CN115646537B - Mosaic catalyst and preparation method and application thereof - Google Patents
Mosaic catalyst and preparation method and application thereof Download PDFInfo
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- CN115646537B CN115646537B CN202211289366.6A CN202211289366A CN115646537B CN 115646537 B CN115646537 B CN 115646537B CN 202211289366 A CN202211289366 A CN 202211289366A CN 115646537 B CN115646537 B CN 115646537B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002808 molecular sieve Substances 0.000 claims abstract description 101
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 101
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 89
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 89
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 83
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 63
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 60
- 239000010703 silicon Substances 0.000 claims abstract description 60
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims abstract description 55
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 23
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 20
- 230000029936 alkylation Effects 0.000 claims abstract description 16
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 15
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 15
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 59
- 239000000243 solution Substances 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000003795 chemical substances by application Substances 0.000 claims description 36
- 239000011259 mixed solution Substances 0.000 claims description 36
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 34
- 239000001099 ammonium carbonate Substances 0.000 claims description 34
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 34
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 30
- 238000005342 ion exchange Methods 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000003513 alkali Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 19
- 239000002244 precipitate Substances 0.000 claims description 19
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 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 14
- 239000007787 solid Substances 0.000 claims description 14
- 238000000975 co-precipitation Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 239000012495 reaction gas Substances 0.000 claims description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 5
- 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
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 4
- 239000012702 metal oxide precursor Substances 0.000 claims description 4
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 230000008878 coupling Effects 0.000 abstract description 11
- 238000010168 coupling process Methods 0.000 abstract description 11
- 238000005859 coupling reaction Methods 0.000 abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 239000002168 alkylating agent Substances 0.000 abstract description 8
- 229940100198 alkylating agent Drugs 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 4
- 238000002161 passivation Methods 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 23
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000012716 precipitator Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 239000002243 precursor Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000001311 chemical methods and process Methods 0.000 description 3
- BKBMACKZOSMMGT-UHFFFAOYSA-N methanol;toluene Chemical compound OC.CC1=CC=CC=C1 BKBMACKZOSMMGT-UHFFFAOYSA-N 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 239000000178 monomer Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of catalysts, and particularly relates to a mosaic catalyst and a preparation method and application thereof. According to the invention, after the metal oxide is fully combined with the silicon species, the metal oxide is epitaxially grown on the surface of the molecular sieve, so that the metal oxide is inlaid on the surface of the molecular sieve, and the catalyst with double-function components in close contact and high activity and high para-xylene selectivity, which is obtained by acidic passivation of the outer surface of the molecular sieve, is prepared. The method is concise, good in repeatability and potential in industrial application value. The catalyst provided by the invention has the advantages that in the application of preparing paraxylene by coupling benzene/toluene alkylation through carbon monoxide/carbon dioxide hydrogenation, a reliable technical scheme is provided for CO 2 utilization while paraxylene is generated efficiently and with high selectivity, carbon dioxide is used as a carbon source of an alkylating agent, carbon emission reduction can be realized, and the catalyst has economic value and remarkable social benefit.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a mosaic catalyst and a preparation method and application thereof.
Background
The high emissions of CO 2 have caused serious global climate problems. Reduction of CO 2 emissions, and the immobilization or conversion of large amounts of CO 2 to chemicals by physical and chemical means, have become a hotspot for research worldwide. CO 2 is an important carbon source, is a very important node in the natural carbon circulation, is also an important substance in the carbon-chemical process, has important significance for controlling carbon emission and occurrence in the activation and conversion of CO 2, and is a key problem of sustainable utilization of fossil energy and greening of chemical process.
Benzene, toluene and xylene are important chemical raw materials. Benzene and toluene are alkylated to produce dimethylbenzene, and terephthalic acid prepared by oxidizing p-dimethylbenzene is an important monomer for producing various degradable plastics. Para-xylene extends the critical materials of the aromatic industry chain. The current production route of paraxylene mainly comprises: the combined production process of petrochemical aromatic hydrocarbon with naphtha as raw material includes toluene disproportionation process, xylene isomerization process, direct methanol para-xylene production process [ Angew.chem.2022,134, e202114786], benzene and synthetic gas alkylation process [ APPLIED ENERGY 226 (2018) 22-30], direct synthetic gas aromatic hydrocarbon production process [ ACS CATALYSIS,2019,9,6,5147], methanol toluene alkylation process [ Nature Communication,2019,10,4348] and carbon monoxide/carbon dioxide hydrogenation coupled benzene/toluene alkylation. The ratio of methyl to benzene ring in petroleum is about 1.3, which is smaller than the ratio of methyl to benzene ring in paraxylene, so that the petrochemical aromatic hydrocarbon joint production process and the toluene disproportionation process both generate byproduct benzene, the xylene yield is relatively low, and the separation problem of benzene and xylene is also caused. The technology for directly preparing aromatic hydrocarbon from synthesis gas and methanol has complex aromatic hydrocarbon products and is difficult to obtain relatively single paraxylene products. Methanol toluene alkylation is a research hot spot because of the advantages of high conversion rate, high paraxylene selectivity, low cost, small pollution and the like. Methanol toluene alkylation process uses methanol as alkylating agent. Methanol is mainly obtained from coal chemical processes. The process for producing methanol has the problems of high energy consumption and large carbon emission. If CO 2 is used as a source of alkylating reagent for producing paraxylene, the technical route of paraxylene can be enriched and carbon emission reduction can be achieved.
The production of paraxylene using CO 2 as toluene alkylating agent and the catalyst is critical to the process. The catalyst needs to possess three key elements: the active center of the activated CO 2, the methane alkylation reaction center with shape selective catalytic effect, and the two active centers are in intimate contact. How to construct a bifunctional catalyst with CO 2 as toluene alkylating agent is the focus of research and development.
Patent CN 113070094a discloses that the selectivity of xylene in toluene alkylation reaction with CO 2 as alkylating agent reaches 92.7% by using a new catalyst prepared by mixing Cu-based catalyst and molecular sieve. Patent CN 110743609B discloses a combined catalyst, a preparation method thereof and a method for preparing xylene by coupling toluene alkylation with carbon dioxide hydrogenation. The catalyst is used for preparing dimethylbenzene by coupling hydrogenation of carbon dioxide and alkylation of methylbenzene, and the selectivity of dimethylbenzene reaches 92.4%. How to improve the selectivity of paraxylene in the product in toluene conversion with CO 2 as toluene alkylating agent is an important direction of technical development.
Disclosure of Invention
The invention provides a mosaic catalyst, a preparation method and application thereof, and aims to solve the problem of low selectivity of paraxylene in the methane conversion process by taking CO 2 as a toluene alkylating agent. The mosaic catalyst of the present invention comprises three elements: the metal oxide and the molecular sieve are inlaid on the surface of the molecular sieve through a passivation layer epitaxially grown on the molecular sieve. The metal oxide is mainly used for hydrogenation of carbon monoxide/carbon dioxide to produce methanol or methoxy species, the molecular sieve is mainly used for benzene/toluene alkylation reaction, and after the outer surface of the molecular sieve is passivated by silicon species, the shape selective catalytic effect of the molecular sieve is enhanced, and the selectivity of paraxylene after the benzene/toluene alkylation reaction is improved. The invention constructs a catalyst configuration of tightly combined metal oxide and molecular sieve, shortens the distance of the methanol or methoxy of the alkylate to diffuse to the active site of the molecular sieve, inhibits the occurrence of side reaction in benzene/toluene alkylation reaction, improves the selectivity of paraxylene in the product, and provides a utilization way of carbon dioxide.
In order to achieve the above purpose, the present invention is realized by the following technical scheme:
In one aspect, the invention provides a method for preparing a mosaic catalyst, which comprises the steps of fully combining metal oxide with silicon species, and then epitaxially growing on the surface of a molecular sieve to enable the metal oxide to be inlaid on the surface of the molecular sieve, thereby obtaining the mosaic catalyst.
Preferably, the metal oxide comprises at least one of ZnZrO x、ZnCrOx、ZnAlOx, the silicon species is tetraethoxysilane or silica sol, the molecular sieve is ZSM-5 or MCM-22, and the silicon-aluminum atomic ratio in the molecular sieve is 30-200.
Preferably, znZrO x is calculated by mass of ZnO and ZrO 2, znCrO x is calculated by mass of ZnO and Cr 2O3, znAlO x is calculated by mass of ZnO and Al 2O3, and the mass ratio of metal oxide to molecular sieve is 1 (0.1-10).
Preferably, the preparation method of the mosaic catalyst specifically comprises the following steps:
Step 1: dispersing metal oxide or metal oxide precursor in ethanol/water mixed solution, adding high molecular organic matters, fully stirring to obtain mixed solution, then adding silicon species, fully stirring, adding ammonia water, adjusting pH to be less than 10, continuously stirring and carrying out precipitation reaction;
Step 2: filtering, washing, drying and roasting the precipitate to obtain a species in which the metal oxide and the silicon species are fully combined;
Step 3: mixing the metal oxide with the silicon species, a molecular sieve, an alkali source, a template agent and water to form a gel mixture, and carrying out crystallization reaction;
Step 4: filtering, washing, drying and roasting the crystallized product;
Step 5: and (3) performing ion exchange, drying and roasting on the mixture obtained in the step (4) to obtain the mosaic catalyst.
Preferably, the metal oxide is prepared by adopting a coprecipitation method, specifically: zinc nitrate and zirconium nitrate, cadmium nitrate or aluminum nitrate are dissolved in water to form a metal nitrate mixed solution; then adding ammonium carbonate solution to carry out coprecipitation reaction to obtain a metal oxide precursor; and finally roasting to obtain the metal oxide.
Preferably, the molar ratio of zinc to zirconium, cadmium or aluminum in the metal nitrate mixed solution is 1 (1-15); the concentration of zinc nitrate is 0.01-0.10mol/L; the concentration of the ammonium carbonate solution is 0.8-1.5mol/L; the molar ratio of the ammonium carbonate to the metal ions is 1.5:1; the coprecipitation reaction temperature is 60-80 ℃ and the time is 4-12h; the roasting temperature is 400-600 ℃ and the roasting time is 4-8h.
Preferably, the volume ratio of the ethanol to the water in the ethanol/water mixed solution in the step 1 is 1 (0.5-2); the mass percentage of the solid in the mixed solution is 10-30%; the macromolecular organic matter is polyvinylpyrrolidone or polyethylene glycol, and the addition amount is 10-20% of the mass of the metal oxide; the mass ratio of the silicon species to the molecular sieve is (0.01-0.1) 1, and the mass ratio of the molecular sieve, the metal oxide and the silicon species is (0.1-10) 1 (0.01-0.1) based on the content of SiO 2 and the content of OH -; the roasting temperature in the step 2 is 400-600 ℃ and the time is 4-8h.
Preferably, the template agent in the step 3 comprises at least one of tetrapropylammonium hydroxide and n-butylamine, and the alkali source is sodium hydroxide; the molar ratio of the silicon species to the template agent to the alkali source to the water is 1 (0.002-0.008) (0.01-0.001) (40.0-100.0) based on the content of SiO 2 and the content of OH -; the crystallization reaction temperature is 140-180 ℃ and the crystallization time is 12-36h; the roasting temperature in the step 4 is 500-600 ℃ and the time is 8-15h; the concentration of the ammonium nitrate or ammonium chloride solution in the step 5 is 0.2-1.0mol/L; the ion exchange temperature is 60-80 ℃, and the solid-liquid ratio is 1 (20-40); the roasting temperature is 500-600 ℃ and the roasting time is 8-15h.
In another aspect, the invention provides a mosaic catalyst prepared by the method.
The invention also provides an application of the mosaic catalyst in preparing paraxylene by coupling carbon monoxide/carbon dioxide hydrogenation with benzene/toluene alkylation, which is characterized in that: the reaction conditions are as follows: the ratio of the reaction raw material gas H 2/CO or H 2/CO2 is 1-5, the reaction pressure is 3-6MPa, the reaction temperature is 300-500 ℃, the space velocity of the reaction gas is 5000-12000 mL.g -1·h-1, and the space velocity of benzene/toluene liquid is 1-4H -1.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention builds the catalyst with high activity and high para-xylene selectivity, which has the advantages of close contact of difunctional components and acidic passivation of the outer surface of the molecular sieve by adopting an epitaxial growth method, and has simple preparation method, good repeatability and potential industrial application value.
(2) The catalyst provided by the invention has the advantages that in the application of preparing paraxylene by coupling benzene/toluene alkylation through carbon monoxide/carbon dioxide hydrogenation, a reliable technical scheme is provided for CO 2 utilization while paraxylene is generated efficiently and with high selectivity, carbon dioxide is used as a carbon source of an alkylating agent, carbon emission reduction can be realized, and the catalyst has economic value and remarkable social benefit.
(3) The invention uses the carbon monoxide/carbon dioxide hydrogenation process to replace methanol for alkylation, which can further reduce the energy consumption of methane alkylation.
Detailed Description
The present invention will be described more fully hereinafter in order to facilitate an understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Example 1
A mosaic catalyst comprises a metal oxide and a molecular sieve, wherein the metal oxide is inlaid on the outer surface of the molecular sieve in a mode that a silicon-containing species grows epitaxially on the outer surface of the molecular sieve. The metal oxide is ZnZrO x, the molecular sieve is ZSM-5, and the mass ratio of the inlaid ZnZrO x (calculated by ZnO and ZrO 2) to the molecular sieve ZSM-5 is 1:0.1. The molecular sieve ZSM-5 silicon-aluminum atomic ratio is 200.
The mosaic catalyst is prepared by epitaxial growth on the surface of a molecular sieve after metal oxide and silicon species are fully combined, and specifically comprises the following steps:
(1) Dispersing metal oxide ZnZrO x in an ethanol/water mixed solution, adding a certain amount of polymer organic matters, fully stirring at 50 ℃, wherein the volume ratio of ethanol to water is 1:0.5, the solid mass content in the solution is 10%, and the addition amount of the polymer organic matters is 10% of the mass of the oxide;
(2) Adding silicon species ethyl orthosilicate into the solution, and fully stirring, wherein the mass ratio of the ethyl orthosilicate (calculated by SiO 2) to the molecular sieve in the step (5) is 0.01:1, and in the formed catalyst, the mass ratio of the molecular sieve, the metal oxide and the silicon species is 1:0.1:0.01;
(3) Slowly adding ammonia water into the mixed solution until the pH value of the mixed solution is=10, and continuously stirring for 4 hours;
(4) After the steps are finished, filtering, washing and drying the precipitate at 110 ℃ for 6 hours, and roasting the precipitate at 400 ℃ for 8 hours under air to fully combine the metal oxide and the silicon species;
(5) The metal oxide is thoroughly mixed with the fully bound species of silicon species, molecular sieve, alkali source, templating agent and water to form an initial gel mixture having the following molar ratios, silicon species (based on SiO 2 content): template agent: alkali source (in terms of OH - content): water=1:0.002:0.01:40.0; the template agent is tetrapropylammonium hydroxide; the alkali source is sodium hydroxide;
(6) Placing the mixture into a autogenous pressure kettle, and crystallizing at 140 ℃ for 36h;
(7) Filtering, washing and drying the crystallized molecular sieve at 110 ℃ for 6 hours, and roasting the molecular sieve at 500 ℃ for 15 hours in air to remove the template agent;
(8) And (3) carrying out ion exchange on the molecular sieve with the template agent removed in an ammonium nitrate solution for three times, drying at 110 ℃ for 6 hours after the ion exchange is finished, and roasting at 500 ℃ for 15 hours in air to obtain the mosaic catalyst. Wherein the concentration of the ammonium nitrate solution is 0.2mol/L, the ratio of ion exchange solid (in terms of mass) liquid (in terms of volume) is 1:20, the ion exchange temperature is 60 ℃, the time of each exchange is 5 hours,
Further, the metal oxide ZnZrO x in the step (1) is prepared by adopting a coprecipitation method, and specifically includes the following steps:
(1.1) zinc nitrate and zirconium nitrate are dissolved in deionized water to form a metal nitrate mixed solution, wherein the molar ratio of zinc to zirconium in the solution is 1:1, and the concentration of zinc nitrate is 0.01mol/L;
(1.2) dissolving ammonium carbonate in water with the concentration of 0.8mol/L by taking ammonium carbonate as a precipitator;
(1.3) slowly adding an ammonium carbonate solution into the solution dissolved with the metal nitrate under vigorous stirring, wherein the molar ratio of the ammonium carbonate to the metal ions is 1.5:1, the precipitation reaction temperature is 60 ℃, and the reaction time is 4 hours.
(1.4) After the above steps are completed, the precipitate is filtered, washed, dried at 110℃for 6 hours, and then calcined at 400℃for 8 hours under air to obtain the metal oxide ZnZrO x.
The mosaic catalyst prepared by the method is applied to the preparation of paraxylene by coupling benzene alkylation with carbon monoxide hydrogenation, and the application conditions are as follows: the ratio of H 2/CO of the reaction raw material gas is 1, the reaction pressure is 3MPa, the reaction temperature is 300 ℃, the space velocity of the reaction gas is 5000 mL.g -1·h-1, and the space velocity of the benzene liquid is 1H -1. The reaction results are shown in Table 1:
TABLE 1 reaction evaluation results of the mosaic catalyst prepared in example 1
Example 2
A mosaic catalyst comprises a metal oxide and a molecular sieve, wherein the metal oxide is inlaid on the outer surface of the molecular sieve in a mode that a silicon-containing species grows epitaxially on the outer surface of the molecular sieve. The metal oxide is ZnCrO x, the molecular sieve is MCM-22, and the mass ratio of the inlaid ZnCrO x (calculated by ZnO and Cr 2O3) to the molecular sieve MCM-22 is 1:0.5. The molecular sieve MCM-22 has a silicon-aluminum atomic ratio of 150.
The mosaic catalyst is prepared by epitaxial growth on the surface of a molecular sieve after metal oxide and silicon species are fully combined, and specifically comprises the following steps:
(1) Dispersing a metal oxide ZnCrO x in an ethanol/water mixed solution, adding a certain amount of polymer organic matters, fully stirring at 50 ℃, wherein the volume ratio of ethanol to water is 1:0.5, the solid mass content in the solution is 10%, and the addition amount of the polymer organic matters is 20% of the mass of the oxide;
(2) Adding silicon species ethyl orthosilicate into the solution, and fully stirring, wherein the mass ratio of the ethyl orthosilicate (calculated by SiO 2) to the molecular sieve in the step (5) is 0.01:1, and in the formed catalyst, the mass ratio of the molecular sieve, the metal oxide and the silicon species is 1:0.5:0.01;
(3) Slowly adding ammonia water into the mixed solution until the pH value of the mixed solution is=10, and continuously stirring for 4 hours;
(4) After the steps are finished, filtering, washing and drying the precipitate at 110 ℃ for 6 hours, and roasting the precipitate at 500 ℃ for 8 hours in air to fully combine the metal oxide and the silicon species;
(5) The metal oxide is thoroughly mixed with the fully bound species of silicon species, molecular sieve, alkali source, templating agent and water to form an initial gel mixture having the following molar ratios, silicon species (based on SiO 2 content): template agent: alkali source (in terms of OH - content): water=1:0.004:0.01:40.0, the template agent is tetrapropylammonium hydroxide; the alkali source is sodium hydroxide;
(6) Placing the mixture into a autogenous pressure kettle, and crystallizing at 140 ℃ for 36h;
(7) Filtering, washing and drying the crystallized molecular sieve at 110 ℃ for 6 hours, and roasting the molecular sieve at 500 ℃ for 15 hours in air to remove the template agent;
(8) And (3) carrying out ion exchange on the molecular sieve with the template agent removed in an ammonium nitrate solution for three times, drying at 110 ℃ for 6 hours after the ion exchange is finished, and roasting at 500 ℃ for 15 hours in air to obtain the mosaic catalyst. Wherein the concentration of the ammonium nitrate solution is 0.2mol/L, the ion exchange solid (in terms of mass) liquid (in terms of volume) ratio is 1:20, the ion exchange temperature is 60 ℃, and the exchange time is 5h each time.
Further, the metal oxide ZnCrO x in the step (1) is prepared by adopting a coprecipitation method, and specifically comprises the following steps:
(1.1) zinc nitrate and cadmium nitrate are dissolved in deionized water to form a metal nitrate mixed solution, wherein the molar ratio of zinc to cadmium in the solution is 1:3, and the concentration of zinc nitrate in the solution is 0.02mol/L;
(1.2) dissolving ammonium carbonate in water with the concentration of the ammonium carbonate being 1.5mol/L by taking the ammonium carbonate as a precipitator;
(1.3) slowly adding an ammonium carbonate solution into the solution dissolved with the metal nitrate under vigorous stirring, wherein the molar ratio of the ammonium carbonate to the metal ions is 1.5:1, the reaction temperature is 80 ℃, and the precipitation reaction time is 6 hours.
(1.4) After the above steps are completed, the precipitate is filtered, washed, dried at 110℃for 8 hours, and then calcined at 500℃for 8 hours in air to obtain the metal oxide ZnCrO x.
The mosaic catalyst prepared by the method is applied to the preparation of paraxylene by coupling benzene alkylation with carbon monoxide hydrogenation, and the application conditions are as follows: the ratio of H 2/CO of the reaction raw material gas is 2, the reaction pressure is 3MPa, the reaction temperature is 450 ℃, the space velocity of the reaction gas is 8000 mL.g -1·h-1, and the space velocity of the benzene liquid is 2H -1. The reaction results are shown in Table 2:
TABLE 2 reaction evaluation results of the mosaic catalyst prepared in example 2
Example 3
A mosaic catalyst comprises a metal oxide and a molecular sieve, wherein the metal oxide is inlaid on the outer surface of the molecular sieve in a mode that a silicon-containing species grows epitaxially on the outer surface of the molecular sieve. The metal oxide is ZnAlO x, the molecular sieve is ZSM-5, and the mass ratio of the inlaid ZnAlO x (calculated by ZnO and Al 2O3) to the molecular sieve ZSM-5 is 1:1. The molecular sieve ZSM-5 silicon-aluminum atomic ratio is 100.
The mosaic catalyst is prepared by epitaxial growth on the surface of a molecular sieve after metal oxide and silicon species are fully combined, and specifically comprises the following steps:
(1) Dispersing a metal oxide ZnAlO x in an ethanol/water mixed solution, adding a certain amount of polymer organic matters, fully stirring at 60 ℃, wherein the volume ratio of ethanol to water is 1:1, the solid mass content in the solution is 20%, the polymer organic matters are polyethylene glycol, and the addition amount is 15% of the mass of the oxide;
(2) Adding silica sol of a silicon species into the solution, and fully stirring, wherein the mass ratio of the silica sol (calculated by SiO 2) to the molecular sieve in the step (5) is 0.02:1, and in the formed catalyst, the mass ratio of the molecular sieve to the metal oxide to the silicon species is 1:1:0.02;
(3) Slowly adding ammonia water into the mixed solution until the pH value of the mixed solution is=10, and continuously stirring for 6 hours;
(4) After the steps are finished, filtering, washing and drying the precipitate at 110 ℃ for 8 hours, and roasting the precipitate at 500 ℃ for 8 hours in air to fully combine the metal oxide and the silicon species;
(5) The metal oxide is thoroughly mixed with the fully bound species of silicon species, molecular sieve, alkali source, templating agent and water to form an initial gel mixture having the following molar ratios, silicon species (based on SiO 2 content): template agent: alkali source (in terms of OH - content): water=1:0.006:0.05:60.0, the templating agent is n-butylamine; the alkali source is sodium hydroxide;
(6) Placing the mixture into a autogenous pressure kettle, and crystallizing at 140 ℃ for 36h;
(7) Filtering, washing, drying at 110 ℃ for 8 hours, and roasting at 600 ℃ for 8 hours in air to remove a template agent;
(8) And (3) carrying out ion exchange on the molecular sieve with the template agent removed in an ammonium nitrate solution for three times, drying at 110 ℃ for 8 hours after ion exchange is finished, and roasting at 600 ℃ for 9 hours in air to obtain the mosaic catalyst. Wherein the concentration of the ammonium nitrate solution is 0.5mol/L, the ion exchange solid (in terms of mass) liquid (in terms of volume) ratio is 1:30, the ion exchange temperature is 70 ℃, and the exchange time is 4h each time.
Further, the metal oxide ZnAlO x in the step (1) is prepared by adopting a coprecipitation method, and specifically comprises the following steps:
(1.1) zinc nitrate and aluminum nitrate are dissolved in deionized water to form a metal nitrate mixed solution, wherein the molar ratio of zinc to aluminum in the solution is 1:6, and the concentration of zinc nitrate in the solution is 0.05mol/L;
(1.2) dissolving ammonium carbonate in water by taking the ammonium carbonate as a precipitator, wherein the concentration of the ammonium carbonate is 1.0mol/L;
(1.3) slowly adding an ammonium carbonate solution into the solution dissolved with the metal nitrate under vigorous stirring, wherein the molar ratio of the ammonium carbonate to the metal ions is 1.5:1, the reaction temperature is 80 ℃, and the precipitation reaction time is 8 hours.
(1.4) After the above steps are completed, the precipitate is filtered, washed, dried at 110℃for 8 hours, and then calcined at 500℃for 8 hours in air to obtain the metal oxide ZnAlO x.
The mosaic catalyst prepared by the method is applied to the preparation of paraxylene by coupling hydrogenation of carbon dioxide with alkylation of toluene, and the application conditions are as follows: the ratio of the reaction raw material gas H 2/CO2 is 3, the reaction pressure is 4MPa, the reaction temperature is 400 ℃, the space velocity of the reaction gas is 12000 mL.g -1·h-1, and the space velocity of toluene liquid is 3H -1. The reaction results are shown in Table 3:
table 3 reaction evaluation results of the mosaic catalyst prepared in example 3:
Example 4
A mosaic catalyst comprises a metal oxide and a molecular sieve, wherein the metal oxide is inlaid on the outer surface of the molecular sieve in a mode that a silicon-containing species grows epitaxially on the outer surface of the molecular sieve. The metal oxide is ZnZrOx, the molecular sieve is MCM-22, and the mass ratio of the embedded ZnZrO x (calculated by ZnO and ZrO 2) to the molecular sieve MCM-22 is 1:2. The molecular sieve MCM-22 has a silicon-aluminum atomic ratio of 50.
The mosaic catalyst is prepared by epitaxial growth on the surface of a molecular sieve after metal oxide and silicon species are fully combined, and specifically comprises the following steps:
(1) Dispersing a metal oxide ZnZrO x precursor in an ethanol/water mixed solution, adding a certain amount of high molecular organic matters, fully stirring at 60 ℃, wherein the volume ratio of ethanol to water is 1:1, the solid mass content in the solution is 20%, the high molecular organic matters are ethylene glycol, and the addition amount is 20% of the mass of the oxide;
(2) Adding silica sol of a silicon species into the solution, and fully stirring, wherein the mass ratio of the silica sol (calculated by SiO 2) to the molecular sieve in the step (5) is 0.05:1, and in the formed catalyst, the mass ratio of the molecular sieve to the metal oxide to the silicon species is 1:1:0.05;
(3) Slowly adding ammonia water into the mixed solution until the pH value of the mixed solution is=10, and continuously stirring for 6 hours;
(4) After the steps are finished, filtering, washing and drying the precipitate at 110 ℃ for 10 hours, and roasting the precipitate at 500 ℃ for 8 hours in air to fully combine the metal oxide and the silicon species;
(5) The metal oxide is thoroughly mixed with the fully bound species of silicon species, molecular sieve, alkali source, templating agent and water to form an initial gel mixture having the following molar ratios, silicon species (based on SiO 2 content): template agent: alkali source (in terms of OH - content): water=1:0.008:0.05:60.0, the templating agent is tetrapropylammonium hydroxide; the alkali source is sodium hydroxide;
(6) Placing the mixture into a autogenous pressure kettle, and crystallizing at 150 ℃ for 24 hours;
(7) Filtering, washing, drying at 110 ℃ for 8 hours, and roasting at 600 ℃ for 8 hours in air to remove a template agent;
(8) And (3) carrying out ion exchange on the molecular sieve with the template agent removed in an ammonium nitrate solution for three times, drying at 110 ℃ for 6 hours after the ion exchange is finished, and roasting at 600 ℃ for 8 hours in air to obtain the mosaic catalyst. Wherein the concentration of the ammonium nitrate solution is 0.5mol/L, the ion exchange solid (in terms of mass) liquid (in terms of volume) ratio is 1:30, the ion exchange temperature is 70 ℃, and the exchange time is 5h each time.
Further, the metal oxide ZnZrO x in the step (1) is prepared by adopting a coprecipitation method, and specifically includes the following steps:
(1.1) zinc nitrate and zirconium nitrate are dissolved in deionized water to form a metal nitrate mixed solution, wherein the molar ratio of zinc to zirconium in the solution is 1:6, and the concentration of zinc nitrate in the solution is 0.1mol/L;
(1.2) dissolving ammonium carbonate in water by taking the ammonium carbonate as a precipitator, wherein the concentration of the ammonium carbonate is 1.2mol/L;
(1.3) slowly adding an ammonium carbonate solution into the solution dissolved with the metal nitrate under vigorous stirring, wherein the molar ratio of the ammonium carbonate to the metal ions is 1.5:1, the reaction temperature is 60 ℃, and the precipitation reaction time is 8 hours.
(1.4) After the above steps are completed, the precipitate is filtered, washed, and dried at 110℃for 12 hours to obtain a metal oxide ZnZrO x precursor.
The mosaic catalyst prepared by the method is applied to the preparation of paraxylene by coupling hydrogenation of carbon dioxide with alkylation of toluene, and the application conditions are as follows: the ratio of the reaction raw material gas H 2/CO2 is 3, the reaction pressure is 6MPa, the reaction temperature is 450 ℃, and the space velocity of the reaction gas is 10000mL g -1·h-1. The toluene liquid space velocity was 4h -1. The reaction results are shown in Table 4:
table 4 reaction evaluation results of the mosaic catalyst prepared in example 4:
Example 5
A mosaic catalyst comprises a metal oxide and a molecular sieve, wherein the metal oxide is inlaid on the outer surface of the molecular sieve in a mode that a silicon-containing species grows epitaxially on the outer surface of the molecular sieve. The metal oxide is ZnCrO x, the molecular sieve is ZSM-5, and the mass ratio of the inlaid ZnCrO x (calculated by ZnO and Cr 2O3) to the molecular sieve ZSM-5 is 1:5. The molecular sieve ZSM-5 silicon-aluminum atomic ratio is 50.
The mosaic catalyst is prepared by epitaxial growth on the surface of a molecular sieve after metal oxide and silicon species are fully combined, and specifically comprises the following steps:
(1) Dispersing a metal oxide ZnCrO x precursor in an ethanol/water mixed solution, adding a certain amount of high molecular organic matters, fully stirring at 80 ℃, wherein the volume ratio of ethanol to water is 1:2, the solid mass content in the solution is 30%, and the adding amount of the high molecular organic matters is 10% of the mass of the oxide;
(2) Adding silicon species ethyl orthosilicate into the solution, and fully stirring, wherein the mass ratio of the ethyl orthosilicate (calculated by SiO 2) to the molecular sieve in the step (5) is 0.1:1, and in the formed catalyst, the mass ratio of the molecular sieve, the metal oxide and the silicon species is 1:5:0.1;
(3) Slowly adding ammonia water into the mixed solution until the pH value of the mixed solution is=10, and continuously stirring for 6 hours;
(4) After the steps are finished, filtering, washing and drying the precipitate at 110 ℃ for 6 hours, and roasting the precipitate at 400 ℃ for 12 hours under air to fully combine the metal oxide and the silicon species;
(5) The metal oxide is thoroughly mixed with the fully bound species of silicon species, molecular sieve, alkali source, templating agent and water to form an initial gel mixture having the following molar ratios, silicon species (based on SiO 2 content): template agent: alkali source (in terms of OH - content): water=1:0.005:0.001:100.0, the template agent is a mixture of tetrapropylammonium hydroxide and n-butylamine (the molar ratio of the two species is 1); the alkali source is sodium hydroxide;
(6) Placing the mixture into a autogenous pressure kettle, and crystallizing for 12 hours at 180 ℃;
(7) Filtering, washing, drying at 110 ℃ for 10 hours, and roasting at 550 ℃ for 10 hours in air to remove the template agent;
(8) And (3) carrying out ion exchange on the molecular sieve with the template agent removed in an ammonium nitrate solution for three times, drying at 110 ℃ for 6 hours after the ion exchange is finished, and roasting at 550 ℃ for 10 hours in air to obtain the mosaic catalyst. Wherein the concentration of the ammonium nitrate solution is 1.0mol/L, the ion exchange solid (in terms of mass) liquid (in terms of volume) ratio is 1:40, the ion exchange temperature is 80 ℃, and the exchange time is 2h each time.
Further, the metal oxide ZnCrO x in the step (1) is prepared by adopting a coprecipitation method, and specifically comprises the following steps:
(1.1) zinc nitrate and cadmium nitrate are dissolved in deionized water to form a metal nitrate mixed solution, wherein the molar ratio of zinc to cadmium in the solution is 1:9, and the concentration of zinc nitrate in the solution is 0.05mol/L;
(1.2) dissolving ammonium carbonate in water by taking the ammonium carbonate as a precipitator, wherein the concentration of the ammonium carbonate is 1.2mol/L;
(1.3) slowly adding an ammonium carbonate solution into the solution dissolved with the metal nitrate under vigorous stirring, wherein the molar ratio of the ammonium carbonate to the metal ions is 1.5:1, the reaction temperature is 70 ℃, and the precipitation reaction time is 10 hours.
(4) After the steps are finished, the sediment is filtered, washed and dried for 12 hours at the temperature of 110 ℃ to obtain the metal oxide ZnCrO x precursor.
The mosaic catalyst prepared by the method is applied to the preparation of paraxylene by coupling hydrogenation of carbon dioxide with alkylation of toluene, and the application conditions are as follows: the ratio of the reaction raw material gas H 2/CO2, the reaction pressure 5MPa, the reaction temperature 500 ℃ and the space velocity of the reaction gas 12000 mL.g -1·h-1. The toluene liquid space velocity was 4h -1. The reaction results are shown in Table 5:
TABLE 5 reaction evaluation results of the mosaic catalyst prepared in example 5
Example 6
A mosaic catalyst comprises a metal oxide and a molecular sieve, wherein the metal oxide is inlaid on the outer surface of the molecular sieve in a mode that a silicon-containing species grows epitaxially on the outer surface of the molecular sieve. The metal oxide is ZnAlOx, the molecular sieve is MCM-22, and the mass ratio of the inlaid ZnAlO x (calculated by ZnO and ZrO 2) to the molecular sieve MCM-22 is 1:10. The molecular sieve MCM-22 has a silicon-aluminum atomic ratio of 30.
The mosaic catalyst is prepared by epitaxial growth on the surface of a molecular sieve after metal oxide and silicon species are fully combined, and specifically comprises the following steps:
(1) Dispersing a metal oxide ZnAlO x in an ethanol/water mixed solution, adding a certain amount of polymer organic matters, fully stirring at 80 ℃, wherein the volume ratio of ethanol to water is 1:2, the solid mass content in the solution is 30%, the polymer organic matters are polyethylene glycol, and the addition amount is 20% of the mass of the oxide;
(2) Adding silica sol of a silicon species into the solution, and fully stirring, wherein the mass ratio of the silica sol (calculated by SiO 2) to the molecular sieve in the step (5) is 0.1:1, and in the formed catalyst, the mass ratio of the molecular sieve to the metal oxide to the silicon species is 1:10:0.1;
(3) Slowly adding ammonia water into the mixed solution until the pH value of the mixed solution is=10, and continuously stirring for 8 hours;
(4) After the steps are finished, filtering, washing and drying the precipitate at 110 ℃ for 12 hours, and roasting the precipitate at 600 ℃ for 4 hours under air to fully combine the metal oxide and the silicon species;
(5) The metal oxide is thoroughly mixed with the fully bound species of silicon species, molecular sieve, alkali source, templating agent and water to form an initial gel mixture having the following molar ratios, silicon species (based on SiO 2 content): template agent: alkali source (in terms of OH - content): water=1:0.005:0.001:10.0, the template agent is a mixture of tetrapropylammonium hydroxide and n-butylamine (the molar ratio of the two species is 1); the alkali source is sodium hydroxide;
(6) Putting the mixture into a autogenous pressure kettle, and crystallizing at 160 ℃ for 24 hours;
(7) Filtering, washing and drying the crystallized molecular sieve at 110 ℃ for 12 hours, and roasting the molecular sieve at 550 ℃ for 15 hours under air to remove the template agent;
(8) And (3) carrying out ion exchange on the molecular sieve with the template agent removed in an ammonium nitrate solution for three times, drying at 110 ℃ for 6 hours after the ion exchange is finished, and roasting at 500 ℃ for 15 hours in air to obtain the mosaic catalyst. Wherein the concentration of the ammonium nitrate solution is 1.0mol/L, the ion exchange solid (in terms of mass) liquid (in terms of volume) ratio is 1:40, the ion exchange temperature is 80 ℃, and the exchange time is 2.5h each time.
Further, the metal oxide ZnAlO x in the step (1) is prepared by adopting a coprecipitation method, and specifically comprises the following steps:
(1.1) zinc nitrate and aluminum nitrate are dissolved in deionized water to form a metal nitrate mixed solution, wherein the molar ratio of zinc to aluminum in the solution is 1:15, and the concentration of zinc nitrate in the solution is 0.1mol/L;
(1.2) dissolving ammonium carbonate in water with the concentration of 0.8mol/L by taking ammonium carbonate as a precipitator;
(1.3) slowly adding an ammonium carbonate solution into the solution dissolved with the metal nitrate under vigorous stirring, wherein the molar ratio of the ammonium carbonate to the metal ions is 1.5:1, the reaction temperature is 70 ℃, and the precipitation reaction time is 12 hours.
(1.4) After the above steps are completed, the precipitate is filtered, washed, dried at 110℃for 12 hours, and then calcined at 600℃for 4 hours under air to obtain the metal oxide ZnAlO x.
The mosaic catalyst prepared by the method is applied to the preparation of paraxylene by coupling benzene alkylation with carbon monoxide hydrogenation, and the application conditions are as follows: the ratio of H 2 to CO of the reaction raw material gas is 5, the reaction pressure is 6MPa, the reaction temperature is 450 ℃, and the space velocity of the reaction gas is 9000 mL.g -1·h-1. The benzene liquid space velocity is 4h -1. The reaction results are shown in Table 6:
TABLE 6 reaction evaluation results of the mosaic catalyst prepared in EXAMPLE 6
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (8)
1. A preparation method of a mosaic catalyst is characterized by comprising the following steps: after the metal oxide is fully combined with the silicon species, the metal oxide is epitaxially grown on the surface of the molecular sieve, so that the metal oxide is inlaid on the surface of the molecular sieve, and the inlaid catalyst is obtained; the metal oxide comprises at least one of ZnZrO x、ZnCrOx、ZnAlOx, the silicon species is tetraethoxysilane or silica sol, the molecular sieve is ZSM-5 or MCM-22, and the silicon-aluminum atomic ratio in the molecular sieve is 30-200;
the method comprises the following steps:
Step 1: dispersing metal oxide or metal oxide precursor in ethanol/water mixed solution, adding high molecular organic matters, fully stirring to obtain mixed solution, then adding silicon species, fully stirring, adding ammonia water, adjusting pH to be less than 10, continuously stirring and carrying out precipitation reaction;
Step 2: filtering, washing, drying and roasting the precipitate to obtain a species in which the metal oxide and the silicon species are fully combined;
Step 3: mixing the metal oxide with the silicon species, a molecular sieve, an alkali source, a template agent and water to form a gel mixture, and carrying out crystallization reaction;
Step 4: filtering, washing, drying and roasting the crystallized product;
Step 5: and (3) performing ion exchange, drying and roasting on the mixture obtained in the step (4) to obtain the mosaic catalyst.
2. The method for preparing the mosaic catalyst according to claim 1, wherein: znZrO x by mass of ZnO and ZrO 2, znCrO x by mass of ZnO and Cr 2O3, znAlO x by mass of ZnO and Al 2O3, and the mass ratio of metal oxide to molecular sieve is 1 (0.1-10).
3. The method for preparing the mosaic catalyst according to claim 1, wherein: the metal oxide is prepared by adopting a coprecipitation method, and concretely comprises the following steps: zinc nitrate and zirconium nitrate, cadmium nitrate or aluminum nitrate are dissolved in water to form a metal nitrate mixed solution; then adding ammonium carbonate solution to carry out coprecipitation reaction to obtain a metal oxide precursor; and finally roasting to obtain the metal oxide.
4. A process for preparing a mosaic catalyst according to claim 3, wherein: the molar ratio of zinc to zirconium, cadmium or aluminum in the metal nitrate mixed solution is 1 (1-15); the concentration of zinc nitrate is 0.01-0.10mol/L; the concentration of the ammonium carbonate solution is 0.8-1.5mol/L; the molar ratio of the ammonium carbonate to the metal ions is 1.5:1; the coprecipitation reaction temperature is 60-80 ℃ and the time is 4-12h; the roasting temperature is 400-600 ℃ and the roasting time is 4-8h.
5. The method for preparing the mosaic catalyst according to claim 1, wherein: the volume ratio of the ethanol to the water in the ethanol/water mixed solution in the step 1 is 1 (0.5-2); the mass percentage of the solid in the mixed solution is 10-30%; the macromolecular organic matter is polyvinylpyrrolidone or polyethylene glycol, and the addition amount is 10-20% of the mass of the metal oxide; the mass ratio of the silicon species to the molecular sieve is (0.01-0.1) 1, and the mass ratio of the molecular sieve, the metal oxide and the silicon species is (0.1-10) 1 (0.01-0.1) based on the content of SiO 2 and the content of OH -; the roasting temperature in the step 2 is 400-600 ℃ and the time is 4-8h.
6. The method for preparing the mosaic catalyst according to claim 1, wherein: the template agent in the step 3 comprises at least one of tetrapropylammonium hydroxide and n-butylamine, and the alkali source is sodium hydroxide; the molar ratio of the silicon species to the template agent to the alkali source to the water is 1 (0.002-0.008) (0.01-0.001) (40.0-100.0) based on the content of SiO 2 and the content of OH -; the crystallization reaction temperature is 140-180 ℃ and the crystallization time is 12-36h; the roasting temperature in the step 4 is 500-600 ℃ and the time is 8-15h; in the step 5, the mixture obtained in the step 4 is placed in ammonium nitrate or ammonium chloride solution with the concentration of 0.2-1.0mol/L for ion exchange; the ion exchange temperature is 60-80 ℃, and the solid-liquid ratio is 1 (20-40); the roasting temperature is 500-600 ℃ and the roasting time is 8-15h.
7. A mosaic catalyst prepared by the process of any one of claims 1 to 6.
8. Use of the mosaic catalyst of claim 7 for the preparation of para-xylene by carbon monoxide/carbon dioxide hydrogenation coupled benzene/toluene alkylation, characterized in that: the reaction conditions are as follows: the ratio of the reaction raw material gas H 2/CO or H 2/CO2 is 1-5, the reaction pressure is 3-6MPa, the reaction temperature is 300-500 ℃, the space velocity of the reaction gas is 5000-12000 mL.g -1·h-1, and the space velocity of benzene/toluene liquid is 1-4H -1.
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