CN117960234A - Composite catalytic material and preparation method and application thereof - Google Patents
Composite catalytic material and preparation method and application thereof Download PDFInfo
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- CN117960234A CN117960234A CN202211282673.1A CN202211282673A CN117960234A CN 117960234 A CN117960234 A CN 117960234A CN 202211282673 A CN202211282673 A CN 202211282673A CN 117960234 A CN117960234 A CN 117960234A
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- 239000000463 material Substances 0.000 title claims abstract description 80
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 42
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052802 copper Inorganic materials 0.000 claims abstract description 40
- 239000010949 copper Substances 0.000 claims abstract description 40
- 239000002707 nanocrystalline material Substances 0.000 claims abstract description 26
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002149 hierarchical pore Substances 0.000 claims abstract description 7
- 238000003795 desorption Methods 0.000 claims abstract description 6
- 238000010521 absorption reaction Methods 0.000 claims abstract description 4
- 239000012265 solid product Substances 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 23
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 238000004523 catalytic cracking Methods 0.000 claims description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- 239000010703 silicon Substances 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 17
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 14
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 14
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 10
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 235000019270 ammonium chloride Nutrition 0.000 claims description 7
- 238000010304 firing Methods 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- 229960004643 cupric oxide Drugs 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 3
- 229940116318 copper carbonate Drugs 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 3
- 229940112669 cuprous oxide Drugs 0.000 claims description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical group CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 20
- 239000002808 molecular sieve Substances 0.000 description 18
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000001035 drying Methods 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
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- 230000000052 comparative effect Effects 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
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- 238000006722 reduction reaction Methods 0.000 description 5
- 230000005284 excitation Effects 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000000571 coke Substances 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
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- 230000008569 process Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- -1 ethylene, propylene, butylene Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
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- 238000004438 BET method Methods 0.000 description 1
- 239000005751 Copper oxide Substances 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
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
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- 239000012670 alkaline solution Substances 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 239000002775 capsule Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 239000011258 core-shell material Substances 0.000 description 1
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Abstract
The invention relates to a composite catalytic material, a preparation method and application thereof, wherein the composite catalytic material has a structure that a hollow hierarchical pore ZSM-5 nanocrystalline material encapsulates a copper-containing heating material; wherein the hollow multistage hole ZSM-5 nanocrystalline material has a closed hollow structure, the average grain size is 0.4-3.0 mu m, the ratio of bulk phase silicon aluminum mol ratio to surface silicon aluminum mol ratio is 1.0-1.2, the total specific surface area is 340-400m 2/g, and the mesoporous specific surface area is 40-150m 2/g,N2 absorption and desorption curve presents an H4 type hysteresis ring. The composite catalytic material has good catalytic activity and good heat-emitting performance and carbon deposition resistance.
Description
Technical Field
The invention relates to a composite catalytic material, a preparation method and application thereof.
Background
The hollow material has special micro-environment in the capsule and unique space limiting effect, and has excellent performance in heterogeneous catalysis, biomedicine, adsorption separation, energy storage and other aspects. The hollow ZSM-5 molecular sieve has a nanoscale hierarchical pore shell and a relatively closed internal structure, has the advantages of strong acidity, excellent diffusion performance, outstanding encapsulation capacity and the like, and is a high-value material with extremely rich potential in the fields of industrial catalysis, adsorption separation and the like. CN106082263B develops a shell layer hole-rich nano hollow ZSM-5 molecular sieve, which is prepared by mixing ethyl orthosilicate, tetrapropylammonium hydroxide, aluminum nitrate, sodium hydroxide and deionized water as raw materials, and aging, crystallizing, centrifuging, washing, drying and roasting the solution to obtain the nano ZSM-5 molecular sieve; the nanometer ZSM-5 molecular sieve is added with inorganic alkaline solution, stirred for 10 to 50 hours, separated, washed and dried to obtain the nanometer ZSM-5 with a hollow structure, the raw materials used in the preparation method are single, the size of the obtained product is 50 to 100nm, the mesopores are too large, and the hydrothermal stability and the mechanical strength are further improved.
The catalytic cracking device is a core device for secondary processing of a refinery, and is used for converting distillate oil or residual oil raw oil obtained by an atmospheric and vacuum tower into liquefied gas, gasoline, diesel oil and other fuels or ethylene, propylene, butylene, BTX and other chemical raw materials under the action of a catalyst and high temperature. The catalyst is not only the reactive center of the catalytic cracking reaction, but also the heat and mass transfer carrier of the catalytic cracking reverse-recycling system. The catalyst is introduced into the reactor from a high-temperature regenerator to bring in a large amount of heat, so that catalytic cracking reaction is promoted to occur, and coke generated by the reaction is loaded on the surface of the catalyst. And then the air enters the regenerator to be burnt with oxygen in the air to generate a large amount of heat, so that heat transfer and generation are completed.
With the heavy and poor quality of the processed raw materials, the oil refining device is required to transform to chemical industry. The reaction conditions are more severe. However, the heat capacity of the catalyst is limited, resulting in limited heat supplied to the reaction part, so that it is difficult to further increase the reaction temperature; meanwhile, in order to transfer more heat, the agent-oil ratio is increased, so that more side reactions are brought.
In the field of catalytic cracking engineering design, an empirical formula is adopted for calculating the heat capacity of a catalyst: cp (J/(k·g))=0.00233×alumina% +1.08. Typically, the alumina has a heat capacity of from about 1.16 to about 1.22J/(. Degree.C.g) between about 35 and about 60%. In addition, the alumina content in the catalyst is stable, the fluctuation is small, and the heat capacity lifting amplitude is limited.
The heat generating material is heat released by the continuous oxidation-reduction reaction of metal and oxide thereof, and mainly utilizes the following reactions:
2Cu+O2→2CuO ΔH＝-156KJ/mol＝-1914J/g，
CuO+2H2→Cu+2H2O ΔH＝-95KJ/mol＝-1190J/g，
the heating effect of the heating material is obvious, but the contact of the heating material and heavy oil hydrocarbon molecules easily causes obvious increase of coke generation, and the problem of how to avoid or reduce the influence of the heating material on the reaction performance of the catalytic cracking catalyst is needed to be solved.
Disclosure of Invention
The invention aims to provide a composite catalytic material, a preparation method and application thereof, wherein the composite catalytic material has good catalytic activity and good heating effect, and can effectively inhibit dehydrogenation coking reaction of heavy oil hydrocarbon molecules on the surface of a catalyst.
In order to achieve the above object, a first aspect of the present invention provides a composite catalytic material having a structure in which a hollow multi-level pore ZSM-5 nanocrystalline material encapsulates a copper-containing heat generating material;
Wherein the hollow multistage hole ZSM-5 nanocrystalline material has a closed hollow structure, the average grain size is 0.4-3.0 mu m, the ratio of bulk phase silicon aluminum mol ratio to surface silicon aluminum mol ratio is 1.0-1.2, the total specific surface area is 340-400m 2/g, and the mesoporous specific surface area is 40-150m 2/g,N2 absorption and desorption curve presents an H4 type hysteresis ring.
Optionally, the composite catalytic material contains the hollow multistage pore ZSM-5 nanocrystalline material and the copper-containing heating material in a molar ratio of 1: (0.01-0.1), wherein the hollow hierarchical pore ZSM-5 nanocrystalline material is calculated as SiO 2, and the copper-containing heating material is calculated as CuO.
Optionally, the copper-containing heat generating material contains cuprous oxide and/or cupric oxide.
Optionally, the average grain size of the hollow multistage hole ZSM-5 nanocrystalline material is 0.4-2.5 mu m, the ratio of the bulk phase silicon aluminum molar ratio to the surface silicon aluminum molar ratio is 1-1.1, the total specific surface area is 360-400m 2/g, and the mesoporous specific surface area is 50-140m 2/g.
In a second aspect, the present invention provides a method for preparing the composite catalytic material provided in the first aspect, the method comprising:
S1, mixing a silicon source, a first copper source and a first solvent at 30-50 ℃ for reaction for 0.5-5 hours, heating to 70-100 ℃ for mixing and stirring for 2-10 hours, and mixing the obtained mixed liquid with a template agent at 20-30 ℃ for 0.5-3.0 hours to obtain a first mixed product;
S2, the molar ratio is (1.5-5): (60-350): 1, a second solvent and an aluminum source calculated as Al 2O3 at 20-80 ℃ for 0.5-2 hours to obtain a second mixed product;
s3, mixing the first mixed product and the second mixed product, then carrying out dynamic crystallization, taking out the obtained solid, and carrying out first roasting to obtain a first solid product;
S4, mixing the first solid product with a solution containing alkali, and reacting for 10-90min at the reaction temperature after the temperature rises to the reaction temperature at a heating rate of 1-5 ℃/min to obtain a second solid product; wherein the reaction temperature is 60-90 ℃, and the alkali content in the alkali-containing solution is 0.45-2mol/L;
S5, carrying out ammonium exchange on the second solid product, and carrying out second roasting on the solid product obtained by the ammonium exchange to obtain the composite catalytic material.
Optionally, the molar ratio of the total amount of the first copper source, the template agent, the first solvent and the second solvent, the alkali metal hydroxide, and the silicon source is (0.01-0.1): (0.06-0.55): (10-100): (0.02-1.5): 1, the molar ratio of the silicon source to the aluminum source is (20-500): 1, a step of; wherein the first copper source is calculated as CuO, the silicon source is calculated as SiO 2, the alkali metal hydroxide is calculated as alkali metal oxide, and the aluminum source is calculated as Al 2O3.
Optionally, in step S2, the molar ratio of the alkali metal hydroxide calculated as alkali metal oxide, the second solvent and the aluminum source calculated as Al 2O3 is (2-4.5): (80-350): 1.
Optionally, in step S4, the molar ratio of the first solid product to the amount of the alkali-containing solution is 1: (2-10), preferably 1: (4-8) the first solid product is in terms of SiO 2;
The ratio of the bulk silicon aluminum molar ratio to the surface silicon aluminum molar ratio of the first solid product is 1.2-5.0.
Optionally, step S5 further includes: in a reducing atmosphere, carrying out reduction treatment on the solid obtained by the second roasting to obtain the composite catalytic material;
The conditions of the reduction treatment include: the temperature is 600-750deg.C, and the time is 0.5-5min.
Optionally, in step S5, said subjecting said second solid product to ammonium exchange comprises: the weight ratio is 1: (0.5-1.0): after mixing the second solid product of (8-10), an ammonium source and a third solvent, reacting the resulting mixture at 70-90 ℃ for 0.5-2 hours; the ammonium source is selected from one or more of ammonium chloride, ammonium sulfate and ammonium nitrate.
Optionally, the conditions of the dynamic crystallization include: the temperature is 160-180 ℃ and the time is 12-60 hours;
The conditions of the first firing and the second firing each independently include: the temperature is 400-600 ℃ and the time is 2-6 hours.
Optionally, the template agent is selected from one or more of tetrapropylammonium bromide, tetrapropylammonium hydroxide, n-butylamine and hexamethylenediamine;
the silicon source is methyl orthosilicate and/or ethyl orthosilicate;
The first copper source is selected from one or more of copper sulfate, copper chloride, copper nitrate and copper carbonate;
the aluminum source is one or more of sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum isopropoxide and aluminum sol;
the alkali metal hydroxide is selected from one or more of lithium hydroxide, sodium hydroxide and potassium hydroxide;
The first solvent and the second solvent are each independently water.
The third aspect of the invention provides an application of the composite catalytic material provided by the first aspect of the invention in catalytic cracking reaction of heavy hydrocarbon oil.
Through the technical scheme, the composite catalytic material has good catalytic activity and good heating effect, can effectively inhibit dehydrogenation coking reaction of heavy oil hydrocarbon molecules on the surface of the catalyst, and can improve the yield of the low-carbon olefin.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present invention in detail. 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 first aspect of the invention provides a composite catalytic material, which has a structure that a hollow hierarchical pore ZSM-5 nanocrystalline material encapsulates a copper-containing heating material;
Wherein the hollow multistage hole ZSM-5 nanocrystalline material has a closed hollow structure, the average grain size is 0.4-3.0 mu m, the ratio of bulk phase silicon aluminum mol ratio to surface silicon aluminum mol ratio is 1.0-1.2, the total specific surface area is 340-400m 2/g, and the mesoporous specific surface area is 40-150m 2/g,N2 absorption and desorption curve presents an H4 type hysteresis ring.
The invention discloses a copper-containing heating material packaged by a hollow multi-level hole ZSM-5 nanocrystalline material, which means that the copper-containing heating material is contained in an intragranular hollow structure of the hollow multi-level hole ZSM-5 nanocrystalline material, the outer surface of the copper-containing heating material can be connected with the inner surface of the hollow multi-level hole ZSM-5 nanocrystalline material or not, and the composite catalytic material can also be called as having a core-shell structure when being connected together. According to the composite catalytic material, hydrocarbon molecules entering the surface of the internal copper-containing heating material are screened through the hollow multi-level hole ZSM-5 nanocrystalline material, so that the increase of coke generation caused by the fact that the copper-containing heating material is directly contacted with heavy oil hydrocarbon molecules as a dehydrogenation center is avoided, the influence of the copper-containing heating material on the reaction performance of a catalytic cracking catalyst is reduced, the heating effect and good catalytic activity of the composite catalytic material are simultaneously considered, and the yield of low-carbon olefin can be improved.
In one embodiment of the present invention, the copper-containing heat generating material is contained in an amount of 1 to 50% by weight, preferably 1 to 30% by weight, based on the dry weight of the composite catalytic material. In the invention, the XRF method is used for measuring the content of the copper-containing heating material in the composite catalytic material. The catalyst with the composition has good catalytic activity and better heating performance.
In the present invention, the molar ratio of the hollow multistage pore ZSM-5 nanocrystalline material to the copper-containing heat-generating material contained in the composite catalytic material may vary within a wide range, for example, may be 1: (0.01-0.1), wherein the hollow hierarchical pore ZSM-5 nanocrystalline material is calculated as SiO 2, and the copper-containing heating material is calculated as CuO.
In one embodiment of the present invention, the copper-containing heat generating material contains cuprous oxide and/or cupric oxide. In the invention, the XPS method can be used for detecting the valence state of copper.
In one embodiment of the present invention, the hollow, multi-stage pore ZSM-5 nanocrystalline material has an average crystallite size of 0.4 to 2.5. Mu.m. In the present invention, the grain size refers to the size of the widest part of the grains, which can be obtained by measuring the size of the widest part of the projection surface of the grains in an SEM or TEM image of a sample, and the average grain size is obtained by selecting any 10 molecular sieves in the SEM or TEM image and calculating the average value thereof.
In a specific embodiment of the invention, the ratio of bulk silica alumina molar ratio to surface silica alumina molar ratio of the hollow multistage hole ZSM-5 nanocrystalline material is 1-1.1, the total specific surface area is 360-400m 2/g, and the mesoporous specific surface area is 50-140m 2/g. Wherein, the bulk silicon-aluminum molar ratio refers to the silicon-aluminum molar ratio of the hollow multi-level pore ZSM-5 nanocrystalline material as a whole. Bulk silica to alumina molar ratio was determined by XRF method and surface silica to alumina molar ratio was determined by XPS method, specific test methods are well known to those skilled in the art and will not be described in detail herein. The total specific surface area and the mesoporous specific surface area are obtained by BET analysis.
In one embodiment of the present invention, the hollow, multi-stage pore ZSM-5 nanocrystalline material has a relative crystallinity of from 75 to 95%. In the invention, the relative crystallinity of the molecular sieve is based on an XRD standard ZSM-5 molecular sieve standard sample of China national institute of petrochemical industry, and the crystallinity of the standard sample is regarded as 100%.
In a second aspect, the present invention provides a method of preparing the composite catalytic material provided in the first aspect of the present invention, the method comprising: s1, mixing a silicon source, a first copper source and a first solvent at 30-50 ℃ for reaction for 0.5-5 hours, heating to 70-100 ℃ for mixing and stirring for 2-10 hours, and mixing the obtained mixed liquid with a template agent at 20-30 ℃ for 0.5-3.0 hours to obtain a first mixed product; s2, the molar ratio is (1.5-5): (60-350): 1, a second solvent and an aluminum source calculated as Al 2O3 at 20-80 ℃ for 0.5-2 hours to obtain a second mixed product; s3, mixing the first mixed product and the second mixed product, then carrying out dynamic crystallization, taking out the obtained solid, and carrying out first roasting to obtain a first solid product; s4, mixing the first solid product with a solution containing alkali, and reacting for 10-90min at the reaction temperature after the temperature rises to the reaction temperature at a heating rate of 1-5 ℃/min to obtain a second solid product; wherein the reaction temperature is 60-90 ℃, and the alkali content in the alkali-containing solution is 0.45-2mol/L; s5, carrying out ammonium exchange on the second solid product, and carrying out second roasting on the solid product obtained by the ammonium exchange to obtain the composite catalytic material.
According to the present invention, the molar ratio of the total amount of the first copper source, the template agent, the first solvent and the second solvent, the alkali metal hydroxide, and the silicon source is (0.01 to 0.1): (0.06-0.55): (10-100): (0.02-1.5): 1, preferably (0.02-0.08): (0.1-0.50): (15-85): (0.03-1.2): 1, the molar ratio of the silicon source to the aluminum source is (20-500): 1, preferably (30-450): 1, a step of; wherein the first copper source is calculated as CuO, the silicon source is calculated as SiO 2, the alkali metal hydroxide is calculated as alkali metal oxide (e.g., when the alkali metal hydroxide is sodium hydroxide, the alkali metal hydroxide is calculated as Na 2 O), and the aluminum source is calculated as Al 2O3.
In one embodiment of the present invention, in step S2, the molar ratio of the alkali metal hydroxide calculated as alkali metal oxide, the second solvent and the aluminum source used as Al 2O3 is (2.0-4.5): (80-450): 1, for example (2.2-4.2): (85-330): 1.
In one embodiment of the present invention, in step S3, dynamic crystallization is well known to those skilled in the art, and the conditions of the dynamic crystallization may include: the temperature is 80-200 ℃ and the time is 4-80 hours: preferably, the temperature is 160-180℃and the time is 12-60 hours.
In one embodiment of the present invention, in step S4, the molar ratio of the first solid product to the amount of the alkali-containing solution is 1: (2-10), preferably 1: (4-8) the first solid product is in terms of SiO 2; the ratio of the bulk silicon aluminum molar ratio to the surface silicon aluminum molar ratio of the first solid product is 1.2-5.0.
In a specific embodiment of the present invention, step S5 further includes: in a reducing atmosphere, carrying out reduction treatment on the solid obtained by the second roasting to obtain the composite catalytic material; the conditions of the reduction treatment include: the temperature is 600-750deg.C, and the time is 0.5-5min. The composite catalytic material obtained by the method contains copper which is mainly in a low valence state (+ 1 valence and/or 0 valence), so that the heating performance of the composite catalytic material can be further improved, and the problem of coking of the composite catalytic material can be further and more effectively avoided.
In one embodiment of the present invention, in step S5, said subjecting said second solid product to ammonium exchange comprises: the weight ratio is 1: (0.5-1.0): after mixing the second solid product of (8-10), an ammonium source and a third solvent, reacting the resulting mixture at 70-90 ℃ for 0.5-2 hours; the ammonium source is selected from one or more of ammonium chloride, ammonium sulfate and ammonium nitrate.
In one embodiment of the present invention, the firing may be performed in a muffle furnace, a tube furnace, or the like, as is conventional to those skilled in the art. In one embodiment, the conditions of the first firing and the second firing each independently include: the temperature is 400-600 ℃ for 2-6 hours, preferably 450-580 ℃ for 3-5 hours.
In one embodiment of the present invention, the specific surface area of the mesoporous is increased by 100-500%, the volume of the mesoporous is increased by 150-600%, and the total acid amount is increased by 50-250% compared with the first solid product. In the present invention, the mesoporous volume can be obtained by BET test, and the total acid amount can be detected by NH3-TPD method.
In one specific embodiment of the invention, the template agent is selected from one or more of tetrapropylammonium bromide, tetrapropylammonium hydroxide, n-butylamine and hexamethylenediamine; the silicon source is methyl orthosilicate and/or ethyl orthosilicate; the first copper source is selected from one or more of copper sulfate, copper chloride, copper nitrate and copper carbonate; the aluminum source is one or more of sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum isopropoxide and aluminum sol; the alkali metal hydroxide is selected from one or more of lithium hydroxide, sodium hydroxide and potassium hydroxide; the first solvent and the second solvent are each independently water.
The third aspect of the invention provides an application of the composite catalytic material provided by the first aspect of the invention in catalytic cracking of raw oil and catalytic cracking, in particular to an application in catalytic cracking reaction of heavy hydrocarbon oil.
The composite catalytic material is used in catalytic cracking and catalytic cracking reaction, and has the advantages of raising reaction temperature and raising yield of low carbon olefin (e.g. ethylene and propylene). In one embodiment of the present invention, the feedstock is contacted with a composite catalytic material to perform a catalytic cracking reaction or a catalytic cracking reaction. Preferably, the composite catalytic material is a reinforced reduced composite catalytic material.
In one embodiment, the reinforced reduced composite catalytic material is obtained by a method comprising the steps of: and (3) in a reducing atmosphere, carrying out a reduction reaction on the catalytic cracking auxiliary agent for 0.5-3min at 600-750 ℃. According to the invention, the reducing atmosphere contains dry gas and/or hydrogen, preferably from the dry gas produced by the catalytic cracker.
The invention is further illustrated by the following examples, which are not intended to be limiting in any way.
The raw materials used in the following examples and comparative examples are commercially available without particular description. The catalytic cracking equilibrium catalyst ECAT is purchased from the medium petrochemical catalyst company, ziluta corporation COKC-1 industrial agent. Comparative example 4 copper nitrate trihydrate was purchased from Sigma-Aldrich and ZSM-5 molecular sieves were used from ziluda, a medium petrochemical catalyst company.
In examples and comparative examples, the grain size of the molecular sieve was measured by SEM, 10 grain sizes were randomly measured, and the average value thereof was taken to obtain the average grain size of the molecular sieve sample.
The bulk silica alumina molar ratio of the sample was determined by XRF method, the instrument was a ZSX Primus II (Rigaku) X-ray fluorescence spectrometer; test conditions: excitation voltage is 50kV, excitation current is 50mA, rhodium and palladium are adopted. And measuring the peak intensity of each element spectrum by using a scintillation counter and a proportional counter, and analyzing the element composition of the molecular sieve.
The silicon-aluminum molar ratio of the surface of the sample is determined by XPS method, and the instrument adopts ESCALab type X-ray photoelectron spectrometer of thermo Fisher company, test conditions: the excitation source is monochromized AlK alpha X-ray, and the excitation energy is 1496.6eV and the power is 150W. The electron binding energy was corrected for the C1s peak of the contaminating carbon (284.8 eV).
The total specific surface area and the mesoporous specific surface area of the sample are detected by adopting a BET method. Instrument: ASAP 2420 adsorbent of Micromeritics, USA. Test conditions: the samples are subjected to vacuum degassing at 100 ℃ and 300 ℃ for 0.5h and 6h respectively, N 2 adsorption and desorption tests are carried out at 77.4K, and the adsorption amount and the desorption amount of the purified samples on nitrogen under different specific pressure conditions are tested to obtain an N 2 adsorption-desorption isothermal curve. BET specific surface area is calculated by using a BET formula, micropore area is calculated by using t-plot, and aperture distribution is calculated by using BJH.
The valence of copper and the content of copper in the copper-containing heating material in the sample are detected by adopting an XPS method.
The molar quantity of the hollow hierarchical pore ZSM-5 nanocrystalline material calculated by SiO 2 in the sample and the molar quantity of the copper-containing heating material calculated by CuO are detected by an XRF method.
Example 1
S1, weighing 4.88 g of copper chloride and 91.2 g of ethyl orthosilicate, adding 639.14 g of deionized water, stirring and heating for 2 hours under the water bath condition at 40 ℃, heating the water bath temperature to 70 ℃ under stirring for 4 hours to remove ethanol generated by hydrolysis of a silicon source, intermittently supplementing water which is evaporated simultaneously with the ethanol into a system in the process, and mixing and stirring the obtained mixed liquid with 111.65 g of tetrapropylammonium hydroxide solution (the weight fraction of tetrapropylammonium hydroxide is 25.0 percent) for 1 hour at 25 ℃ to obtain a first mixed product;
S2, adding 3.44 g of sodium hydroxide particles into 60.8 g of deionized water to completely dissolve sodium hydroxide, adding 8.16 g of aluminum nitrate nonahydrate, and stirring at room temperature for 1.0h to obtain a second mixed product (namely an aluminum source solution);
S3, slowly adding the second mixed product into the first mixed product, uniformly mixing, and stirring for 4.0h at room temperature; transferring the obtained precursor liquid into a synthesis kettle, and carrying out dynamic crystallization for 48 hours at 170 ℃; after crystallization, centrifugally filtering, washing and drying the obtained mixture, and roasting at 550 ℃ for 4 hours to obtain a first solid product (marked as a molecular sieve C-M1);
S4, uniformly mixing the first solid product and a sodium hydroxide solution with the concentration of 0.65mol/L, wherein the weight ratio of the molecular sieve to the alkali solution is 1:10, heating and stirring for 30min at the temperature after the temperature rising rate of 2 ℃/min to 80 ℃, filtering, washing and drying to obtain a second solid product (marked as molecular sieve C-S1-Na);
S5, carrying out second solid product: ammonium chloride: deionized water was prepared according to 1:1:10, stirring and heating for 30min in a water bath at 80 ℃, filtering, washing, drying, and then mixing with a second solid product: ammonium chloride: deionized water is 1:0.5:10, carrying out secondary ammonium exchange, filtering, washing, drying and roasting for 2 hours at 550 ℃ to obtain the composite catalytic material (marked as C-S1-H). The composition of the catalyst is shown in Table 1.
Example 2
Composite catalytic material C-S2-H was prepared in the same manner as in example 1 except that 9.77 g of copper chloride and 91.2 g of ethyl orthosilicate were weighed in step S1, 639.14 g of deionized water were further added, and after stirring and heating for 2 hours under water bath conditions at 40 ℃, the water bath temperature was raised to 70 ℃ and stirring and heating was carried out for 4 hours to remove ethanol generated by hydrolysis of the silicon source, water evaporated simultaneously with ethanol was intermittently supplemented to the system during the process, and the obtained mixed liquid was mixed and stirred with 111.65 g of tetrapropylammonium hydroxide solution (tetrapropylammonium hydroxide weight fraction 25.0 wt%) at 25 ℃ for 1 hour to obtain a first mixed product.
Comparative example 1
Catalysts D-S1-H were prepared in the same manner as in example 1 except that copper chloride was not added in step S1.
Comparative example 2
Kaolin carrier, alumina sol and cupric chloride are mixed according to the following steps of kaolin: and (2) a binder: the weight ratio of the copper chloride is 50:40:10, and carrying out spray drying on the obtained slurry, and roasting a product obtained by spray drying at 550 ℃ for 3 hours to obtain the copper oxide-containing auxiliary Z-1.
Comparative example 3
S1, weighing 4.88 g of copper chloride and 91.2 g of ethyl orthosilicate, adding 639.14 g of deionized water, stirring and heating for 2 hours under the water bath condition at 40 ℃, heating the water bath temperature to 70 ℃ under stirring for 4 hours to remove ethanol generated by hydrolysis of a silicon source, intermittently supplementing water which is evaporated simultaneously with the ethanol into a system in the process, and mixing and stirring the obtained mixed liquid with 111.65 g of tetrapropylammonium hydroxide solution (the weight fraction of tetrapropylammonium hydroxide is 25.0 percent) for 1 hour at 25 ℃ to obtain a first mixed product;
S2, adding 3.44 g of sodium hydroxide particles into 60.8 g of deionized water to completely dissolve sodium hydroxide, adding 8.16 g of aluminum nitrate nonahydrate, and stirring at room temperature for 1.0h to obtain a second mixed product (namely an aluminum source solution);
S3, slowly adding the second mixed product into the first mixed product, uniformly mixing, and stirring for 4.0h at room temperature; transferring the obtained precursor liquid into a synthesis kettle, and carrying out dynamic crystallization for 24 hours at 120 ℃; after crystallization, centrifugally filtering, washing and drying the obtained mixture, and roasting at 550 ℃ for 4 hours to obtain a first solid product (marked as a molecular sieve D-M3);
S4, uniformly mixing the first solid product and a sodium hydroxide solution with the concentration of 0.65mol/L, wherein the weight ratio of the molecular sieve to the alkali solution is 1:10, heating and stirring for 30min at the temperature after the temperature rising rate of 2 ℃/min to 80 ℃, filtering, washing and drying to obtain a second solid product (named as molecular sieve D-S3-Na);
S5, carrying out second solid product: ammonium chloride: deionized water was prepared according to 1:1:10, stirring and heating for 30min in a water bath at 80 ℃, filtering, washing, drying, and then mixing with a second solid product: ammonium chloride: deionized water is 1:0.5:10, carrying out secondary ammonium exchange, filtering, washing, drying and roasting for 2 hours at 550 ℃ to obtain the composite catalytic material (marked as D-S3-H). The composition of the catalyst is shown in Table 1.
Comparative example 4
3.8 Grams of copper nitrate trihydrate was completely dissolved in 3.7 grams of deionized water. Subsequently, copper nitrate trihydrate dissolved in deionized water was added dropwise to 15g of slightly crushed ZSM-5 molecular sieve with stirring. The resulting solid was dried in an oven at 110℃for 4 hours and then calcined in air at 650℃for 4 hours to prepare catalytic material Z-2.
Test case
The catalytic materials prepared in the above examples and comparative examples were evaluated for ACE in terms of 10% by weight of a catalytic cracking Equilibrium Catalyst (ECAT) (C-S1-H or C-S2-H or D-S1-H or Z-1 or D-S3-H or Z-2) +90% by weight, the reaction temperature was set at 530℃and the catalyst oil quality ratio was 8, and the exothermic effect was examined by recording the change in the reaction temperature. The results shown in tables 2 and 3 were obtained.
TABLE 1
Wherein, the CuO/SiO 2 in the composite catalytic material refers to the mole ratio of the copper-containing heating material and the hollow multi-level hole ZSM-5 nanocrystalline material contained in the composite catalytic material.
TABLE 2
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TABLE 3 Table 3
As can be seen from tables 2 and 3, the composite catalytic material of the present invention has both good reactivity and heat generating properties, and can increase the yield of low-carbon olefin.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (13)
1. The composite catalytic material has a structure that a hollow multistage hole ZSM-5 nanocrystalline material encapsulates a copper-containing heating material;
Wherein the hollow multistage hole ZSM-5 nanocrystalline material has a closed hollow structure, the average grain size is 0.4-3.0 mu m, the ratio of bulk phase silicon aluminum mol ratio to surface silicon aluminum mol ratio is 1.0-1.2, the total specific surface area is 340-400m 2/g, and the mesoporous specific surface area is 40-150m 2/g,N2 absorption and desorption curve presents an H4 type hysteresis ring.
2. The composite catalytic material of claim 1, wherein the composite catalytic material comprises the hollow, multi-stage pore ZSM-5 nanocrystalline material and the copper-containing heat-generating material in a molar ratio of 1: (0.01-0.1), wherein the hollow hierarchical pore ZSM-5 nanocrystalline material is calculated as SiO 2, and the copper-containing heating material is calculated as CuO.
3. The composite catalytic material of claim 1, wherein the copper-containing heat generating material contains cuprous oxide and/or cupric oxide.
4. The composite catalytic material of claim 1, wherein the hollow multistage pore ZSM-5 nanocrystalline material has an average grain size of 0.4-2.5 μm, a ratio of bulk phase silica alumina molar ratio to surface silica alumina molar ratio of 1-1.1, a total specific surface area of 360-400m 2/g, and a mesoporous specific surface area of 50-140m 2/g.
5. A method of making the composite catalytic material of any one of claims 1-4, the method comprising:
S1, mixing a silicon source, a first copper source and a first solvent at 30-50 ℃ for reaction for 0.5-5 hours, heating to 70-100 ℃ for mixing and stirring for 2-10 hours, and mixing the obtained mixed liquid with a template agent at 20-30 ℃ for 0.5-3.0 hours to obtain a first mixed product;
S2, the molar ratio is (1.5-5): (60-350): 1, a second solvent and an aluminum source calculated as Al 2O3 at 20-80 ℃ for 0.5-2 hours to obtain a second mixed product;
s3, mixing the first mixed product and the second mixed product, then carrying out dynamic crystallization, taking out the obtained solid, and carrying out first roasting to obtain a first solid product;
S4, mixing the first solid product with a solution containing alkali, and reacting for 10-90min at the reaction temperature after the temperature rises to the reaction temperature at a heating rate of 1-5 ℃/min to obtain a second solid product; wherein the reaction temperature is 60-90 ℃, and the alkali content in the alkali-containing solution is 0.45-2mol/L;
S5, carrying out ammonium exchange on the second solid product, and carrying out second roasting on the solid product obtained by the ammonium exchange to obtain the composite catalytic material.
6. The method of claim 5, wherein the molar ratio of the total amount of the first copper source, the templating agent, the first solvent, and the second solvent, the alkali metal hydroxide, and the silicon source is (0.01-0.1): (0.06-0.55): (10-100): (0.02-1.5): 1, the molar ratio of the silicon source to the aluminum source is (20-500): 1, a step of; wherein the first copper source is calculated as CuO, the silicon source is calculated as SiO 2, the alkali metal hydroxide is calculated as alkali metal oxide, and the aluminum source is calculated as Al 2O3.
7. The method according to claim 5, wherein in step S2, the molar ratio of the alkali metal hydroxide as alkali metal oxide, the second solvent and the aluminum source as Al 2O3 is (2-4.5): (80-350): 1.
8. The method of claim 5, wherein in step S4, the molar ratio of the first solid product to the amount of the alkali-containing solution is 1: (2-10), preferably 1: (4-8) the first solid product is in terms of SiO 2;
The ratio of the bulk silicon aluminum molar ratio to the surface silicon aluminum molar ratio of the first solid product is 1.2-5.0.
9. The method of claim 5, wherein step S5 further comprises: in a reducing atmosphere, carrying out reduction treatment on the solid obtained by the second roasting to obtain the composite catalytic material;
The conditions of the reduction treatment include: the temperature is 600-750deg.C, and the time is 0.5-5min.
10. The method of claim 5, wherein in step S5, said subjecting the second solid product to ammonium exchange comprises: the weight ratio is 1: (0.5-1.0): after mixing the second solid product of (8-10), an ammonium source and a third solvent, reacting the resulting mixture at 70-90 ℃ for 0.5-2 hours; the ammonium source is selected from one or more of ammonium chloride, ammonium sulfate and ammonium nitrate.
11. The method of claim 5, wherein the conditions of dynamic crystallization comprise: the temperature is 160-180 ℃ and the time is 12-60 hours;
The conditions of the first firing and the second firing each independently include: the temperature is 400-600 ℃ and the time is 2-6 hours.
12. The method of claim 5, wherein the template agent is selected from one or more of tetrapropylammonium bromide, tetrapropylammonium hydroxide, n-butylamine, and hexamethylenediamine;
the silicon source is methyl orthosilicate and/or ethyl orthosilicate;
The first copper source is selected from one or more of copper sulfate, copper chloride, copper nitrate and copper carbonate;
the aluminum source is one or more of sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum isopropoxide and aluminum sol;
the alkali metal hydroxide is selected from one or more of lithium hydroxide, sodium hydroxide and potassium hydroxide;
The first solvent and the second solvent are each independently water.
13. Use of the composite catalytic material according to any one of claims 1-4 in catalytic cracking reactions of heavy hydrocarbon oils.
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