CN113828350B - A catalytic cracking catalyst and its preparation method - Google Patents
A catalytic cracking catalyst and its preparation method Download PDFInfo
- Publication number
- CN113828350B CN113828350B CN202010581808.9A CN202010581808A CN113828350B CN 113828350 B CN113828350 B CN 113828350B CN 202010581808 A CN202010581808 A CN 202010581808A CN 113828350 B CN113828350 B CN 113828350B
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- China
- Prior art keywords
- molecular sieve
- catalytic cracking
- cracking catalyst
- nsy
- silicon
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- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title abstract description 51
- 239000002808 molecular sieve Substances 0.000 claims abstract description 161
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 161
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 238000005336 cracking Methods 0.000 claims abstract description 14
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- 239000004927 clay Substances 0.000 claims abstract description 12
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001948 sodium oxide Inorganic materials 0.000 claims abstract description 9
- 238000001694 spray drying Methods 0.000 claims abstract description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 83
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 79
- 238000000034 method Methods 0.000 claims description 77
- 238000002425 crystallisation Methods 0.000 claims description 61
- 230000008025 crystallization Effects 0.000 claims description 61
- 239000005995 Aluminium silicate Substances 0.000 claims description 52
- 235000012211 aluminium silicate Nutrition 0.000 claims description 52
- 238000011065 in-situ storage Methods 0.000 claims description 43
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 36
- 229910052710 silicon Inorganic materials 0.000 claims description 35
- 239000010703 silicon Substances 0.000 claims description 35
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 33
- 229910002027 silica gel Inorganic materials 0.000 claims description 29
- 150000002910 rare earth metals Chemical class 0.000 claims description 28
- 239000000741 silica gel Substances 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 26
- 239000011148 porous material Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 25
- 239000011734 sodium Substances 0.000 claims description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 16
- 238000005342 ion exchange Methods 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 239000004115 Sodium Silicate Substances 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- -1 rectorite Inorganic materials 0.000 claims description 13
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 238000002441 X-ray diffraction Methods 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 4
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012013 faujasite Substances 0.000 claims description 4
- 229910052621 halloysite Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
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- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000004113 Sepiolite Substances 0.000 claims description 2
- 229960000892 attapulgite Drugs 0.000 claims description 2
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- 229910000278 bentonite Inorganic materials 0.000 claims description 2
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
- 229910052624 sepiolite Inorganic materials 0.000 claims description 2
- 235000019355 sepiolite Nutrition 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 239000005909 Kieselgur Substances 0.000 claims 1
- 229910000275 saponite Inorganic materials 0.000 claims 1
- 239000000571 coke Substances 0.000 abstract description 17
- 238000005406 washing Methods 0.000 abstract description 16
- 238000001035 drying Methods 0.000 abstract description 13
- 238000001914 filtration Methods 0.000 abstract description 7
- 239000000295 fuel oil Substances 0.000 abstract description 6
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- 239000013078 crystal Substances 0.000 description 13
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- 239000004005 microsphere Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910021536 Zeolite Inorganic materials 0.000 description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 8
- 125000003636 chemical group Chemical group 0.000 description 7
- 239000000543 intermediate Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910002796 Si–Al Inorganic materials 0.000 description 3
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- 239000003502 gasoline Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
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- 238000010899 nucleation Methods 0.000 description 3
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- 239000012266 salt solution Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000010561 standard procedure Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- JCCZVLHHCNQSNM-UHFFFAOYSA-N [Na][Si] Chemical compound [Na][Si] JCCZVLHHCNQSNM-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 238000004537 pulping Methods 0.000 description 2
- 239000012066 reaction slurry Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- B01J29/80—Mixtures of different zeolites
-
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
本发明属于催化剂制备领域，涉及一种催化裂化催化剂及其制备方法，所述催化裂化催化剂，包括：10～70重量％的裂化活性组元、10～60重量％的粘结剂和10～70重量％的粘土，其中，所述的裂化活性组元包括5～100重量％第一Y型分子筛和0～95重量％的第二分子筛；所述的第一Y型分子筛是改性NSY型分子筛，其氧化钠含量小于2重量％。所述催化剂的制备方法，包括将包含改性NSY分子筛的裂化活性组元、粘结剂和粘土打浆，喷雾干燥，洗涤，过滤和干燥的步骤。该催化剂用于重油催化裂化反应，具体良好焦炭选择性，同时具有较高的重油转化率。The present invention belongs to the field of catalyst preparation, and relates to a catalytic cracking catalyst and a preparation method thereof, wherein the catalytic cracking catalyst comprises: 10-70 wt% of a cracking active component, 10-60 wt% of a binder and 10-70 wt% of clay, wherein the cracking active component comprises 5-100 wt% of a first Y-type molecular sieve and 0-95 wt% of a second molecular sieve; the first Y-type molecular sieve is a modified NSY-type molecular sieve, and its sodium oxide content is less than 2 wt%. The preparation method of the catalyst comprises the steps of slurrying the cracking active component, the binder and the clay containing the modified NSY molecular sieve, spray drying, washing, filtering and drying. The catalyst is used for heavy oil catalytic cracking reaction, and has good coke selectivity and high heavy oil conversion rate.
Description
Technical Field
The invention relates to a catalytic cracking catalyst, in particular to a catalytic cracking catalyst with low coking and a preparation method thereof
Background
Catalytic Cracking (FCC) is an important crude oil secondary process and plays a significant role in the oil refining industry. In the catalytic cracking process, a heavy fraction such as vacuum distillate or a residue of a heavier component is reacted in the presence of a catalyst to be converted into high value-added products such as liquefied gas, gasoline, diesel oil, etc., in which a catalytic material having high cracking activity is generally required. Y-type zeolite is widely used in catalytic cracking reactions due to its excellent shape selective catalytic properties and high cracking reactivity. The Y-type zeolite is obtained by adopting two techniques, namely, firstly adopting alkaline silica-alumina gel for synthesis to obtain the Y-type zeolite, then mixing the Y-type zeolite with a matrix, and spray-drying to obtain the microsphere catalyst, wherein the Y-type zeolite synthesized by the alkaline silica-alumina gel has the characteristics of high molecular sieve content and high silica-alumina ratio, adopts different modification methods and can have various reaction characteristics, and the other technique is an in-situ crystallization technique, firstly forming microspheres, and then crystallizing on the microspheres to generate molecular sieves to directly obtain the catalyst microspheres containing active components, namely the molecular sieves and non-molecular sieve components, and the catalyst synthesized by the in-situ crystallization technique has the characteristics of strong heavy metal pollution resistance, high activity index, good hydrothermal stability, good structural stability and the like. However, the existing Y-type molecular sieve synthesized by in-situ crystallization is used for heavy oil conversion, and the coke yield is relatively high.
Bao Xiaojun CN103043680A provides all silicon sources and aluminum sources synthesized by molecular sieves through natural kaolin minerals and natural diatomite minerals, and is used as a substrate for growth of the molecular sieves, and crystal products are formed through in-situ crystallization. In the composite material, the mass percentage of the NaY molecular sieve is 25-50%, and the silicon-aluminum ratio of the NaY molecular sieve is 3-5.5.
Zheng Shuqin (Si-Al gel, kaolin hydrothermal crystallization synthesis of multi-stage pore canal catalytic material, petroleum journal (petroleum processing), V30 (1), 32-37) reports Si-Al gel, kaolin hydrothermal synthesis of multi-stage pore canal catalytic material, which is prepared by using sodium silicate and sodium metaaluminate as silicon source and aluminum source respectively, spraying the Si-Al gel with kaolin to form balls, and synthesizing.
The above disclosure does not relate to how to reduce the coke selectivity of a catalyst containing an in situ crystallized Y-type molecular sieve for heavy oil conversion.
Disclosure of Invention
The invention aims to solve the technical problem of high coke formation of an in-situ crystallization Y-type molecular sieve catalytic cracking catalyst in the prior art, and provides a catalytic cracking catalyst with less coke formation under the condition of higher heavy oil conversion rate, which contains NSY molecular sieve active components.
A catalytic cracking catalyst comprises 10-70 wt% of cracking active components, 10-60 wt% of binders and 10-70 wt% of clay, wherein the cracking active components comprise 5-100 wt% of first Y-type molecular sieves and 0-95 wt% of second molecular sieves, the first Y-type molecular sieves are modified NSY molecular sieves, and the modified NSY molecular sieves are obtained by modifying NSY molecules synthesized based on kaolin in-situ crystallization.
The NSY molecular sieve synthesized by the kaolin through in-situ crystallization is measured by an X-ray diffraction method, the crystallinity of a peak height method is more than or equal to 60%, the ratio of the crystallinity to the crystallinity of a peak area method is K1, K1=0.76-0.89, the silicon-aluminum ratio measured by a unit cell constant a 0 is 5.0-5.5, the ratio of the silicon-aluminum ratio measured by a chemical method is K2, K2=0.87-0.93, and the silicon-aluminum ratio is the molar ratio of silicon oxide to aluminum oxide. The crystallinity of the peak height method is more than or equal to 80 percent. K1=0.80 to 0.89 or k1=0.80 to 0.85. K2=0.87 to 0.92 or k2=0.88 to 0.90.
In a preferred embodiment, k1=0.77-0.88 and k2=0.87-0.91 of the NSY molecular sieve synthesized by in-situ crystallization of kaolin.
In one embodiment, the large mesoporosity of the NSY molecular sieve synthesized by in-situ crystallization of kaolin is 10-20%.
In one embodiment, the silicon-aluminum ratio of the NSY molecular sieve synthesized by in-situ crystallization of kaolin is 5.2-5.5 measured by a unit cell constant a 0.
In a preferred embodiment, the modified NSY molecular sieve contains rare earth (the rare earth-containing modified Y-type molecular weight is also called a rare earth-containing NSY molecular sieve), and the rare earth content is preferably 10-20 wt% based on RE 2O3. The rare earth of the modified NSY molecular sieve is in the content range, and the catalytic cracking catalyst can have higher heavy oil conversion activity.
The invention provides a preparation method of a catalytic cracking catalyst, which comprises the following steps:
(S1) preparing a modified NSY molecular sieve;
(S2) slurrying the clay, the cracking active component comprising the modified NSY molecular sieve and optionally the second molecular sieve, and the binder;
(S3) spray-drying the slurry obtained in the step S2.
According to the preparation method of the catalytic cracking catalyst provided by the invention, the modified NSY molecular sieve is a NSY molecular sieve which is obtained by modifying a NSY molecular sieve synthesized by in-situ crystallization of kaolin (namely a NSY molecular sieve synthesized by in-situ crystallization) and is synthesized by in-situ crystallization of modified kaolin.
According to the preparation method of the catalytic cracking catalyst provided by the invention, the preparation method of the modified NSY molecular sieve can be obtained by modifying the NSY molecular sieve synthesized by in-situ crystallization of kaolin. The NSY molecular sieve synthesized by the kaolin in-situ crystallization is a Y-type molecular sieve composite material, the crystallinity of the NSY molecular sieve synthesized by the kaolin in-situ crystallization (or called the Y-type molecular sieve composite material) is more than or equal to 60% by using an X-ray diffraction method, the ratio of the crystallinity to the crystallinity of the peak area method is K1, K1=0.76-0.89, the silicon-aluminum ratio measured by using a unit cell constant a 0 is 5.0-5.5, the ratio of the silicon-aluminum ratio measured by using a chemical method is K2, K2=0.87-0.90, and the silicon-aluminum ratio is the molar ratio of silicon oxide to aluminum oxide. The modified NSY molecular sieve is a molecular sieve material obtained by modifying NSY molecular sieve synthesized by in-situ crystallization of kaolin, wherein the modifying treatment reduces the sodium oxide content in NSY molecular sieve synthesized by in-situ crystallization of kaolin to below 2 wt%, and the modifying treatment is ion exchange.
The NSY molecular sieve synthesized by in-situ crystallization of kaolin disclosed by the invention has a similar sphere of 5-20 microns, wherein the crystallinity of a peak height method is more than or equal to 60%, namely the mass percentage of the NaY molecular sieve is at least 60%. Preferably, the crystallinity by the peak height method is greater than 75%, more preferably equal to or greater than 80%.
The difference between the crystallinity measured by the peak height method and the crystallinity measured by the peak area method is related to the size of crystal grains based on the common knowledge of crystal crystallization. The Y-type molecular sieve composite material (the composite material for short) provided by the invention is provided with a crystal grain coefficient K1, K1=S peak height /S peak area , namely the ratio of the crystallinity of the peak height method to the crystallinity of the peak area method. The size of the K1 value indicates the size of the crystal grains, the K1 value is large, and the grain size is large. Preferably, K1 is 0.80 to 0.89, more preferably 0.80 to 0.85.
The molar ratio of silicon oxide to aluminum oxide calculated from the unit cell constant a 0 is the framework silica-alumina ratio of the molecular sieve, and the molar ratio of silicon oxide to aluminum oxide measured by a chemical method is the overall silica-alumina ratio of the composite material. The NSY molecular sieve synthesized by in-situ crystallization of kaolin disclosed by the invention has a framework silicon-aluminum ratio of 5.0-5.5, preferably 5.2-5.5, which is calculated and measured by a unit cell constant a 0, and the whole silicon-aluminum ratio measured by a chemical method is the macroscopic silicon-aluminum ratio of the whole material. The two values of the framework silica alumina ratio and the overall silica alumina ratio are related to the framework integrity and the purity of the molecular sieve in the composite material, and the NSY molecular sieve synthesized by the kaolin in-situ crystallization is obtained by the metakaolin through crystal transformation, wherein a part of metakaolin is positioned in an intermediate for transforming the metakaolin into the Y-type molecular sieve, so that an intermediate coefficient K2, namely K2=framework silica alumina ratio/overall silica alumina ratio, is set. The magnitude of the K2 value indicates the degree of recombination of the composite material, with smaller K2 values containing more intermediates. Preferably, K2 is 0.87 to 0.92, more preferably=0.88 to 0.90.
The NSY molecular sieve (also called as Y-type molecular sieve composite material) synthesized by in-situ crystallization of kaolin disclosed by the invention is preferable, and K1=0.77-0.88 such as K1=0.81-0.88 or K1=0.86-0.88 and K2=0.87-0.91 are preferable.
In the present invention, pores having a pore diameter of more than 0.8nm are defined as mesopores and macropores. The NSY molecular sieve synthesized by in-situ crystallization of kaolin disclosed by the invention has proper medium-large porosity, wherein the large porosity is 10-20%.
According to the preparation method of the catalytic cracking catalyst, NSY molecular sieve synthesized by in-situ crystallization of kaolin is a Y-type molecular sieve composite material, and the preparation method comprises the following steps of (1) roasting and dehydrating kaolin at 500-900 ℃ to convert the kaolin into metakaolin, crushing the metakaolin to prepare metakaolin powder with the particle size smaller than 10 microns, (2) adding sodium silicate, a guiding agent, sodium hydroxide solution and water into the metakaolin powder to prepare a reaction raw material A with the molar ratio of (1-2.5) Na 2O：Al2O3：(4～9)SiO2：(40～100)H2 O, wherein the mass ratio of the guiding agent to the metakaolin is 0.01-1.0, (3) crystallizing the reaction raw material A under 88-98 ℃, supplementing a second silicon source after the crystallization time reaches 1-70 h to obtain a reaction raw material B, wherein the second silicon source accounts for 0.1-10 wt% of the total silicon content by using a silicon oxide meter, and (4) crystallizing the reaction raw material B under 88-98 ℃ and recycling products.
According to the preparation method of the catalytic cracking catalyst provided by the invention, in the preparation method of NSY molecular sieves synthesized by in-situ crystallization of kaolin, the guiding agent can be synthesized according to a conventional method, such as the preparation method of USP3574538, USP3639099, USP3671191, USP4166099 and EUP 0435625. The molar composition of the guiding agent is (10-17) SiO 2：(0.7～1.3)Al2O3：(11～18)Na2O：(200～350)H2 O. The raw materials are aged at 4-35 ℃, preferably 4-20 ℃ during synthesis to obtain the guiding agent.
According to the preparation method of the catalytic cracking catalyst provided by the invention, in the preparation method of NSY molecular sieve synthesized by in-situ crystallization of kaolin, the content of sodium in the second silicon source is 0.01-10 wt% calculated by Na 2 O, and preferably <1 wt%. The preferred second silicon source is solid silica gel from a cost control standpoint. The solid silica gel is counted in the total synthesis proportion, and the adopted solid silica gel can be solid silica gel with different pore diameters. The pore size is divided into fine pore silica gel, coarse pore silica gel and intermediate pore silica gel between them. Conventionally, silica gels having an average pore diameter of 1.5 to 2.0nm or less are called fine pore silica gels (for example, A-type solid silica gels in Qingdao ocean chemical group special silica gel factories) and silica gels having an average pore diameter of 4.0 to 5.0nm or more are called coarse pore silica gels (for example, C-type solid silica gels in Qingdao ocean chemical group special silica gel factories), and silica gels having an average pore diameter of 10.0nm or more are called extra-coarse pore silica gels and an average pore diameter of 0.8nm or less are called extra-fine pore silica gels (for example, B-type solid silica gels in Qingdao ocean chemical group special silica gel factories). The second silicon source may also be liquid silica gel, preferably having a SiO 2 mass content of at least 30% when liquid silica gel is used as the second silicon source.
According to the preparation method of the catalytic cracking catalyst, the preparation method of the NSY molecular sieve synthesized by in-situ crystallization of kaolin is a hierarchical pore Y-type molecular sieve composite material product containing certain macropores and macropores, which is obtained by crystallization under stirring, but is not limited to, and the crystallization stirring speed is 50-1000 revolutions per minute, preferably 300-500 revolutions per minute, and the time is 16-48 hours, preferably 24-32 hours. The drying temperature of the crystallized zeolite is 100-120 ℃.
According to the preparation method of the catalytic cracking catalyst provided by the invention, in the preparation method of NSY molecular sieve synthesized by kaolin in-situ crystallization, the second silicon source accounts for 0.1-10 wt% of the total silicon dosage, preferably 4-10 wt% of the total silicon dosage, calculated by silicon oxide.
According to the preparation method of the catalytic cracking catalyst provided by the invention, in the preparation method of NSY molecular sieve synthesized by kaolin in-situ crystallization, sodium silicate and a second silicon source are added into a synthesis preparation system in different processes, and particularly the adding period of the second silicon source is in the crystal growth period. The invention combines the synthesis proportion technology and the kaolin in-situ crystallization synthesis technology (natural minerals are adopted as main aluminum sources and silicon sources) by adding different silicon sources at different stages in the crystallization process, changes the crystal growth environment through the silicon sources, and adopts two completely different material proportions at two stages of a crystal nucleation stage and a crystal growth stage. In the method, a large sodium-silicon ratio (Na 2O/SiO2) is adopted in the material in the crystal nucleation period, so that the rapid nucleation of the Y-type molecular sieve is facilitated, a low sodium or sodium-free silicon source is added in the crystal growth period, the sodium-silicon ratio (Na 2O/SiO2) in the material is reduced while the silicon-aluminum ratio (SiO 2/A12O3) in the synthetic material is improved, and the improvement of the silicon-aluminum ratio of the product and the improvement of the skeleton silicon-aluminum ratio to 5.0-5.5 are facilitated on the premise of shortening the crystallization time.
According to the preparation method of the catalytic cracking catalyst provided by the invention, in the preparation step (4) of the NSY molecular sieve synthesized by the kaolin in situ crystallization, products are recovered after crystallization is finished, and the NSY molecular sieve synthesized by the kaolin in situ crystallization is obtained. The recovery generally includes a filtration step and optionally may also include one or more of washing, drying, and roasting.
According to the preparation method of the catalytic cracking catalyst provided by the invention, the preparation method of the modified NSY molecular sieve comprises the step of carrying out modification treatment such as ion exchange on the recovered product to obtain the modified NSY molecular sieve.
According to the preparation method of the catalytic cracking catalyst provided by the invention, the NSY molecular sieve synthesized by in-situ crystallization of the kaolin can be treated by any method capable of reducing the sodium content of the kaolin so that the sodium oxide content of the kaolin is not more than 2 weight percent, for example, the modified NSY molecular sieve is obtained by ion exchange. The ion exchange can be carried out by adopting ammonium salt and/or rare earth salt solution, and the invention has no special requirement. Preferably, the ion exchange is performed, so that the rare earth content in the obtained modified NSY molecular sieve is 10-20 wt% calculated by RE 2O3, and the sodium oxide content is less than 2 wt%. In one embodiment, the NSY molecular sieve synthesized by in-situ crystallization of kaolin is mixed with the exchange solution, and stirred for 10-120 minutes at 20-90 ℃, and the process can be carried out one or more times, and the exchange solution exchanged each time can contain ammonium ions, rare earth ions or both ammonium ions and rare earth ions. Preferably, the concentration of ammonium salt in the exchange solution is 5-700 g/L, for example 5-100 g/L, and/or the concentration of rare earth salt is 5-400 g/L, for example 5-200 g/L, calculated by RE 2O3. Such as one or more of ammonium chloride, ammonium nitrate, ammonium sulfate. Such as one or more of rare earth chloride and rare earth nitrate. The rare earth may include one or more of lanthanide rare earth, actinide rare earth, including, for example, one or more of La, ce, pr, nd, pm, sm, eu, gd, TB, dy, ho, er, tm, yb, lu.
According to the preparation method of the catalytic cracking catalyst provided by the invention, the NSY molecular sieve synthesized by the kaolin in-situ crystallization can further comprise one or more steps of filtering, washing, drying and roasting after ion exchange, and the steps can refer to filtering, washing, drying and roasting methods which are well known to those skilled in the art.
According to the preparation method of the catalytic cracking catalyst, in the step S2, clay, a modified NSY molecular sieve, an optional second molecular sieve and a binder are formed into slurry, and the clay, the modified NSY molecular sieve, the optional second molecular sieve and the binder can be mixed with water and stirred uniformly.
According to the preparation method of the catalytic cracking catalyst provided by the invention, in the step S3, the slurry obtained in the step S2 is spray-dried to obtain the catalyst microsphere particles, wherein the catalyst microsphere particles can be further roasted and/or washed, and the washing can be performed before and/or after the roasting. The spray drying, washing and roasting can be performed according to the existing method for producing the spray drying and roasting of the catalytic cracking catalyst. For example, the washing may be performed with an ammonium salt solution, and the calcination may be performed at 350 to 650 ℃ for 1 to 4 hours.
The catalytic cracking catalyst provided by the invention has good coke formation selectivity, and can reduce coke selectivity on the basis of high hydrocarbon oil conversion catalytic activity. Preferably, the catalytic cracking catalyst provided by the invention can also have higher hydrocarbon oil conversion activity and/or liquid product yield.
Detailed Description
The following detailed description and examples are provided to further illustrate the invention. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The catalytic cracking catalyst provided by the invention comprises 10-70 wt%, such as 20-60 wt% or 25-65 wt%, of cracking active components, 10-60 wt%, such as 20-45 wt%, of binder and 10-70 wt%, such as 20-60 wt% or 25-55 wt% of clay, wherein the cracking active components comprise 5-100 wt%, such as 40-100 wt%, of a first Y-type molecular sieve and 0-95 wt%, such as 0-60 wt%, of a second molecular sieve.
The catalytic cracking catalyst provided by the invention can also contain a second molecular sieve, wherein the second molecular sieve is preferably faujasite and/or a molecular sieve with a five-membered ring structure, and the faujasite is one or more of HY, REY, REHY, USY, REUSY, DASY and REDASY. The molecular sieve with five-membered ring structure is, for example, one or more of BEA structure molecular sieve, MFI structure molecular sieve and mordenite, preferably BEA structure molecular sieve and MFI structure molecular sieve. The BEA structure molecular sieve can be obtained by amine-free crystallization or can be obtained by roasting a molecular sieve prepared by a template agent method, for example, the BEA structure molecular sieve is a beta molecular sieve, the MFI structure molecular sieve is at least one of a rare earth-containing MFI structure molecular sieve, a phosphorus-containing MFI structure molecular sieve, an iron-containing MFI structure molecular sieve and a phosphorus-containing and transition metal-containing MFI structure molecular sieve, and the mordenite is at least one of high-silicon mordenite or low-silicon mordenite.
The catalytic cracking catalyst provided by the invention contains clay, wherein the clay can be one or more of kaolin, halloysite, montmorillonite, diatomite, halloysite, quasi halloysite, soapstone, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite.
The catalytic cracking catalyst provided by the invention contains a binder, wherein the binder can be one or more selected from silica sol, alumina sol, acidified aluminum stone (pseudo-boehmite for short) and metal modified aluminum stone.
In the catalytic cracking catalyst provided by the invention, the first Y-type molecular sieve is a modified NSY molecular sieve, preferably a NSY molecular sieve containing rare earth, wherein the rare earth content is 10-20 wt% calculated by RE 2O3, and the sodium oxide content is not more than 2 wt%, preferably not more than 1.5 wt%.
In one embodiment, the modified NSY molecular sieve is prepared according to the following steps:
(1) Roasting and dehydrating kaolin at 500-900 ℃ to convert the kaolin into metakaolin, and crushing the metakaolin to prepare powder with the particle size smaller than 10 microns;
(2) Adding sodium silicate, a guiding agent, sodium hydroxide solution and water into metakaolin powder to prepare reaction slurry, wherein the mass ratio of the guiding agent to the metakaolin is 0.01-1.0;
(3) Crystallizing the reaction slurry prepared in the step (2) for 1-70 hours, such as 5-40 hours, 6-30 hours or 8-16 hours under stirring at 88-98 ℃, and then supplementing solid silica gel, wherein the mass ratio of the solid silica gel to metakaolin is 0.01-1.0;
(4) Crystallizing the reaction raw material prepared in the step (3) at 88-98 ℃ under stirring for 1-20 h, such as 8-20 h or 12-16 h, filtering and drying to obtain NSY molecular sieve synthesized by in-situ crystallization, and
(5) And (3) contacting the NSY molecular sieve synthesized by in-situ crystallization with ammonium salt and/or rare earth salt solution for ion exchange, filtering, washing, drying and roasting to obtain the modified NSY molecular sieve, wherein the rare earth content in the modified NSY molecular sieve is preferably 10-20 wt% based on RE 2O3, and the sodium oxide content is less than 2 wt%. The contacting may be performed one or more times, and each contact exchange may be performed by contacting with a solution containing both rare earth ions and ammonium ions, or may be performed by performing ammonium ion exchange or rare earth ion exchange with a solution containing one of the ions.
In one embodiment, the NSY molecular sieve synthesized by in-situ crystallization has a mass percentage of 20% -30% which is an intermediate for transferring metakaolin into a Y-type molecular sieve, and K2 is in a range of 0.87-0.93 due to the intermediate.
Examples and comparative examples:
the element content in the catalyst is determined by XRF, and the specific surface area and the pore volume are determined by adopting a low-temperature nitrogen adsorption-desorption method.
The raw materials used in the catalyst preparation were as follows:
pseudo-boehmite (aluminum stone for short) product of Shandong aluminum company, with a solid content of 75 wt%;
Kaolin, 75% by weight solids, produced by chinese kaolin limited (su zhou);
REY molecular sieve, qilu division product of China petrochemical catalyst Co., ltd, rare earth content 17.6 wt%;
ZSP-3 molecular sieve, qilu division of China petrochemical catalyst Co., ltd, and P 2O5 in the amount of 3.02 wt%.
Alumina sol, qilu division product of China petrochemical catalyst Co, with 23 weight percent of solid content.
The content of NaY zeolite in the composite material in the examples was determined according to RIPP146,146-90 standard method (RIPP standard method, see petrochemical analysis method (RIPP test method), yang Cuiding et al, scientific Press, 1990, supra).
The unit cell constant a 0 was determined according to the RIPP145,145-90 standard method. The Si/Al ratio of the framework is calculated from the unit cell constant a 0 (angstrom) according to the formula SiO 2/Al2O3 (molar ratio) =2× (25.858-a 0)/(a0 -24.191).
The specific surface area was measured by the nitrogen adsorption method (GB/T5816-1995), the pore volume was measured by the nitrogen adsorption method (RIPP-90), the pores with a pore diameter of more than 0.8nm measured by the nitrogen adsorption method were defined as macropores, and the calculation formula of the macropore ratio was (V Total hole -V Micropores )/V Total hole X100%).
In the examples and comparative examples, a guide agent was prepared by taking 250 kg of a sodium silicate solution (containing 20.05 wt% SiO 2, 6.41 wt% Na 2 O), slowly adding 120 kg of a sodium metaaluminate solution (containing 3.15 wt% Al 2O3, 21.1 wt% Na 2 O) with rapid stirring at 30℃and aging at 20℃for 48 hours. The composition of the guiding agent is 16Na 2O：Al2O3：15SiO2：320H2 O.
Molecular sieve preparation example 1
100 Kg of the pulverized metakaolin powder were added with stirring 400 kg of sodium silicate solution (containing 20.05% by weight of SiO 2, 6.41% by weight of Na 2 O), 60 kg of a directing agent and 100 kg of a 5% strength by weight sodium hydroxide solution. Heating to 95deg.C, stirring at constant temperature, adding 10 kg of solid silica gel (type A of Qingdao ocean chemical group special silica gel factory) after 8 hr, crystallizing for 12 hr, and stirring at 400 rpm. After crystallization, the crystallization tank is quenched, filtered and washed until the pH value of the washing liquid is less than 10. Drying at 120℃for 2 hours gives zeolite material Y-1. The X-ray diffraction method was used to measure Y-1, the K1 value of the ratio of the crystallinity of the peak height method to the crystallinity of the peak area method, the Si/Al ratio measured with the unit cell constant a0, the K2 value of the ratio of the Si/Al ratio measured with the unit cell constant a 0 to the Si/Al ratio measured with the chemical method, and the mesoporosity are shown in Table 1.
Molecular sieve preparation example 2
Preparation of example 1 by molecular sieves 100 kg of crushed metakaolin powder were stirred with 380 kg of sodium silicate solution (containing 20.05% by weight of SiO 2, 6.41% by weight of Na 2 O), 60 kg of directing agent and 100 kg of sodium hydroxide solution with a concentration of 5% by weight. Heating to 93 deg.C, stirring at constant temperature, adding 15 kg of solid silica gel (type A of Qingdao ocean chemical group special silica gel factory) after 8 hr, crystallizing for 14 hr, and stirring at 400 rpm. After crystallization, the crystallization tank is quenched, filtered and washed until the pH value of the washing liquid is less than 10. Drying at 120℃for 2 hours gives zeolite material Y-2. The X-ray diffraction method was used to measure Y-2, the K1 value of the ratio of the crystallinity of the peak height method to the crystallinity of the peak area method, the Si/Al ratio measured with the unit cell constant a0, the K2 value of the ratio of the Si/Al ratio measured with the unit cell constant a 0 to the Si/Al ratio measured with the chemical method, and the mesoporosity are shown in Table 1.
Molecular sieve preparation example 3
Preparation of example 1 by molecular sieves 100 kg of crushed metakaolin powder were stirred with 360 kg of sodium silicate solution (containing 20.05% by weight of SiO 2, 6.41% by weight of Na 2 O), 60 kg of directing agent and 100 kg of sodium hydroxide solution with a concentration of 5% by weight. Heating to 95deg.C, stirring at constant temperature, adding 20 kg of solid silica gel (type A of Qingdao ocean chemical group special silica gel factory) after 8 hr, crystallizing for 16 hr, and stirring at 400 rpm. After crystallization, the crystallization tank is quenched, filtered and washed until the pH value of the washing liquid is less than 10. Drying at 120℃for 2 hours gives zeolite material Y-3. The X-ray diffraction method was used to measure Y-3, the K1 value of the ratio of the crystallinity of the peak height method to the crystallinity of the peak area method, the Si/Al ratio measured with the unit cell constant a0, the K2 value of the ratio of the Si/Al ratio measured with the unit cell constant a 0 to the Si/Al ratio measured with the chemical method, and the mesoporosity are shown in Table 1.
Preparation of molecular sieves comparative example 1
This comparative example illustrates the case where two silicon sources are added to the reaction system at once.
100 Kg of crushed metakaolin powder was added with stirring to 400 kg of sodium silicate solution (containing 20.05 wt% of SiO 2 and 6.41 wt% of Na 2 O), 60 kg of guiding agent, 105 kg of sodium hydroxide solution with a concentration of 5 wt% and 10kg of solid silica gel (Qingdao ocean chemical group specialty silica gel Co., A) according to the method of molecular sieve preparation example 1. Heating to 94 ℃, stirring at constant temperature, crystallizing for 24 hours, and stirring at 400 rpm during feeding and crystallizing. After crystallization, the crystallization tank is quenched, filtered and washed until the pH value of the washing liquid is less than 10. Drying at 120℃for 2 hours gives the zeolitic material DY-1. DY-1 was measured by an X-ray diffraction method, and the values of K1, the ratio of the crystallinity by the peak height method to the crystallinity by the peak area method, K2, and the ratio of Si/Al ratio measured by the cell constant a0 to Si/Al ratio measured by the chemical method, and the macroporosity are shown in Table 1. DY-1 has low crystallinity and has mixed crystal.
Molecular sieve preparation comparative example 2
This comparative example illustrates the case where the second silicon source is not added.
Preparation of example 1 by molecular sieves 100 kg of crushed metakaolin powder were stirred with 400 kg of sodium silicate solution (containing 20.05% by weight of SiO 2, 6.41% by weight of Na 2 O), 60 kg of directing agent and 100 kg of sodium hydroxide solution with a concentration of 5% by weight. Heating to 94 ℃, stirring at constant temperature, crystallizing for 24 hours, and stirring at 400 rpm during feeding and crystallizing. After crystallization, the crystallization tank is quenched, filtered and washed until the pH value of the washing liquid is less than 10. Drying at 120℃for 2 hours gives zeolite DY-2. DY-2 was measured by an X-ray diffraction method, and the values of K1, the ratio of the crystallinity by the peak height method to the crystallinity by the peak area method, K2, and the ratio of Si/Al ratio measured by the cell constant a0, si/Al ratio measured by the cell constant a0 to Si/Al ratio measured by the chemical method, and macroporosity are shown in Table 1. DY-2 has no poor crystallinity, but has a low silica-alumina ratio.
Molecular sieve preparation comparative example 3
This comparative example illustrates a NaY molecular sieve prepared according to the method of CN101468803 a.
189Ml of deionized water, 86.6g of a directing agent, 130ml of an aluminum sulfate solution (Chang Ling refinery catalyst plant product, specific gravity 1.28, al 2O3 content 88.2 g/L) and 100ml of a low sodium metaaluminate solution (Chang Ling refinery catalyst plant product, specific gravity 1.23, al 2O3 content 102g/L, na 2 O content 151.9 g/L) were added to 401ml of sodium silicate, and the mixture was stirred vigorously for 30 minutes, left to crystallize at 100℃for 33 hours, and the product No. DY-3 was recovered.
DY-3 was measured by an X-ray diffraction method, and the values of K1, K2, and medium-to-large porosity of the ratio of the crystallinity by the peak height method to the crystallinity by the peak area method, the Si/Al ratio measured by the cell constant a 0, the Si/Al ratio measured by the cell constant a 0, and the Si/Al ratio measured by the chemical method are shown in Table 1.
TABLE 1
Catalyst preparation example 1
(1) The preparation method of the modified NSY molecular sieve comprises the steps of adding deionized water into zeolite material Y-1 to pulp to obtain molecular sieve slurry with the solid content of 10 weight percent, adding water into lanthanum chloride to pulp to form lanthanum chloride solution with the La 2O3 concentration of 5 weight percent, adding the lanthanum chloride solution into the molecular sieve slurry, stirring the lanthanum chloride (calculated by La 2O3) and the molecular sieve (calculated by dry basis) for 1h at the weight ratio of 1:6, filtering, washing, drying at 150 ℃ for 8h, and roasting at 500 ℃ for 4h to obtain the modified NSY molecular sieve containing rare earth.
(2) The catalyst preparation method comprises the steps of pulping kaolin and water to obtain kaolin slurry with the solid content of 20 wt%, pulping a rare earth-containing modified NSY molecular sieve with water, dispersing with a homogenizer to obtain modified NSY molecular sieve slurry with the solid content of 35 wt%, mixing and stirring the kaolin slurry and the modified NSY molecular sieve slurry, adding acidified aluminum stone with the solid content of 10 wt% (wherein the molar ratio of HCl to aluminum stone calculated as Al 2O3 is 0.2), stirring for 10min, adding aluminum sol, and stirring for 30min to obtain the catalyst slurry. And (3) carrying out spray drying on the catalyst slurry to obtain catalyst microspheres, roasting the obtained catalyst microspheres at 500 ℃ for 2 hours, and then washing with an ammonium sulfate solution with the concentration of 2 wt% of ammonium sulfate, wherein the weight ratio of the ammonium sulfate solution to the dry basis of the catalyst microspheres is 10:1, so as to obtain the catalytic cracking catalyst C1.
Catalyst preparation examples 2 to 6
A catalyst was prepared as in example 1 by adjusting the weight ratio of lanthanum chloride (in terms of La 2O3) to molecular sieve (in terms of dry basis) or by conducting multiple passes to give a modified NSY molecular sieve. Wherein the zeolite material used and the rare earth content of the resulting modified NSY molecular sieve are shown in table 2, wherein the ZSP-3 molecular sieve is slurried with water to form a ZSP-3 molecular sieve slurry having a solids content of 35 wt%, and mixed with kaolin slurry and modified NSY molecular sieve slurry, and then the acidified bauxite is added, stirred for 10 minutes, then the alumina sol is added, stirred for 30 minutes, and spray-dried and the calcination and washing are performed. The catalyst formulation is shown in table 2.
TABLE 2
The formulation in Table 2 is composed on a dry basis, and the rare earth content in the modified NSY molecular sieve is RE 2O3, and B in the number of catalyst preparation examples represents a comparative example.
In Table 2, in the catalysts DB 2-DB 4, the content of the rare earth in the modified NSY molecular sieve, the content of the rare earth in the modified NSY molecular sieve and the content of Na 2 O in the modified NSY molecular sieve are respectively the percentage content of the modified Y molecular sieve in the catalyst, the rare earth content and the sodium oxide content in the corresponding modified Y molecular sieve, which are obtained after DY-1-DY-3 rare earth exchange.
Catalyst preparation comparative examples 1 to 4
Catalyst preparation A catalyst was prepared according to the procedure of catalyst preparation example 1, the catalyst formulation being shown in Table 2.
Catalyst evaluation:
The catalyst was subjected to a deactivation treatment with 100% steam at 800 ℃ for 24 hours. The evaluation was carried out on a fixed fluidized bed micro-reverse ACE, the raw oil was a mixed three raw oil (composition and physical properties are shown in Table 3, the evaluation condition is that the reaction temperature was 500 ℃, the catalyst to oil ratio (weight) was 6, and the WHSV was 16h -1. The results are shown in Table 4.
Wherein conversion = gasoline yield + liquefied gas yield + dry gas yield + coke yield
Total liquid yield = gasoline yield + liquefied gas yield + cycle oil yield
Coke selectivity = coke yield/conversion x 100
Green coke factor = coke yield x (1-conversion)/conversion x 100
The coke formation factor is an important index for judging the coke selectivity of the catalyst, and the smaller the coke formation factor is, the better the coke selectivity of the catalyst is.
TABLE 3 Table 3
TABLE 4 Table 4
As can be seen from table 4, compared with the catalytic cracking catalyst provided in the comparative example, the catalytic cracking catalyst provided in the present invention can reduce coke selectivity and coke formation factor in the catalytic cracking reaction with higher conversion. Preferably, the conversion rate can be further increased, and the total liquid yield can be increased.
Claims (24)
1. A catalytic cracking catalyst comprises 10-70 wt% of cracking active components, 10-60 wt% of binders and 10-70 wt% of clay, wherein the cracking active components comprise 5-100 wt% of a first Y-type molecular sieve and 0-95 wt% of a second molecular sieve, the first Y-type molecular sieve is a modified NSY molecular sieve obtained by modifying NSY molecular sieves based on kaolin in-situ crystallization synthesis, the sodium oxide content of the modified NSY molecular sieve is less than 2 wt%, the NSY molecular sieve synthesized by kaolin in-situ crystallization is measured by an X-ray diffraction method, the crystallinity of a peak height method is more than or equal to 60%, the crystallinity ratio of the peak height method is K1, K1=0.76-0.89, the silicon-aluminum ratio measured by a unit cell constant a 0 is 5.0-5.5, the silicon-aluminum ratio measured by a chemical method is K2, K2=0.87-0.93, the ratio is the molar ratio of silicon oxide to aluminum oxide, and the method for preparing the kaolin in-situ crystallization synthesis comprises the following steps:
(1) Roasting, dehydrating and converting the kaolin into metakaolin at 500-900 ℃, and crushing the metakaolin into metakaolin powder with the particle size smaller than 10 microns;
(2) Adding a guiding agent, sodium silicate, sodium hydroxide solution and water into the metakaolin powder to prepare a reaction raw material A, wherein the mass ratio of the guiding agent to the metakaolin is 0.01-1.0, and the proportion of the reaction raw material A is (1-2.5) Na 2O：Al2O3：(4～9)SiO2：(40～100)H2 O mol ratio;
(3) Crystallizing the reaction raw material A for 1-70 hours under the condition of stirring at 88-98 ℃ and then supplementing a second silicon source to obtain a reaction raw material B, wherein the second silicon source accounts for 0.1-10% by weight of the total silicon feeding amount in terms of silicon oxide;
(4) Crystallizing the reaction raw material B at 88-98 ℃ under stirring, and recovering a product;
The second silicon source has a sodium content of <1 wt.% in terms of Na 2 O.
2. The catalytic cracking catalyst according to claim 1, wherein the crystallinity of the peak height method is not less than 80%.
3. The catalytic cracking catalyst of claim 1, wherein k1=0.80 to 0.89.
4. The catalytic cracking catalyst of claim 1, wherein k1=0.80 to 0.85.
5. The catalytic cracking catalyst of claim 1, wherein k2=0.87 to 0.92.
6. The catalytic cracking catalyst of claim 1, wherein k2=0.88 to 0.90.
7. The catalytic cracking catalyst of claim 1, wherein k1=0.77 to 0.88 and k2=0.87 to 0.91.
8. The catalytic cracking catalyst according to claim 1, wherein the large mesoporosity of NSY molecular sieve synthesized by in situ crystallization of kaolin is 10 to 20%.
9. The catalytic cracking catalyst according to claim 1, wherein the ratio of silicon to aluminum as measured by unit cell constant a 0 is 5.2 to 5.5.
10. The catalytic cracking catalyst according to any one of claims 1 to 9, wherein the modified NSY molecular sieve contains rare earth, and the rare earth content in the modified NSY molecular sieve is 10 wt% to 20 wt% in terms of RE 2O3.
11. The catalytic cracking catalyst according to claim 1, wherein the second molecular sieve is selected from the group consisting of faujasite and/or molecular sieves with five-membered ring structures, wherein the faujasite is one or more of HY, REY, REHY, USY, REUSY, DASY and REDASY, the molecular sieves with five-membered ring structures comprise one or more of BEA structure molecular sieves, MFI structure molecular sieves and mordenite, the binder is one or more of silica sol, alumina sol, acidified pseudo-boehmite and metal modified pseudo-boehmite, and the clay is one or more of kaolin, montmorillonite, diatomaceous earth, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite.
12. The method for preparing the catalytic cracking catalyst according to any one of claims 1 to 11, comprising the following steps:
(1) Preparing a modified NSY molecular sieve;
(2) Forming a slurry of clay, a cracking active component, and a binder, said cracking active component comprising said modified NSY molecular sieve and optionally a second molecular sieve;
(3) And (3) spray drying the slurry obtained in the step (2).
13. The method for preparing a catalytic cracking catalyst according to claim 12, wherein the method for preparing the modified NSY molecular sieve comprises the steps of:
(1) Roasting and dehydrating kaolin at 500-900 ℃ to convert the kaolin into metakaolin, and crushing the metakaolin into metakaolin powder with the particle size smaller than 10 microns;
(2) Adding sodium silicate, a guiding agent, sodium hydroxide solution and water into metakaolin powder to prepare a reaction raw material A with the proportion of (1-2.5) Na 2O:Al2O3:(4～9)SiO2:(40～100)H2 O, wherein the mass ratio of the guiding agent to the metakaolin is 0.01-1.0;
(3) Crystallizing the reaction raw material A under the condition of stirring at 88-98 ℃, and supplementing a second silicon source after the crystallization time reaches 1-70 h to obtain a reaction raw material B, wherein the second silicon source accounts for 0.1-10% by weight of the total silicon amount in terms of silicon oxide;
(4) Crystallizing the reaction raw material B at 88-98 ℃ under stirring, and recovering a product;
(5) And (5) recovering the product for ion exchange.
14. The method for preparing a catalytic cracking catalyst according to claim 13, wherein the composition of the guiding agent is (10-17) SiO 2:(0.7～1.3)Al2O3:(11～18)Na2O:(200～350)H2 O.
15. The method of claim 13 wherein said second silicon source has a sodium content of <1 wt.% as Na 2 O.
16. The method for preparing a catalytic cracking catalyst according to claim 15, wherein the second silicon source is solid silica gel.
17. The method for producing a catalytic cracking catalyst according to claim 16, wherein the average pore diameter of the solid silica gel is 1.5 to 2.0nm, or the average pore diameter of the solid silica gel is 4.0 to 5.0nm, or the average pore diameter of the solid silica gel is 10.0nm or more, or the average pore diameter of the solid silica gel is 0.8nm or less.
18. The method for preparing a catalytic cracking catalyst according to claim 15, wherein the second silicon source is liquid silica gel.
19. The method for preparing a catalytic cracking catalyst according to claim 18, wherein the mass content of SiO 2 in the liquid silica gel is 1-30%.
20. The method for preparing a catalytic cracking catalyst according to claim 13, wherein the second silicon source accounts for 4-10 wt% of the total silicon charged, based on silicon oxide.
21. The method for producing a catalytic cracking catalyst according to claim 13, wherein the ion exchange in step (5) is ammonium ion exchange and/or rare earth ion exchange.
22. The method for producing a catalytic cracking catalyst according to claim 21, wherein the ion-exchanged product obtained in step (5) is further calcined.
23. The method for preparing a catalytic cracking catalyst according to claim 22, wherein the ion exchange comprises rare earth ion exchange, the rare earth content in the modified NSY molecular sieve obtained in the step (5) is 10-20 wt% calculated by RE 2O3, and the sodium oxide content is less than 2 wt%.
24. A catalytic cracking method comprising the step of contacting a hydrocarbon oil with the catalytic cracking catalyst of any one of claims 1 to 11.
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| CA2000327A1 (en) * | 1988-11-16 | 1990-05-16 | Lawrence B. Dight | Ultra high zeolite content fcc catalysts and method for making same from microspheres composed of a mixture of calcined kaolin clays |
| CN101746778B (en) * | 2008-11-28 | 2012-08-29 | 中国石油化工股份有限公司 | Composite material containing double-pore structure Y-type zeolite, and preparation method thereof |
| CN110523428B (en) * | 2018-05-24 | 2022-02-01 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst containing NaY molecular sieve composite material and preparation method thereof |
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| CN1621349A (en) * | 2003-11-28 | 2005-06-01 | 中国石油化工股份有限公司 | Preparation method of NaY molecular sieve |
| CN1709794A (en) * | 2004-06-16 | 2005-12-21 | 中国石油化工股份有限公司 | A kind of synthetic method of Y-type zeolite composite material |
| CN101250428A (en) * | 2008-04-07 | 2008-08-27 | 华东理工大学 | A kind of in-situ crystallization cracking catalyst and preparation method thereof |
| CN103657712A (en) * | 2012-09-14 | 2014-03-26 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
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