous oxide:Can also be containing upper
The salt for stating element, such as the nitrate in alkaline-earth metal, the rare earth chloride in lanthanide series metal, silicate, one kind in phosphate or
It is several.When the additive is the oxide and/or water oxycompound of the element, the mixing is to obtain the step 2
The product arrived is directly mixed；When the additive is one or more of the salt containing the element, the mixing
It is preferred that the product that the salt is configured to obtain with the step (2) again after aqueous solution is mixed first.It is mixed described in each step
It closes, existing various methods can be used and realize that the method on excellent side is to be enough to make the material (such as:Boehmite, addition
Agent) it mixes under conditions of pulp, the pulp is known to those skilled in the art, including to make material pulp introduce foot
The introduction volume of the water enough measured, the water makes the solid content of slurries be usually 10-50 weight %, preferably 15-30 weight %.
In catalytic cracking catalyst of the present invention, preferably also contain alumina binder, using the weight of catalyst as base
Standard, in terms of aluminium oxide, the content of the alumina binder is no more than 32 weight %, the weight % of preferably 5 weight~32.It is described
In aluminium oxide, hydrated alumina and Aluminum sol of the alumina binder selected from the commonly used various forms of Cracking catalyst
One or more, for example, selected from gama-alumina, η-aluminium oxide, θ-aluminium oxide, χ-aluminium oxide, boehmite
(Pseudoboemite), a diaspore (Boehmite), gibbsite (Gibbsite), bayerite (Bayerite) or aluminium are molten
Containing with dry in one or more of glue, preferably boehmite and/or Aluminum sol, such as the catalytic cracking catalyst
2~15 weight % of base the meter preferably aluminium sol adhesive of 3~10 weight %, in terms of butt 10~30 weight % preferably 15~25 weights
Measure the boehmite binder of %.
It is preferred that on the basis of the weight of catalyst, alumina binder described in catalyst of the present invention and containing addition
The total content of the aluminium oxide of agent is that 10 weight %-40 weight % are, for example, containing for 20~35 weight % and the aluminium oxide containing additive
Amount is 2 weight %-20 weight %.
In catalyst of the present invention, on the basis of the weight of catalyst, preferably comprise：In terms of butt 10 weight %~50
The Modified Zeolite Y of weight % such as 15~45 weight % or 25~40 weight %, in terms of butt 50 weight %-90 weights
Measure the matrix of % such as 55~85 weight % or 60~75 weight %.The matrix includes the aluminium oxide containing additive, viscous
Native and optional binder, the binder are preferably alumina binder.
Catalyst provided by the invention also contains other molecular sieves other than the Modified Zeolite Y, described other
The molecular sieve that molecular sieve uses in catalytic cracking catalyst, such as with MFI structure zeolite, Beta zeolites, the boiling of other Y types
The one or more of stone, non-zeolite molecular sieve.The content of other molecular sieves can be that 0~40 weight % is, for example, 0~30
Weight % or 1~20 weight %.Preferably, the content of other Y type molecular sieves is no more than 40 weight % for example in terms of butt
Can be 1~40 weight % or 0~20 weight %.In described other y-type zeolites such as REY, REHY, DASY, SOY, PSRY
One or more, one or more in described MFI structure zeolite such as HZSM-5, ZRP, the ZSP, described beta zeolite examples
Such as H β, one in non-zeolite molecular sieve such as aluminium phosphate molecular sieve (AlPO molecular sieves), sial phosphorus molecular sieve (SAPO molecular sieve)
Kind is a variety of.It is preferred that on the basis of the weight of catalyst, the content of other molecular sieves is no more than 20 weight %.
Method for preparing catalyst of the present invention be existing method, these preparation methods patent CN1916116A,
There is detailed description in CN1362472A, CN1727442A, CN1132898C, CN1727445A, CN1098130A, here together
As with reference to reference.It generally includes to be formed the slurries including Modified Zeolite Y, binder, clay and water, spray drying, appoint
Choosing washing and dry step.Spray drying, washing, drying are the prior art, and the present invention does not have particular/special requirement.Such as a kind of system
Preparation Method includes by the Modified Zeolite Y, the aluminium oxide containing additive, clay, optional alumina binder and water
The step be mixed with beating, be spray-dried and wash, filter, drying.
Catalytic cracking catalyst preparation method provided by the invention, a kind of embodiment, including prepare modified Y type molecules
Sieve, formed include the Modified Zeolite Y, the aluminium oxide containing additive, clay, water and optional alumina binder slurry
The step of liquid, spray drying, wherein the method for preparing the Modified Zeolite Y includes the following steps:
(1) NaY molecular sieve is contacted with earth solution and carries out ion-exchange reactions, be filtered, washed, obtain
The Y type molecular sieve for the conventional unit cell dimension containing rare earth that sodium oxide content reduces；Wherein earth solution is also referred to as
Rare-earth salt solution；
(2) Y type molecular sieve for the conventional unit cell dimension containing rare earth that the sodium oxide content reduces is modified
Processing, optionally drying obtain the Y type molecular sieve of lattice constant reduction, and the modification is will be described
Sodium oxide content reduce the conventional unit cell dimension containing rare earth Y type molecular sieve 350~520 DEG C of temperature,
Atmosphere (also referred to as 30~95 volume % water vapour atmospheres or 30~95% water containing 30~95 volume % water vapours
Steam) under roast 4.5~7 hours；Wherein, the water for the Y type molecular sieve sample that the lattice constant reduces
Content is preferably more than 1 weight %；If water contains in the Y type molecular sieve that step (2) modification obtains
For amount more than 1 weight %, step (2), which is also dried, makes its water content be less than 1 weight %；A kind of drying side
Formula is dried by the way of roasting, is 450~650 DEG C in the temperature of roasting, in the gas of dry air
Atmosphere is dried in (vapour content is less than 1 weight %) and for example dries 1~5 hour or 2~4 hours,
Its water content is set to be less than 1 weight %；
(3) Y type molecular sieve and SiCl reduced the lattice constant4Gas haptoreaction；Wherein preferred, contact is anti-
It is 200~650 DEG C to answer temperature, SiCl4：The weight for the Y type molecular sieve that the lattice constant that the step of in terms of butt (2) obtains reduces
Than=0.1~0.7：1, in 10 minutes to 5 hours reaction time, it is super steady modified to obtain gas phase for then optionally washed, optional filtering
Y type molecular sieve；
(4) the super steady Modified Zeolite Y of gas phase that step (3) obtains is contacted with acid solution and is modified.
Catalytic cracking catalyst provided by the invention, heat and hydrothermal stability are high, and activity is high, and coke selectivity is good, is used for
Heavy oil catalytic cracking, more existing Cracking catalyst have higher heavy oil conversion activity and lower coke selectivity, have more
High yield of gasoline, yield of light oil and total liquid yield.
Catalytic cracking catalyst preparation method provided by the invention, Modified Zeolite Y preparation method therein, can make
The high-Si Y-type molecular sieve rich in second hole of standby high-crystallinity, high thermal stability and high hydrothermal stability, can make molecular sieve exist
Super stabilizing degree has higher crystallinity in the case of greatly improving, and aluminium is evenly distributed in prepared molecular sieve, non-skeleton
Aluminium content is few, and second hole duct is unimpeded, and with higher specific surface area with higher second hole, prepared urges
Agent is used for heavy oil conversion, and coke selectivity is good, and heavy oil cracking activity is high, can improve vapour of the molecular sieve for heavy oil conversion when
Oil yield, yield of liquefied gas and total liquid yield.
Specific implementation mode
Catalytic cracking catalyst provided by the invention contains in terms of butt 10 weight % on the basis of the weight of catalyst
Aluminium oxide described in the Modified Zeolite Y of~50 weight %, in terms of butt 2~40 weight % containing additive, with dry
The clay of the weight % of the alumina binder of the weight % of 0 weight of base meter~40 and in terms of butt 10 weight~80.Preferably, described
Catalytic cracking catalyst contains the Modified Zeolite Y of in terms of butt 25 weight of weight %~40 %, in terms of butt 2~20
The alumina binder of the weight % of the aluminium oxide containing additive of weight %, in terms of butt 5 weight~30 and in terms of butt
The clay of the weight % of 30 weight~50, and the total content of alumina binder and the aluminium oxide containing additive is 20~35 weights
Measure %.
In catalytic cracking catalyst provided by the invention, containing Modified Zeolite Y, a kind of embodiment, the present invention carries
The Modified Zeolite Y of confession, rare earth oxide content are 5~12 weight %, preferably 5.5~10 weight %, sodium oxide content
It is, for example, 0.1~0.4 weight % or 0.15~0.3 weight % for 0.05~0.5 weight %, preferably smaller than 0.2 weight %, total hole
Volume is 0.4~0.48mL/g, and it is 20% that the pore volume for the second hole that aperture is 2nm~100nm, which accounts for the percentage of total pore volume,
~38%, preferably 25%~35%, lattice constant are the preferred 2.442nm~2.453nm of 2.440nm~2.455nm, framework silicon-aluminum
Than (SiO2/Al2O3Molar ratio) be：7~14 be, for example, 7.8-12.6, and non-framework aluminum content accounts for the hundred of total aluminium content in molecular sieve
Divide than being not higher than 10%, preferably 3~9, relative crystallinity is preferably not less than 71% not less than 70%, and lattice collapse temperature is preferred
It it is 1065 DEG C~1080 DEG C, also, B in the Modified Zeolite Y total acid content measured at 200 DEG C with pyridine adsorption infrared method
Acid amount and the ratio of L acid amounts are not less than 3.50, for example, 3.6~4.6.
In catalytic cracking catalyst provided by the invention, the Modified Zeolite Y, to contain rare earth rich in second hole
Ultra-steady Y molecular sieve, the two level pore distribution curve that aperture is 2nm~100nm in the molecular sieve in it is double can several pore size distributions, wherein smaller
The most probable pore size of aperture second hole is 2nm~5nm, and the most probable pore size of the second hole of larger aperture is 8nm~20nm, preferably
8nm~18nm.Preferably, the second hole that aperture is 8nm~100nm account for total second hole (2nm~100nm) ratio be 40%~
80%, preferably 45%~77% is, for example, 45~55% or 55~77%.The SiO of the molecular sieve2/Al2O3It is 7~14, preferably
7.8~13, lattice constant is 2.440nm~2.455nm, preferably 2.442nm~2.453nm.
Catalytic cracking catalyst provided by the invention, the Modified Zeolite Y preparation process include by Y type molecules
Sieve contacts the step of carrying out dealumination complement silicon reaction with silicon tetrachloride.
Catalytic cracking catalyst preparation method provided by the invention, in the Modified Zeolite Y preparation method, step
(1) NaY molecular sieve and earth solution are subjected to ion-exchange reactions in, to obtain the routine containing rare earth of sodium oxide content reduction
The Y type molecular sieve of unit cell dimension.The NaY molecular sieve, can be commercially available or prepares, a kind of embodiment according to existing method,
The NaY molecular sieve lattice constant is 2.465~2.472nm, framework si-al ratio (SiO2/Al2O3Molar ratio) it is 4.5~5.2,
It is, for example, 85~95% that relative crystallinity, which is 85% or more, and sodium oxide content is 13.0~13.8 weight %.Described in step (1)
NaY molecular sieve carries out ion-exchange reactions with earth solution, and it is, for example, 20~65 DEG C or 65 that exchange temperature, which is preferably 15~95 DEG C,
~95 DEG C, swap time is preferably such as 45~90 minutes 30~120 minutes.NaY molecular sieve (in terms of butt):Rare-earth salts (with
RE2O3Meter):H2O=1:0.01~0.18:5~20 weight ratios.A kind of embodiment, the NaY molecular sieve and earth solution
Carrying out ion-exchange reactions includes, according to NaY molecular sieve:Rare-earth salts:H2O=1:0.01~0.18:5~15 weight ratio will
NaY molecular sieve (also referred to as NaY zeolite), rare-earth salts and water form mixture, in 15~95 DEG C of such as room temperatures to 60 DEG C or 20~60
DEG C or 30-45 DEG C or 65~95 DEG C stirring, preferably stir 30~120 minutes and carry out exchanging for rare earth ion and sodium ion.It is a kind of
The weight ratio of embodiment, described NaY molecular sieve and water is：1:6~20, preferably：7~15.By NaY molecular sieve, rare-earth salts
Form mixture with water, NaY molecular sieve and water can be formed slurries, be then added in the slurries rare-earth salts and/or
The aqueous solution of rare-earth salts, the earth solution are the solution of rare-earth salts, and the rare-earth salts is preferably rare earth chloride and/or nitre
Acid rare earth.It is one or more in the rare earth such as La, Ce, Pr, Nd and mischmetal, it is preferred that the mixing
Containing one or more in La, Ce, Pr and Nd in rare earth, or also contain in the rare earth in addition to La, Ce, Pr and Nd at least
It is a kind of.Washing described in step (1), it is therefore an objective to wash away the sodium ion being swapped out, it is, for example, possible to use deionized water or the exhaustion of yang from
Sub- water washing.It is preferred that the Y type molecular sieve for the conventional unit cell dimension containing rare earth that the sodium oxide content that step (1) obtains reduces
Content of rare earth is with RE2O3It is, for example, that 7~14 weight or 7.5~13 weight %, sodium oxide content do not surpass to be calculated as 5.5~14 weight %
It is, for example, 5.5~8.5 weight % or 5.5~7.5 weight % to cross 9 weight %, and lattice constant is 2.465nm~2.472nm.
Catalytic cracking catalyst preparation method provided by the invention, in the Modified Zeolite Y preparation method, step
(2) by the Y type molecular sieve of the conventional unit cell dimension containing rare earth in 350-520 DEG C such as 350~480 DEG C of temperature, 30~95 bodies in
It roasts 4.5~7 hours and is handled under product % water vapour atmospheres, it is preferred that the calcination temperature described in step (2) is 380~500
DEG C be, for example, 380~480 DEG C, calcination atmosphere be 40~80 volume % or 70~95 volume % water vapour atmospheres, roasting time 5
~6 hours.Contain 30~95 volume % vapor in the water vapour atmosphere, also contains other gases, such as air, helium
Or it is one or more in nitrogen.The Y type molecular sieve that lattice constant described in step (2) reduces, lattice constant are
2.450nm~2.462nm.It is preferred that also the molecular sieve that roasting obtains is dried in step (2), so that the lattice constant
Water content in the Y type molecular sieve of reduction is preferably more than 1 weight %.The Y type molecular sieve that lattice constant reduces obtained by step (2)
The solid content of sample is preferably not less than 99 weight %.
Catalytic cracking catalyst preparation method provided by the invention, in the Modified Zeolite Y preparation method, step
(3) in, SiCl4：The weight ratio of y-type zeolite (in terms of butt) is preferably 0.3~0.6：1, the temperature of the reaction is preferably 350
~500 DEG C, step (3) can be washed or not washed, and can be dried or not dried after washing, and the washing methods may be used
Such as decationized Y sieve water or deionized water washing can be washed with water, it is therefore an objective to remove remaining in zeolite in conventional washing methods
Na+, Cl-And Al3+Waiting soluble by-products, such as wash conditions can be：The weight ratio of washings and molecular sieve can be 5~
20：1, molecular sieve：H2Weight ratio=1 O:6~15, pH value is preferably 2.5~5.0, and wash temperature is 30~60 DEG C.It is usually described
Washing, make to detect in the cleaning solution after washing do not go on a tour from Na+, Cl-And Al3+Plasma, usually the molecular sieve sample after washing
Na in product+, Cl-And Al3+The respective content of ion is no more than 0.05 weight %.
Catalytic cracking catalyst preparation method provided by the invention, in the Modified Zeolite Y preparation method, step
(4) in, the super steady Modified Zeolite Y of gas phase that step (3) obtains is contacted with acid solution and is reacted that (present invention is known as duct
Cleaning is modified, and the cleaning of abbreviation duct, or acid processing are modified).A kind of embodiment, the gas phase that step (3) is obtained
Super steady Modified Zeolite Y is contacted with acid solution is reacted, and is that the molecular sieve Jing Guo the super steady modification of gas phase is i.e. described
The super steady Modified Zeolite Y of gas phase mixed with acid solution, and react a period of time, then by after reaction molecular sieve and acid it is molten
Liquid separation is for example separated by filtration, and then through optional washing and optional drying, obtains modified Y types provided by the invention point
Son sieve, wherein washing purpose is to remove Na remaining in zeolite+, Cl-And Al3+Equal soluble by-products, such as wash conditions can
Think：The weight ratio of washings and molecular sieve can be 5~20：1, usual molecular sieve：H2Weight ratio=1 O:6~15, pH value is excellent
2.5~5.0 are selected as, wash temperature is 30~60 DEG C.The super steady Modified Zeolite Y of gas phase and acid that the step (3) obtains are molten
Liquid contacts, wherein the weight ratio of acid and molecular sieve (in terms of butt) is 0.001~0.15：1 is, for example, 0.002~0.1：1 or
0.01~0.05：1, water is 5~20 with the molecular sieve ratio in terms of butt：1 is, for example, 8~15：1, the contact carries out anti-
The temperature answered is 60~100 DEG C such as 80~99 DEG C preferably 88~98 DEG C.
Preferably, the acid in described acid solution (sour aqueous solution) is that at least one organic acid and at least one are medium strong
Degree or more inorganic acid.Described organic acid can be oxalic acid, malonic acid, succinic acid (succinic acid), dimethyl succinic acid, apple
One or more in acid, tartaric acid, citric acid, salicylic acid, inorganic acid more than moderate strength is to have phosphoric acid, hydrochloric acid, nitric acid
And it is one or more in sulfuric acid.The temperature of the contact is preferably 80~99 DEG C such as 85~98 DEG C, and the time of contact is 60
Minute or more, for example, 60~240 minutes or 90~180 minutes.The weight ratio of the organic acid and molecular sieve is 0.01
~0.10：1 is, for example, 0.02~0.05：1 or 0.03~0.1：1, the weight of more than moderate strength inorganic acid and molecular sieve
Amount ratio is 0.01~0.05：1 is, for example, 0.02~0.05：1, the weight ratio of water and molecular sieve is preferably 5~20：1 for example
It is 8~15：1.
Preferably, the described duct cleaning is modified, and is carried out in two steps, first with it is more than moderate strength inorganic acid with described point
Son sieve contact, the wherein weight ratio of inorganic acid more than moderate strength and molecular sieve are 0.01~0.05：1 for example, 0.02~
0.05：1, the weight ratio of water and molecular sieve is preferably 5~20：1 is, for example, 8~15：1, catalytic temperature is 80~99
DEG C preferably 90-98 DEG C, the reaction time be 60~120 minutes；Then the molecular sieve obtained after the processing is contacted with organic acid, institute
The weight ratio of the organic acid and molecular sieve stated is 0.02~0.10：1 is, for example, 0.02~0.10：1 or 0.05~0.08：1, water
Weight ratio with molecular sieve is preferably 5~20：1 is, for example, 8~15：1, catalytic temperature is 80~99 DEG C of preferred 90-
98 DEG C, the reaction time is 60~120 minutes.In the wherein described weight ratio, molecular sieve is in terms of butt.
Catalytic cracking catalyst preparation method provided by the invention, including will include the Modified Zeolite Y, viscous
The step of soil, the raw material of alumina binder and water formation slurries, spray drying, a kind of embodiment, the modification Y types
The preparation method of molecular sieve includes the following steps：
(1) NaY molecular sieve (also referred to as NaY zeolite) is subjected to ion-exchange reactions with earth solution, filtered, washing obtains
The Y type molecular sieve for the conventional unit cell dimension containing rare earth that sodium oxide content reduces；The ion exchange usually stirring, temperature be
It is exchanged 30~120 minutes under conditions of 15~95 DEG C preferably 65~95 DEG C；
(2) Y type molecular sieve for the conventional unit cell dimension containing rare earth for reducing the sodium oxide content temperature 350~
480 DEG C, contains and roasted 4.5~7 hours under the atmosphere of 30~90 volume % water vapours, it is dry, water content is obtained less than 1 weight %'s
The Y type molecular sieve that lattice constant reduces；The lattice constant for the Y type molecular sieve that the lattice constant reduces be 2.450nm~
2.462nm；
(3) the Y type molecular sieve sample that the lattice constant by water content less than 1 weight % reduces and heated vaporization
SiCl4Gas contacts, wherein SiCl4：The Y type molecular sieve (in terms of butt) that lattice constant of the water content less than 1 weight % reduces
Weight ratio=0.1~0.7：1, the haptoreaction 10 minutes to 5 hours under conditions of temperature is 200~650 DEG C, optionally washing and
Optionally filtering obtains the super Modified Zeolite Y surely handled of gas phase；
(4) the super Modified Zeolite Y surely handled of gas phase that step (3) obtains progress acid processing is contacted with acid solution to change
Property.Wherein, the gas phase that step (3) obtain will first be surpassed to the inorganic acid of the Modified Zeolite Y and moderate strength surely handled or more
And water mixing, at least 30 minutes are contacted at 80~99 DEG C preferably 90~98 DEG C such as 60~120 minutes, be then added organic
Acid contacts at least 30 minutes such as 60~120 minutes at 80~99 DEG C preferably 90~98 DEG C, through filtering, optional washing and
Optional drying obtains Modified Zeolite Y provided by the invention；It is wherein preferred, organic acid and the molecular sieve in terms of butt
Weight ratio be 0.02~0.10：1, the weight ratio of inorganic acid more than moderate strength and the molecular sieve in terms of butt is 0.01~
0.06：1, the weight ratio of water and molecular sieve is 5~20：1.
The following examples will be further described the present invention, but not thereby limiting the invention.
In embodiment and in comparative example, NaY molecular sieve (also referred to as NaY zeolite) is Sinopec catalyst Co., Ltd Shandong
Branch company provides, and sodium oxide content is 13.5 weight %, framework si-al ratio (SiO2/Al2O3Molar ratio)=4.6, relative crystallinity
It is 90%；Rare earth chloride and the chemically pure reagent that nitric acid rare earth is Beijing Chemical Plant's production.Boehmite is given birth to for Shandong Aluminum Plant
Produce industrial products, 61 weight % of solid content；Kaolin is the special kaolinite of Cracking catalyst of Suzhou China Kaolin Co., Ltd production
Soil, 76 weight % of solid content；Aluminum sol is provided by asphalt in Shenli Refinery of Sinopec catalyst Co., Ltd, wherein aluminium oxide contains
Measure 21 weight %.
Analysis method：In each comparative example and embodiment, the constituent content of zeolite is by x-ray fluorescence spectrometry；Boiling
Lattice constant, the relative crystallinity of stone use the standard side RIPP145-90, RIPP146-90 by x-ray powder diffraction (XRD)
Method (see《Petrochemical analysis method》(RIPP test methods) Yang Cui is surely equal to be compiled, and Science Press, nineteen ninety publishes) it measures, boiling
The framework si-al ratio of stone is calculated by following formula and is obtained：SiO2/Al2O3=(2.5858-a0) × 2/ (a0-2.4191) wherein, a0For crystalline substance
Born of the same parents' constant, unit nm；Total silica alumina ratio of zeolite is calculated according to Si and the Al constituent content of x-ray fluorescence spectrometry,
The framework si-al ratio measured by XRD methods can calculate the ratio of skeleton Al and total Al with the XRF total silica alumina ratios measured, and then calculate non-
The ratio of skeleton Al and total Al.Crystal structure collapse temperature is measured by differential thermal analysis (DTA).
In each comparative example and embodiment, the acid site type and its acid amount of molecular sieve are divided using the infrared method of pyridine adsorption
Analysis measures.Laboratory apparatus：The U.S. Bruker companies IFS113V types FT-IR (fourier-transform infrared) spectrometer.Use pyridine adsorption
Infrared method measures the experimental method of B acid amount and L acid amounts in total acid content at 200 DEG C：By sample self-supporting tabletting, it is placed in infrared light
It is sealed in the pond in situ of spectrometer.400 DEG C are warming up to, and is evacuated to 10-3Pa, constant temperature 2h, the gas molecule of removing sample absorption.
It is down to room temperature, it is that 2.67Pa pyridine steams keep adsorption equilibrium 30min to import pressure.200 DEG C are then heated to, is evacuated to
10-330min is desorbed under Pa, is down to room temperature and takes the photograph spectrum, scan wave-number range：1400cm-1~1700cm-1, sample is obtained through 200 DEG C
The Pyridine adsorption IR spectra figure of desorption.According to 1540cm in Pyridine adsorption IR spectra figure-1And 1450cm-1Feature adsorption peak
Intensity, obtain in molecular sieve totalAcid site (acid sites B) is opposite with the acid sites Lewis (acid sites L)
Amount.
In each comparative example and embodiment, wherein the assay method of described two level pore volume is as follows：According to RIPP151-90
Standard method《Petrochemical egineering analysis method (RIPP test methods)》(Yang Cui is surely equal to be compiled, and Science Press, nineteen ninety publishes) root
The total pore volume of molecular sieve is determined according to adsorption isotherm, then determines molecular sieve from adsorption isotherm according to T graphing methods
Total pore volume is subtracted micro pore volume and obtains two level pore volume by micro pore volume,
Chemical reagent used is not specifically specified in comparative example and embodiment, and specification is that chemistry is pure.
Embodiment 1
By 2000Kg (dry basis) skeletons SiO2/Al2O3For 4.6 NaY types zeolite (13.5 heavy % of sodium oxide content, middle stone
Change catalyst asphalt in Shenli Refinery to produce) it is added to equipped with 20m3It is added after being stirred evenly at 25 DEG C in swap tank of water
600L RECl3Solution (RECl3Rare earth concentration in solution is with RE2O3It is calculated as 319g/L), continue stirring after sixty minutes, filtering,
Washing, filter cake are sent into expansion drying stove and are dried；Obtain the Y types of the conventional unit cell dimension containing rare earth of sodium oxide content reduction
Molecular sieve, sodium oxide content are 7.0 weight %, lattice constant 2.471nm；Then, it is sent into roaster in 390 DEG C of temperature,
50% water vapour roasts 6 hours under (containing 50 volume % water vapours in atmosphere)；Then, in 500 DEG C of temperature, dry air atmosphere
(vapour content is less than 1 volume %) roasting 2.5 hours, makes its water content be less than 1 weight %, obtains the Y of lattice constant reduction
Type molecular sieve, lattice constant 2.455nm；Then, the Y type molecular sieve material directly reduced the lattice constant, which is sent into, to be connected
The super steady reaction of gas phase is carried out in the super steady reactor of continuousization gas phase.Gas phase of the molecular sieve in the super steady reactor of serialization gas phase is super steady
Reaction process and its follow-up tail gas absorption technology are carried out according to the method for the embodiment 1 of CN103787352A patent disclosures, technique
Condition is SiCl4：Weight ratio=0.5 of y-type zeolite：1, the inlet amount of molecular sieve is 800kg/ hours, reaction temperature 400
℃.Molecular sieve material after the super steady reaction of gas phase is sent into after gas-solid separator detaches in secondary swap tank, in secondary swap tank
In advance added with 20m3Water, it is 2000Kg (dry basis) that molecular sieve weight of material in secondary swap tank, which is added, is stirred evenly, it
Afterwards, it is slowly added to the hydrochloric acid 0.6m of a concentration of 10 weight %3, and 90 DEG C are warming up to, it stirs 60 minutes, then, 140Kg lemons is added
Lemon is sour, after continuing stirring at 90 DEG C 60 minutes, filters, washs, and drying obtains Modified Zeolite Y (molecular sieve is also referred to as zeolite)
Product is denoted as SZ-1.Table 1 gives the composition of SZ-1, lattice constant, relative crystallinity, framework si-al ratio, structural breakdown temperature
Degree, specific surface area and larger aperture (aperture is 8nm~100nm) second hole account for the percentage of total second hole (2~100nm),
Total two level pore volume.
By SZ-1 in naked state after aging under 800 DEG C, 100% water vapour atmosphere 17 hours, analyzed with the method for XRD
The relative crystallinity of molecular sieve before and after SZ-1 agings simultaneously calculates the opposite crystal retention after aging, the results are shown in Table 2, wherein：
It is that the boehmite of 61 weight % is added in 7818 grams of decationized Y sieve water to take 1572 grams of alumina contents, is being stirred
It mixes and the pure hydrochloric acid of 195ml chemistry (containing 36 weight %HCl) is added under state, in 70 DEG C of agings 1 hour, 165ml phosphorus is added later
Acid (Beijing Chemical Plant produces, concentration 85%, and analysis is pure) and magnesium chloride hexahydrate (the bicyclic chemical reagent work's production in Beijing, analysis are pure) are water-soluble
390 grams of liquid (wherein 204 grams of magnesium chloride hexahydrate), mashing, obtains the slurries of the aluminium oxide containing additive.
It takes the Aluminum sol that 5715 grams of alumina contents are 21 weight % to be added in 15642 grams of decationized Y sieve water, is then stirring
The lower kaolin that 7302 grams of solid contents are added as 76 weight % is mixed, is beaten 60 minutes, obtains kaolin slurry.3839 grams are aoxidized
Aluminium content is that the boehmite of 61 weight % is added in 9381 grams of decationized Y sieve water, is beaten, then under stiring thereto
231ml chemistry pure hydrochloric acid (containing 36 weight %HCl) is added, prepared kaolin slurry is added in aging after sixty minutes, adds
Then SZ-1 molecular sieves 4200 grams (butts) and REY molecular sieves is added in the slurries of the prepared aluminium oxide containing additive, mashing
[asphalt in Shenli Refinery of Sinopec catalyst Co., Ltd produces, and content of rare earth is (with RE2O3Meter) 18 weight %, silica alumina ratio (SiO2/
Al2O3Molar ratio 4.6)] 750 grams (butts), mashing, then to carry out at 650 DEG C of inlet temperature, 180 DEG C of exhaust temperature spraying dry
It is dry, it is washed with deionized, drying obtains catalyst, is denoted as SC-1.
Embodiment 2
By 2000Kg (dry basis) skeletons SiO2/Al2O3For 4.6 NaY types zeolite (13.5 heavy % of sodium oxide content, middle stone
Change catalyst asphalt in Shenli Refinery to produce) it is added to equipped with 20m3In swap tank of decationized Y sieve water, at 90 DEG C, stirring is equal
After even, 800L RECl are added3Solution (RECl3Rare earth concentration in solution is with RE2O3It is calculated as 319g/L), it stirs 60 minutes；
Filtering, washing, filter cake are sent into expansion drying stove and are dried, and the conventional unit cell dimension containing rare earth of sodium oxide content reduction is obtained
Y type molecular sieve, sodium oxide content be 5.5 weight %, lattice constant 2.471nm, then, be sent into roaster in temperature
It is roasted 5.5 hours under 450 DEG C of (atmosphere temperature), 80% water vapour atmosphere；Then, molecular sieve material enters roaster and is roasted
It is dried, 500 DEG C of calcination temperature, atmosphere is dry air atmosphere, and roasting time 2 hours makes its water content be less than 1 weight
% is measured, the Y type molecular sieve of lattice constant reduction, lattice constant 2.461nm are obtained；Then, directly lattice constant is reduced
Y type molecular sieve material be sent into the super steady reactor of serialization gas phase in carry out the super steady reaction of gas phase.Molecular sieve is in serialization gas phase
The super steady reaction process of gas phase and its follow-up tail gas absorption technology in super steady reactor is according to CN103787352A patent disclosures
The method of embodiment 1 carries out, and process conditions are：SiCl4：Weight ratio=0.25 of y-type zeolite：1, the inlet amount of molecular sieve is
800kg/ hours, reaction temperature was 490 DEG C.Molecular sieve material after the super steady reaction of gas phase is sent into two after gas-solid separator detaches
In secondary swap tank, in advance added with 20m in secondary swap tank3Decationized Y sieve water, the molecular sieve material in secondary swap tank is added
Weight is 2000Kg (dry basis), stirs evenly, later, is slowly added to the sulfuric acid solution 0.9m of a concentration of 7 weight %3, and rise
Temperature stirs 80 minutes to 93 DEG C, then, 70Kg citric acids and 50Kg tartaric acid is added, after continuing stirring at 93 DEG C 70 minutes,
Filtering is washed, and drying obtains Modified Zeolite Y product, is denoted as SZ-2.Table 1 gives the composition of SZ-2, lattice constant, phase
The second hole of crystallinity, framework si-al ratio, structural breakdown temperature, specific surface area and larger aperture (aperture is 8~100nm) is accounted for
Percentage, the total two level pore volume of total second hole (2~100nm).
By SZ-2 in naked state through 800 DEG C, (100% vapor aging in 17 hours is for 100% vapor aging in 17 hours
Refer to aging 17 hours under 100% steam atmosphere) after, the crystallization of the zeolite before and after analyzing SZ-2 agings with the method for XRD
The opposite crystal retention after aging is spent and calculated, the results are shown in Table 2.
The boehmite that 1476 grams of alumina contents are 61 weight % is added in 7344 grams of decationized Y sieve water, is being stirred
The pure hydrochloric acid of lower addition 185ml chemistry (containing 36 weight %HCl) is mixed, then in 70 DEG C of agings 1 hour, six water chlorinations are added later
Magnesium (production of the bicyclic chemical reagent work in Beijing, analysis are pure) 1080 grams of aqueous solution (wherein 617 grams of magnesium chloride hexahydrate), mashing are obtained containing adding
Add the slurries of the aluminium oxide of agent.
It takes the Aluminum sol that 4284 grams of alumina contents are 21 weight % to be added in 3753 grams of decationized Y sieve water, is added with stirring
The kaolin that 6908 grams of solid contents are 76 weight % is beaten 60 minutes, obtains kaolin slurry.It is by 4423 grams of alumina contents
The boehmite of 61 weight % is added in 22037 grams of decationized Y sieve water, and 482ml hydrochloric acid (chemistry is added under stirring
It is pure, 36 weight % of concentration), prepared kaolin slurry is added in aging after sixty minutes, and mashing adds prepared containing and adds
Then the slurries of the aluminium oxide of agent, mashing are added SZ-2 molecular sieves 4950 grams (butts), mashing, then are spray-dried and are washed
Processing (with example 1) is washed, drying obtains catalyst SC-2.
Embodiment 3
By 2000Kg (dry basis) skeletons SiO2/Al2O3For 4.6 NaY types zeolite (13.5 heavy % of sodium oxide content, middle stone
Change catalyst asphalt in Shenli Refinery to produce) it is added to equipped with 20m3It is stirred at 95 DEG C in swap tank of decationized Y sieve water
It is even, then add 570L RECl3Solution (RECl3Rare earth concentration in solution is with RE2O3It is calculated as 319g/L), continue stirring 60
After minute, filter, washing, filter cake is continuously introduced into expansion drying stove and is dried, obtain sodium oxide content reduction containing rare earth
The Y type molecular sieve of conventional unit cell dimension, sodium oxide content are 7.5 weight %, lattice constant 2.471nm；Then, it is sent into roasting
Stove is burnt in 470 DEG C of calcination temperature, is contained and is roasted 5 hours under 70 volume % water vapour atmospheres；Then, molecular sieve material enters roaster
Roasting drying process, wherein 500 DEG C of calcination temperature are carried out, calcination atmosphere is dry air atmosphere, and roasting time 1.5 hours makes
Its water content is less than 1 heavy %, obtains the Y type molecular sieve of lattice constant reduction, lattice constant 2.458nm；Then, by structure cell
The Y type molecular sieve material that constant reduces, which is sent into the super steady reactor of serialization gas phase, carries out the super steady reaction of gas phase.Molecular sieve is even
The super steady reaction process of gas phase and its follow-up tail gas absorption technology in the super steady reactor of continuousization gas phase is special according to CN103787352A
The method of sharp disclosed embodiment 1 carries out, and process conditions are：SiCl4：Weight ratio=0.45 of y-type zeolite：1, molecular sieve into
Doses is 800kg/ hours, and reaction temperature is 400 DEG C.Molecular sieve material after the super steady reaction of gas phase is after gas-solid separator detaches
It is sent into secondary swap tank, in advance added with 20m in secondary swap tank3Decationized Y sieve water, the molecule in secondary swap tank is added
Sieve weight of material is 2000Kg (dry basis), stirs evenly, later, is slowly added to the nitric acid 1.2m of 5 weight %3, and be warming up to
95 DEG C, continue stirring 90 minutes, then, 90Kg citric acids and 40Kg oxalic acid is added, after continuing stirring at 93 DEG C 70 minutes, mistake
Filter, washing, sampling drying, sample are denoted as SZ-3.Table 1 gives the composition of SZ-3, lattice constant, relative crystallinity, framework silicon
Aluminium ratio, structural breakdown temperature, specific surface area and larger aperture (aperture is 80~100nm) second hole account for total second hole (2~
Percentage, total second hole pore volume 100nm).By SZ-3 in naked state through 800 DEG C, 100% vapor aging in 17 hours
Afterwards, the crystallinity of the zeolite before and after SZ-3 agings is analyzed with the method for XRD and calculates the opposite crystal retention after aging, is tied
Fruit is shown in Table 2.
It is that the boehmite of 61 weight % is added in 9792 grams of decationized Y sieve water to take 1968 grams of alumina contents, is being stirred
The pure hydrochloric acid of lower addition 246ml chemistry (HCl contents are 36 weight %) is mixed, in 70 DEG C of agings 1 hour, 588ml phosphorus is added later
Acid (Beijing Chemical Plant produces, concentration 85%, and analysis is pure), mashing obtains the slurries of the aluminium oxide containing additive.
It takes the Aluminum sol that 5712 grams of alumina contents are 21 weight % to be added in 9405 grams of decationized Y sieve water, is added with stirring
The kaolin that 12684 grams of solid contents are 76 weight % is beaten 60 minutes, obtains kaolin slurry.Take 7866 grams of alumina contents
It is added in 25458 grams of decationized Y sieve water for the boehmite of 61 weight %, the pure salt of 852ml chemistry is added under stirring
Prepared kaolin slurry is added in acid (36 weight % of concentration), aging after sixty minutes, and mashing adds prepared containing and adds
Then SZ-3 molecular sieves 5820 grams (butts), REY molecular sieves [Sinopec catalyst is added in the slurries of the aluminium oxide of agent, mashing
Asphalt in Shenli Refinery of Co., Ltd produces, and content of rare earth is (with RE2O3Meter) 18 weight %, silica alumina ratio (SiO2/Al2O3Molar ratio 4.6)]
(asphalt in Shenli Refinery of Sinopec catalyst Co., Ltd produces, 0.5 weight of content of rare earth for 1863 grams (butts) and ZRP-5 molecular sieves
Measure %, silica alumina ratio 45) 1164 grams (butts), mashing carries out spray drying and carrying out washing treatment (with example 1), and drying is catalyzed
Agent is denoted as SC-3.
Comparative example 1
Taking 2000 grams of NaY molecular sieves (butt) to be added to stirring in 20 liters of decationized Y sieve aqueous solutions makes it be uniformly mixed, and adds
Enter 1000 grams of (NH4)2SO4, stirring, be warming up to 90~95 DEG C keep 1 hour, be then filtered, washed, filter cake in 120 DEG C it is dry it
Hydrothermal modification treatment (650 DEG C of temperature, 100% water vapour under roast 5 hours) is carried out afterwards, later, is added to 20 liters of decationized Y sieves
Stirring makes it be uniformly mixed in aqueous solution, and 1000 grams of (NH are added4)2SO4, stirring, be warming up to 90~95 DEG C keep 1 hour, then
It is filtered, washed, second hydrothermal modification treatment is carried out after filter cake is dry in 120 DEG C, and (650 DEG C of temperature roasts under 100% water vapour
Burn 5 hours), ion exchange super steady hydro-thermal super-stable Y molecular sieves without rare earth of hydro-thermal twice twice are obtained, DZ1 is denoted as.Table
1 gives the composition of DZ-1, lattice constant, relative crystallinity, framework si-al ratio, structural breakdown temperature, specific surface area and larger
The second hole in aperture (aperture is 8~100nm) accounts for the percentage of total second hole (2~100nm), total second hole pore volume.By DZ-
1 in naked state through 800 DEG C, after 100% vapor aging in 17 hours, the boiling before and after analyzing DZ-1 agings with the method for XRD
The crystallinity of stone simultaneously calculates the opposite crystal retention after aging, the results are shown in Table 2.
The Aluminum sol that 714.5 grams of alumina contents are 21 weight % is taken to be added in 1565.5 grams of decationized Y sieve water, unlatching is stirred
It mixes, the kaolin that 2763 grams of solid contents are 76 weight % is added and disperses 60 minutes.It is 61 weight % to take 2049 grams of alumina contents
Boehmite be added 8146 grams of decationized Y sieve water in, under stirring be added 210ml a concentration of 36% hydrochloric acid, acidification
Scattered kaolin slurry is added after sixty minutes, levigate DZ-1 molecular sieves 1500 grams (butts) are then added, stir evenly
Afterwards, spray drying and carrying out washing treatment are carried out, drying obtains catalyst, is denoted as DC-1.Contain in wherein obtained DC-1 catalyst
There are 30 weight % of DZ-1 molecular sieves, 42 weight % of kaolin, 25 weight % of boehmite, 3 weight % of Aluminum sol.
Comparative example 2
Taking 2000 grams of NaY molecular sieves (butt) to be added to stirring in 20 liters of decationized Y sieve aqueous solutions makes it be uniformly mixed, and adds
Enter 1000 grams of (NH4)2SO4, stirring, be warming up to 90~95 DEG C keep 1 hour, be then filtered, washed, filter cake in 120 DEG C it is dry it
After carry out hydrothermal modification treatment, hydrothermal modification treatment：It roasts 5 hours under 650 DEG C of temperature, 100% water vapour, later, is added to
Stirring makes it be uniformly mixed in 20 liters of decationized Y sieve aqueous solutions, and the RE (NO of 200ml are added3)3Solution is (with RE2O3Count earth solution
It is a concentration of：319g/L) and 900 grams of (NH4)2SO4, stir, be warming up to 90~95 DEG C and kept for 1 hour, is then filtered, washed, filter cake
In 120 DEG C it is dry after carry out second hydrothermal modification treatment (650 DEG C of temperature, 100% water vapour under roast 5 hours), obtain
Ion exchange super steady hydro-thermal super-stable Y molecular sieves containing rare earth of hydro-thermal twice twice, are denoted as DZ-2.Table 1 gives DZ-2's
Composition, lattice constant, relative crystallinity, framework si-al ratio, structural breakdown temperature, specific surface area and larger aperture (aperture is 8~
Second hole 100nm) accounts for the percentage of total second hole (2~100nm), total second hole pore volume.DZ-2 is passed through in naked state
800 DEG C, after 100% vapor aging in 17 hours, the crystallinity and meter of the zeolite before and after analyzing DZ-2 agings with the method for XRD
The opposite crystal retention after aging has been calculated, the results are shown in Table 2.
By the catalytic cracking catalysis of DZ-2 molecular sieves, kaolin, water, boehmite adhesive and Aluminum sol routinely
The preparation method of agent forms slurries, spray drying is prepared into microspherical catalyst, and prepared catalytic cracking catalyst is denoted as DC-2
(preparation method for referring to comparative example 1).Wherein in terms of butt, 30 weight of DZ-2 molecular sieves is contained in obtained DC-2 catalyst
Measure %, 42 weight % of kaolin, 25 weight % of boehmite, 3 weight % of Aluminum sol.
Comparative example 3
2000 kilograms of NaY molecular sieves (butt) are taken to be added to 20m3Stirring makes it be uniformly mixed in water, and the RE of 650L is added
(NO3)3Solution (319g/L), stirring are warming up to 90~95 DEG C and are kept for 1 hour, be then filtered, washed, filter cake is continuously introduced into flash distillation
And roaster carries out roasting drying process, controls 500 DEG C of calcination temperature, calcination atmosphere is dry air atmosphere, and roasting time 2 is small
When, so that its water content is less than 1 heavy %, then, molecular sieve material after drying is sent into the super steady reactor of serialization gas phase and is carried out
The super steady reaction of gas phase.Gas phase super steady reaction process and its follow-up tail gas absorption of the molecular sieve in the super steady reactor of serialization gas phase
Technique is carried out according to the method for the embodiment 1 of CN103787352A patent disclosures, and process conditions are：SiCl4：The weight of y-type zeolite
Measure ratio=0.4：1, the inlet amount of molecular sieve is 800kg/ hours, and reaction temperature is 580 DEG C.Molecular sieve after the super steady reaction of gas phase
Material is sent into after gas-solid separator detaches in secondary swap tank, in advance added with 20m in secondary swap tank3Water, be added it is secondary
Molecular sieve weight of material in swap tank is 2000Kg (dry basis), stirs evenly, later, is slowly added to the nitric acid of 5 weight %
1.2m3, and 95 DEG C are warming up to, continue stirring 90 minutes, then, 90Kg citric acids and 40Kg oxalic acid is added, continues to stir at 93 DEG C
It after mixing 70 minutes, filters, washing, sampling drying, sample is denoted as DZ-3.Table 1 gives the composition of DZ-3, lattice constant, phase
The second hole of crystallinity, framework si-al ratio, structural breakdown temperature, specific surface area and larger aperture (aperture is 8~100nm) is accounted for
Percentage, the total second hole pore volume of total second hole (2~100nm).By DZ-3 in naked state through 800 DEG C, 17 hours 100%
After vapor aging, the crystallinity of the zeolite before and after analyzing DZ-3 agings with the method for XRD simultaneously calculates opposite after aging
Crystal retention the results are shown in Table 2.
By the catalytic cracking catalysis of DZ-3 molecular sieves, kaolin, water, boehmite adhesive and Aluminum sol routinely
The preparation method of agent forms slurries, spray drying is prepared into microspherical catalyst, and prepared catalytic cracking catalyst is denoted as DC-3
(preparation method for referring to comparative example 1).Wherein, 30 weight % of DZ-3 molecular sieves, kaolinite are contained in obtained DC-3 catalyst
Soil 42 weight %, 25 weight % of boehmite, 3 weight % of Aluminum sol.
Comparative example 4
Catalyst DC-4 is prepared according to the method for embodiment 2, the difference is that the molecular sieve DZ-3 prepared with comparative example 3 is replaced
Molecular sieve SZ-2 therein.
The catalytic cracking catalyst prepared to Examples 1 to 3 and comparative example 1~4 carries out light oil microactivity evaluation.Gently
Oily micro-activity evaluation：Using RIPP92-90 standard method (see《Petrochemical analysis method》(RIPP test methods) Yang Cui
Fixed equal to compile, Science Press, nineteen ninety publishes) light oil microactivity of evaluation sample, catalyst loading 5.0g, reaction temperature
It it is 460 DEG C, feedstock oil is the huge port light diesel fuel of 235-337 DEG C of boiling range, and product is formed by gas chromatographic analysis, formed according to product
Light oil microactivity is calculated, as a result in table 3.
Light oil microactivity (MA)=(gasoline production+gas yield+coke output for being less than 216 DEG C in product)/charging
Total amount × 100%
Catalytic cracking catalyst main character prepared by Examples 1 to 3 and comparative example 1~4 is listed in Table 3 below.
Embodiment 4~6
Heavy oil cracking performance evaluation is carried out to catalytic cracking catalyst prepared by Examples 1 to 3, is as a result listed in table 5.
Heavy oil cracking performance evaluation condition：First aging 17 hours under 800 DEG C, 100% water vapour atmosphere of catalyst, then
It is evaluated on ACE (fixed fluidized bed) device, feedstock oil is military mixed three -2007 (property is shown in Table 4), 500 DEG C of reaction temperature.
Wherein, conversion ratio=yield of gasoline+yield of liquefied gas+dry gas yield+coking yield
Yield of light oil=yield of gasoline+diesel yield
Liquid yield=liquefied gas+gasoline+diesel oil
Coke selectivity=coke yield/conversion ratio
Comparative example 5~8
The catalysis for evaluating the catalytic cracking catalyst of the preparation of comparative example 1~4 respectively according to 4~6 method of above-described embodiment is split
Change performance, is as a result listed in table 5.
Table 1
By table 1 as it can be seen that the Modified Zeolite Y of high stability provided by the invention, sodium oxide content is low, the silicon of molecular sieve
Non-framework aluminum content when aluminium is relatively high is less, and 2.0nm~100nm second holes pore volume accounts for total pore volume percentage in molecular sieve
It is higher, also, B acid/L acid (the ratio between total B acid acid amounts and L acid acid amounts) is higher, and crystallinity height is especially normal in molecular sieve structure cell
Crystallinity value when the smaller content of rare earth of number is higher is higher, and lattice collapse temperature is high, has high thermal stability.
Table 2
As shown in Table 2, Modified Zeolite Y provided by the invention passes through 800 DEG C under sieve sample naked state,
After harsh conditions aging in 17 hours, sample has higher opposite crystal retention, shows modified Y types provided by the invention point
Sub- sifter device has higher hydrothermal stability.
Table 3
Table 4ACE evaluates raw material oil nature
Table 5
| Example number | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 |
| Sample number into spectrum | SC-1 | SC-2 | SC-3 | DC-1 | DC-2 | DC-3 | DC-4 |
| Molecular sieve used | SZ-1 | SZ-2 | SZ-3 | DZ-1 | DZ-2 | DZ-3 | DZ-3 |
| Oil ratio (weight ratio) | 4 | 4 | 4 | 9 | 8 | 5 | 5 |
| Product distribution/weight % | |||||||
| Dry gas | 1.04 | 0.98 | 1.01 | 1.55 | 1.48 | 1.47 | 1.45 |
| Liquefied gas | 15.41 | 15.81 | 16.09 | 16.86 | 15.33 | 16.31 | 16.32 |
| Coke | 3.51 | 3.65 | 3.7 | 8.33 | 7.61 | 6.19 | 6.01 |
| Gasoline | 56.75 | 56.97 | 57.09 | 38.55 | 43.91 | 51.19 | 51.45 |
| Diesel oil | 16.98 | 16.65 | 16.13 | 20.17 | 19.25 | 16.67 | 16.83 |
| Heavy oil | 6.31 | 5.94 | 5.98 | 14.54 | 12.42 | 8.17 | 7.94 |
| It is total | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Conversion ratio/weight % | 76.71 | 77.41 | 77.89 | 65.29 | 68.33 | 75.16 | 75.23 |
| Coke selectivity/weight % | 4.58 | 4.72 | 4.75 | 12.76 | 11.14 | 8.24 | 7.99 |
| Yield of light oil/weight % | 73.73 | 73.62 | 73.22 | 58.72 | 63.16 | 67.86 | 68.28 |
| Total liquid yield/weight % | 89.14 | 89.43 | 89.31 | 75.58 | 78.49 | 84.17 | 84.6 |
By table 5 as it can be seen that catalytic cracking catalyst produced by the present invention has higher conversion ratio, higher yield of light oil
And total liquid yield, there is excellent coke selectivity.It can be seen that Modified Zeolite Y provided by the invention has very high hydro-thermal
Stability has significantly lower coke selectivity, and there is considerably higher liquid to receive, and yield of light oil is considerably higher, and gasoline is received
Rate improves, heavy oil conversion activity higher.
Claims (24)
1. a kind of catalytic cracking catalyst contains the Modified Zeolite Y of in terms of butt 10 weight of weight %~50 %, with butt
Count the clay of the aluminium oxide containing additive and the weight % of in terms of butt 10 weight~80 of the weight % of 2 weight~40；Wherein, with dry
Base meter, the aluminium oxide containing 60 weight %-99.5 weight % in the aluminium oxide containing additive, 0.5 weight %-40 weight %
Additive, the one kind of the additive in the compound containing alkaline-earth metal, lanthanide series metal, silicon, gallium, boron or P elements
Or it is several；The rare earth oxide content of the Modified Zeolite Y is the 5 weight % of weight %~12, and sodium oxide content is no more than 0.5
Weight %, total pore volume are 0.36mL/g~0.48mL/g, and aperture is that the pore volume of the second hole of 2nm~100nm accounts for total hole body
Long-pending percentage is 20%~38%, and lattice constant is 2.440nm~2.455nm, and non-framework aluminum contains in the Modified Zeolite Y
The percentage that amount accounts for total aluminium content is not higher than 10%, and lattice collapse temperature is not less than 1060 DEG C, also, with pyridine adsorption infrared method
B acid amount and the ratio of L acid amounts are not less than 3.50 in the total acid content of the Modified Zeolite Y measured at 200 DEG C.
2. catalytic cracking catalyst described in accordance with the claim 1, which is characterized in that aperture in the Modified Zeolite Y
For the pore volume of the second hole of 2nm~100nm, to account for the percentage of total pore volume be 28%~38%.
3. according to catalytic cracking catalyst as claimed in claim 1 or 2, which is characterized in that the Modified Zeolite Y mesoporous
Diameter isPore volume/aperture of second hole beThe ratio of the pore volume of total second hole is 40%
~80%.
4. catalytic cracking catalyst described in accordance with the claim 1, which is characterized in that non-bone in the Modified Zeolite Y
The percentage that frame aluminium content accounts for total aluminium content is 5~9.5%, and framework si-al ratio is with SiO2/Al2O3Molar ratio computing is 7~14.
5. catalytic cracking catalyst described in accordance with the claim 1, which is characterized in that the Modified Zeolite Y lattice collapses
1060 DEG C~1085 DEG C of temperature of collapsing.
6. catalytic cracking catalyst described in accordance with the claim 1, which is characterized in that with pyridine adsorption infrared method at 200 DEG C
It can be 3.5~4.6 that the ratio of B acid amount and L acid amounts, which is 3.5~6, in the Modified Zeolite Y total acid content measured.
7. catalytic cracking catalyst described in accordance with the claim 1, which is characterized in that 800 DEG C, normal pressure, 100% vapor gas
After atmosphere aging 17 hours, it for example can be 38~65 that the opposite crystal retention of the Modified Zeolite Y, which is 38% or more,.
8. catalytic cracking catalyst described in accordance with the claim 1, which is characterized in that the Modified Zeolite Y it is opposite
Crystallinity is 70~80%.
9. according to any catalytic cracking catalyst of claim 1~8, which is characterized in that the Modified Zeolite Y
Rare earth oxide content be 5.5~10 weight %, sodium oxide content be 0.15~0.3 weight %, lattice constant be 2.442~
2.453nm and framework si-al ratio are 7.8~12.6.
10. catalytic cracking catalyst described in accordance with the claim 1, which is characterized in that the catalyst includes in terms of butt
Oxidation containing additive described in the Modified Zeolite Y of 25 weight of weight %~40 %, in terms of butt 2~20 weight %
The clay of the weight % of the alumina binder of the weight % of aluminium, in terms of butt 5 weight~30 and in terms of butt 30 weight~50.
11. catalytic cracking catalyst described in accordance with the claim 1, which is characterized in that it is high that the clay is selected from kaolin, more water
Ridge soil, montmorillonite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, one kind in bentonite or
It is a variety of；The alumina binder is selected from gama-alumina, η-aluminium oxide, θ-aluminium oxide, χ-aluminium oxide, boehmite, a water
One or more of aluminium stone, gibbsite, bayerite or Aluminum sol；
The preparation method of the aluminium oxide containing additive includes the following steps：
(1), boehmite is mixed under stiring with being enough to make the water of its pulp and acid, wherein the dosage of acid make the acid with
The weight ratio of aluminium oxide is 0.01-0.5 in boehmite；
(2), by the mixed serum of step (1) at a temperature of room temperature~90 DEG C aging 0~24 hour；
(3), the product of step (2) is mixed with additive, optionally drying and optionally roasting.
12. a kind of preparation method of catalytic cracking catalyst, including Modified Zeolite Y is prepared, formation includes the modified Y types
The step of slurries of molecular sieve, the aluminium oxide containing additive, clay and water, spray drying, wherein with the oxygen containing additive
On the basis of the weight for changing aluminium, the aluminium oxide containing 60 weight %-99.5 weight % in the aluminium oxide containing additive, 0.5 weight
The additive of %-40 weight % is measured, the additive, which is selected from, contains alkaline-earth metal, lanthanide series metal, silicon, gallium, boron or P elements
One or more of compound；Wherein, the preparation method of the Modified Zeolite Y includes the following steps：
(1) NaY molecular sieve is contacted with rare-earth salt solution and carries out ion-exchange reactions, be filtered, washed, optionally drying obtains oxygen
Change the Y type molecular sieve for the conventional unit cell dimension containing rare earth that sodium content reduces；
(2) Y type molecular sieve for the conventional unit cell dimension containing rare earth for reducing above-mentioned sodium oxide content 350~520 DEG C of temperature,
It is roasted 4.5~7 hours under 30~95 volume % water vapour atmospheres, optionally drying, obtains the Y type molecular sieve of lattice constant reduction；
(3) according to SiCl4：Y type molecular sieve=0.1~0.7 that the lattice constant in terms of butt reduces：1 weight ratio is by institute
Y type molecular sieve and the silicon tetrachloride gas haptoreaction of lattice constant reduction are stated, reaction temperature is 200 DEG C~650 DEG C, when reaction
Between be 10 minutes to 5 hours, optionally washing and optionally filtering, obtain the super steady Modified Zeolite Y of gas phase；
(4) the super steady Modified Zeolite Y of gas phase that step (3) obtains is contacted with acid solution.
13. according to the method described in claim 12, which is characterized in that sodium oxide content described in step (1) reduced contains rare earth
Conventional unit cell dimension Y type molecular sieve, lattice constant be 2.465~2.472nm, sodium oxide content be no more than 9 weight %.
14. according to the method for claim 12, which is characterized in that in step (1), what the sodium oxide content reduced contains dilute
In the Y type molecular sieve of the conventional unit cell dimension of soil, content of rare earth is with RE2O3It is calculated as 5.5~14 weight %, sodium oxide content is 4~
9 weight % are, for example, 5.5~8.5 weight %, and lattice constant is 2.465nm~2.472nm.
15. according to the method for claim 12, which is characterized in that step (1) is described by NaY molecular sieve and rare-earth salt solution
Contact carries out ion-exchange reactions：According to NaY molecular sieve：Rare-earth salts：H2O=1：0.01~0.18：5~20 weight ratio
NaY molecular sieve, rare-earth salts and water are formed into mixture, stirring.
16. the method according to claim 12 or 15, which is characterized in that step (1) is described molten with rare earth by NaY molecular sieve
Liquid contact carries out ion-exchange reactions, including：NaY molecular sieve is mixed with decationized Y sieve water, under stirring, be added rare-earth salts and/
Or rare-earth salt solution carries out ion-exchange reactions, filters, washing；The condition of ion-exchange reactions is：Exchange temperature is 15~95
DEG C, swap time is 30~120 minutes, and the rare-earth salt solution is the aqueous solution of rare-earth salts.
17. according to the method for claim 12, which is characterized in that the rare-earth salts is that rare earth chloride or nitric acid are dilute
Soil.
18. according to the method for claim 12, which is characterized in that step (2) described calcination temperature is 380~480 DEG C, institute
It is 40~80% water vapour atmospheres to state calcination atmosphere, and the roasting time is 5~6 hours.
19. according to the method for claim 12, which is characterized in that the Y that the lattice constant obtained in step (2) reduces
The lattice constant of type molecular sieve is 2.450nm~2.462nm, the water content in the Y type molecular sieve that the lattice constant reduces
No more than 1 weight %.
20. according to the method for claim 12, which is characterized in that the washing methods described in step (3) is to be washed with water, and is washed
The condition of washing is molecular sieve：H2O=1:6~15, pH value the most 2.5~5.0, wash temperature is 30~60 DEG C.
21. according to the method for claim 12, which is characterized in that the gas phase for obtaining (3) described in step (4) is super steady to be changed
Property Y type molecular sieve contacted with acid solution, wherein acid is 0.001~0.15 with the weight ratio of molecular sieve：1, the weight of water and molecular sieve
Amount is than being 5~20：1, the acid is one or more in organic acid and inorganic acid, and time of contact is 60 minutes or more preferred
1~4 hour, the temperature of contact was 80~99 DEG C.
22. according to the method for claim 12, which is characterized in that in the acid solution described in step (4) containing organic acid and
The weight ratio of inorganic acid more than moderate strength, more than moderate strength inorganic acid and molecular sieve is 0.01~0.05：1；It is organic
The weight ratio of acid and molecular sieve is 0.02~0.1：1, the weight ratio of water and molecular sieve is 5~20：1, the temperature of contact is 80~
99 DEG C, time of contact is 1~4 hour.
23. according to the method for claim 12, which is characterized in that being contacted with acid solution described in step (4), first with it is medium
Inorganic acid contact more than intensity, then contacts with organic acid, the condition contacted with inorganic acid more than moderate strength is：It is medium
The weight ratio of more than intensity inorganic acid and molecular sieve is 0.01~0.06：1, the weight ratio of water and molecular sieve is 5~20：1, it connects
The tactile time is：60-120 minutes, Contact Temperature was 90~98 DEG C；It is with organic acid contact conditions：The weight of organic acid and molecular sieve
Amount is than being 0.02~0.14：1, the weight ratio of water and molecular sieve is 5~20：1, time of contact is 60~120 minutes, Contact Temperature
It is 90-98 DEG C.
24. the method according to claim 22 or 23, which is characterized in that the organic acid is oxalic acid, malonic acid, fourth two
It is one or more in acid, dimethyl succinic acid, malic acid, tartaric acid, citric acid, salicylic acid；It is more than the moderate strength
Inorganic acid is one or more in phosphoric acid, hydrochloric acid, nitric acid and sulfuric acid.
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710097154.0A CN108452838B (en) | 2017-02-22 | 2017-02-22 | Catalytic cracking catalyst |
| GB1911860.3A GB2573252B (en) | 2017-02-22 | 2018-02-12 | Catalytic cracking catalyst and preparation thereof |
| PCT/CN2018/076430 WO2018153302A1 (en) | 2017-02-22 | 2018-02-12 | Catalytic cracking catalyst and preparation method therefor |
| MYPI2019004689A MY191917A (en) | 2017-02-22 | 2018-02-12 | Catalytic cracking catalyst and preparation thereof |
| RU2019126112A RU2755891C2 (en) | 2017-02-22 | 2018-02-12 | Catalytic cracking catalyst and its preparation |
| US16/484,418 US10888848B2 (en) | 2017-02-22 | 2018-02-12 | Catalytic cracking catalyst and preparation thereof |
| JP2019565603A JP7083360B2 (en) | 2017-02-22 | 2018-02-12 | Catalytic cracking catalyst and its production method |
| SG11201907656VA SG11201907656VA (en) | 2017-02-22 | 2018-02-12 | Catalytic cracking catalyst and preparation thereof |
| TW107105496A TWI760436B (en) | 2017-02-22 | 2018-02-14 | Catalytic cracking catalyst and preparation method thereof |
| SA519402430A SA519402430B1 (en) | 2017-02-22 | 2019-08-12 | Catalytic Cracking Catalyst and Preparation Thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710097154.0A CN108452838B (en) | 2017-02-22 | 2017-02-22 | Catalytic cracking catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108452838A true CN108452838A (en) | 2018-08-28 |
| CN108452838B CN108452838B (en) | 2020-06-16 |
Family
ID=63220798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710097154.0A Active CN108452838B (en) | 2017-02-22 | 2017-02-22 | Catalytic cracking catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108452838B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111185223A (en) * | 2018-11-15 | 2020-05-22 | 中国石油天然气股份有限公司 | Heavy oil hydro-conversion catalyst and preparation method thereof |
| CN112237909A (en) * | 2019-07-18 | 2021-01-19 | 中国石油化工股份有限公司 | Modified alumina and preparation method and application thereof |
| CN112473723A (en) * | 2019-09-12 | 2021-03-12 | 中国石油化工股份有限公司 | High-acid-content catalyst, preparation method thereof and method for carbon four-alkylation reaction |
| CN112473724A (en) * | 2019-09-12 | 2021-03-12 | 中国石油化工股份有限公司 | Catalyst and preparation method and application thereof |
| CN113952969A (en) * | 2020-07-20 | 2022-01-21 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, preparation method and application thereof |
| CN114100671A (en) * | 2020-08-26 | 2022-03-01 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst, preparation method and application thereof |
| CN115634710A (en) * | 2021-07-20 | 2023-01-24 | 中国石油化工股份有限公司 | Preparation method of catalytic cracking catalyst without ammonia nitrogen pollution |
| CN115703070A (en) * | 2021-08-17 | 2023-02-17 | 中国石油化工股份有限公司 | Preparation method of catalytic cracking catalyst capable of producing BTX in high yield |
| CN114100671B (en) * | 2020-08-26 | 2024-06-25 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5236877A (en) * | 1990-12-04 | 1993-08-17 | W. R. Grace & Co.-Conn. | Dual zeolite fluid cracking catalyst composition for improved gasoline octane |
| CN1388064A (en) * | 2001-05-30 | 2003-01-01 | 中国石油化工股份有限公司 | Prepn of high-silicon Y-Zeolite |
| CN1727445A (en) * | 2004-07-29 | 2006-02-01 | 中国石油化工股份有限公司 | Cracking catalyst for hydrocarbon and preparation method |
| CN1916116A (en) * | 2005-08-17 | 2007-02-21 | 中国石油化工股份有限公司 | Catalytic cracking catalyst |
| CN101745418A (en) * | 2008-11-28 | 2010-06-23 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, preparation and application thereof |
-
2017
- 2017-02-22 CN CN201710097154.0A patent/CN108452838B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5236877A (en) * | 1990-12-04 | 1993-08-17 | W. R. Grace & Co.-Conn. | Dual zeolite fluid cracking catalyst composition for improved gasoline octane |
| CN1388064A (en) * | 2001-05-30 | 2003-01-01 | 中国石油化工股份有限公司 | Prepn of high-silicon Y-Zeolite |
| CN1727445A (en) * | 2004-07-29 | 2006-02-01 | 中国石油化工股份有限公司 | Cracking catalyst for hydrocarbon and preparation method |
| CN1916116A (en) * | 2005-08-17 | 2007-02-21 | 中国石油化工股份有限公司 | Catalytic cracking catalyst |
| CN101745418A (en) * | 2008-11-28 | 2010-06-23 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, preparation and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 赵建辉: "超稳Y分子筛的化学改性研究", 《齐鲁石油化工》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111185223A (en) * | 2018-11-15 | 2020-05-22 | 中国石油天然气股份有限公司 | Heavy oil hydro-conversion catalyst and preparation method thereof |
| CN111185223B (en) * | 2018-11-15 | 2023-02-24 | 中国石油天然气股份有限公司 | Heavy oil hydro-conversion catalyst and preparation method thereof |
| CN112237909B (en) * | 2019-07-18 | 2022-09-27 | 中国石油化工股份有限公司 | Modified alumina and preparation method and application thereof |
| CN112237909A (en) * | 2019-07-18 | 2021-01-19 | 中国石油化工股份有限公司 | Modified alumina and preparation method and application thereof |
| CN112473724A (en) * | 2019-09-12 | 2021-03-12 | 中国石油化工股份有限公司 | Catalyst and preparation method and application thereof |
| CN112473723A (en) * | 2019-09-12 | 2021-03-12 | 中国石油化工股份有限公司 | High-acid-content catalyst, preparation method thereof and method for carbon four-alkylation reaction |
| CN113952969A (en) * | 2020-07-20 | 2022-01-21 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, preparation method and application thereof |
| CN113952969B (en) * | 2020-07-20 | 2023-07-11 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method and application thereof |
| CN114100671A (en) * | 2020-08-26 | 2022-03-01 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst, preparation method and application thereof |
| CN114100671B (en) * | 2020-08-26 | 2024-06-25 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst and preparation method and application thereof |
| CN115634710A (en) * | 2021-07-20 | 2023-01-24 | 中国石油化工股份有限公司 | Preparation method of catalytic cracking catalyst without ammonia nitrogen pollution |
| CN115703070A (en) * | 2021-08-17 | 2023-02-17 | 中国石油化工股份有限公司 | Preparation method of catalytic cracking catalyst capable of producing BTX in high yield |
| CN115703070B (en) * | 2021-08-17 | 2024-06-04 | 中国石油化工股份有限公司 | Preparation method of catalytic cracking catalyst for producing BTX in high yield |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108452838B (en) | 2020-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108452838A (en) | A kind of catalytic cracking catalyst | |
| TWI760435B (en) | Modified Y-type molecular sieve, its preparation method and catalyst comprising the same | |
| CN108452837A (en) | A kind of catalytic cracking catalyst | |
| TWI760436B (en) | Catalytic cracking catalyst and preparation method thereof | |
| CN108452830B (en) | Catalytic cracking catalyst | |
| CN108452827B (en) | Catalytic cracking catalyst | |
| CN108452832B (en) | Phosphorus-containing and rare earth-containing modified Y-type molecular sieve rich in secondary pores and preparation method thereof | |
| CN108452833A (en) | A kind of catalytic cracking catalyst | |
| CN108452834A (en) | A kind of catalytic cracking catalyst | |
| CN108452829B (en) | Catalytic cracking catalyst | |
| CN108452825A (en) | Magnesium-modified high silicon super-stable Y molecular sieves of one kind and preparation method thereof | |
| CN110193377A (en) | A kind of catalytic cracking petroleum hydrocarbons catalyst | |
| CN110193376A (en) | A kind of catalytic cracking petroleum hydrocarbons catalyst | |
| CN108452835A (en) | A kind of catalytic cracking catalyst | |
| CN108452831B (en) | Rare earth-containing modified Y-type molecular sieve rich in secondary pores and preparation method thereof | |
| CN108452828B (en) | Ultrastable Y-type molecular sieve containing phosphorus and rare earth and its preparing process | |
| CN108452826A (en) | A kind of catalytic cracking catalyst | |
| CN110841693B (en) | Modified Y-type molecular sieve and preparation method thereof | |
| CN110833863B (en) | Catalytic cracking catalyst, preparation method and application thereof | |
| CN108455625B (en) | High-stability modified Y-type molecular sieve and preparation method thereof | |
| CN110841697B (en) | Modified Y-type molecular sieve and preparation method thereof | |
| CN110652998B (en) | High-stability modified Y-type molecular sieve for producing more isomeric hydrocarbon and preparation method thereof | |
| CN110841695A (en) | Modified Y-type molecular sieve and preparation method thereof | |
| CN110841690B (en) | Modified Y-type molecular sieve and preparation method thereof | |
| CN110841694B (en) | Catalytic cracking catalyst for processing hydrogenated LCO and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |