CN110841697B - Modified Y-type molecular sieve and preparation method thereof - Google Patents
Modified Y-type molecular sieve and preparation method thereof Download PDFInfo
- Publication number
- CN110841697B CN110841697B CN201810949482.3A CN201810949482A CN110841697B CN 110841697 B CN110841697 B CN 110841697B CN 201810949482 A CN201810949482 A CN 201810949482A CN 110841697 B CN110841697 B CN 110841697B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- acid
- rare earth
- mass
- content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 234
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 231
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011148 porous material Substances 0.000 claims abstract description 117
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 72
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011734 sodium Substances 0.000 claims abstract description 14
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 13
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 13
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 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 abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- 239000011701 zinc Substances 0.000 claims abstract description 8
- 239000011787 zinc oxide Substances 0.000 claims abstract description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 46
- 239000002253 acid Substances 0.000 claims description 33
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- -1 rare earth salt Chemical class 0.000 claims description 20
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- 238000005342 ion exchange Methods 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
- 150000007524 organic acids Chemical class 0.000 claims description 15
- 239000012266 salt solution Substances 0.000 claims description 14
- 150000007522 mineralic acids Chemical class 0.000 claims description 12
- 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 description 11
- 239000005049 silicon tetrachloride Substances 0.000 claims description 11
- 238000010306 acid treatment Methods 0.000 claims description 9
- 238000001179 sorption measurement Methods 0.000 claims description 9
- 150000003751 zinc Chemical class 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- WXUAQHNMJWJLTG-UHFFFAOYSA-N 2-methylbutanedioic acid Chemical compound OC(=O)C(C)CC(O)=O WXUAQHNMJWJLTG-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 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 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- 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 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 150000002500 ions Chemical group 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 3
- 229960004889 salicylic acid Drugs 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract description 27
- 229910001948 sodium oxide Inorganic materials 0.000 abstract description 26
- 238000004523 catalytic cracking Methods 0.000 abstract description 14
- 239000003921 oil Substances 0.000 abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000571 coke Substances 0.000 abstract description 8
- 239000000377 silicon dioxide Substances 0.000 abstract description 6
- 229910052681 coesite Inorganic materials 0.000 abstract description 4
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 4
- 229910052682 stishovite Inorganic materials 0.000 abstract description 4
- 229910052905 tridymite Inorganic materials 0.000 abstract description 4
- 239000000376 reactant Substances 0.000 abstract description 2
- 239000010457 zeolite Substances 0.000 description 36
- 229910021536 Zeolite Inorganic materials 0.000 description 34
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 34
- 239000003054 catalyst Substances 0.000 description 28
- 239000007789 gas Substances 0.000 description 27
- 238000005406 washing Methods 0.000 description 26
- 238000001035 drying Methods 0.000 description 25
- 239000000243 solution Substances 0.000 description 21
- 239000000463 material Substances 0.000 description 20
- 238000003756 stirring Methods 0.000 description 19
- 230000032683 aging Effects 0.000 description 17
- 238000001914 filtration Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 238000012986 modification Methods 0.000 description 14
- 230000004048 modification Effects 0.000 description 14
- 238000005336 cracking Methods 0.000 description 11
- 239000012065 filter cake Substances 0.000 description 11
- 229910052746 lanthanum Inorganic materials 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 9
- 238000000634 powder X-ray diffraction Methods 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- 229910052684 Cerium Inorganic materials 0.000 description 6
- 229910003910 SiCl4 Inorganic materials 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000003570 air Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 150000003863 ammonium salts Chemical class 0.000 description 5
- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000005995 Aluminium silicate Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 238000010561 standard procedure Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000004846 x-ray emission Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000004140 cleaning Methods 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
- 238000011156 evaluation Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 230000009469 supplementation Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 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
- 239000010779 crude oil Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 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
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000008096 xylene Substances 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
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
-
- B01J35/60—
-
- B01J35/647—
-
- B01J35/651—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/24—Type Y
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Abstract
One embodiment of the invention provides a modified Y-type molecular sieve and a preparation method thereof, wherein in the modified Y-type molecular sieve, the content of rare earth is 5-12 wt% calculated by rare earth oxide, the content of sodium is not more than 0.5 wt% calculated by sodium oxide, the content of zinc is 0.5-5 wt% calculated by zinc oxide, and the ratio of framework silicon to aluminum is SiO2/Al2O3The molar ratio is 7-14, the mass of non-framework aluminum accounts for not more than 10% of the total mass of aluminum, and the pore volume of secondary pores with the pore diameter of 2-100 nm accounts for 20-38% of the total pore volume. The modified Y-type molecular sieve provided by the embodiment of the invention has higher crystallinity, thermal stability and hydrothermal stability, is rich in secondary pores, is used for catalytic cracking of hydrogenated LCO (light cycle oil), has lower coke selectivity, and has higher conversion efficiency of reactants.
Description
Technical Field
The invention relates to a Y-type molecular sieve, in particular to a modified Y-type molecular sieve for processing hydrogenation LCO catalytic cracking and a preparation method thereof.
Background
Y-type molecular sieves (also known as Y-zeolites) have been the main active component of catalytic cracking (FCC) catalysts since their first use in the last 60 th century. However, as crude oil heavies increase, the content of polycyclic compounds in the FCC feedstock increases significantly, and their ability to diffuse through the zeolite channels decreases significantly. The aperture of the Y-type molecular sieve as the main active component is only 0.74nm, and the Y-type molecular sieve is directly used for processing heavy fractions such as residual oil and the like, and the accessibility of the active center of the catalyst can become a main obstacle for cracking polycyclic compounds contained in the Y-type molecular sieve.
The molecular sieve pore structure has close relationship with the cracking reaction performance, especially for a residual oil cracking catalyst, the secondary pores of the molecular sieve can increase the accessibility of residual oil macromolecules and the active center thereof, thereby improving the cracking capability of residual oil.
Hydrothermal dealumination is one of the most widely used methods in industry by first exchanging NaY zeolite with an aqueous solution of ammonium ions to reduce the sodium ion content of the zeolite. And then, roasting the zeolite subjected to ammonium ion exchange at 600-825 ℃ in a water vapor atmosphere to ensure that the zeolite is ultra-stabilized. The method has low cost and is easy for industrialized mass production, and the obtained ultrastable Y-type zeolite has rich secondary pores, but the loss of the crystallinity of the ultrastable Y-type zeolite is serious.
At present, the industrial production of ultrastable Y-type zeolite is generally an improvement on the above-mentioned hydrothermal roasting process, and adopts twice exchange and twice roasting method, and its goal is to adopt milder roasting condition step by step so as to solve the problem of serious loss of crystallinity under the harsh roasting condition, and the prepared ultrastable Y-type zeolite also has a certain quantity of secondary pores. However, the proportion of larger pore size secondary pores in the total secondary pores is lower; in addition, the specific surface and crystallinity of ultrastable zeolites are yet to be further improved.
US5,069,890 and US5,087,348 disclose a method for preparing a mesoporous Y-type molecular sieve, which mainly comprises the following steps: commercially available USY was used as a starting material and treated at 760 ℃ for 24 hours in an atmosphere of 100% steam. The Y-type molecular sieve obtained by the methodThe mesoporous volume is increased from 0.02mL/g to 0.14mL/g, but the crystallinity is reduced from 100 percent to 70 percent, and the surface area is 683m2The/g is reduced to 456m2The acid density drops sharply from 28.9% to 6% even more.
In the method for preparing the mesoporous-containing Y-shaped molecular sieve disclosed in US5,601,798, HY or USY is taken as a raw material and is put into an autoclave to react with NH4NO3Solution or NH4NO3With HNO3The mixed solution is mixed and treated for 2 to 20 hours at the temperature of 115 to 250 ℃ higher than the boiling point, the volume of the mesoporous of the obtained Y-shaped molecular sieve can reach 0.2 to 0.6ml/g, but the crystallinity and the surface area are obviously reduced.
The patent application with the application number of 201310240740.8 discloses a combined modification method of a rich-mesoporous ultrastable Y molecular sieve, which is characterized in that an organic acid and an inorganic salt dealuminization reagent are simultaneously added in the modification process to carry out combined modification of the organic acid and the inorganic salt, and the optimal process conditions such as the optimal concentration, the volume ratio, the reaction time, the reaction temperature and the like of the organic acid and the inorganic salt solution are determined through an orthogonal test. Compared with an industrial USY molecular sieve, the USY obtained by the method has the advantages that the secondary pore content is obviously improved, higher crystallinity can be maintained, the silicon-aluminum ratio is increased, the unit cell constant is reduced, and the molecular sieve is suitable for a high and medium oil type hydrocracking catalyst carrier.
CN 1388064 discloses a method for preparing high-silicon Y zeolite with a unit cell constant of 2.420-2.440 nanometers (Dongdong billow; Li Xuan Wen; Li Da Dong; Scheinen; Niehr; Shiyawa), which comprises the steps of carrying out one or more times of ammonium exchange, hydrothermal treatment and/or chemical dealumination on NaY zeolite or Y-type zeolite which is subjected to ultra-stabilization treatment; in the ammonium exchange, at least the first ammonium exchange before the hydrothermal treatment and/or the chemical dealumination adopts low-temperature selective ammonium exchange at the temperature of room temperature to below 60 ℃, and the rest ammonium exchange is either the low-temperature selective ammonium exchange at the temperature of room temperature to below 60 ℃ or the conventional ammonium exchange at the temperature of 60-90 ℃. The high-silicon Y zeolite prepared by the patent still has higher crystal retention degree when the unit cell constant is smaller, and simultaneously has more secondary holes, and is suitable for being used as a middle distillate oil hydrocracking catalyst.
Although the ultrastable Y molecular sieve prepared by the method disclosed in the above patent application contains a certain amount of secondary pores, has a small unit cell constant and a high Si/Al ratio, these modified molecular sieves are only suitable for hydrogenation catalysts and are difficult to meet the requirement of high cracking activity required for processing heavy oil by catalytic cracking.
CN 1629258 discloses a preparation method of a cracking catalyst containing rare earth ultrastable Y-type molecular sieve (mu Xuhong; Wang Ying; Shuxintian; Royi bin; Zongning; He Ming Yuan; Wujia; Wanxuan), which is characterized in that NaY molecular sieve and ammonium salt aqueous solution containing 6-94 wt% of ammonium salt are contacted twice or more according to the mass ratio of 0.1-24 of ammonium salt to molecular sieve under the conditions of normal pressure and the boiling temperature of more than 90 ℃ to not more than the boiling point of the ammonium salt aqueous solution, so that Na in the molecular sieve is enabled to be in contact with the molecular sieve for two times or more than two times2Reducing the O content to below 1.5 weight percent, and then contacting the molecular sieve with an aqueous solution with the rare earth salt content of 2-10 weight percent at the temperature of 70-95 ℃ to ensure that the rare earth in the molecular sieve is RE2O30.5-18 wt%, and mixing with carrier and drying. In the preparation process of the molecular sieve, multiple ammonium salt exchanges are needed, the preparation process is complicated, the ammonia nitrogen pollution is serious, and the cost is high. In addition, the molecular sieve has low degree of ultrastability, low silicon-aluminum ratio and less secondary pores.
CN 1127161 discloses a method for preparing a rare earth-containing silicon-rich ultrastable Y-type molecular sieve (Dujun; plum-Caiyin; plum-towering; Heliang; Shamegen), which uses NaY as a raw material in a solid RECl3In the presence of SiCl4And carrying out gas-phase dealuminization and silicon supplementation reaction to complete the ultra-stabilization of NaY and the rare earth ion exchange in one step. The unit cell constant a of the molecular sieve prepared by the methodo2.430-2.460 nm, rare earth content of 0.15-10.0 wt%, and Na2The O content is less than 1.0 wt%. However, the molecular sieve is prepared only by a gas phase ultrastable method, and although the ultrastable Y molecular sieve containing rare earth can be prepared, the prepared molecular sieve is lack of secondary pores.
CN 1031030 discloses a method for preparing an ultrastable Y-type molecular sieve with low rare earth content, which provides an ultrastable Y-type molecular sieve with low rare earth content for hydrocarbon cracking, and takes a NaY-type molecular sieve as the original materialThe material is prepared by the steps of primary mixed exchange of ammonium ions and rare earth ions, stabilization treatment, partial framework aluminum atom removal, heat or hydrothermal treatment and the like. Rare earth content (RE) of the molecular sieve2O3) 0.5 to 6 wt% of SiO2/Al2O3Up to 9 to 50, unit cell constant a02.425 to 2.440 nm. The ultrastable molecular sieve prepared by the method has high silicon-aluminum ratio and small unit cell constant, contains a certain amount of rare earth, but does not relate to the preparation of a high-stability molecular sieve in a molecular sieve with secondary pores, and has poor accessibility of an active center and low activity.
In conclusion, the ultrastable Y-type molecular sieve prepared by the prior art is difficult to have higher heavy oil catalytic cracking activity and better coke selectivity at the same time.
Disclosure of Invention
The invention mainly aims to provide a modified Y-type molecular sieve, wherein the content of rare earth is 5-12 wt% calculated by rare earth oxide, the content of sodium is not more than 0.5 wt% calculated by sodium oxide, the content of zinc is 0.5-5 wt% calculated by zinc oxide, and the ratio of framework silicon to aluminum is SiO2/Al2O3The molar ratio is 7-14, the mass of non-framework aluminum accounts for not more than 10% of the total mass of aluminum, and the pore volume of secondary pores with the pore diameter of 2-100 nm accounts for 20-38% of the total pore volume.
According to an embodiment of the present invention, the total pore volume is 0.36 to 0.48 mL/g.
According to an embodiment of the present invention, the secondary pores having a pore diameter of 2 to 100nm have a pore volume of 28 to 38% by volume of the total pores.
According to an embodiment of the present invention, the pore volume of the secondary pores having a pore diameter of 8 to 100nm accounts for 40 to 80% of the pore volume of the secondary pores having a pore diameter of 2 to 100 nm.
According to an embodiment of the present invention, the unit cell constant of the modified Y-type molecular sieve is 2.440-2.455 nm.
According to one embodiment of the present invention, the rare earth content is 5.5 to 10 wt%, the sodium content is 0.15 to 0.3 wt%, the unit cell constant is 2.442 to 2.453nm, and the framework silica-alumina ratio is 8.5 to 12.6.
According to an embodiment of the present invention, the non-framework aluminum accounts for 5 to 9.5% by mass of the total aluminum.
According to one embodiment of the present invention, the ratio of the amount of B acid to the amount of L acid is not less than 3.50 as measured by pyridine adsorption infrared method at 350 ℃.
The embodiment of the invention further provides a preparation method of the modified Y-type molecular sieve, which comprises the following steps:
(1) carrying out ion exchange on the NaY molecular sieve and a rare earth salt solution;
(2) roasting the ion exchanged molecular sieve;
(3) reacting the roasted molecular sieve with silicon tetrachloride;
(4) carrying out acid treatment on the molecular sieve reacted with the silicon tetrachloride; and
(5) and (3) impregnating the acid-treated molecular sieve with a zinc salt solution.
According to an embodiment of the invention, in the step (1), the exchange temperature of ion exchange is 15-95 ℃, the exchange time is 30-120 minutes, and the mass ratio of the NaY molecular sieve, the rare earth salt and the solvent water is 1 (0.01-0.18) to (5-20).
According to an embodiment of the present invention, the calcination in the step (2) is performed at 350 to 520 ℃ in an atmosphere having a water vapor content of 30 to 95 vol%, and the calcination time is 4.5 to 7 hours.
According to one embodiment of the invention, in the step (3), the reaction temperature is 200-650 ℃, the reaction time is 10 minutes to 5 hours, and the mass ratio of the silicon tetrachloride to the calcined molecular sieve is (0.1-0.7): 1.
According to an embodiment of the present invention, in the step (4), the temperature of the acid treatment is 60 to 100 ℃, and the treatment time is 1 to 4 hours.
According to one embodiment of the invention, the acid treatment comprises the step of reacting the molecular sieve treated in the step (3) with acid in solvent water, wherein the mass ratio of the acid to the molecular sieve treated in the step (3) is (0.001-0.15): 1, and the mass ratio of the water to the molecular sieve treated in the step (3) is (5-20): 1.
According to one embodiment of the invention, the acid comprises one or more of organic acid and inorganic acid, the mass ratio of the inorganic acid to the molecular sieve treated in the step (3) is (0.001-0.05): 1, and the mass ratio of the organic acid to the molecular sieve treated in the step (3) is (0.02-0.10): 1.
According to an embodiment of the present invention, the organic acid is selected from one or more of oxalic acid, malonic acid, succinic acid, methylsuccinic acid, malic acid, tartaric acid, citric acid, and salicylic acid; the inorganic acid is selected from one or more of phosphoric acid, hydrochloric acid, nitric acid and sulfuric acid.
According to an embodiment of the invention, the step (5) comprises roasting the impregnated molecular sieve, wherein the impregnation temperature is 10-60 ℃, the roasting temperature is 350-600 ℃, and the roasting time is 1-4 hours.
The modified Y-type molecular sieve provided by the embodiment of the invention has higher crystallinity, thermal stability and hydrothermal stability, is rich in secondary pores, is used for LCO (light cycle oil) hydrocatalytic cracking, has lower coke selectivity, and has higher conversion efficiency of reactants.
Detailed Description
Exemplary embodiments that embody features and advantages of the invention are described in detail below. It is to be understood that the invention is capable of other and different embodiments and its several details are capable of modification without departing from the scope of the invention, and that the description is intended to be illustrative in nature and not to be construed as limiting the invention. Wherein, the mass of each molecular sieve is calculated on a dry basis; the mass (content) of the rare earth salt and the rare earth is calculated according to the mass (content) of the rare earth oxide; the mass (content) of sodium is calculated by the mass (content) of sodium oxide; the mass (content) of zinc and zinc salt is calculated by the mass (content) of zinc oxide.
One embodiment of the invention provides a modified Y-type molecular sieve which is high in crystallinity, thermal stability and hydrothermal stability, rich in secondary pores and capable of being used as an active component of an LCO catalytic cracking catalyst.
An embodiment of the inventionThe modified Y-type molecular sieve of formula (I) wherein the rare earth content is 5-12 wt% in terms of rare earth oxide, the sodium content is not more than 0.5 wt% in terms of sodium oxide, for example less than 0.2 wt%, the zinc content is 0.5-5 wt% in terms of zinc oxide, and the framework silica-alumina ratio is SiO2/Al2O3The molar ratio is 7-14, the mass of non-framework aluminum accounts for not more than 10% of the total mass of aluminum, and the pore volume of secondary pores with the pore diameter of 2-100 nm accounts for 20-38% of the total pore volume.
In one embodiment, the framework silica to alumina ratio (SiO) of the modified Y-type molecular sieve2/Al2O3The molar ratio) may be 7.8 to 13, further may be 8.5 to 12.6, further may be 8.7 to 12, for example, 8.79, 10.87, 11.95, and the like.
In one embodiment, the rare earth content (rare earth oxide content) of the modified Y-type molecular sieve may be 5.5 to 10 wt%, for example, 5.7%, 6.4%, 8.6%, etc.
In one embodiment, the sodium content (sodium oxide content) of the modified Y-type molecular sieve may be 0.05 to 0.5 wt%, further 0.1 to 0.4 wt%, further 0.15 to 0.3 wt%, further 0.2 to 0.3 wt%, for example, 0.22%, 0.26%, 0.29%, or the like.
In one embodiment, the zinc content (zinc oxide content) of the modified Y-type molecular sieve may be 1 to 4 wt%, for example, 1%, 2%, 4%, etc.
In one embodiment, the percentage of the non-framework aluminum in the modified Y-type molecular sieve to the total aluminum may be 5 to 9.5% by mass or 3 to 9% by mass, and further may be 6 to 9.5% by mass, for example, 6.5%, 8.2%, 9.3% by mass.
In one embodiment, the unit cell constant of the modified Y-type molecular sieve may be 2.440-2.455 nm, further 2.442-2.453 nm, and further 2.442-2.451 nm, such as 2.442nm, 2.445nm, 2.45nm, etc.
In one embodiment, the total pore volume of the modified Y-type molecular sieve may be 0.36-0.48 mL/g, further 0.38-0.45 mL/g or 0.4-0.48 mL/g, further 0.38-0.42 mL/g, such as 0.387mL/g, 0.398mL/g, 0.415mL/g, and the like.
In one embodiment, the pore volume of the secondary pores having a pore diameter (diameter) of 2.0nm to 100nm may be 0.08 to 0.18mL/g, and further may be 0.10 to 0.16mL/g, for example, 0.112mL/g, 0.118mL/g, 0.156mL/g, and the like.
In one embodiment, the pore volume percentage of the secondary pores having a pore diameter (diameter) of 2.0nm to 100nm to the total pore volume may be 25% to 38%, further 28% to 38%, and also 25% to 35%, for example, 28.94%, 29.65%, 37.59%, and the like.
In one embodiment, the modified Y-type molecular sieve is an ultrastable Y molecular sieve rich in secondary pores, and the secondary pore distribution curve with the pore diameter of 2nm to 100nm is in double-variable pore distribution, wherein the most variable pore diameter of the secondary pores with smaller pore diameter is 2nm to 5nm, and the most variable pore diameter of the secondary pores with larger pore diameter is 8nm to 20nm, preferably 8nm to 18 nm.
In one embodiment, the ratio of the pore volume of the secondary pores having a pore diameter of 8nm to 100nm (total volume of pores having a pore diameter of 2nm to 100 nm)/the pore volume of the total secondary pores (total volume of pores having a pore diameter of 2nm to 100nm) may be 40 to 80%, further 45 to 77%, further 45 to 55% or 55 to 77%, for example, 59.81%, 68.15%, 75%, 75.21%, etc.
In one embodiment, the specific surface area of the modified Y-type molecular sieve can be 600-680 m2A concentration of 610 to 670m2(ii) a total of 640 to 670m2Per g, e.g. 648m2/g、654m2/g、669m2And/g, etc.
In one embodiment, the lattice collapse temperature of the modified Y-type molecular sieve is not lower than 1060 ℃, may be 1060 to 1085 ℃, may be 1064 to 1081 ℃, and may be 1065 to 1080 ℃, for example, 1064 ℃, 1075 ℃, 1081 ℃ and the like.
In one embodiment, the ratio of the amount of the B acid to the amount of the L acid in the strong acid amount of the modified Y-type molecular sieve measured at 350 ℃ by pyridine adsorption infrared method is not less than 3.50, for example, 3.5 to 6.0, further 3.6 to 5.5, 3.5 to 5.0, or not less than 4.5, further 3.5 to 4.6, or 3.8 to 5.6, and particularly 3.65, 4.12, 4.70, etc.
In one embodiment, the modified Y-type molecular sieve has a crystal retention of 38% or more, for example, 38 to 65%, further 46 to 60%, further 52 to 60%, for example, 52.65%, 58.52%, 59.39%, or the like, after aging for 17 hours at 800 ℃, under normal pressure (1atm) and in a 100 vol% steam atmosphere.
In one embodiment, the relative crystallinity of the modified Y-type molecular sieve is not less than 70%, for example, 70 to 80%; further, the content may be not less than 71%, for example, 71 to 77%, specifically 71.5%, 72.3%, 75.8%, or the like.
The modified Y-type molecular sieve provided by the embodiment of the invention has strong cracking capability and weaker hydrogen transfer performance, can be used as an active component of a catalytic cracking catalyst, and is used for processing catalytic cracking of hydrogenated LCO; the catalytic cracking catalyst with the molecular sieve as an active component is used for processing hydrogenated LCO and has high LCO conversion efficiency, lower coke selectivity, higher gasoline yield rich in BTX, and more ethylene and propylene in a gas product.
An embodiment of the present invention further provides a preparation method of the modified Y-type molecular sieve, which comprises the following steps:
(1) carrying out ion exchange reaction on the NaY molecular sieve and a rare earth salt solution to obtain a Y-type molecular sieve with reduced sodium oxide content and unchanged unit cell size and containing rare earth;
(2) roasting the Y-type molecular sieve which contains rare earth and has unchanged unit cell size after ion exchange to obtain the Y-type molecular sieve with reduced unit cell constant;
(3) contacting and reacting the Y-shaped molecular sieve with the reduced unit cell constant obtained by roasting with silicon tetrachloride gas to perform dealuminization and silicon supplementation to obtain a gas-phase ultra-stable modified Y-shaped molecular sieve;
(4) carrying out acid treatment on the gas-phase ultra-stable modified Y-type molecular sieve reacted with silicon tetrachloride; and (5) impregnating the acid-treated molecular sieve with a zinc salt solution.
In one embodiment, step (1) comprises contacting NaY molecular sieve with a rare earth salt solution to perform an ion exchange reaction, filtering, washing, and drying to obtain a rare earth-containing Y-type molecular sieve with reduced sodium oxide content.
In one embodiment, the NaY molecular sieve in step (1) has a unit cell constant of 2.465-2.472 nm and a framework silicon-aluminum ratio (SiO)2/Al2O3Molar ratio) of 4.5 to 5.2, a relative crystallinity of 85% or more, for example, 85 to 95%, and a sodium oxide content of 13.0 to 13.8 wt%.
In one embodiment, after the ion exchange treatment in step (1), the unit cell constant of the molecular sieve is 2.465-2.472 nm, and the sodium content is not more than 9.0 wt% in terms of sodium oxide.
In one embodiment, after the ion exchange treatment in step (1), the sodium oxide content of the molecular sieve may be 4 to 9 wt%, and further may be 5.5 to 8.5 wt% or 5.5 to 7.5 wt%; the content of the rare earth oxide may be 5.5 to 14 wt%, further 7 to 14 wt%, and further 7.5 to 13 wt%.
In one embodiment, the mass ratio of the NaY molecular sieve (calculated on a dry basis), the rare earth salt (calculated on a rare earth oxide) and the water in the step (1) can be 1 (0.01-0.18) to (5-20), or 1 (0.01-0.18) to (5-15).
In one embodiment, the rare earth salt is rare earth chloride or rare earth nitrate, and the rare earth may be, but is not limited to, one or more of La, Ce, Pr, and Nd.
In one embodiment, the exchange temperature of the ion exchange reaction is 15-95 ℃, for example, 90 ℃; further, the temperature can be 20-65 ℃ or 65-95 ℃, and further, the temperature can be 20-60 ℃, for example, 25 ℃; further, the temperature can be 30-45 ℃; the exchange time may be 30 to 120 minutes, further 45 to 90 minutes, for example 60 minutes.
In one embodiment, step (1) comprises: mixing NaY molecular sieve with water, adding rare earth salt and/or rare earth salt solution while stirring to exchange rare earth ions and sodium ions, filtering and washing; wherein, the purpose of washing is to wash out the exchanged sodium ions, and deionized water or decationized water can be used for washing.
In one embodiment, the NaY molecular sieve, the rare earth salt, and the water are mixed to form a mixture, and the NaY molecular sieve and the water are slurried prior to adding the aqueous solution of the rare earth salt and/or the rare earth salt to the slurry.
In one embodiment, according to the NaY molecular sieve rare earth salt H2And (5) 15-15) mixing NaY molecular sieve, rare earth salt and water to form a mixture, and stirring at 15-95 ℃ for 30-120 minutes to exchange rare earth ions and sodium ions.
In one embodiment, the mass ratio of the NaY molecular sieve to water in step (1) may be 1 (6-20), and further may be 1 (7-15).
In one embodiment, the calcination treatment in step (2) is to calcine the ion exchanged molecular sieve at 350-520 ℃ for 4.5-7 hours in an atmosphere of 30-95 vol% steam (also referred to as 30-90 vol% steam or 30-90 vol% steam).
In one embodiment, the baking temperature in step (2) is 380-500 ℃, and further 380-480 ℃.
In one embodiment, the calcination in step (2) is performed in an atmosphere of 40-80 vol% or 70-95 vol% steam.
In one embodiment, the baking time in step (2) is 5 to 6 hours.
In one embodiment, the calcination treatment may be performed at a temperature of 390 ℃, 450 ℃ or 470 ℃, under an atmosphere of 50 vol%, 70 vol% or 80 vol% water vapor.
In one embodiment, the water vapor atmosphere in step (2) further contains other gases, such as one or more of air, helium or nitrogen.
In one embodiment, the unit cell constant of the molecular sieve treated in step (2) is reduced to 2.450nm to 2.462nm, and the water content is not more than 1 wt%.
In one embodiment, the molecular sieve calcined in step (2) is dried such that the water content of the Y-type molecular sieve having a reduced unit cell constant is less than 1 wt%. The drying can be carried out in a roasting mode, the roasting temperature can be 450-650 ℃, the drying can be carried out in the atmosphere of dry air, the drying time can be 1-5, and the drying time can be further 2-4 hours.
In one embodiment, the reduced unit cell constant Y-type molecular sieve sample obtained in step (2) has a solids content of not less than 99 wt%.
In one embodiment, the mass ratio of the silicon tetrachloride used in step (3) to the molecular sieve subjected to calcination treatment (on a dry basis) may be (0.1 to 0.7):1, and may further be (0.3 to 0.6):1, for example, 0.25:1, 0.45:1, 0.5:1, and the like.
In one embodiment, the reaction temperature of the molecular sieve and the silicon tetrachloride in the step (3) may be 200 ℃ to 650 ℃, and further may be 350 ℃ to 500 ℃, for example, 400 ℃, 490 ℃, and the like.
In one embodiment, the reaction time of the molecular sieve in the step (3) and the silicon tetrachloride is 10 minutes to 5 hours, and then washing and filtering are carried out to remove Na remained in the molecular sieve+、Cl-And Al3+And the like soluble by-products.
In one embodiment, the washing operation of step (3) may be performed using water, such as decationized water or deionized water. The washing conditions were: the mass ratio of the water to the molecular sieve can be (5-20): 1, and further can be (6-15): 1; the washing temperature is 30-60 ℃; the pH value of the washing liquid can be 2.5-5.0. Usually, no free Na is detected in the washing solution after washing+，Cl-And Al3+And (3) plasma.
In one embodiment, step (4) is to contact the molecular sieve obtained in step (3) with an acid solution to perform a reaction, so as to perform channel cleaning (modification), or acid treatment modification.
In one embodiment, step (4) comprises mixing the molecular sieve obtained in step (3) with an acid solution, reacting for a certain period of time, separating the reacted molecular sieve from the acid solution, for example by filtration, and optionally washing to remove Na remaining in the zeolite and optionally drying+，Cl-And Al3+And the like soluble by-products.
In step (4) of one embodiment, the washing conditions may be: the mass ratio of the washing water to the molecular sieve can be (5-20): 1, further can be (6-15): 1, the pH value of the washing liquid can be 2.5-5.0, and the washing temperature is 30-60 ℃.
In step (4) of an embodiment, the temperature of the reaction between the molecular sieve and the acid solution is 60 to 100 ℃, further 80 to 99 ℃, further 85 to 98 ℃, further 88 to 98 ℃, for example, 90 ℃, 93 ℃, 95 ℃.
In step (4) of an embodiment, the contact time/reaction time of the molecular sieve and the acid solution is 60 minutes or more, may be 60 to 240 minutes, and may be 90 to 180 minutes.
In step (4) of one embodiment, the mass ratio of the acid to the molecular sieve (on a dry basis) may be (0.001-0.15): 1, further may be (0.002-0.1): 1, and further may be (0.01-0.05): 1; the mass ratio of water to the molecular sieve on a dry basis is (5-20): 1, and further may be (8-15): 1.
In step (4) of an embodiment, the acid includes at least one organic acid and at least one inorganic acid. Preferably, the mineral acid is an acid of medium or greater strength.
In one embodiment, the organic acid may be oxalic acid, malonic acid, succinic acid (succinic acid), methylsuccinic acid, malic acid, tartaric acid, citric acid, salicylic acid, or the like.
In one embodiment, the medium-strength or higher inorganic acid may be phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, or the like.
In one embodiment, the mass ratio of the organic acid to the molecular sieve obtained in step (3) may be (0.01 to 0.10):1, further may be (0.02 to 0.14):1, further may be (0.02 to 0.1):1, (0.02 to 0.05):1, (0.05 to 0.08):1, or (0.03 to 0.1): 1.
In one embodiment, the mass ratio of the inorganic acid to the molecular sieve may be (0.001-0.06): 1, further may be (0.01-0.05): 1, and further may be (0.02-0.05): 1.
In one embodiment, the pore cleaning modification in the step (4) is performed in two steps, wherein an inorganic acid with a medium strength or higher is firstly used for contact reaction with a molecular sieve, the temperature of the contact reaction can be 80-99 ℃, preferably 90-98 ℃, and the reaction time can be 60-120 minutes; and then contacting the treated molecular sieve with organic acid, wherein the temperature of the contact reaction can be 80-99 ℃, preferably 90-98 ℃, and the reaction time can be 60-120 minutes.
In one embodiment, the zinc salt of step (5) may be zinc nitrate or zinc chloride.
In one embodiment, the step (5) includes preparing the zinc salt into a solution, wherein the weight ratio of the zinc salt (calculated as ZnO) to the molecular sieve is ZnO-molecular sieve (0.5-5.0): 100, and the concentration of the zinc salt solution may be 0.020-0.080 g/ml.
In one embodiment, the dipping temperature in step (5) is 10 to 60 ℃, the dipped sample can be dried for 5 hours at a temperature of 130 ℃, and then roasted, the roasting temperature can be 350 to 600 ℃, and the roasting time can be 1 to 4 hours.
The preparation method of the modified Y-type molecular sieve of one embodiment of the invention comprises the following steps:
(1) carrying out ion exchange reaction on a NaY molecular sieve (also called NaY zeolite) and a rare earth salt solution, filtering and washing to obtain a Y-type molecular sieve containing rare earth and having a conventional unit cell size and a reduced sodium oxide content; ion exchange is carried out for 30-120 minutes under the conditions of stirring and the temperature of 15-95 ℃, preferably 65-95 ℃;
(2) roasting the rare earth-containing Y-type molecular sieve with the normal unit cell size and reduced sodium oxide content obtained in the step (1) at the temperature of 350-480 ℃ for 4.5-7 hours in an atmosphere containing 30-90 vol% of water vapor, and drying to obtain the Y-type molecular sieve with the reduced unit cell constant and the water content of less than 1 wt%, wherein the unit cell constant is 2.450-2.462 nm;
(3) a sample of Y-type molecular sieve having a reduced unit cell constant and a water content of less than 1 wt% was mixed with heat vaporized SiCl4Gas contact of SiCl4The mass ratio of the Y-type molecular sieve with the reduced unit cell constant and the water content of less than 1 wt% (calculated on a dry basis) is (0.1-0.7): 1, the Y-type molecular sieve is contacted and reacted for 10 minutes to 5 hours under the condition of the temperature of 200-650 ℃, and the Y-type molecular sieve is optionally washed and optionally filtered to obtain the modified ultra-stable gas phase treatmentA Y-type molecular sieve;
(4) and (4) contacting the gas-phase superstable modified Y-shaped molecular sieve obtained in the step (3) with an acid solution for acid treatment modification. Mixing the modified Y-type molecular sieve subjected to gas phase ultra-stable treatment in the step (3), inorganic acid with medium strength and water, contacting for at least 30 minutes, such as 60-120 minutes, at 80-99 ℃, preferably 90-98 ℃, then adding organic acid, contacting for at least 30 minutes, such as 60-120 minutes, at 80-99 ℃, preferably 90-98 ℃, filtering, optionally washing and optionally drying to obtain the modified Y-type molecular sieve; wherein the mass ratio of the organic acid to the molecular sieve on a dry basis is preferably (0.02-0.10): 1, the mass ratio of the inorganic acid having a medium strength or higher to the molecular sieve on a dry basis is preferably (0.01-0.06): 1, and the mass ratio of the water to the molecular sieve is preferably (5-20): 1.
(5) And (3) dipping the modified Y molecular sieve obtained in the step (4) by using a zinc salt solution, wherein the dipping temperature is 10-60 ℃, the dipped sample is dried for 5 hours at 130 ℃, and then roasted for 1-4 hours at the roasting condition of 350-600 ℃.
The preparation method of the modified Y-type molecular sieve provided by the embodiment of the invention can be used for preparing the high-silicon Y-type molecular sieve which is high in crystallinity, high in thermal stability and high in hydrothermal stability and is rich in secondary pores.
The preparation method of the modified Y-type molecular sieve provided by the embodiment of the invention can ensure that the molecular sieve has higher crystallinity under the condition of greatly improving the ultrastable degree, and the prepared molecular sieve has the advantages of uniform aluminum distribution, low non-framework aluminum content, smooth secondary pore channels and higher specific surface area under the condition of higher secondary pores.
The modified Y-type molecular sieve prepared by the preparation method provided by the embodiment of the invention can be used for processing hydrogenated LCO, and has the advantages of high LCO conversion efficiency (high LCO effective conversion rate), low coke selectivity, higher gasoline yield rich in BTX, and more ethylene and propylene in gas products.
The preparation and application of the modified Y-type molecular sieve according to an embodiment of the present invention will be described in detail with reference to the following specific examples, wherein the details of the raw materials and the related tests are as follows.
Raw materials
In the examples and comparative examples, the NaY molecular sieve (also called NaY zeolite) was supplied by the zeuginese corporation, petrochemical catalyst ltd, china, and had a sodium oxide content of 13.5 wt% and a framework silica-to-alumina ratio (SiO) of2/Al2O3Molar ratio) of 4.6, unit cell constant 2.470nm, relative crystallinity 90%.
The chlorinated rare earth and the nitric acid rare earth are chemical pure reagents produced by Beijing chemical plants; the zinc nitrate or the zinc chloride is a chemical pure reagent produced by a Beijing chemical plant; the pseudoboehmite is an industrial product produced by Shandong aluminum factories, and has the solid content of 61 wt%; the kaolin is kaolin specially used for a cracking catalyst produced by Suzhou China kaolin company, and the solid content is 76 wt%; the alumina sol was provided by the Qilu division of China petrochemical catalyst, Inc., in which the alumina content was 21 wt%. The chemical reagents used in the comparative examples and examples are not specifically noted, and are specified to be chemically pure.
Analytical method
In each comparative example and example, the elemental content of the zeolite was determined by X-ray fluorescence spectroscopy.
The cell constants and relative crystallinity of zeolite were measured by X-ray powder diffraction (XRD) using RIPP 145-90 and RIPP146-90 standard methods (compiled by petrochemical analysis (RIPP test methods) Yancui et al, published by scientific Press, 1990).
The framework silica to alumina ratio of the zeolite is calculated from the formula: SiO 22/Al2O3＝(2.5858-a0)×2/(a0-2.4191)]Wherein, a0Is the unit cell constant in nm.
The total silicon-aluminum ratio of the zeolite is calculated according to the content of Si and Al elements measured by an X-ray fluorescence spectrometry, and the ratio of the framework Al to the total Al can be calculated by the framework silicon-aluminum ratio measured by an XRD method and the total silicon-aluminum ratio measured by an XRF method, so that the ratio of non-framework Al to the total Al can be calculated.
The crystal structure collapse temperature was determined by Differential Thermal Analysis (DTA).
Infrared ray of pyridine adsorption is adopted for acid center type and acid amount of molecular sieveAnd (4) analyzing and measuring. An experimental instrument: model Bruker IFS113V FT-IR (fourier transform infrared) spectrometer, usa. The experimental method for measuring the acid content at 350 ℃ by using a pyridine adsorption infrared method comprises the following steps: and (3) carrying out self-supporting tabletting on the sample, and placing the sample in an in-situ cell of an infrared spectrometer for sealing. Heating to 400 deg.C, and vacuumizing to 10 deg.C-3And Pa, keeping the temperature for 2h, and removing gas molecules adsorbed by the sample. The temperature is reduced to room temperature, pyridine vapor with the pressure of 2.67Pa is introduced to keep the adsorption equilibrium for 30 min. Then heating to 350 ℃, and vacuumizing to 10 DEG C-3Desorbing for 30min under Pa, reducing to room temperature for spectrography, scanning wave number range: 1400cm-1～1700cm-1And obtaining the pyridine absorption infrared spectrogram of the sample desorbed at 350 ℃. According to pyridine absorption infrared spectrogram of 1540cm-1And 1450cm-1The strength of the adsorption peak is characterized to obtain the medium-strength molecular sieve
Relative amount of acid center (B acid center) to Lewis acid center (L acid center).
The secondary pore volume was determined as follows: the total pore volume of the molecular sieve was determined from the adsorption isotherm according to RIPP 151-90 Standard method, "petrochemical analysis method (RIPP test method)," compiled by Yankee corporation, published in 1990 ", then the micropore volume of the molecular sieve was determined from the adsorption isotherm according to the T-plot method, and the secondary pore volume was obtained by subtracting the micropore volume from the total pore volume.
Example 1
2000Kg (dry basis) of SiO skeleton2/Al2O34.6 NaY zeolite (sodium oxide content 13.5 wt%, available from the Kikukushi company, China petrochemical catalyst, Qilu division) was charged in a vessel containing 20m3Stirring the mixture evenly at 25 ℃ in a primary exchange tank of water, and then adding 600L of RECl3Solutions (RECl)3Rare earth concentration in solution as RE2O3Calculated as 319g/L, RE is the mixed rare earth of La and Ce, and La is calculated by the mass of the rare earth oxide2O3:Ce2O32) continuously stirring for 60 minutes, filtering, washing, and drying a filter cake in a flash evaporation drying furnace; obtaining conventional cells containing rare earths with reduced sodium oxide contentThe size Y-type molecular sieve had a sodium oxide content of 7.0 wt% and a unit cell constant of 2.471 nm.
Then, the Y-type molecular sieve with the normal unit cell size and the reduced sodium oxide content and containing rare earth is sent into a roasting furnace to be roasted for 6 hours at the temperature of 390 ℃ and under the condition of 50% of water vapor (the atmosphere contains 50% of water vapor by volume); then, the zeolite was calcined at 500 ℃ in a dry air atmosphere (water vapor content less than 1 vol%) for 2.5 hours to a water content of less than 1 wt% to obtain a Y-type molecular sieve having a reduced unit cell constant of 2.455 nm.
Then, directly feeding the Y-shaped molecular sieve material with the reduced unit cell constant into a continuous gas-phase ultra-stable reactor for gas-phase ultra-stable reaction. The gas phase hyperstable reaction process of the molecular sieve in the continuous gas phase hyperstable reactor and the subsequent tail gas absorption process are carried out according to the method disclosed in embodiment 1 of the CN103787352A patent, and the process conditions are that SiCl is adopted4The mass ratio of the Y-type zeolite is 0.5:1, the feeding amount of the molecular sieve is 800 kg/h, and the reaction temperature is 400 ℃.
Separating the molecular sieve material after gas phase superstable reaction by a gas-solid separator, and feeding into a secondary exchange tank, wherein 20m is added in advance in the secondary exchange tank3The molecular sieve material (2) added into the secondary exchange tank has a mass of 2000Kg (dry basis), stirred uniformly, and then added with 0.6m hydrochloric acid with a concentration of 10 wt%3Then, the temperature is raised to 90 ℃, the mixture is stirred for 60 minutes, then, 140Kg of citric acid is added, the stirring is continued for 60 minutes at 90 ℃, and then, the mixture is filtered and washed.
2300 ml of Zn (NO) with a concentration of 0.020 g/ml were slowly added to the obtained filter cake3)2And (3) drying the sample after the solution is soaked for 4 hours at 130 ℃ for 5 hours, then roasting the sample for 3 hours at 400 ℃ to obtain a modified Y-type molecular sieve (molecular sieve is also called zeolite) product, which is recorded as SZ-1.
Table 1 shows the composition of SZ-1, unit cell constant, relative crystallinity, framework Si/Al ratio, structural collapse temperature, specific surface area, percentage of secondary pores with larger pore diameter (8 nm-100 nm) in total secondary pores (2-100 nm), and total secondary pore volume.
After SZ-1 is aged for 17 hours at 800 ℃, 1atm and 100 percent of water vapor in a naked state, the relative crystallinity of the molecular sieve before and after the SZ-1 is aged is analyzed by an XRD method and the relative crystallinity retention after the aging is calculated, and the result is shown in a table 2, wherein:
example 2
2000Kg (dry basis) of SiO skeleton2/Al2O34.6 NaY zeolite (sodium oxide content 13.5 wt%, available from the Kikukushi company, China petrochemical catalyst, Qilu division) was charged in a vessel containing 20m3In a first exchange tank for removing the cationic water, stirring evenly at 90 ℃, and then adding 800L RECl3Solutions (RECl)3Rare earth concentration in solution as RE2O3Calculated as 319g/L, RE is the mixed rare earth of La and Ce, and La is calculated by the mass of the rare earth oxide2O3:Ce2O33:2), stirring for 60 minutes; filtering, washing, and drying the filter cake in a flash drying furnace to obtain the rare earth-containing Y-type molecular sieve with the normal unit cell size and the reduced sodium oxide content, wherein the sodium oxide content is 5.5 wt%, and the unit cell constant is 2.471 nm.
Then, the Y-type molecular sieve with the normal unit cell size and the reduced sodium oxide content and containing the rare earth is sent into a roasting furnace to be roasted for 5.5 hours at the temperature (atmosphere temperature) of 450 ℃ and in the atmosphere of 80 percent of water vapor; and then, roasting and drying the molecular sieve material in a roasting furnace at the roasting temperature of 500 ℃ in a dry air atmosphere for 2 hours to ensure that the water content is lower than 1 wt%, thus obtaining the Y-type molecular sieve with the reduced unit cell constant of 2.461 nm.
Then, the Y-shaped molecular sieve material with the reduced unit cell constant is directly sent into a continuous gas-phase ultra-stable reactor for gas-phase ultra-stable reaction. The gas phase hyperstable reaction process of the molecular sieve in the continuous gas phase hyperstable reactor and the subsequent tail gas absorption process are carried out according to the method disclosed in embodiment 1 of the CN103787352A patent, and the process conditions are as follows: SiCl4The mass ratio of Y-type zeolite is 0.25:1, the molecular sieve is addedThe amount of the feed was 800 kg/h and the reaction temperature was 490 ℃.
Separating the molecular sieve material after gas phase superstable reaction by a gas-solid separator, and feeding into a secondary exchange tank, wherein 20m is added in advance in the secondary exchange tank3Adding the decationized water into a molecular sieve material with the mass of 2000Kg (dry basis weight) in a secondary exchange tank, uniformly stirring, and then adding a sulfuric acid solution with the concentration of 7 wt% and the mass of 0.9m3And heated to 93 deg.C, stirred for 80 min, then added with 70Kg of citric acid and 50Kg of tartaric acid, stirred for 70 min at 93 deg.C, filtered and washed.
2300 ml of ZnCl with a concentration of 0.030 g/ml are slowly added to the obtained filter cake2And (3) soaking the solution for 4 hours, drying the soaked sample at 130 ℃ for 5 hours, then roasting the sample for 3.5 hours under the roasting condition of 380 ℃ to obtain a modified Y-type molecular sieve product, which is recorded as SZ-2.
Table 1 shows the composition of SZ-2, unit cell constant, relative crystallinity, framework Si/Al ratio, structural collapse temperature, specific surface area, percentage of secondary pores with larger pore diameter (8-100 nm) in total secondary pores (2-100 nm), and total secondary pore volume.
After aging SZ-2 in a naked state by 100% steam at 800 ℃ for 17 hours, the crystallinity of the zeolite before and after aging of the SZ-2 is analyzed by an XRD method and the relative crystal retention after aging is calculated, and the result is shown in Table 2.
Example 3
2000Kg (dry basis) of SiO skeleton2/Al2O34.6 NaY zeolite (sodium oxide content 13.5 wt%, available from the Kikukushi company, China petrochemical catalyst, Qilu division) was charged in a vessel containing 20m3Stirring in a first exchange tank for removing cationic water at 95 deg.C, and adding 570L RECl3Solutions (RECl)3Rare earth concentration in solution as RE2O3Calculated as 319g/L, RE is the mixed rare earth of La and Ce, and La is calculated by the mass of the rare earth oxide2O3:Ce2O32) is continuously stirred for 60 minutes, then the mixture is filtered and washed, and the filter cake is continuously sent into a flash evaporation drying furnace for drying to obtain the conventional unit cell size containing rare earth with reduced sodium oxide contentThe Y-type molecular sieve of (1) has a sodium oxide content of 7.5% by weight and a unit cell constant of 2.471 nm.
Then, the Y-shaped molecular sieve with the normal unit cell size and the reduced sodium oxide content and containing the rare earth is sent into a roasting furnace to be roasted for 5 hours at the roasting temperature of 470 ℃ under the atmosphere containing 70 volume percent of water vapor; and then, roasting and drying the molecular sieve material in a roasting furnace, wherein the roasting temperature is 500 ℃, the roasting atmosphere is a dry air atmosphere, the roasting time is 1.5 hours, the water content is lower than 1 weight percent, and the Y-type molecular sieve with the reduced unit cell constant is obtained, and the unit cell constant is 2.458 nm.
Then, the Y-shaped molecular sieve material with the reduced unit cell constant is sent into a continuous gas-phase ultra-stable reactor to carry out gas-phase ultra-stable reaction. The gas phase hyperstable reaction process of the molecular sieve in the continuous gas phase hyperstable reactor and the subsequent tail gas absorption process are carried out according to the method disclosed in embodiment 1 of the CN103787352A patent, and the process conditions are as follows: SiCl4The mass ratio of the Y-type zeolite is 0.45:1, the feeding amount of the molecular sieve is 800 kg/h, and the reaction temperature is 400 ℃.
Separating the molecular sieve material after gas phase superstable reaction by a gas-solid separator, and feeding into a secondary exchange tank, wherein 20m is added in advance in the secondary exchange tank3The decationized water was added to a mass of 2000Kg (dry basis) of the molecular sieve material in the secondary exchange tank, stirred well, and then 5 wt% nitric acid 1.2m was slowly added3And heated to 95 deg.c, and stirred for 90 min, then added with citric acid 90Kg and oxalic acid 40Kg, stirred for 70 min at 93 deg.c, filtered and washed.
To the resulting filter cake was slowly added 2500 ml of Zn (NO) at a concentration of 0.070 g/ml3)2The sample after 4 hours of solution impregnation is firstly dried for 5 hours at 130 ℃, then roasted for 2 hours under the roasting condition of 500 ℃, and the sample is recorded as SZ-3.
Table 1 shows the composition of SZ-3, unit cell constant, relative crystallinity, framework Si/Al ratio, structural collapse temperature, specific surface area, percentage of secondary pores with larger pore diameter (pore diameter of 80-100 nm) to total secondary pores (2-100 nm), and total secondary pore volume.
After aging SZ-3 in a bare state with 100% steam at 800 ℃ for 17 hours, the crystallinity of the zeolite before and after aging of SZ-3 was analyzed by XRD and the relative crystal retention after aging was calculated, and the results are shown in Table 2.
Comparative example 1
2000 g of NaY molecular sieve (dry basis) is added into 20L of decationized aqueous solution, stirred to be uniformly mixed, and 1000 g of (NH) is added4)2SO4Stirring, heating to 90-95 ℃ and keeping for 1 hour, then filtering, washing, drying a filter cake at 120 ℃, and then carrying out hydrothermal modification treatment (roasting at 650 ℃ under 100% of water vapor for 5 hours).
Then, the molecular sieve after the hydrothermal modification treatment is added into 20 liters of decationized aqueous solution to be stirred and evenly mixed, and 1000 g (NH) is added4)2SO4Stirring, heating to 90-95 ℃, keeping for 1 hour, then filtering, washing, drying a filter cake at 120 ℃, and then carrying out second hydrothermal modification treatment (roasting at 650 ℃ under 100% of water vapor for 5 hours) to obtain the rare earth-free hydrothermal ultrastable Y-type molecular sieve which is subjected to twice ion exchange and twice hydrothermal ultrastable, and is marked as DZ-1.
Table 1 shows the composition of DZ-1, unit cell constant, relative crystallinity, framework Si/Al ratio, structural collapse temperature, specific surface area, percentage of secondary pores with larger pore diameter (8-100 nm) to total secondary pores (2-100 nm), and total secondary pore volume.
After aging DZ-1 in the bare state with 100% steam at 800 ℃ for 17 hours, the crystallinity of the zeolite before and after aging DZ-1 was analyzed by XRD and the relative crystal retention after aging was calculated, the results are shown in Table 2.
Comparative example 2
2000 g of NaY molecular sieve (dry basis) is added into 20L of decationized aqueous solution, stirred to be uniformly mixed, and 1000 g of (NH) is added4)2SO4Stirring, heating to 90-95 ℃, keeping for 1 hour, then filtering, washing, drying a filter cake at 120 ℃, and then carrying out hydrothermal modification treatment, wherein the conditions of the hydrothermal modification treatment are as follows: the mixture is roasted for 5 hours at the temperature of 650 ℃ under 100 percent of water vapor.
Then, the water is heatedAdding the modified molecular sieve into 20L of decationized aqueous solution, stirring to mix well, adding 200ml of RE (NO)3)3Solutions (with RE)2O3The concentration of the rare earth salt solution is measured as follows: 319g/L, RE is mixed rare earth of La and Ce, and La is calculated by the mass of rare earth oxide2O3:Ce2O33:2) and 900 g (NH)4)2SO4Stirring, heating to 90-95 ℃, keeping for 1 hour, then filtering, washing, drying a filter cake at 120 ℃, and then carrying out second hydrothermal modification treatment (roasting at 650 ℃ and 100% water vapor for 5 hours) to obtain the rare earth-containing hydrothermal ultrastable Y-type molecular sieve with twice ion exchange and twice hydrothermal ultrastable, and the molecular sieve is marked as DZ-2.
Table 1 shows the composition of DZ-2, unit cell constant, relative crystallinity, framework Si/Al ratio, structural collapse temperature, specific surface area, percentage of secondary pores with larger pore diameter (8-100 nm) to total secondary pores (2-100 nm), and total secondary pore volume.
After aging DZ-2 in the bare state with 100% steam at 800 ℃ for 17 hours, the crystallinity of the zeolite before and after aging DZ-2 was analyzed by XRD and the relative crystal retention after aging was calculated, the results are shown in Table 2.
Comparative example 3
2000kg of NaY molecular sieve (dry basis) was added to 20m3Stirring in water to mix well, adding 650L RE (NO)3)3Solutions (with RE)2O3The concentration of the rare earth salt solution is measured as follows: 319g/L, RE is mixed rare earth of La and Ce, and La is calculated by the mass of rare earth oxide2O3:Ce2O33:2), stirring, heating to 90-95 ℃, keeping for 1 hour, filtering and washing.
And continuously feeding the obtained filter cake into a flash evaporation and roasting furnace for roasting and drying treatment, controlling the roasting temperature to be 500 ℃, roasting atmosphere to be dry air atmosphere, roasting for 2 hours, and feeding the dried molecular sieve material into a continuous gas-phase hyperstable reactor for gas-phase hyperstable reaction, wherein the water content of the molecular sieve material is lower than 1 weight percent. Gas phase hyperstable reaction process of molecular sieve in continuous gas phase hyperstable reactor and subsequent tail gas thereofThe absorption process is carried out according to the method disclosed in example 1 of the CN103787352A patent, and the process conditions are as follows: SiCl4The mass ratio of the Y-type zeolite is 0.4:1, the feeding amount of the molecular sieve is 800 kg/h, and the reaction temperature is 580 ℃.
Separating the molecular sieve material after gas phase superstable reaction by a gas-solid separator, and feeding into a secondary exchange tank, wherein 20m is added in advance in the secondary exchange tank3The water (2) is added into a molecular sieve material in a secondary exchange tank, the mass of the molecular sieve material is 2000Kg (dry basis weight), the mixture is stirred evenly, and then 5 weight percent of nitric acid with the mass of 1.2m is slowly added3And the temperature is raised to 95 ℃, the stirring is continued for 90 minutes, then 90Kg of citric acid and 40Kg of oxalic acid are added, the stirring is continued for 70 minutes at 93 ℃, then the filtration, the washing, the sampling and the drying are carried out, and the sample is recorded as DZ-3.
Table 1 shows the composition of DZ-3, unit cell constant, relative crystallinity, framework Si/Al ratio, structural collapse temperature, specific surface area, percentage of secondary pores with larger pore diameter (8-100 nm) to total secondary pores (2-100 nm), and total secondary pore volume.
After aging DZ-3 in the bare state with 100% steam at 800 ℃ for 17 hours, the crystallinity of the zeolite before and after aging DZ-3 was analyzed by XRD and the relative crystal retention after aging was calculated, the results are shown in Table 2.
Application example 1
Mixing the materials with water according to the mass ratio of (material dry basis) molecular sieve kaolin, pseudo-boehmite and aluminum sol being 30:38:22:10, pulping, and then spray drying at 450 ℃ to obtain the spherical catalytic cracking catalyst. The molecular sieves were selected from the modified Y-type molecular sieves SZ-1, SZ-2 and SZ-3 obtained in examples 1-3, respectively, to obtain catalysts SC-1, SC-2 and SC-3, respectively, the main properties of which are shown in Table 3.
Comparative application example 1
According to the method for preparing the catalytic cracking catalyst and the material ratio of the catalyst in application example 1, the molecular sieves DZ-1, DZ-2 and DZ-3 prepared in comparative examples 1-3 were used to prepare reference catalysts DC-1, DC-2 and DC-3, respectively, the main properties of which are shown in Table 3.
Catalytic cracking reaction Performance of molecular sieves of application example 2
Evaluation of light oil microreflection: the light oil microreflection activity of the samples was evaluated by the standard method of RIPP92-90 (compiled by "petrochemical analysis method" (RIPP test method) Yangcui et al, published by scientific publishing Co., Ltd. 1990), the catalyst loading was 5.0g, the reaction temperature was 460 ℃, the raw oil was Hongkong light diesel oil with distillation range of 235-.
Light oil Microreactivity (MA) (gasoline production at less than 216 ℃ in product + gas production + coke production)/total feed amount × 100%
Cracking performance evaluation conditions for processing hydrogenated LCO: the catalyst was first aged at 800 deg.C for 12 hours with 100% steam, then evaluated on an ACE (fixed fluidized bed) apparatus, the feed oil was SJZHLCO (hydrogenated LCO) (properties are shown in Table 4), and the reaction temperature was 500 deg.C.
Wherein the LCO effective conversion/% -100-diesel yield-dry gas yield-coke yield-heavy oil yield
The catalysts prepared in application example 1 and comparative application example 1 and the HAC catalyst used in the example of CN104560187A were each evaluated for catalytic cracking performance according to the above-described method, and the results are shown in table 5.
TABLE 1
As can be seen from table 1, the high-stability modified Y-type molecular sieve provided in the embodiment of the present invention has a low sodium oxide content, a low non-framework aluminum content when the silicon-aluminum content of the molecular sieve is high, a pore volume of secondary pores of 2.0nm to 100nm in the molecular sieve accounts for a high percentage of the total pore volume, and a high B acid/L acid (a ratio of a strong B acid amount to an L acid amount) and a high crystallinity, and particularly has a high crystallinity value and a high lattice collapse temperature when the unit cell constant of the molecular sieve is small and the rare earth content is high, and has high thermal stability.
TABLE 2
As can be seen from table 2, after the modified Y-type molecular sieve provided in the embodiment of the present invention is aged under the harsh conditions of 800 ℃ and 17 hours in the exposed state of the molecular sieve sample, the sample has a higher relative crystal retention, which indicates that the modified Y-type molecular sieve provided in the embodiment of the present invention has a higher hydrothermal stability.
TABLE 3
| Catalyst numbering | SC-1 | SC-2 | SC-3 | DC-1 | DC-2 | DC-3 |
| Molecular sieve numbering | SZ-1 | SZ-2 | SZ-3 | DZ-1 | DZ-2 | DZ-3 |
| Al2O3Content/wt% | 47.5 | 47.9 | 48.4 | 49.5 | 51.8 | 50.5 |
| Na2O content/wt% | 0.02 | 0.03 | 0.04 | 0.14 | 0.16 | 0.18 |
| Ignition decrement/wt% | 11.3 | 11.2 | 11.5 | 11.5 | 11.9 | 11.4 |
| Pore volume/(mL. g)-1) | 0.47 | 0.45 | 0.44 | 0.36 | 0.36 | 0.38 |
| Specific surface area/(m)2·g-1) | 283 | 285 | 291 | 264 | 271 | 287 |
| Abrasion index/(%. h)-1) | 1.0 | 1.0 | 1.1 | 1.2 | 1.5 | 1.3 |
| Apparent bulk density/(g. mL)-1) | 0.71 | 0.72 | 0.73 | 0.73 | 0.73 | 0.72 |
| Micro-counteractive activity (800, 4 h)/% | 86 | 89 | 85 | 41 | 52 | 81 |
| Sieve distribution/wt% | ||||||
| 0-20μm | 3.5 | 3.2 | 3.4 | 3.3 | 3.3 | 2.9 |
| 0-40μm | 17.5 | 17.6 | 16.5 | 18.7 | 18.7 | 16.5 |
| 0-149μm | 91.8 | 92.1 | 91.7 | 92.4 | 92.4 | 91.5 |
| Average particle diameter (micrometers) | 71.5 | 72.8 | 70.5 | 69.7 | 69.7 | 72.9 |
TABLE 4 Properties of hydrogenated LCO
TABLE 5
As can be seen from the results listed in table 5, the catalytic cracking catalyst prepared by using the molecular sieve provided in the embodiment of the present invention as an active component has significantly lower coke selectivity, higher LCO conversion rate, and significantly higher gasoline yield than the catalyst of the comparative example, the yield of BTX (benzene + toluene + xylene) in gasoline is significantly increased, and the total yield of ethylene and propylene is significantly increased.
Unless otherwise defined, all terms used herein have the meanings commonly understood by those skilled in the art.
The described embodiments of the present invention are for illustrative purposes only and are not intended to limit the scope of the present invention, and those skilled in the art may make various other substitutions, alterations, and modifications within the scope of the present invention, and thus, the present invention is not limited to the above-described embodiments but only by the claims.
Claims (16)
1. A modified Y-type molecular sieve contains rare earth (5-12 wt.%) in terms of rare earth oxide, sodium (not more than 0.5 wt.%), zinc (0.5-5 wt.%) in terms of zinc oxide, and SiO in terms of Si/Al ratio of skeleton2/Al2O3The molar ratio is 7-14, the mass of non-framework aluminum accounts for not more than 10% of the total mass of aluminum, and the pore volume of secondary pores with the pore diameter of 2-100 nm accounts for 20-38% of the total pore volume.
2. The molecular sieve of claim 1, wherein the total pore volume is from 0.36 to 0.48 mL/g.
3. The molecular sieve of claim 1, wherein the secondary pores having a pore diameter of 2 to 100nm have a pore volume percentage of 28 to 38% of the total pore volume.
4. The molecular sieve according to any one of claims 1 to 3, wherein the percentage of the pore volume of the secondary pores having a pore diameter of 8 to 100nm to the pore volume of the secondary pores having a pore diameter of 2 to 100nm is 40 to 80%.
5. The molecular sieve of claim 4, wherein the rare earth content is 5.5 to 10 wt%, the sodium content is 0.15 to 0.3 wt%, the unit cell constant is 2.442 to 2.453nm, and the framework silicon to aluminum ratio is 8.5 to 12.6.
6. The molecular sieve of claim 4, wherein the non-framework aluminum is present in an amount of 5 to 9.5% by mass of the total aluminum.
7. The molecular sieve of claim 1 or 2, wherein the ratio of the amount of B acid to the amount of L acid is not less than 3.50 as measured by pyridine adsorption infrared at 350 ℃.
8. A preparation method of a modified Y-type molecular sieve comprises the following steps:
(1) carrying out ion exchange on the NaY molecular sieve and a rare earth salt solution;
(2) roasting the ion exchanged molecular sieve;
(3) reacting the roasted molecular sieve with silicon tetrachloride;
(4) carrying out acid treatment on the molecular sieve reacted with the silicon tetrachloride; and
(5) and (3) impregnating the acid-treated molecular sieve with a zinc salt solution.
9. The method as claimed in claim 8, wherein in the step (1), the exchange temperature of ion exchange is 15-95 ℃, the exchange time is 30-120 minutes, the mass ratio of the NaY molecular sieve to the rare earth salt to the solvent water is 1 (0.01-0.18) to (5-20), the mass of the NaY molecular sieve is calculated by dry basis, and the mass of the rare earth salt is calculated by rare earth oxide.
10. The method as claimed in claim 8, wherein the calcination in the step (2) is carried out at 350 to 520 ℃ in an atmosphere having a water vapor content of 30 to 95 vol% for 4.5 to 7 hours.
11. The method as claimed in claim 8, wherein in the step (3), the reaction temperature is 200-650 ℃, the reaction time is 10 minutes to 5 hours, the mass ratio of the silicon tetrachloride to the calcined molecular sieve is (0.1-0.7): 1, and the mass of the calcined molecular sieve is calculated on a dry basis.
12. The method according to claim 8, wherein in the step (4), the temperature of the acid treatment is 60 to 100 ℃ and the treatment time is 1 to 4 hours.
13. The method according to claim 8, wherein the acid treatment comprises reacting the molecular sieve treated in the step (3) with an acid in a solvent water, wherein the mass ratio of the acid to the molecular sieve treated in the step (3) is (0.001-0.15): 1, the mass ratio of the water to the molecular sieve treated in the step (3) is (5-20): 1, and the mass of the molecular sieve treated in the step (3) is calculated on a dry basis.
14. The method according to claim 13, wherein the acid comprises one or more of an organic acid and an inorganic acid, the mass ratio of the inorganic acid to the molecular sieve treated in the step (3) is (0.001-0.05): 1, and the mass ratio of the organic acid to the molecular sieve treated in the step (3) is (0.02-0.10): 1.
15. The method of claim 14, wherein the organic acid is selected from one or more of oxalic acid, malonic acid, succinic acid, methylsuccinic acid, malic acid, tartaric acid, citric acid, and salicylic acid; the inorganic acid is selected from one or more of phosphoric acid, hydrochloric acid, nitric acid and sulfuric acid.
16. The method as claimed in claim 8, wherein the step (5) comprises roasting the impregnated molecular sieve, wherein the impregnation temperature is 10-60 ℃, the roasting temperature is 350-600 ℃, and the roasting time is 1-4 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810949482.3A CN110841697B (en) | 2018-08-20 | 2018-08-20 | Modified Y-type molecular sieve and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810949482.3A CN110841697B (en) | 2018-08-20 | 2018-08-20 | Modified Y-type molecular sieve and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110841697A CN110841697A (en) | 2020-02-28 |
| CN110841697B true CN110841697B (en) | 2021-06-01 |
Family
ID=69595563
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810949482.3A Active CN110841697B (en) | 2018-08-20 | 2018-08-20 | Modified Y-type molecular sieve and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110841697B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3770615A (en) * | 1971-10-22 | 1973-11-06 | Grace W R & Co | Fluid catalytic cracking process with addition of molecular sieve catalyst-liquid mixture |
| CN1597850A (en) * | 2003-09-15 | 2005-03-23 | 中国石油天然气股份有限公司 | Catalyst of catalyzing, cracking for reducing sulfur content in gasoline and preparation process thereof |
| CN1872957A (en) * | 2005-05-31 | 2006-12-06 | 中国石油化工股份有限公司 | Method for catalytic cracking petroleum hydrocarbons |
| 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 |
| CN102744092A (en) * | 2011-04-22 | 2012-10-24 | 中国石油天然气股份有限公司 | Phosphor and rare earth modified molecular sieve |
| CN107973314A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of phosphorous and Y molecular sieve of rare earth and preparation method thereof |
-
2018
- 2018-08-20 CN CN201810949482.3A patent/CN110841697B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3770615A (en) * | 1971-10-22 | 1973-11-06 | Grace W R & Co | Fluid catalytic cracking process with addition of molecular sieve catalyst-liquid mixture |
| CN1597850A (en) * | 2003-09-15 | 2005-03-23 | 中国石油天然气股份有限公司 | Catalyst of catalyzing, cracking for reducing sulfur content in gasoline and preparation process thereof |
| CN1872957A (en) * | 2005-05-31 | 2006-12-06 | 中国石油化工股份有限公司 | Method for catalytic cracking petroleum hydrocarbons |
| 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 |
| CN102744092A (en) * | 2011-04-22 | 2012-10-24 | 中国石油天然气股份有限公司 | Phosphor and rare earth modified molecular sieve |
| CN107973314A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of phosphorous and Y molecular sieve of rare earth and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110841697A (en) | 2020-02-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108452837B (en) | Catalytic cracking catalyst | |
| US10888848B2 (en) | Catalytic cracking catalyst and preparation thereof | |
| CN108452830B (en) | Catalytic cracking catalyst | |
| CN108452838B (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 | |
| TW201833028A (en) | Modified y-type molecular sieve, preparation method therefor, and catalyst containing same | |
| CN108452833B (en) | Catalytic cracking catalyst | |
| CN108452831B (en) | Rare earth-containing modified Y-type molecular sieve rich in secondary pores and preparation method thereof | |
| CN110833857A (en) | Catalytic cracking catalyst, preparation method and application thereof | |
| US11517887B2 (en) | Modified Y-type molecular sieve, catalytic cracking catalyst comprising the same, their preparation and application thereof | |
| CN110841693B (en) | Modified Y-type molecular sieve and preparation method thereof | |
| TWI812773B (en) | Modified Y-type molecular sieve, catalytic cracking catalyst containing it, and its preparation and use | |
| CN110841697B (en) | Modified Y-type molecular sieve and preparation method thereof | |
| CN110841695B (en) | Modified Y-type molecular sieve and preparation method thereof | |
| CN110835114B (en) | Modified Y-type molecular sieve and preparation method thereof | |
| CN110833859B (en) | Modified Y-type molecular sieve and preparation method and application thereof | |
| CN110833863B (en) | Catalytic cracking catalyst, preparation method and application thereof | |
| CN110833851B (en) | Catalytic cracking catalyst, preparation method and application thereof | |
| CN110841690B (en) | Modified Y-type molecular sieve and preparation method thereof | |
| CN110841692B (en) | Catalytic cracking catalyst for processing hydrogenated LCO and preparation method thereof | |
| CN110841694B (en) | Catalytic cracking catalyst for processing hydrogenated LCO and preparation method thereof | |
| CN110833849B (en) | Modified Y-type molecular sieve and preparation method and application thereof | |
| CN110833853A (en) | Modified Y-type molecular sieve and preparation method thereof | |
| CN110833858B (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 |
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 |