CN111672534B - Hydrocracking catalyst, and preparation method and application thereof - Google Patents
Hydrocracking catalyst, and preparation method and application thereof Download PDFInfo
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- CN111672534B CN111672534B CN202010521157.4A CN202010521157A CN111672534B CN 111672534 B CN111672534 B CN 111672534B CN 202010521157 A CN202010521157 A CN 202010521157A CN 111672534 B CN111672534 B CN 111672534B
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- hydrocracking catalyst
- alumina
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- 239000003054 catalyst Substances 0.000 title claims abstract description 128
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 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 96
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 70
- 239000010457 zeolite Substances 0.000 claims abstract description 70
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000002131 composite material Substances 0.000 claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 claims abstract description 46
- 239000002184 metal Substances 0.000 claims abstract description 42
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 38
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000000295 fuel oil Substances 0.000 claims abstract description 8
- 238000005216 hydrothermal crystallization Methods 0.000 claims abstract description 4
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 36
- -1 ammonium fluorosilicate Chemical compound 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 14
- 238000005342 ion exchange Methods 0.000 claims description 11
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 11
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 235000019353 potassium silicate Nutrition 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 150000002910 rare earth metals Chemical class 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims 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 claims description 4
- 239000010451 perlite Substances 0.000 claims description 4
- 235000019362 perlite Nutrition 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 150000004684 trihydrates Chemical class 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 230000032683 aging Effects 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
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims 7
- 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 5
- 229910052708 sodium Inorganic materials 0.000 claims 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 239000004115 Sodium Silicate Substances 0.000 claims 1
- 238000013019 agitation Methods 0.000 claims 1
- 150000003841 chloride salts Chemical class 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 229910052911 sodium silicate Inorganic materials 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 27
- 238000005336 cracking Methods 0.000 abstract description 13
- 238000009826 distribution Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 11
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 239000002808 molecular sieve Substances 0.000 description 31
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 30
- 239000003921 oil Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000002994 raw material Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000004438 BET method Methods 0.000 description 5
- 241000219782 Sesbania Species 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000002283 diesel fuel Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000011964 heteropoly acid Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- GGKNTGJPGZQNID-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-trimethylazanium Chemical compound CC1(C)CC([N+](C)(C)C)CC(C)(C)N1[O] GGKNTGJPGZQNID-UHFFFAOYSA-N 0.000 description 3
- 101710194905 ARF GTPase-activating protein GIT1 Proteins 0.000 description 3
- 102100029217 High affinity cationic amino acid transporter 1 Human genes 0.000 description 3
- 101710081758 High affinity cationic amino acid transporter 1 Proteins 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910001960 metal nitrate Inorganic materials 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 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 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 102100035959 Cationic amino acid transporter 2 Human genes 0.000 description 2
- 102100021391 Cationic amino acid transporter 3 Human genes 0.000 description 2
- 102100021392 Cationic amino acid transporter 4 Human genes 0.000 description 2
- 101710195194 Cationic amino acid transporter 4 Proteins 0.000 description 2
- 108091006231 SLC7A2 Proteins 0.000 description 2
- 108091006230 SLC7A3 Proteins 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005303 weighing Methods 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
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- B01J35/615—
-
- B01J35/617—
-
- B01J35/633—
-
- B01J35/635—
-
- B01J35/69—
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
-
- 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
-
- 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
Abstract
The invention provides a hydrocracking catalyst, a preparation method and application thereof. The hydrocracking catalyst comprises a carrier, a hydrogenation metal component and an auxiliary agent, wherein the hydrogenation metal component and the auxiliary agent exist in the form of metal oxides, the metal component comprises an oxide of a VIB group metal and an oxide of a VIII group metal, the carrier is prepared from an ammonium fluosilicate modified Y-type zeolite/alumina composite material, and the ammonium fluosilicate modified Y-type zeolite/alumina composite material is prepared by mixing active alumina, a guiding agent, a silicon source and water, performing hydrothermal crystallization and modifying ammonium fluosilicate. The invention also provides a preparation method of the hydrocracking catalyst. The invention further provides application of the hydrocracking catalyst in heavy oil hydrocracking. The hydrocracking catalyst provided by the invention has high hydrogenation activity, moderate acidity and cascade pore distribution, and can reduce secondary cracking of cracking products.
Description
Technical Field
The invention relates to the field of hydrocracking catalysis, in particular to a hydrocracking catalyst and a preparation method and application thereof.
Background
As crude oil becomes heavier and inferior, the hydrocracking unit feed becomes more heavier, which causes problems such as higher unit hydrogen consumption, lower yield, poorer product quality, and shorter operating cycle. In the secondary processing technology of crude oil, the distillate oil hydrocracking technology has the characteristics of strong raw material adaptability, high flexibility of production operation and product scheme, good product quality and the like, can directly convert various heavy and inferior raw materials into high-quality jet fuel, diesel oil, lubricating oil base materials, chemical naphtha and tail oil steam cracking ethylene raw materials and the like which are urgently needed in the market, plays the role of a product distribution and product quality regulator in the whole factory production flow, is the core of oil-chemical-fiber combination, and becomes one of the most important heavy oil deep processing technologies in the modern oil refining and petrochemical industry. The development of high-level hydrocracking catalysts is key to the advancement of hydrocracking technology.
The hydrogenation process is the only way to realize the heavy oil lightening and cleaning process, and the technology depends on the improvement of the catalyst performance, namely the core is the research and development of the hydrogenation catalyst. The hydrocracking catalyst is a bifunctional catalyst having both an acidic function and a hydrogenation function, the cracking function being provided by an acidic support, particularly a molecular sieve, and the hydrogenation function being provided by an active metal component. The innovation of the molecular sieve is a source spring for improving the flexibility of the hydrocracking catalyst, mainly realizes the improvement of performances in the aspects of activity, selectivity, temperature sensitivity and the like of the hydrocracking catalyst by the innovation of the preparation and modification modes of the molecular sieve, improves the surface acidity of a catalyst carrier, enlarges and prepares multistage pore channels and improves the dispersion degree of active metals on the surface of the carrier, is an effective method for improving the activity of the catalyst, and particularly has great influence on the service life and the catalytic effect of the catalyst due to the structure of the pores of the catalyst carrier.
The acid function of the hydrocracking catalysts referred to in US5536687, US5447623 and EP0028938A1 is mainly provided by molecular sieves, whereas the hydrogenation component is selected from Mo-Ni or W-Ni. The catalyst of CN1389545A contains Y zeolite 20-40 wt%, phosphotungstic heteropoly acid or silicotungstic heteropoly acid 5-20 wt%, nickel oxide 5-10 wt% and alumina 40-60 wt%. The hydrocracking catalyst containing the molecular sieve has the advantages of strong acidity and large specific surface, but has the defect that the molecular sieve has small pore diameter, so that the diffusion resistance of reactants and products is increased, and the probability of secondary cracking reaction is increased.
Cn20110350796. X discloses a hydrocracking catalyst and a method of preparing the same. The catalyst comprises an acidic component, a hydrogenation component and a carrier, wherein the acidic component is heteropolyacid alkali metal salt, the hydrogenation component is nickel, and the carrier is silicon oxide; the catalyst comprises, by mass, 10% -20% of an acidic component, 3% -8% of a hydrogenation component and the balance of a carrier. The method adopts a sol-gel method to prepare a catalyst carrier, introduces a hydrogenation metal component and alkali metal salt in the carrier preparation process, immerses the carrier in a heteropolyacid solution, and dries to obtain the catalyst. The catalyst disclosed by the invention has the advantages that heteropolyacid salt is uniformly dispersed in a carrier, and the catalyst has low acid content and relatively low activity, and shows high liquid hydrocarbon selectivity.
In summary, the dual-function hydrocracking catalyst plus dehydrogenation function is provided primarily by the hydrogenation metal, which typically comprises conventional non-noble metal components, such as W, mo, ni, co, etc., with the noble metals typically being selected from Pt, pa. Typically the cracking function is provided by the acidic support component, which consists essentially of molecular sieves and amorphous oxides. The hydrocracking catalyst carrier is mainly an acidic component and plays a very important role in the activity, selectivity and product quality of the catalyst. For hydrocracking catalysts, the selectivity of the target product must be considered while the activity of the catalyst is important, so that a relatively reasonable balance must be found between the activity of the catalyst and the selectivity of the target product to better exert the performance of the catalyst. Y-type molecular sieves are commonly used hydrocracking catalyst supports. The current methods for the industrial production of Y-type molecular sieves are essentially all the guiding agent methods proposed by the us GRACE company in USP 3639099 and USP 4166099. The pore diameter of the pore canal of the Y-type molecular sieve raw powder is 0.74nm multiplied by 0.74nm, and the micropore volume of the Y-type molecular sieve raw powder accounts for more than 95 percent of the total pore volume. The diameter of the polycyclic heavy component molecules in the hydrocracking raw material is generally more than 1nm, and for the cracking reaction of heavy component macromolecules, the ideal pore diameter range suitable for the reaction and product diffusion is the mesoporous range of 2 nm-10 nm, so that more accessible acid centers can be exposed, and the adsorption and reaction of the raw material macromolecules and the desorption and diffusion of target products are facilitated, thereby improving the hydrocracking selectivity of the molecular sieve. In order to improve the condition that the mesoporous volume content of the Y-type molecular sieve is low and is not beneficial to the macromolecular reaction of the raw oil, the modification treatment is generally carried out on the raw powder of the Y-type molecular sieve, so that the modified Y-type molecular sieve with different pore structures and acid distribution can be obtained.
The total pore volume and the mesoporous pore volume of the molecular sieve prepared by the conventional modification method are smaller, the conversion of raw material macromolecules is not facilitated, the acid distribution is unreasonable, the heavy oil cracking performance of the catalyst is relatively poor, and zeolite components dispersed in the catalyst can be gradually sealed and embedded in a severe repeated reaction-regeneration cycle, so that the due catalytic effect is lost.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a hydrocracking catalyst, and a preparation method and application thereof. The hydrocracking catalyst has high hydrogenation activity, moderate acidity and cascade pore distribution through the mutual coordination among a carrier prepared from the ammonium fluosilicate modified Y-type zeolite/alumina composite material, a hydrogenation metal component and an auxiliary agent, so that the primary cracking product is more in hydrogenation saturation and isomerization on a hydrogenation active center, and the secondary cracking of the cracking product is reduced.
In order to achieve the above object, the present invention provides a hydrocracking catalyst comprising: the catalyst comprises a carrier, a hydrogenation metal component and an auxiliary agent, wherein the hydrogenation metal component and the auxiliary agent exist in the form of metal oxides, and the metal component comprises oxides of VIB group metals and VIII group metals; the catalyst comprises, based on 100% of the total weight of the catalyst: 55-88% of carrier, 10-25% of oxide of VIB group metal, 1-10% of oxide of VIII group metal and 1-10% of auxiliary agent;
wherein the carrier is prepared from an ammonium fluosilicate modified Y-type zeolite/alumina composite material; the ammonium fluosilicate modified Y-type zeolite/alumina composite material is prepared by mixing active alumina, a guiding agent, a silicon source and water, performing hydrothermal crystallization and modifying the ammonium fluosilicate, wherein the dosage ratio of the active alumina, the guiding agent, the silicon source and the water is as follows 2 O：Al 2 O 3 ：SiO 2 ：H 2 O= (0.1-1.5): 1: (0.1-5): (2-100) by firing one of kaolin, expanded perlite and gamma-alumina.
In a specific embodiment of the present invention, the ammonium fluorosilicate modified Y-zeolite/alumina composite is a composite formed by intimate bonding of activated alumina and a Y-molecular sieve. The ammonium fluosilicate modified Y-type zeolite/alumina composite material not only has the characteristic that activated alumina and a Y-type molecular sieve are compounded to form specific gradient pore distribution, but also has the characteristic that single activated alumina or Y-type molecular sieve does not have, for example, the ammonium fluosilicate modified Y-type zeolite/alumina composite material has good heat conduction capability in practical application, and good reaction performance and stability are both considered.
In the above hydrocracking catalyst, preferably, the hydrocracking catalyst carrier has SiO 2 /Al 2 O 3 The molar ratio is 4-50.
In a particular embodiment of the invention, the support generally has a specific surface area of 650m or less 2 Preferably less than or equal to 500m 2 /g。
In the hydrocracking catalyst, the auxiliary agent can improve the carrier of the hydrocracking catalyst and the pore structure of the hydrocracking catalyst, and can effectively improve the surface acidity of the catalyst. Preferably, the metal element in the auxiliary agent comprises one or a combination of more than two of Zn, ga, B, ti and Zr.
In the above hydrocracking catalyst, preferably, the group VIB metal comprises W and/or Mo.
In the above hydrocracking catalyst, preferably, the group VIII metal comprises Ni and/or Co.
According to a specific embodiment of the present invention, in the preparation of the ammonium fluorosilicate modified Y-zeolite/alumina composite, the gamma-alumina preferably comprises pseudo-boehmite and/or alumina trihydrate.
According to a specific embodiment of the present invention, the silicon source may comprise water glass and/or silica sol during the preparation of the ammonium fluorosilicate modified Y-zeolite/alumina composite.
According to a specific embodiment of the present invention, during the preparation of the ammonium fluorosilicate modified Y-type zeolite/alumina composite, the directing agent may be obtained according to the method disclosed in CN1785808A (application number: CN200410097108.3, title: a method for preparing a small-grain NaY molecular sieve having a high silica-alumina ratio, publication day: 20060614), the entire contents of which are incorporated herein by reference.
In a specific embodiment of the invention, in the preparation process of the ammonium fluosilicate modified Y-type zeolite/alumina composite material, the activated alumina is used as an aluminum source for preparing the Y-type zeolite, and has high heat-resistant stability, good pore characteristics and surface properties. The active alumina is crystallized after being mixed with a guiding agent, a silicon source and water to generate Y-type zeolite, and then is modified by ammonium fluosilicate to finally form the ammonium fluosilicate modified Y-type zeolite/alumina composite material. In the crystallization process, the special pore properties of the activated alumina are reserved to the greatest extent; the Y-type zeolite formed by crystallization is used as an active component of the composite material, so that the acidity of the obtained composite material is improved to a great extent, which is far higher than that of a catalyst carrier formed by pure active alumina or an impregnated modified active alumina matrix. Meanwhile, the Y-type zeolite contained in the composite material can reduce the dosage of expensive molecular sieves and reduce the cost.
According to a specific embodiment of the present invention, in the ammonium fluorosilicate modified Y-type zeolite/alumina composite, the Y-type zeolite may include one or a combination of two or more of HY-type zeolite, ultrastable Y-type zeolite, and rare earth ultrastable Y-type zeolite.
According to a specific embodiment of the present invention, in the preparation of the activated alumina, the time for firing one of kaolin, expanded perlite and gamma-alumina is generally controlled to be 4 to 10 hours, and the temperature for firing is generally controlled to be 450 to 1000 ℃, preferably 450 to 900 ℃.
According to a specific embodiment of the present invention, in the preparation process of the ammonium fluorosilicate modified Y-type zeolite/alumina composite, the crystallization temperature is generally controlled to be 70-120 ℃, and the crystallization time is generally controlled to be 0.5-72h, preferably 2-16h.
According to a specific embodiment of the present invention, the ammonium fluorosilicate modification method may include: adding (slowly dropwise adding) ammonium fluosilicate solution (preferably with concentration of 0.1-1.0 mol/L) into slurry formed by the Y-type zeolite/alumina composite material and water, stirring (the time can be controlled to be 1-2 h), filtering, washing and drying to obtain the ammonium fluosilicate modified Y-type zeolite/alumina composite material. In some embodiments, the ammonium fluorosilicate modification process described above may be performed at a temperature of 90 ℃.
According to a specific embodiment of the present invention, in the above-mentioned ammonium fluorosilicate modification method, the dosage ratio of the ammonium fluorosilicate to the Y-type zeolite/alumina composite material may be controlled to be 0.05 to 0.4mol:100g.
According to a specific embodiment of the present invention, the preparation process of the ammonium fluorosilicate modified Y-type zeolite/alumina composite may further include: the crystallized product is subjected to post-treatment prior to modification with ammonium fluorosilicate, which may include ion exchange, calcination, etc. of the crystallized product. In particular embodiments, the ion exchange may be an ammonium ion exchange, or may be a combination of ammonium ion and rare earth ion exchange (i.e., "ammonium+rare earth" ion exchange), and the rare earth ion used may be from a single rare earth element or from a combination of two or more rare earth elements. After ion exchange, na-type Y zeolite in the Y-type zeolite can be converted into one or a combination of more than two of HY-type zeolite, ultrastable Y-type zeolite and rare earth ultrastable Y-type zeolite. In the post-treatment process, the roasting temperature is generally controlled to be 300-900 ℃, and the roasting time is generally controlled to be 1-6 hours.
According to a specific embodiment of the invention, the carrier can be prepared by mixing an ammonium fluosilicate modified Y-type zeolite/alumina composite material with a binder (such as an aluminum sol) and sesbania powder.
According to a specific embodiment of the present invention, the preparation process of the carrier may specifically include:
step 1, roasting one of kaolin, expanded perlite and gamma-alumina to obtain activated alumina;
step 2, mixing active alumina, a guiding agent, a silicon source and water, and performing hydrothermal crystallization to obtain the Y-type zeolite/alumina composite material, wherein the dosage ratio of the active alumina to the guiding agent to the silicon source to the water is as follows Na 2 O：Al 2 O 3 ：SiO 2 ：H 2 O= (0.1-1.5): 1: (0.1-5): a molar ratio of (2-100); carrying out ammonium fluosilicate modification on the Y-type zeolite/alumina composite material to obtain an ammonium fluosilicate modified Y-type zeolite/alumina composite material;
and step 3, mixing the ammonium fluosilicate modified Y-type zeolite/alumina composite material with an adhesive and sesbania powder to obtain the hydrocracking catalyst carrier.
In a specific embodiment of the present invention, step 3 may further include, during the preparation of the above-mentioned carrier: grinding, extruding, forming, drying and roasting the mixture of the ammonium fluosilicate modified Y-type zeolite/alumina composite material, the adhesive and sesbania powder to obtain the hydrocracking catalyst carrier. In some embodiments, the binder used to prepare the hydrocracking catalyst support may be a conventional binder, such as an alumina sol.
In the specific embodiment of the invention, in the preparation process of the carrier, the mass ratio of the ammonium fluosilicate modified Y-type zeolite/alumina composite material, the binder and sesbania powder can be controlled to be 20:18:3.
The invention also provides a preparation method of the hydrocracking catalyst, which comprises the following steps:
preparing a metal salt co-soaking solution comprising metal elements in an auxiliary agent and metal elements in a hydrogenation metal component;
and step two, immersing the carrier in the metal salt co-impregnating solution, and drying and roasting to obtain the hydrocracking catalyst.
In the above-mentioned method for preparing a hydrocracking catalyst, the metal salt co-impregnating solution preferably includes one or a combination of two or more of nitrate, sulfate and chloride of a metal.
In the above-mentioned method for producing a hydrocracking catalyst, the concentration of the metal salt co-impregnating solution is preferably 1 to 100g/100mL.
In the above method for preparing a hydrocracking catalyst, preferably, in the second step, the roasting temperature is 450-1000 ℃ and the roasting time is 2-10 hours. More preferably, the calcination temperature is 500-600 ℃ and the calcination time is 4-6 hours.
The invention further provides application of the hydrocracking catalyst in heavy oil hydrocracking. The catalyst can be used as a treatmentHydrocracking catalysts for heavy oils, for example: at a total reaction pressure of 15MPa, the hydrogen-oil volume ratio is 1500:1, liquid hourly space velocity 1.5h -1 Adopts a series one-step process flow, adopts the hydrocracking catalyst to treat vacuum distillate (VGO), and the selectivity of the middle distillate of the catalyst can reach 84.5 percent.
The invention has the beneficial effects that:
1. the carrier, the hydrogenation active component and the auxiliary agent in the hydrocracking catalyst provided by the invention are matched with each other, so that the hydrocracking catalyst has high hydrogenation activity, moderate acidity and cascade pore distribution, and the primary cracking product is subjected to hydrogenation saturation and isomerization on the hydrogenation active center more, so that the secondary cracking of the cracking product is reduced.
2. The hydrocracking catalyst provided by the invention has the advantages of both the activity of the catalyst and the selectivity of the catalyst to target products, can be modulated and controlled in pore distribution and acidity, and is beneficial to better playing the performance of the catalyst.
3. When the hydrocracking catalyst provided by the invention is used for hydrocracking heavy oil, particularly when heavy wax oil (VGO, CGO and DAO) is treated under high pressure (12-20 MPa), and poor diesel oil (coked diesel oil, catalytic diesel oil and the like) can be added, the hydrocracking catalyst has very high catalytic activity and middle distillate oil selectivity, the condensation point of diesel oil fraction is greatly reduced, the product property of middle distillate oil is improved, and the requirements of increasing the operation flexibility, increasing the device processing capacity and further increasing the yield of middle distillate oil of a refinery can be met.
Drawings
FIG. 1 is an XRD spectrum of sample A-1 of example 1, scanned over a range of 2 theta of 5 deg. -70 deg..
FIG. 2 is an XRD spectrum of sample A-1 of example 1, scanned over a range of 15-35.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
In the examples below, pseudo-boehmite was thermally converted to activated alumina at 450-900 ℃. The pseudo-boehmite may be selected from industrial products such as pseudo-boehmite from Shanxi aluminum factory; pseudo-boehmite synthesized by a pH swing method is also possible.
The guiding agent used in the following examples is obtained according to the preparation method of the guiding agent disclosed in CN1785808A (application number: CN200410097108.3, title of the invention: a preparation method of a small-grain NaY molecular sieve with high silicon-aluminum ratio, publication date: 20060614), specifically, the guiding agent is prepared by uniformly mixing a silicon source, an aluminum source, an alkali solution and water according to a certain molar ratio, stirring and aging.
The silicon source used in the examples below was water glass (available from Lanzhou petrochemical catalyst plant).
In the following examples and comparative examples, the relative crystallinity measurement was an XRD measurement produced by the Panac instruments Inc. of the Netherlands, instrument model PANalytical EMPYREAN, conventional analytical conditions were: cuK alpha radiation (wavelength is) The tube voltage was 40kV and the tube current was 40mA.
The Si/Al ratio was determined according to SH/T0339-92 standard method (see "chemical industry Standard Association", china Standard Press, 2000) and the unit cell constant a of NaY molecular sieves was calculated according to the following formula:
wherein lambda is the radiation wavelength of CuK alpha, h 2 +k 2 +l 2 Is the square of the X-ray diffraction miller index.
And then calculating the silicon-aluminum ratio of the NaY molecular sieve according to the Breck-Flanigen formula:
SiO 2 /Al 2 O 3 =2× (25.858-a)/(a-24.191), a being the unit cell constant of the NaY molecular sieve.
Specific surface area measurement the specific surface area was measured by BET method using ASAP2020 type automatic physical adsorption instrument from Micromeritics, USA, and the mesoporous volume and pore size distribution were measured by BJH method.
The catalyst reactivity prepared in examples and comparative examples was evaluated on a fixed bed hydrogenation test apparatus.
Example 1
The embodiment provides a preparation method of a hydrocracking catalyst, which comprises the following steps:
1. preparation of ammonium fluorosilicate modified Y-type zeolite/alumina composite material:
1. 200.06g of industrial pseudo-boehmite is placed in a muffle furnace, heated to 600 ℃ at a speed of 4 ℃/min and roasted for 4 hours to obtain the activated alumina.
2. 120.51g of water glass is placed in a beaker, the temperature in the beaker is controlled to be 60 ℃, 80g of guiding agent and 220.23g of deionized water are added, 100g of activated alumina is added, and the materials are fully and uniformly mixed to obtain a raw material mixture, wherein the guiding agent is prepared according to the method provided in the example 1 in CN 1785808A.
3. And (3) filling the raw material mixture into a stainless steel reaction kettle, crystallizing for 4 hours at 100 ℃, and then filtering, washing and drying to obtain the Y-type zeolite/alumina composite material.
4. The 300gY zeolite/alumina composite was weighed and added to 3000g of ammonium nitrate solution (0.1 mol/L concentration) and ion exchanged in a 90℃water bath for 1h. Filtering, washing, drying at 120 ℃ for 10h, and roasting at 540 ℃ for 4h for later use.
5. 0.5mol/L ammonium fluorosilicate solution was prepared, and the 100gY zeolite/alumina composite was added to 1L deionized water to form a slurry, which was stirred in a constant temperature water bath at 90 ℃. And (3) dropwise adding 500mL of the prepared ammonium fluosilicate solution into the slurry of the Y-type zeolite/alumina composite material within 2h, and continuously stirring for 1h after the dropwise adding is finished. And (3) carrying out suction filtration, washing and drying for 12 hours at 120 ℃ to obtain the ammonium fluosilicate modified Y-type zeolite/alumina composite material.
2. Preparation of the carrier:
6. weighing the ammonium fluosilicate modified Y-type zeolite/alumina composite material, the adhesive and sesbania powder according to the mass ratio of 20:18:3, mixing, grinding, extruding and forming. Then drying for 10h at room temperature, drying for 10h at 120 ℃, and roasting for 4h at 550 ℃, wherein the finally obtained carrier is the hydrocracking catalyst carrier, and is marked as an A-1 sample.
XRD characterization was performed on sample A-1, with scan ranges 2 theta of 5 deg. -70 deg. and 15 deg. -35 deg., respectively, and the XRD diffraction patterns obtained are shown in figures 1 and 2. As can be seen from fig. 1 and 2, sample a-1 has characteristic peaks of the Y-type molecular sieve.
According to the result of XRD scanning, the crystallinity of sample A-1 was 15%, siO 2 /Al 2 O 3 The molar ratio is 10.51; specific surface area of sample A-1 measured by BET method was 309m 2 Per gram, total pore volume of 0.565cm 3 BJH method for measuring mesoporous volume of sample A-1 to 0.395cm 3 The peak values of the mesoporous pore size distribution were at 4.1nm and 9.8 nm.
3. Preparation of hydrocracking catalyst:
7. the carrier A-1 is immersed in a mixed metal nitrate solution containing Zn, zr, ni and W for 2 hours at room temperature, dried for 4 hours at 120 ℃, and baked for 4 hours at 500 ℃ with a programmed temperature, and the catalyst is named CAT-1.
The catalyst CAT-1 has a mass fraction of 61% of the support, a mass fraction of 7% of NiO and WO 3 The mass fraction of (2) was 22%, the mass fraction of ZnO was 5%, and the mass fraction of ZrO was 5%.
Example 2
The embodiment provides a preparation method of a hydrocracking catalyst, which comprises the following steps:
1. preparation of ammonium fluorosilicate modified Y-type zeolite/alumina composite material:
1. 500.15g of industrial pseudo-boehmite is placed in a muffle furnace, heated to 700 ℃ at a speed of 4 ℃/min and roasted for 4 hours to obtain the activated alumina.
2. 140.84g of water glass is placed in a beaker, the temperature in the beaker is controlled to be 60 ℃, 130.25g of guiding agent and 150g of deionized water are added, 200.7g of activated alumina is added, stirring is carried out for 3 hours, and a raw material mixture is obtained after full and uniform mixing, wherein the guiding agent is prepared by the same method as in example 1.
3. And (3) filling the raw material mixture into a stainless steel reaction kettle, crystallizing at 100 ℃ for 72 hours, and then filtering, washing and drying to obtain the Y-type zeolite/alumina composite material.
4-5 the sample of the Y zeolite/alumina composite was modified with ammonium fluorosilicate in the same manner as in step 4-5 of example 1 except that the ammonium nitrate solution was changed to an ammonium chloride solution to give an ammonium fluorosilicate-modified Y zeolite/alumina composite.
2. Preparation of the carrier:
6. the ammonium fluorosilicate modified Y zeolite/alumina composite described above was prepared as a support, designated A-2, in accordance with the procedure of step 6 of example 1.
XRD characterization was performed on sample A-2, and the obtained XRD diffraction pattern was similar to that obtained in example 1, with sample A-2 having characteristic peaks of the Y-type molecular sieve.
According to the result of XRD scanning, the crystallinity of sample A-2 was 49%, siO 2 /Al 2 O 3 The molar ratio is 6.58; specific surface area of sample A-2 measured by BET method was 509m 2 Per gram, a total pore volume of 0.568cm 3 BJH method for measuring mesoporous volume of sample A-2 to 0.405cm 3 The peak values of the mesoporous pore size distribution were at 4.0nm and 9.8 nm.
3. Preparation of hydrocracking catalyst:
7. the carrier A-2 is immersed in a mixed metal chloride solution containing Zn, zr, ni and Mo for 2 hours at room temperature, dried for 4 hours at 120 ℃, and baked for 4 hours at 540 ℃ with the programmed temperature to obtain the catalyst, which is named CAT-2.
The mass fraction of the carrier in the catalyst CAT-2 is measured to be 60.9%, the mass fraction of NiO is measured to be 7.0%, and MoO is measured to be 7 3 22.1% by mass, 5.0% by mass, and 5.0% by mass of ZrO.
Example 3
The embodiment provides a preparation method of a hydrocracking catalyst, which comprises the following steps:
1. preparation of ammonium fluorosilicate modified Y-type zeolite/alumina composite material:
1. 200.11g of alumina trihydrate is placed in a muffle furnace, heated to 600 ℃ at a heating rate of 4 ℃/min, and baked for 2 hours to obtain the active alumina.
2. 149.66g of water glass is placed in a beaker, 100.02g of a guiding agent and 150g of deionized water are added, 80.51g of activated alumina is added, and the materials are stirred and mixed uniformly to obtain a raw material mixture, wherein the guiding agent is prepared by the same method as in example 1.
3. And (3) filling the raw material mixture into a stainless steel reaction kettle, crystallizing for 5 hours at 110 ℃, and then filtering, washing and drying to obtain the Y-type zeolite/alumina composite material.
4-5, carrying out ammonium fluosilicate modification on the Y-type zeolite/alumina composite material sample according to the method of the step 4-5 in the example 1 to obtain the ammonium fluosilicate modified Y-type zeolite/alumina composite material.
2. Preparation of the carrier:
6. the prepared ammonium fluorosilicate modified Y-type zeolite/alumina composite sample was prepared as a support, designated A-3, in accordance with the procedure of step 6 in example 1.
XRD characterization of sample A-3 gave an XRD diffraction pattern similar to that obtained in example 1. Sample A-3 has a characteristic peak of the Y-type molecular sieve.
According to the result of XRD scanning, the crystallinity of sample A-3 was 15%, siO 2 /Al 2 O 3 The molar ratio is 8.36; specific surface area of sample A-3 measured by BET method was 419m 2 Per gram, total pore volume of 0.468cm 3 BJH method for measuring mesoporous volume of sample A-3 to 0.325cm 3 And/g, the peak value of the mesoporous pore size distribution is 3.8nm and 9.2 nm.
3. Preparation of hydrocracking catalyst:
7. immersing the carrier A-3 in mixed metal nitrate co-soaking solution containing Zn, ga, ni and W for 2 hours at room temperature, drying at 120 ℃ for 4 hours, and roasting at 500 ℃ for 4 hours at a programmed temperature to obtain the catalyst which is named CAT-3.
The catalyst CAT-3 has a mass fraction of 70% of the support, a mass fraction of 5% of NiO and WO 3 20% by mass of ZnO, 2% by mass of GaOThe fraction was 3%.
Example 4
The embodiment provides a preparation method of a hydrocracking catalyst, which comprises the following steps:
1. preparation of ammonium fluorosilicate modified Y-type zeolite/alumina composite material:
1-5, ammonium fluorosilicate modified Y-type zeolite/alumina composite was prepared in substantially the same manner as provided in example 1, except that the crystallization time in step 3 was 32 hours.
2. Preparation of the carrier:
6. the ammonium fluorosilicate modified Y zeolite/alumina composite obtained above was prepared as a support, designated A-4, in accordance with the procedure of step 6 in example 1.
XRD characterization of sample A-4 gave an XRD diffraction pattern similar to that obtained in example 1. Sample A-4 has a characteristic peak of the Y-type molecular sieve.
As a result of XRD scanning, it was found that the crystallinity of sample A-4 was 16%, siO 2 /Al 2 O 3 The molar ratio is 6.16; specific surface area of sample A-4 measured by BET method was 319m 2 Per gram, total pore volume of 0.361cm 3 BJH method for measuring mesoporous volume of sample A-4 to 0.225cm 3 And/g, the peak value of the mesoporous pore size distribution is 3.8nm and 4.2 nm.
3. Preparation of hydrocracking catalyst:
soaking the carrier A-4 in mixed metal nitrate co-soaking solution containing Zn, ti, ni and Mo at room temperature for 2 hr, drying at 120 deg.c for 4 hr, and roasting at 500 deg.c for 4 hr to obtain catalyst named CAT-4.
In the catalyst CAT-4, the mass fraction of the carrier is 55%, the mass fraction of NiO is 6%, and the mass fraction of MoO is measured 3 The mass fraction of (2) is 24%, the mass fraction of ZnO is 6%, and the mass fraction of TiO is 9%.
Test example 1
The CAT-1 catalyst sample prepared in example 1 was evaluated on a fixed bed hydrogenation test apparatus under the following conditions: the total reaction pressure is 15MPa, and the hydrogen-oil volume ratio is 1500:1 liquid time volumeAirspeed 1.5h -1 A series of one-pass process was used, using vacuum distillate (VGO) as the feedstock oil, the properties of which are shown in Table 1, and the evaluation results are shown in Table 2.
Comparative example 1
The comparative example provides a preparation method for preparing a hydrocracking catalyst by taking activated alumina as a carrier, which comprises the following steps:
300.16g of industrial pseudo-boehmite is placed in a muffle furnace, heated to 600 ℃ at a speed of 4 ℃/min and roasted for 4 hours, so that the pseudo-boehmite is subjected to full thermal conversion, and the activated alumina is obtained.
According to the preparation method and the proportion of the catalyst provided in example 1, the active alumina was used instead of the carrier A-1 in example 1 to prepare the catalyst CD-1 for comparison with the catalyst performance in test example 1.
The CD-1 catalyst samples were evaluated on a fixed bed hydrogenation test apparatus under the same conditions as in test example 1. The vacuum distillate (VGO) was used as the raw oil, the properties of the raw oil were shown in Table 1, and the evaluation results are shown in Table 2.
Comparative example 2
This comparative example provides a process for preparing a hydrocracking catalyst, the process being similar to that of test example 1, except that:
according to the crystallinity of the Y-type zeolite in the sample A-1 obtained in example 1, the activated alumina prepared in comparative example 1 and a process USY molecular sieve (manufactured by Lanzhou petrochemical catalyst Co., ltd.) were mechanically mixed to obtain a sample having the same Y molecular sieve content, and the hydrocracking catalyst was prepared by substituting the sample for the support A-1 in example 1, and the preparation method was the same as in example 1, and the obtained catalyst was designated as CD-2.
The CD-2 catalyst samples were evaluated on a fixed bed hydrogenation test apparatus under the same conditions as in test example 1. The vacuum distillate (VGO) was used as the raw oil, the properties of the raw oil were shown in Table 1, and the evaluation results are shown in Table 2.
TABLE 1
| Raw oil | Vacuum distillate |
| Density (20 ℃ C.)/(g/cm) 3 ) | 0.8672 |
| Distillation range, DEG C | |
| IBP,m％ | 304/362 |
| 30％/50％ | 394/418 |
| 70％/90％ | 443/482 |
| 95％/EBP | 507/550 |
| Condensation point, DEG C | 35 |
| Sulfur, wt% | 1.99 |
| Nitrogen, wt% | 1227 |
| Carbon, wt% | 85.27 |
| Hydrogen, wt% | 12.47 |
| BMCI value | 45.0 |
Table 2 comparative hydrocracking performance of catalyst
As can be seen from the evaluation results of Table 2, under the same process conditions, the hydrocracking experiment is carried out by adopting the hydrocracking catalyst provided by the invention, and the selectivity, the yield and the product quality of the measured middle distillate are all superior to those of the comparative catalyst.
Claims (21)
1. A hydrocracking catalyst comprising: the catalyst comprises a carrier, a hydrogenation metal component and an auxiliary agent, wherein the hydrogenation metal component and the auxiliary agent exist in a metal oxide form, and the hydrogenation metal component comprises an oxide of a VIB group metal and an oxide of a VIII group metal;
the catalyst comprises, based on 100% of the total weight of the catalyst: 55-88% of carrier, 10-25% of oxide of VIB group metal, 1-10% of oxide of VIII group metal and 1-10% of auxiliary agent;
wherein the carrier is prepared by mixing ammonium fluosilicate modified Y-type zeolite/alumina composite material with an adhesive and sesbania powder;
the ammonium fluosilicate modified Y-type zeolite/alumina composite material is prepared by mixing active alumina, a guiding agent, a silicon source and water, carrying out hydrothermal crystallization and modifying the ammonium fluosilicate, wherein the dosage ratio of the active alumina, the guiding agent, the silicon source and the water is as follows 2 O：Al 2 O 3 ：SiO 2 ：H 2 O= (0.1-1.5): 1: (0.1-5): the molar ratio of (2-100) is determined, the activated alumina is obtained by roasting one of kaolin, expanded perlite and gamma-alumina, the roasting time is 4-10h, and the roasting temperature is 450-1000 ℃;
the metal element in the auxiliary agent comprises one or more than two of Zn, ga, B, ti and Zr;
the group VIB metal comprises W and/or Mo;
the group VIII metal comprises Ni and/or Co;
the SiO 2/Al 2O3 molar ratio of the carrier is 4-50;
the silicon source comprises water glass and/or silica sol;
the gamma-alumina comprises pseudo-boehmite and/or alumina trihydrate;
the preparation method of the guiding agent comprises the following steps: dissolving 10.53g of sodium hydroxide solid in 30.95g of water, cooling to room temperature, adding 2.22g of sodium metaaluminate to prepare a high-alkali sodium metaaluminate solution, adding 36.73g of sodium silicate into the high-alkali sodium metaaluminate solution, uniformly mixing, and stirring and aging at 40 ℃ for 4 hours to prepare a guiding agent; al of the sodium metaaluminate 2 O 3 45wt% of Na of the sodium metaaluminate 2 O content is 41wt%, siO of the water glass 2 The content of Na of the water glass is 28.83 weight percent 2 The O content was 8.84wt%.
2. The hydrocracking catalyst according to claim 1, wherein the specific surface area of the carrier is 650m or less 2 /g。
3. The hydrocracking catalyst according to claim 1, wherein the specific surface area of the carrier is 500m or less 2 /g。
4. A hydrocracking catalyst according to any one of claims 1 to 3 wherein the calcination temperature is in the range 450-900 ℃ during the preparation of the activated alumina.
5. The hydrocracking catalyst according to claim 4, wherein the crystallization temperature is 70-120 ℃ and the crystallization time is 0.5-72h during the preparation of the ammonium fluosilicate modified Y-type zeolite/alumina composite during the preparation of the activated alumina.
6. The hydrocracking catalyst according to claim 5, wherein the crystallization time is 2 to 16 hours during the preparation of the activated alumina, during the preparation of the ammonium fluorosilicate modified Y-zeolite/alumina composite.
7. A hydrocracking catalyst according to any one of claims 1 to 3 wherein the ammonium fluorosilicate modification process comprises: and adding ammonium fluosilicate solution into slurry formed by the Y-type zeolite/aluminum oxide composite material and water, stirring, filtering, washing and drying to obtain the ammonium fluosilicate modified Y-type zeolite/aluminum oxide composite material.
8. The hydrocracking catalyst of claim 7, wherein the ammonium fluorosilicate to Y zeolite/alumina composite ratio is from 0.05 to 0.4mol:100g.
9. The hydrocracking catalyst of claim 7, wherein the concentration of the ammonium fluorosilicate solution is 0.1-1.0mol/L.
10. The hydrocracking catalyst of claim 7, wherein the ammonium fluorosilicate modification is performed at a temperature of 90 ℃.
11. The hydrocracking catalyst of claim 7, wherein the agitation time is from 1 to 2 hours.
12. A hydrocracking catalyst according to any one of claims 1 to 3 wherein the preparation of the ammonium fluorosilicate modified Y zeolite/alumina composite further comprises: and carrying out post-treatment on the crystallized product before carrying out ammonium fluosilicate modification, wherein the post-treatment comprises ion exchange and roasting on the crystallized product.
13. The hydrocracking catalyst according to claim 12, wherein the calcination temperature is 300-900 ℃ and the calcination time is 1-6h during the post-treatment.
14. The hydrocracking catalyst of claim 12, wherein the ion exchange is ammonium ion exchange or a combination of ammonium ion exchange and rare earth ion exchange.
15. The hydrocracking catalyst of claim 14, wherein the rare earth ions are from a single rare earth element or a combination of two or more rare earth elements.
16. The method for producing a hydrocracking catalyst as claimed in any one of claims 1 to 15, which comprises:
preparing a metal salt co-soaking solution comprising metal elements in an auxiliary agent and metal elements in a hydrogenation metal component;
and secondly, immersing the carrier in the metal salt co-impregnating solution, drying and roasting to obtain the hydrocracking catalyst.
17. The method of claim 16, wherein the metal salt co-impregnating solution comprises one or a combination of two or more of nitrate, sulfate, chloride salts of a metal.
18. The method of claim 16, wherein the concentration of the metal salt co-impregnating solution is 1-100g/100mL.
19. The method according to claim 16, wherein in the second step, the baking temperature is 450-1000 ℃ and the baking time is 2-10 hours.
20. The method according to claim 19, wherein the firing temperature is 500 to 600 ℃ and the firing time is 4 to 6 hours.
21. Use of the hydrocracking catalyst of any one of claims 1-15 in heavy oil hydrocracking.
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