CN109701604B - Multifunctional catalyst system with core-shell structure and application thereof - Google Patents

Abstract

The invention relates to a process for producing aromatic hydrocarbon and coproducing light hydrocarbon by converting synthesis gas and a core-shell structure multifunctional catalyst used in the process. The catalyst system has the catalytic activity of synthesis gas conversion and aromatic hydrocarbon/light hydrocarbon synthesis. Wherein the synthesis gas conversion activity is provided by a metal oxide and the aromatics/lighter hydrocarbons synthesis activity is provided by a molecular sieve. The core layer of the core-shell structure catalyst is a metal oxide, and the active component of the core-shell structure catalyst is preferably one or at least one of Cr, Zr, Mn, Ce, La, Ti, In, Ga and Zn; the shell layer is selected from one or more of MFI or MEL structure molecular sieves, and the silicon-aluminum ratio of the shell layer ranges from 12 to infinity. The invention provides a new route for preparing aromatic hydrocarbon and coproducing light hydrocarbon by directly converting synthesis gas through a non-Fischer-Tropsch route and a one-step method, and the new route can be used for preparing olefin aromatic hydrocarbon through synthesis gas.

Description

Multifunctional catalyst system with core-shell structure and application thereof

Technical Field

The invention relates to a process and a catalyst for producing aromatic hydrocarbon and light hydrocarbon by converting synthesis gas, in particular to a process for producing aromatic hydrocarbon and light hydrocarbon by converting synthesis gas by adopting a core-shell structure multifunctional catalyst system.

Background

Hydrocarbons are an important basic chemical, and have an indispensable role in national economy and human life as energy compositions and synthetic material monomers. For a long time, hydrocarbon products have been derived primarily from petroleum refining. With the increasing shortage of petroleum resources, the development of new hydrocarbon production paths becomes the mitigation of petrochemical energy crisis and the realization of chemical industrySustainable development, and promotion of economic development and energy strategic safety in China. The energy structure of China has the characteristics of rich coal, poor oil and little gas, and the coal resource occupies the leading position in the energy field of China for a long time in the future. Therefore, it is an important strategy in our country in the current situation to fully utilize coal resources and search for a new hydrocarbon synthesis method. The synthesis gas is one of main intermediates for conversion and utilization of coal resources, and related researches have been carried out for nearly a hundred years. Fischer-tropsch synthesis is an important approach to syngas conversion, and its research dates back to the 20's of the last century. The synthesis gas can be converted into C under the action of catalyst containing VIII group transition metal such as Fe, Co, Ni and Ru₂₊Hydrocarbon products, the product distribution of which is limited by Anderson-Schulz-Flory kinetics, have difficulty in achieving a large breakthrough in the selectivity of middle distillates.

In recent years, researchers combine a Fischer-Tropsch synthesis catalyst with an acidic molecular sieve, apply the catalyst to a Fischer-Tropsch synthesis system, and improve the selectivity of a specific product by utilizing the cracking activity and shape-selective effect of the molecular sieve. S.Kang et al, Catalysis Letter,2008,125, 264-; kang et Al, Fuel Processing Technology,2010,91,399-403, supported Fe or Fe-Cu-K on ZSM-5 molecular sieves with Si/Al ratio of 25, the stronger acidity of the ZSM-5 supported catalyst is beneficial to increase the C content in the product compared with bulk Fe or Fe-Cu-K catalyst₂-C₄Selectivity and, in addition, the product olefin/alkane ratio is also increased. In addition, J.Kang et al, Angewandte Chemie International Edition,2011,50,5200-₅-C₁₁And (4) selectivity. The design idea of mesoporous Y molecular sieve supported Co catalyst is provided by X.Peng, Angewandte Chemie International Edition,2015,54,4553-4556, and the supported catalyst obviously improves C by utilizing the weak acidity and the larger pore channel structure (compared with ZSM-5) of the mesoporous Y molecular sieve₁₀-C₂₀Selectivity of (2). In addition to supported catalysts, composite catalyst systems have also been reported in which fischer-tropsch catalysts and acidic molecular sieve catalysts are mixed in different forms. J.Bao, Angewandte Chemie,2008,120,359-362 mixing Co/Al₂O₃Wrapped in an H beta molecular sievePreparing a composite catalyst with a core-shell structure; Q.Lin, Journal of Catalysis,2016,344,378-388 coating Co/Pd/SiO with HZSM-5₂Increase C in the product₅-C₁₁And (4) selectivity. Wangsheng et Al, journal of catalysis, 2002,23, 333-.

The technical current situation of the directional conversion of the synthesis gas based on Fischer-Tropsch synthesis is characterized by high conversion rate, wider product distribution and lower selectivity of aromatic hydrocarbon. In order to break through ASF kinetic limitation of a Fischer-Tropsch synthesis route, the method becomes one of important ideas for realizing the preparation of chemicals by directional conversion of synthesis gas based on the conversion of low-carbon alcohols such as methanol and the like and intermediates such as ether thereof and the like. Javier et al, Industrial&Engineering Chemistry Research,1998,37, 1211-sum 1219 for Cr₂O₃And (3) mechanically mixing-ZnO with an HZSM-5 molecular sieve with the silicon-aluminum ratio of Si/Al being 154, so that the synthesis gas is directly prepared into gasoline through methanol. Q.Zhang et al, Fuel Processing Technology,2004,85,1139-₂The composite system of the methanol synthesis catalyst and the methanol conversion catalyst such as ZSM-5, USY, H beta and the like has the catalytic performance of a synthesis gas conversion system, wherein the composite catalyst system obtained by mechanically mixing Cu-Zn and USY according to the mass ratio of 1:1 has better LPG selectivity. According to K.Cheng et al, Angewandte Chemie International Edition,2016,55, 1-5; jiano et al, Science,2016,351,1065-1068, ZnO-ZrO₂、ZnO-Cr₂O₃The composite catalyst obtained by mechanically mixing the SAPO-34 can directionally convert the synthesis gas to prepare the C₂-C₄A low carbon olefin. Zhang Qingde et Al, modern chemical, 2009,29,112-₂O₃、γ-Al₂O₃The composite catalyst/HZSM-5 (Si/Al-38) is filled in the first and second reaction sections of isobaric series flow system, and the reaction temperature of the first and second reaction sections is controlled at 270 deg.C and 360 deg.C respectively, so that the high-efficiency conversion of synthetic gas to prepare arene is realized. Similar two-stage process technologies are in Zhang Jing et al, clean coal technology, 2013,19, 60-67; zhang et al, Journal of Industrial and Engineering Chemistry,2013,19, 975-. Furthermore, CN201610550701, CN201610348096 uses modified silicon-aluminum molecular sieve as carrier to prepare load type catalyst; patent CN200980149207 adopts Ga-containing silicate zeolite molecular sieve; patent CN200810079957 adopts HNKF-5, an aluminum phosphate molecular sieve and Ga-Zn-Ba composite oxide; in patent CN201310149855, a ZSM-5 molecular sieve with high silica-alumina ratio is used in combination with a methanol synthesis catalyst; the patents CN201610965244 and CN201610609584 use composite catalysts containing Zr composite oxide and ZSM5, and both realize direct conversion of synthesis gas to produce hydrocarbon compounds (containing aromatic hydrocarbons).

In order to realize the direct conversion of synthesis gas to prepare aromatic hydrocarbon, the preferred process technology in the current literature report mainly comprises a one-step process based on Fischer-Tropsch synthesis and acidic molecular sieve shape selection and a two-stage process based on methanol synthesis and acidic molecular sieve shape selection. The former has major problems including: the dynamic limit of product distribution is difficult to break through completely, the carbon deposition inactivation is serious, and the like. The latter needs to control the technological conditions of two-stage reaction, and the complexity of the device and the technology is higher than that of the one-step technology. And the multifunctional catalyst is adopted, so that the possibility of synthesizing hydrocarbon compounds (such as aromatic hydrocarbon and the like) by the synthesis gas through a non-Fischer-Tropsch route in one step is provided.

Disclosure of Invention

The invention aims to solve the technical problems of inconvenient catalyst filling, high industrial application investment, low CO conversion rate, low selectivity of target product aromatic hydrocarbon, low proportion of light aromatic hydrocarbon in aromatic hydrocarbon product, complex catalyst preparation and the like in the prior art, and provides a novel catalyst system which has the advantages of simple catalyst preparation, convenient filling, high CO conversion rate, high selectivity of target product aromatic hydrocarbon, high proportion of light aromatic hydrocarbon in aromatic hydrocarbon, low equipment investment cost and the like when being used for producing aromatic hydrocarbon and coproducing light hydrocarbon by converting synthesis gas.

In order to solve the technical problems, the technical scheme of the invention is as follows: a multifunctional catalyst system with a core-shell structure is characterized in that the catalyst is an integral multifunctional catalyst with a core-shell structure and comprising metal oxide and a molecular sieve.

In the above technical solution, preferably, the metal component of the metal oxide is at least one selected from alkali metals, alkaline earth metals, rare earth metals, elements of groups IVB, VIII, IB, IIB, and IIIA. In the above technical solution, it is more preferable that the metal component of the metal oxide is one or at least one selected from Cr, Zr, Mn, Ce, La, Mo, Ti, In, Ga, and Zn.

In the above technical solution, it is more preferable that the metal component of the metal oxide is one or at least one selected from Cr, Zr, Mn, In, Ga, and Zn.

In the above technical solution, it is more preferable that the metal component of the metal oxide is selected from Zn, In, Cr and Mn.

In the above technical solution, it is more preferable that the metal component of the metal oxide is selected from Zn, Cr and Mn.

In the above technical solution, it is more preferable that the metal component of the metal oxide is selected from Zn, Cr and In.

In the above technical solution, it is more preferable that the metal component of the metal oxide is selected from Zn and Cr.

In the above technical solution, it is more preferable that the metal component of the metal oxide is selected from Zn and Mn.

In the above technical solution, it is more preferable that the metal component of the metal oxide is selected from Ga, Mn, and Cr.

In the above technical solution, it is more preferable that the metal component of the metal oxide is selected from Zn, Cr and Ga. In the above technical solution, preferably, the molecular sieve is selected from one or more of MFI or MEL structure molecular sieves.

In the technical scheme, more preferably, the molecular sieve is selected from one or at least one of ZSM-5, ZSM-11, Silicalite-1 and Silicalite-2.

In the above technical solution, preferably, the silica alumina ratio of the molecular sieve is 12 to infinity.

In the technical scheme, the more preferable silicon-aluminum ratio of the molecular sieve is 12-250.

In the technical scheme, the more preferable silicon-aluminum ratio of the molecular sieve is 70-100.

In the above technical solution, preferably, the core-shell structure catalyst comprises at least 1 layer of the shell layer molecular sieve, and more preferably 2 layers, 3 layers or 4 layers.

In the above technical scheme, preferably, when the core-shell structure catalyst comprises 2 or more than 2 layers of shell layer molecular sieves, the silica-alumina ratio of the outer shell layer molecular sieve is preferably not less than that of the inner shell layer molecular sieve; preferably, the outer shell molecular sieve is selected from one or at least one of Silicalite-1 and Silicalite-2.

In the above technical scheme, preferably, the mass ratio of the core layer metal oxide to the shell layer molecular sieve in the core-shell structure catalyst is within the range of (8: 1) - (1: 8).

In the above technical solution, more preferably, the mass ratio of the core layer metal oxide to the shell layer molecular sieve in the core-shell structure catalyst is in the range of (3: 1) - (1: 3).

In the above technical solution, more preferably, the mass ratio of the core layer metal oxide to the shell layer molecular sieve in the core-shell structure catalyst is within a range from (3:2) to (2: 3).

In order to solve the above technical problems, the second technical solution adopted by the present invention is: a method for producing aromatic hydrocarbon and light hydrocarbon by converting synthesis gas comprises the step of taking the synthesis gas as a raw material, and carrying out contact reaction on the raw material and the catalyst system to obtain a material flow containing the aromatic hydrocarbon and the light hydrocarbon.

In the above technical scheme, preferably, the raw material synthesis gas contains 10-50% by volume of H₂And/or H₂The mol ratio of/CO is 0.25-5.0.

In the above technical solution, more preferably, the raw material synthesis gas H₂The mol ratio of/CO is 0.25-1.0.

In the above technical solution, more preferably, the raw material synthesis gas H₂the/CO molar ratio is in the range of 0.5-1.0.

In the above technical solution, preferably, the reaction conditions are: the reaction temperature is 300-500 ℃, and/or the reaction pressure is 0.5-10.0MPa, and/or the volume space velocity is 1000-20000h^-1。

In the above technical solution, more preferably, the reaction conditions are: the reaction temperature is 300-400 ℃, and/or the reaction pressure is 1.0-8.0 MPa, and/or the volume space velocity is 2000-8000 h^-1。

The technological process of the present invention is realized by a multifunctional catalyst with a core-shell structure, wherein the multifunctional catalyst with the core-shell structure is composed of a metal oxide with synthesis gas conversion activity and a molecular sieve with aromatic hydrocarbon/light hydrocarbon synthesis activity. In the core-shell structure catalyst containing core layer metal oxide and at least one layer of shell layer molecular sieve, the synthetic gas is continuously converted to firstly generate low-carbon intermediate, and then the low-carbon intermediate is further converted to generate products such as aromatic hydrocarbon, light hydrocarbon and the like.

The present invention seeks to provide a new process for the preparation of aromatics and the co-production of light hydrocarbons from synthesis gas. The product contains BTX aromatic hydrocarbon and C₉₊Aromatic hydrocarbons and C₁-C₅₊Light hydrocarbons. For molecular sieves, their acidity is mainly affected by the silica to alumina ratio. Molecular sieves with generally higher low silica to alumina ratios

The acid amount is beneficial to the conversion of intermediates such as methanol and the like and the oligomerization and cyclization of light hydrocarbon, thereby being beneficial to improving the yield of the target product aromatic hydrocarbon. Too strong acidity or too high acid amount may exacerbate the carbon deposition reaction. In addition, due to the shape selection effect of the molecular sieve, the pore structure of the molecular sieve is also an important factor influencing the product distribution, so the type selection of the molecular sieve is also important for the yield of the target product. The component for synthesizing aromatic hydrocarbon/light hydrocarbon in the invention is a shell layer molecular sieve of a core-shell catalyst, and an MFI or MEL structure molecular sieve with the silicon-aluminum ratio in the range of 12 to infinity is selected.

The conversion of synthesis gas to produce aromatic hydrocarbons and light hydrocarbons is a multi-step reaction, and in order to promote the main reaction and simultaneously inhibit the side reactions, the process conditions of the system need to be set within a range suitable for each reaction. At the same time, the catalyst providing the two active centers (syngas conversion, aromatics/lighter synthesis) needs to have a sufficiently strong coupling capacity. For a multi-stage catalyst system, although the multi-stage reaction can be realized by adjusting the process conditions of each stage, the large difference of the process conditions between the stages can lead to the increase of energy consumption and operation cost. Therefore, there is also a need to solve the problem of matching catalysts and process conditions for multi-step reactions. The synthesis gas conversion catalyst selected by the invention is a metal oxide with stronger coupling capacity with the core-shell structure molecular sieve, and the metal component is preferably one or at least one of Cr, Zr, Mn, Ce, La, Mo, Ti, In, Ga and Zn.

The process conditions used were as follows: the raw material synthesis gas comprises 10-50% of H by volume fraction₂And/or H₂The mol ratio of/CO is within the range of 0.25-5.0; remove H₂In addition to CO, N is also included in the system₂、CO₂、H₂O, inert gas and the like; the temperature of a bed layer is 300-500 ℃, and/or the pressure of the system is 0.5-10.0MPa, and/or the airspeed is 1000-20000h^-1。

The reactor type can be selected from fixed bed, fluidized bed, moving bed, etc.

The raw material gas is selected from H₂The mol ratio of/CO is 0.25-5.0. The H of the synthesis gas from different sources can be adjusted by adopting water gas shift treatment/reverse water gas shift treatment₂The mole ratio of/CO. H required for treatment₂O and CO₂Part of the reaction product comes from the separation reflux of the reaction product, and part comes from the pipeline gas supply.

In the present invention, the reacted stream includes unconverted CO and H₂，CO₂And hydrocarbon products consisting of aromatic hydrocarbons and C₁～C₅₊Composition of hydrocarbons, aromatic hydrocarbons including C₆～C₉₊An aromatic hydrocarbon. The selectivity of each product is defined as the proportion (mol%) of each product in the total carbon number of the organic product. The specific calculation method is as follows:

total carbon number of organic product ═ Σ (amount of substance of organic product i × number of carbon atoms in molecule of organic product i)

Selectivity of organic product j ═ amount of substance of organic product j × number of carbon atoms in molecule of organic product j/total number of carbon atoms of organic product × 100%

Aromatic selectivity ═ C₆Aromatic Selectivity + C₇Aromatic Selectivity + C₈Aromatic Selectivity + C₉₊Selectivity to aromatic hydrocarbons

C₆-C₈Aromatic hydrocarbon ratio (C)₆Aromatic Selectivity + C₇Aromatic Selectivity + C₈Arene selectivity)/arene selectivity x 100%

The light aromatic hydrocarbon referred to in the present invention means C₆-C₈Aromatic hydrocarbons; aromatic hydrocarbonC in hydrocarbons₆-C₈The light aromatic hydrocarbon is widely used for producing synthetic rubber, synthetic resin and synthetic fiber, and is also an industrial raw material for synthesizing products such as detergent, plasticizer, explosive, dye, pesticide and the like, and C₉₊Heavy aromatics are in relatively small demand and often need to be converted to light aromatics via a lightening process. Thus, C in total aromatic hydrocarbons is increased₆-C₈The proportion of the aromatic hydrocarbon can effectively reduce the difficulty of subsequent aromatic hydrocarbon product treatment, and has higher economic benefit.

By adopting the technical scheme of the invention, the high-efficiency coupling of multi-step reactions is realized by screening and selecting the catalysts and optimizing the combination form among the catalysts in the composite catalytic system, so that the equipment investment cost is reduced, the selectivity of aromatic hydrocarbon is improved by the directional secondary conversion of intermediate products, the distribution of aromatic hydrocarbon products is optimized, and the high-efficiency production of light aromatic hydrocarbon is realized. The catalyst system is used in the reaction of preparing arene with synthetic gas, arene selectivity up to 70% or higher, C₆-C₈The aromatic hydrocarbon accounts for more than 70 percent of the total aromatic hydrocarbon, and a good technical effect is achieved.

Detailed Description

[ example 1 ]

Preparing Zn-Cr oxide by a sol-gel method according to the Zn/Cr molar ratio of 1:3, and recording the Zn-Cr oxide as ZnCr₃O_x(ii) a Preparing mother liquor containing silica sol, sodium metaaluminate and tetrapropylammonium bromide according to shell layer Si/Al of 12 and core/shell mass ratio of 1/1, and adding a certain amount of ZnCr into the mother liquor₃O_xThe obtained mixed system is subjected to hydrothermal treatment to obtain ZnCr as a core₃O_xAnd a core-shell structure molecular sieve with a shell layer of HZSM-5(Si/Al ═ 12), and is marked as ZnCr₃O_x/HZ5 (12); ZnCr is mixed with₃O_xGranulating and crushing the/HZ 5(12) to obtain 20-40 mesh catalyst particles, and weighing 1.5g of the catalyst particles to be filled in a reactor. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 2000h^-1The catalyst was evaluated under the conditions of (1). The pre-reaction catalyst was reacted with H at 395 deg.C₂And (4) pretreating for 2 h.

Feed gas H₂/CO/N₂The product is analyzed on-line by gas chromatography, wherein N is used₂Quantitative analysis of the product was achieved for the internal standard. And products are separated by three columns, wherein one column is a hayesep-Q packed column, and the separated products enter a thermal conductivity cell detector to detect permanent gases such as hydrogen, nitrogen, carbon monoxide, carbon dioxide, methane and the like. Cutting aliphatic hydrocarbon and aromatic hydrocarbon by two-dimensional center cutting technology, and respectively detecting by two sets of hydrogen flame detectors, one is HP-PLOT Al₂O₃A capillary column, and detecting aliphatic hydrocarbon products such as methane, ethane, ethylene, propane, propylene, butane, butylene and the like by a product in a hydrogen flame detector; the other is a DB-WAXetr capillary column, and the product enters a hydrogen flame detector to detect aromatic hydrocarbon products such as benzene, toluene, xylene and the like. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 1.

[ example 2 ]

Preparing Zn-Cr oxide by coprecipitation method according to Zn/Cr molar ratio of 1:3, and recording the Zn-Cr oxide as ZnCr₃O_x(ii) a Preparing mother liquor containing silica sol, sodium metaaluminate and tetrabutyl ammonium bromide according to the shell layer Si/Al of 12 and core/shell mass ratio of 1/1, and adding a certain amount of ZnCr into the mother liquor₃O_xThe obtained mixed system is subjected to hydrothermal treatment to obtain ZnCr as a core₃O_xAnd a core-shell structure molecular sieve with a shell layer of HZSM-11 (Si/Al-12), and is marked as ZnCr₃O_xHZ11 (12); ZnCr is mixed with₃O_xGranulating and crushing the/HZ 11(12) to obtain 20-40 mesh catalyst particles, and weighing 1.5g of the catalyst particles to be filled in a reactor. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 2000h^-1The catalyst was evaluated under the conditions of (1). The pre-reaction catalyst was reacted with H at 395 deg.C₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 1.

[ example 3 ]

Preparing Zn-Cr oxide by high-temperature sintering according to the Zn/Cr molar ratio of 1:3, and recording the Zn-Cr oxide as ZnCr₃O_x(ii) a Preparing mother liquor containing silica sol, sodium metaaluminate and tetrapropylammonium bromide according to the shell layer Si/Al ratio of 30 and the core/shell mass ratio of 1/1,and adding a certain amount of ZnCr into the mother liquor₃O_xThe obtained mixed system is subjected to hydrothermal treatment to obtain ZnCr as a core₃O_xAnd a core-shell structure molecular sieve with a shell layer of HZSM-5(Si/Al ═ 30), and is marked as ZnCr₃O_x/HZ5 (30); ZnCr is mixed with₃O_xGranulating and crushing the/HZ 5(30) to obtain 20-40 mesh catalyst particles, and weighing 1.5g of the catalyst particles to be filled in a reactor. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 2000h^-1The catalyst was evaluated under the conditions of (1). The pre-reaction catalyst was reacted with H at 395 deg.C₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 1.

[ example 4 ]

Preparing Zn-Cr oxide by coprecipitation method according to Zn/Cr molar ratio of 1:3, and recording the Zn-Cr oxide as ZnCr₃O_x(ii) a Preparing mother liquor containing ethyl orthosilicate, pseudo-boehmite and tetrapropylammonium hydroxide according to shell layer Si/Al of 50 and core/shell mass ratio of 1/1, and adding a certain amount of ZnCr into the mother liquor₃O_xThe obtained mixed system is subjected to hydrothermal treatment to obtain ZnCr as a core₃O_xAnd a core-shell structure molecular sieve with a shell layer of HZSM-5(Si/Al ═ 50), and is marked as ZnCr₃O_x/HZ5 (50); ZnCr is mixed with₃O_xGranulating and crushing the/HZ 5(50) to obtain 20-40 mesh catalyst particles, and weighing 1.5g of the catalyst particles to be filled in a reactor. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 2000h^-1The catalyst was evaluated under the conditions of (1). The pre-reaction catalyst was reacted with H at 395 deg.C₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 1.

[ example 5 ] A method for producing a polycarbonate

Preparing Zn-Cr oxide by coprecipitation method according to Zn/Cr molar ratio of 1:3, and recording the Zn-Cr oxide as ZnCr₃O_x(ii) a Preparing mother liquor containing ethyl orthosilicate, pseudo-boehmite and tetrapropylammonium hydroxide according to shell layer Si/Al of 50 and core/shell mass ratio of 1/1, and adding a certain amount of ZnCr into the mother liquor₃O_xThe obtained mixed system is subjected to hydrothermal treatmentObtaining ZnCr as a core₃O_xAnd a core-shell structure molecular sieve with a shell layer of HZSM-5(Si/Al ═ 70), and is marked as ZnCr₃O_x/HZ5 (70); ZnCr is mixed with₃O_xGranulating and crushing the/HZ 5(70) to obtain 20-40 mesh catalyst particles, and weighing 1.5g of the catalyst particles to be filled in a reactor. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 2000h^-1The catalyst was evaluated under the conditions of (1). The catalyst is reacted at 395 ℃ with H₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 1.

[ example 6 ]

Preparing Zn-Cr oxide by coprecipitation method according to Zn/Cr molar ratio of 1:3, and recording the Zn-Cr oxide as ZnCr₃O_x(ii) a Preparing mother liquor containing ethyl orthosilicate, aluminium isopropoxide and tetrapropylammonium hydroxide according to shell layer Si/Al of 100 and core/shell mass ratio of 1/1, and adding a certain amount of ZnCr into the mother liquor₃O_xThe obtained mixed system is subjected to hydrothermal treatment to obtain ZnCr as a core₃O_xAnd a core-shell structure molecular sieve with a shell layer of HZSM-5(Si/Al 100) and is marked as ZnCr₃O_xHZ5 (100); ZnCr is mixed with₃O_xGranulating and crushing the/HZ 5(100) to obtain 20-40 mesh catalyst particles, and weighing 1.5g of the catalyst particles to be filled in a reactor. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 2000h^-1The catalyst was evaluated under the conditions of (1). The catalyst is reacted at 395 ℃ with H₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 1.

[ example 7 ]

Preparing Zn-Cr oxide by coprecipitation method according to Zn/Cr molar ratio of 1:3, and recording the Zn-Cr oxide as ZnCr₃O_x(ii) a Preparing mother liquor containing ethyl orthosilicate, pseudo-boehmite and tetrapropylammonium hydroxide according to shell layer Si/Al being 12 and core/shell mass ratio 5/1, and adding a certain amount of ZnCr into the mother liquor₃O_xThe obtained mixed system is subjected to hydrothermal treatment to obtain ZnCr as a core₃O_xAnd core-shell structure molecule with shell layer of HZSM-5(Si/Al ═ 12)Sieving, recording as ZnCr₃O_x/HZ5(12) (5: 1); ZnCr is mixed with₃O_xGranulating and crushing the/HZ 5(12) (5:1) to obtain 20-40 mesh catalyst particles, and weighing 1.5g of the catalyst particles to fill the reactor. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 2000h^-1The catalyst was evaluated under the conditions of (1). The pre-reaction catalyst was reacted with H at 395 deg.C₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity, and aromatics product distribution are shown in table 1.

[ example 8 ]

Preparing Zn-Cr oxide by coprecipitation method according to Zn/Cr molar ratio of 1:3, and recording the Zn-Cr oxide as ZnCr₃O_x(ii) a Preparing mother liquor containing ethyl orthosilicate, pseudo-boehmite and tetrapropylammonium hydroxide according to shell layer Si/Al being 12 and core/shell mass ratio 3/2, and adding a certain amount of ZnCr into the mother liquor₃O_xThe obtained mixed system is subjected to hydrothermal treatment to obtain ZnCr as a core₃O_xAnd a core-shell structure molecular sieve with a shell layer of HZSM-5(Si/Al ═ 12), and is marked as ZnCr₃O_x/HZ5(12) (3: 2); ZnCr is mixed with₃O_xGranulating and crushing the/HZ 5(12) (3:2) to obtain 20-40 mesh catalyst particles, and weighing 1.5g of the catalyst particles to fill the reactor. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 2000h^-1The catalyst was evaluated under the conditions of (1). The pre-reaction catalyst was reacted with H at 395 deg.C₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 1.

[ example 9 ]

Preparing Zn-Cr oxide by coprecipitation method according to Zn/Cr molar ratio of 1:3, and recording the Zn-Cr oxide as ZnCr₃O_x(ii) a Preparing mother liquor containing ethyl orthosilicate, pseudo-boehmite and tetrapropylammonium hydroxide according to shell layer Si/Al being 12 and core/shell mass ratio 2/3, and adding a certain amount of ZnCr into the mother liquor₃O_xThe obtained mixed system is subjected to hydrothermal treatment to obtain ZnCr as a core₃O_xAnd a core-shell structure molecular sieve with a shell layer of HZSM-5(Si/Al ═ 12), and is marked as ZnCr₃O_x/HZ5(12) (2: 3); ZnCr is mixed with₃O_xGranulating and crushing the/HZ 5(12) (2:3) to obtain 20-40 mesh catalyst particles, and weighing 1.5g of the catalyst particles to fill the reactor. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 2000h^-1The catalyst was evaluated under the conditions of (1). The pre-reaction catalyst was reacted with H at 395 deg.C₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity, and aromatics product distribution are shown in table 1.

[ example 10 ]

Preparing Zn-Cr oxide by coprecipitation method according to Zn/Cr molar ratio of 1:3, and recording the Zn-Cr oxide as ZnCr₃O_x(ii) a Preparing mother liquor containing ethyl orthosilicate, pseudo-boehmite and tetrapropylammonium hydroxide according to shell layer Si/Al being 12 and core/shell mass ratio 1/5, and adding a certain amount of ZnCr into the mother liquor₃O_xThe obtained mixed system is subjected to hydrothermal treatment to obtain ZnCr as a core₃O_xAnd a core-shell structure molecular sieve with a shell layer of HZSM-5(Si/Al ═ 12), and is marked as ZnCr₃O_xHZ5(12) (1: 5); ZnCr is mixed with₃O_xGranulating and crushing the/HZ 5(12) (1:5) to obtain 20-40 mesh catalyst particles, and weighing 1.5g of the catalyst particles to fill the catalyst particles in a reactor. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 2000h^-1The catalyst was evaluated under the conditions of (1). The pre-reaction catalyst was reacted with H at 395 deg.C₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity, and aromatics product distribution are shown in table 1.

[ example 11 ]

Preparing Zn-Cr oxide by coprecipitation method according to Zn/Cr molar ratio of 1:3, and recording the Zn-Cr oxide as ZnCr₃O_x(ii) a Preparing mother liquor containing ethyl orthosilicate, aluminium nitrate and tetrapropyl ammonium hydroxide according to shell layer Si/Al (12) and core/shell mass ratio 1/1, and adding a certain quantity of ZnCr into the mother liquor₃O_xThe obtained mixed system is subjected to hydrothermal treatment to obtain ZnCr as a core₃O_xAnd a core-shell structure molecular sieve with a shell layer of HZSM-5(Si/Al ═ 12), and is marked as ZnCr₃O_x/HZ5 (12); with ZnCr₃O_xThe core is/HZ 5(12), and the shell layer has Si/Al of 100 and core/shell mass ratio of 4/1Mother liquor of ethyl silicate, aluminum nitrate and tetrapropylammonium hydroxide, and a certain amount of ZnCr is added into the mother liquor₃O_x/HZ5(12), and the obtained mixed system is subjected to hydrothermal treatment to finally obtain the product with ZnCr core₃O_xThe molecular sieve with core-shell structure, whose inner shell layer is HZSM-5(Si/Al is 12) and outer shell layer is HZSM-5(Si/Al is 100), is named as ZnCr₃O_x/HZ5(12)/HZ5 (100); ZnCr is mixed with₃O_xGranulating and crushing the/HZ 5(12)/HZ5(100) to obtain 20-40 mesh catalyst particles, and weighing 1.5g of the catalyst particles to fill the reactor. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 2000h^-1The catalyst was evaluated under the conditions of (1). The pre-reaction catalyst was reacted with H at 395 deg.C₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 1.

[ example 12 ]

Preparing Zn-Cr oxide by coprecipitation method according to Zn/Cr molar ratio of 1:3, and recording the Zn-Cr oxide as ZnCr₃O_x(ii) a Preparing mother liquor containing sodium silicate, aluminium sulfate and tetrapropylammonium hydroxide according to shell layer Si/Al of 12 and core/shell mass ratio of 1/1, and adding a certain quantity of ZnCr into the mother liquor₃O_xThe obtained mixed system is subjected to hydrothermal treatment to obtain a mixed system with ZnCr as a core₃O_xAnd a core-shell structure molecular sieve with a shell layer of HZSM-5(Si/Al ═ 12), and is marked as ZnCr₃O_x/HZ5 (12); with ZnCr₃O_xProviding a mother liquor containing ethyl orthosilicate, aluminum isopropoxide and tetrabutyl ammonium hydroxide according to a shell layer Si/Al ratio of 100 and a core/shell mass ratio of 4/1, wherein the core is/HZ 5(12), and adding a certain amount of ZnCr into the mother liquor₃O_x/HZ5(12), carrying out hydrothermal treatment on the obtained mixed system to finally obtain a mixed system with ZnCr core₃O_xA core-shell structure molecular sieve with an inner shell layer of HZSM-5(Si/Al 12) and an outer shell layer of HZSM-11(Si/Al 100), and is named as ZnCr₃O_x/HZ5(12)/HZ11 (100); ZnCr is mixed with₃O_xGranulating and crushing the/HZ 5(12)/HZ11(100) to obtain 20-40 mesh catalyst particles, and weighing 1.5g of the catalyst particles to fill the reactor. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of the carbon to the oxygen is 1.0,airspeed of 2000h^-1The catalyst was evaluated under the conditions of (1). The pre-reaction catalyst was reacted with H at 395 deg.C₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 1.

[ example 13 ]

Preparing Zn-Cr oxide by coprecipitation method according to Zn/Cr molar ratio of 1:3, and recording the Zn-Cr oxide as ZnCr₃O_x(ii) a Preparing mother liquor containing ethyl orthosilicate, pseudo-boehmite and tetrapropylammonium hydroxide according to shell layer Si/Al being 12 and core/shell mass ratio 1/1, and adding a certain amount of ZnCr into the mother liquor₃O_xThe obtained mixed system is subjected to hydrothermal treatment to obtain ZnCr as a core₃O_xAnd a core-shell structure molecular sieve with a shell layer of HZSM-5(Si/Al ═ 12), and is marked as ZnCr₃O_x/HZ5 (12); with ZnCr₃O_xPreparing mother liquor containing sodium silicate and tetrapropylammonium hydroxide according to a core/shell mass ratio of 4/1 by taking/HZ 5(12) as a core, and adding a certain amount of ZnCr into the mother liquor₃O_x/HZ5(12), the obtained mixed system is subjected to hydrothermal treatment to obtain a mixed system with ZnCr core₃O_xThe inner shell layer is HZSM-5(Si/Al ═ 12), the outer shell layer is Silicalite-1 (full-silicon ZSM-5, Si/Al ═ infinity) core-shell structure molecular sieve, and the molecular sieve is expressed as ZnCr₃O_x(ii)/HZ 5 (12)/S1; ZnCr is mixed with₃O_xGranulating and crushing the/HZ 5(12)/S1 to obtain 20-40 mesh catalyst particles, and weighing 1.5g of the catalyst particles to be filled in a reactor. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 2000h^-1The catalyst was evaluated under the conditions of (1). The pre-reaction catalyst was reacted with H at 395 deg.C₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 1.

[ example 14 ]

Preparing Zn-Cr oxide by coprecipitation method according to Zn/Cr molar ratio of 1:3, and recording the Zn-Cr oxide as ZnCr₃O_x(ii) a Preparing mother liquor containing sodium silicate, aluminium sulfate and tetrapropylammonium hydroxide according to shell layer Si/Al of 12 and core/shell mass ratio of 1/1, and adding a certain quantity of ZnCr into the mother liquor₃O_xThe obtained mixed system is subjected to hydrothermal treatment to obtain ZnCr as a core₃O_xAnd a core-shell structure molecular sieve with a shell layer of HZSM-5(Si/Al ═ 12), and is marked as ZnCr₃O_x/HZ5 (12); with ZnCr₃O_xPreparing mother liquor containing ethyl orthosilicate and tetrabutyl ammonium hydroxide according to a core/shell mass ratio of 4/1 by taking/HZ 5(12) as a core, and adding a certain amount of ZnCr into the mother liquor₃O_x/HZ5(12), and the obtained mixed system is subjected to hydrothermal treatment to finally obtain the product with ZnCr core₃O_xA core-shell molecular sieve having an inner shell layer of HZSM-5(Si/Al ═ 12) and an outer shell layer of Silicalite-2(Si/Al ∞), and referred to as ZnCr₃O_x(ii)/HZ 5 (12)/S2; ZnCr is mixed with₃O_xGranulating and crushing the/HZ 5(12)/S2 to obtain 20-40 mesh catalyst particles, and weighing 1.5g of the catalyst particles to fill the reactor. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 2000h^-1The catalyst was evaluated under the conditions of (1). The pre-reaction catalyst was reacted with H at 395 deg.C₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 1.

[ example 15 ]

Preparing Zn-Cr oxide by coprecipitation method according to Zn/Cr molar ratio of 1:3, and recording the Zn-Cr oxide as ZnCr₃O_x(ii) a Preparing mother liquor containing ethyl orthosilicate, pseudo-boehmite and tetrapropylammonium hydroxide according to shell layer Si/Al being 12 and core/shell mass ratio 2/3, and adding a certain amount of ZnCr into the mother liquor₃O_xThe obtained mixed system is subjected to hydrothermal treatment to obtain ZnCr as a core₃O_xAnd a core-shell structure molecular sieve with a shell layer of HZSM-5(Si/Al ═ 12), and is marked as ZnCr₃O_x/HZ5 (12); with ZnCr₃O_xPreparing mother liquor containing sodium silicate and tetrapropylammonium hydroxide according to a core/shell mass ratio of 5/1 by taking/HZ 5(12) as a core, and adding a certain amount of ZnCr into the mother liquor₃O_x/HZ5(12), the obtained mixed system is subjected to hydrothermal treatment to obtain a mixed system with ZnCr core₃O_xThe molecular sieve with core-shell structure, in which the inner shell layer is HZSM-5(Si/Al ═ 12) and the outer shell layer is Silicalite-1 (full-silicon ZSM-5, Si/Al ∞), is named as ZnCr₃O_x(ii) HZ5(12)/S1(2:3: 1); ZnCr is mixed with₃O_xProduction of/HZ 5(12)/S1(2:3:1)And (3) granulating and crushing to obtain 20-40 mesh catalyst particles, and weighing 1.5g of catalyst particles to be filled in a reactor. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 2000h^-1The catalyst was evaluated under the conditions of (1). The pre-reaction catalyst was reacted with H at 395 deg.C₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 1.

[ example 16 ]

Preparing Zn-Cr oxide by coprecipitation method according to Zn/Cr molar ratio of 1:3, and recording the Zn-Cr oxide as ZnCr₃O_x(ii) a Preparing mother liquor containing ethyl orthosilicate, pseudo-boehmite and tetrapropylammonium hydroxide according to shell layer Si/Al being 12 and core/shell mass ratio 2/3, and adding a certain amount of ZnCr into the mother liquor₃O_xThe obtained mixed system is subjected to hydrothermal treatment to obtain ZnCr as a core₃O_xAnd a core-shell structure molecular sieve with a shell layer of HZSM-5(Si/Al ═ 12), and is marked as ZnCr₃O_x/HZ5 (12); with ZnCr₃O_xPreparing mother liquor containing sodium silicate and tetrapropylammonium hydroxide according to a core/shell mass ratio of 5/2 by taking/HZ 5(12) as a core, and adding a certain amount of ZnCr into the mother liquor₃O_x/HZ5(12), the obtained mixed system is subjected to hydrothermal treatment to obtain a mixed system with ZnCr core₃O_xThe inner shell layer is HZSM-5(Si/Al ═ 12), the outer shell layer is Silicalite-1 (full-silicon ZSM-5, Si/Al ═ infinity) core-shell structure molecular sieve, and the molecular sieve is expressed as ZnCr₃O_x(ii)/HZ 5(12)/S1(2:3: 2); ZnCr is mixed with₃O_xGranulating and crushing the/HZ 5(12)/S1(2:3:2) to obtain 20-40 mesh catalyst particles, and weighing 1.5g of the catalyst particles to be filled in a reactor. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 2000h^-1The catalyst was evaluated under the conditions of (1). The pre-reaction catalyst was reacted with H at 395 deg.C₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 1.

[ example 17 ]

Preparing Zn-Cr oxide, namely ZnCr oxide by adopting a coprecipitation method according to the Zn/Cr molar ratio of 1:3₃O_x(ii) a According to the mass ratio of core to shell 2/1, preparing the mixture containing tetraethoxysilaneMother liquor of tetrapropylammonium hydroxide, and a certain amount of ZnCr is added into the mother liquor₃O_xThe obtained mixed system is subjected to hydrothermal treatment to obtain ZnCr as a core₃O_xAnd a core-shell molecular sieve with a shell layer of Silicalite-1 (all-silicon ZSM-5, Si/Al ═ infinity), which is named as ZnCr₃O_x(S1); with ZnCr₃O_xThe method comprises the steps of taking/S1 as a core, preparing mother liquor containing sodium silicate, sodium aluminate and tetrapropylammonium hydroxide according to the core/shell mass ratio of 1/1, and adding a certain amount of ZnCr into the mother liquor₃O_xS1, carrying out hydrothermal treatment on the obtained mixed system to obtain the product with ZnCr core₃O_xThe inner shell layer is Silicalite-1 (all-silicon ZSM-5, Si/Al ═ infinity), and the outer shell layer is HZSM-5(Si/Al ═ 12), and the molecular sieve is of a core-shell structure and is marked as ZnCr₃O_x(ii)/S1/HZ 5(12) (2:1: 3); ZnCr is mixed with₃O_xGranulating and crushing the/S1/HZ 5(12) (2:1:3) to obtain 20-40 mesh catalyst particles, and weighing 1.5g of the catalyst particles to fill the reactor. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 2000h^-1The catalyst was evaluated under the conditions of (1). The catalyst is reacted at 395 ℃ with H₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 1.

[ example 18 ]

Preparing Zn-Cr oxide by coprecipitation method according to Zn/Cr molar ratio of 1:3, and recording the Zn-Cr oxide as ZnCr₃O_x(ii) a Preparing mother liquor containing ethyl orthosilicate, aluminium nitrate and tetrapropyl ammonium hydroxide according to shell layer Si/Al of 12 and core/shell mass ratio of 1/1, and adding a certain quantity of ZnCr into the mother liquor₃O_xThe obtained mixed system is subjected to hydrothermal treatment to obtain ZnCr as a core₃O_xAnd a core-shell structure molecular sieve with a shell layer of HZSM-5(Si/Al is 12) and is marked as ZnCr₃O_x/HZ5 (12); with ZnCr₃O_xThe core is/HZ 5(12), mother liquor containing ethyl orthosilicate, aluminum nitrate and tetrapropylammonium hydroxide is prepared according to the shell layer Si/Al of 100 and the core/shell mass ratio of 4/0.1, and a certain amount of ZnCr is added into the mother liquor₃O_x/HZ5(12), the obtained mixed system is subjected to hydrothermal treatment to obtain a mixed system with ZnCr core₃O_xA core-shell structure molecular sieve with an inner shell layer of HZSM-5(Si/Al 12) and an outer shell layer of HZSM-5(Si/Al 100), and is named as ZnCr₃O_x/HZ5(12)/HZ5 (100); with ZnCr₃O_xPreparing mother liquor containing ethyl orthosilicate and tetrapropylammonium hydroxide according to the core/shell mass ratio of 4.1/0.9 by using/HZ 5(12)/HZ5(100) as core, and adding a certain quantity of ZnCr into the mother liquor₃O_xThe final core is ZnCr 5(12)/HZ5(100)₃O_xThe molecular sieve having a core-shell structure, in which the inner shell layer is HZSM-5(Si/Al ═ 12), the intermediate shell layer is HZSM-5(Si/Al ═ 100), and the outer shell layer is Silicalite-1 (all-silicon ZSM-5, Si/Al ═ infinity), is referred to as ZnCr₃O_x/HZ5(12)/HZ5(100)/S1(2:2:0.1: 0.9); ZnCr is mixed with₃O_xGranulating and crushing the particles/HZ 5(12)/HZ5(100)/S1(2:2:0.1:0.9) to obtain 20-40 mesh catalyst particles, and weighing 1.5g of the catalyst particles to fill the reactor. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 2000h^-1The catalyst was evaluated under the conditions of (1). The pre-reaction catalyst was reacted with H at 395 deg.C₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 1.

[ example 19 ]

Preparing Zn-Cr oxide by coprecipitation method according to Zn/Cr molar ratio of 1:3, and recording the Zn-Cr oxide as ZnCr₃O_x(ii) a Preparing mother liquor containing ethyl orthosilicate, aluminium nitrate and tetrapropyl ammonium hydroxide according to shell layer Si/Al of 12 and core/shell mass ratio of 1/1, and adding a certain quantity of ZnCr into the mother liquor₃O_xThe obtained mixed system is subjected to hydrothermal treatment to obtain ZnCr as a core₃O_xAnd a core-shell structure molecular sieve with a shell layer of HZSM-5(Si/Al ═ 12), and is marked as ZnCr₃O_x/HZ5 (12); with ZnCr₃O_xThe core is/HZ 5(12), mother liquor containing ethyl orthosilicate, aluminum nitrate and tetrapropylammonium hydroxide is prepared according to the shell layer Si/Al of 100 and the core/shell mass ratio of 4/0.9, and a certain amount of ZnCr is added into the mother liquor₃O_x/HZ5(12), the obtained mixed system is subjected to hydrothermal treatment to obtain a mixed system with ZnCr core₃O_xThe inner shell layer being HZSM-5(Si/Al 12) and the outer shell layer being HZSM-5(Si/Al 100)Core-shell structured molecular sieves, denoted ZnCr₃O_x/HZ5(12)/HZ5 (100); by ZnCr₃O_xPreparing mother liquor containing ethyl orthosilicate and tetrapropylammonium hydroxide according to the core/shell mass ratio of 4.9/0.1 by using/HZ 5(12)/HZ5(100) as core, and adding a certain quantity of ZnCr into the mother liquor₃O_xThe final core is ZnCr 5(12)/HZ5(100)₃O_xThe molecular sieve having a core-shell structure, in which the inner shell layer is HZSM-5(Si/Al ═ 12), the intermediate shell layer is HZSM-5(Si/Al ═ 100), and the outer shell layer is Silicalite-1 (all-silicon ZSM-5, Si/Al ═ infinity), is referred to as ZnCr₃O_x/HZ5(12)/HZ5(100)/S1(2:2:0.9: 0.1); ZnCr is mixed with₃O_xGranulating and crushing the particles/HZ 5(12)/HZ5(100)/S1(2:2:0.9:0.1) to obtain 20-40 mesh catalyst particles, and weighing 1.5g of the catalyst particles to fill the reactor. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 2000h^-1The catalyst was evaluated under the conditions of (1). The pre-reaction catalyst was reacted with H at 395 deg.C₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 1.

[ example 20 ]

Preparing Zn-Zr oxide, noted as ZnZr, by coprecipitation according to the Zn/Zr molar ratio of 1:3₃O_x(ii) a Preparing mother liquor containing sodium silicate, aluminium sulfate and tetrapropylammonium hydroxide according to shell layer Si/Al of 12 and core/shell mass ratio of 2/3, and adding a certain quantity of ZnZr into the mother liquor₃O_xThe obtained mixed system is subjected to hydrothermal treatment to obtain ZnZr serving as a core₃O_xAnd a core-shell structure molecular sieve with a shell layer of HZSM-5(Si/Al ═ 12), and is marked as ZnZr₃O_x/HZ5 (12); with ZnZr₃O_xPreparing mother liquor containing ethyl orthosilicate and tetrapropyl ammonium hydroxide according to a core/shell mass ratio of 5/1 by taking/HZ 5(12) as a core, and adding a certain amount of ZnZr into the mother liquor₃O_x/HZ5(12), carrying out hydrothermal treatment on the obtained mixed system to finally obtain the core ZnZr₃O_xThe inner shell layer is HZSM-5(Si/Al ═ 12), the outer shell layer is Silicalite-1 (full-silicon ZSM-5, Si/Al ═ infinity) core-shell structure molecular sieve, and the molecular sieve is recorded as ZnZr₃O_x(ii)/HZ 5 (12)/S1; ZnZr₃O_xGranulating and crushing the/HZ 5(12)/S1 to obtain 20-40 mesh catalyst particles, and weighing 1.5g of the catalyst particles to be filled in a reactor. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 2000h^-1The catalyst was evaluated under the conditions of (1). The pre-reaction catalyst was reacted with H at 395 deg.C₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 1.

[ example 21 ]

Preparing Zn-Mn oxide by a coprecipitation method according to the Zn/Mn molar ratio of 1:5, and recording the Zn-Mn oxide as ZnMn₅O_x(ii) a Preparing mother liquor containing sodium silicate, aluminium sulfate and tetrapropylammonium hydroxide according to shell layer Si/Al of 12 and core/shell mass ratio of 2/3, and adding a certain quantity of ZnMn into the mother liquor₅O_xCore, the obtained mixed system is subjected to hydrothermal treatment to obtain ZnMn core₅O_xAnd a core-shell structure molecular sieve with a shell layer of HZSM-5(Si/Al ═ 12), and is marked as ZnMn₅O_x/HZ5 (12); with ZnMn₅O_xPreparing mother liquor containing ethyl orthosilicate and tetrapropyl ammonium hydroxide according to a core/shell mass ratio of 5/1 by taking/HZ 5(12) as a core, and adding a certain amount of ZnMn into the mother liquor₅O_x/HZ5(12), and carrying out hydrothermal treatment on the obtained mixed system to finally obtain the product with ZnMn as the core₅O_xThe inner shell layer is HZSM-5(Si/Al ═ 12), the outer shell layer is Silicalite-1 (full-silicon ZSM-5, Si/Al ═ infinity) core-shell structure molecular sieve, and the molecular sieve is expressed as ZnMn₅O_x(iv) HZ5 (12)/S1; ZnMn is mixed with₅O_xGranulating and crushing the/HZ 5(12)/S1 to obtain 20-40 mesh catalyst particles, and weighing 1.5g of the catalyst particles to fill the reactor. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 2000h^-1The catalyst was evaluated under the conditions of (1). The pre-reaction catalyst was reacted with H at 395 deg.C₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 1.

[ example 22 ]

Preparing Zn-In-Cr oxide by a coprecipitation method according to the Zn/In/Cr molar ratio of 4:1:15, and recording the Zn as Zn_0.8In_0.2Cr₃O_x(ii) a Preparing mother liquor containing sodium silicate, aluminium sulfate and tetrapropylammonium hydroxide according to shell layer Si/Al of 12 and core/shell mass ratio 2/3, and adding a certain quantity of Zn into the mother liquor_0.8In_0.2Cr₃O_xThe obtained mixed system is subjected to hydrothermal treatment to obtain Zn serving as a core_0.8In_0.2Cr₃O_xAnd a core-shell structure molecular sieve with a shell layer of HZSM-5(Si/Al ═ 12), and is marked as Zn_0.8In_0.2Cr₃O_x/HZ5 (12); with Zn_0.8In_0.2Cr₃O_xPreparing mother liquor containing ethyl orthosilicate and tetrapropyl ammonium hydroxide according to a core/shell mass ratio of 5/1 by taking/HZ 5(12) as a core, and adding a certain amount of Zn into the mother liquor_0.8In_0.2Cr₃O_x/HZ5(12), and carrying out hydrothermal treatment on the obtained mixed system to finally obtain the core Zn_0.8In_0.2Cr₃O_xThe inner shell layer is HZSM-5(Si/Al ═ 12), the outer shell layer is Silicalite-1 (full-silicon ZSM-5, Si/Al ═ infinity) core-shell structure molecular sieve, and is marked as Zn_0.8In_0.2Cr₃O_x(ii)/HZ 5 (12)/S1; zn is added_0.8In_0.2Cr₃O_xGranulating and crushing the/HZ 5(12)/S1 to obtain 20-40 mesh catalyst particles, and weighing 1.5g of the catalyst particles to fill the reactor. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 2000h^-1The catalyst was evaluated under the conditions of (1). The pre-reaction catalyst was reacted with H at 395 deg.C₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 1.

[ example 23 ] to provide

Preparing Zn-Cr-Mn oxide, namely ZnCr, by adopting a coprecipitation method according to the Zn/Cr/Mn molar ratio of 1:2:2₂Mn₂O_x(ii) a Preparing mother liquor containing sodium silicate, aluminium sulfate and tetrapropylammonium hydroxide according to shell layer Si/Al of 12 and core/shell mass ratio of 2/3, and adding a certain quantity of ZnCr into the mother liquor₂Mn₂O_xThe obtained mixed system is subjected to hydrothermal treatment to obtain ZnCr as a core₂Mn₂O_xAnd a core-shell structure molecular sieve with a shell layer of HZSM-5(Si/Al is 12) and is marked as ZnCr₂Mn₂O_xHZ5 (12); by ZnCr₂Mn₂O_xPreparing mother liquor containing ethyl orthosilicate and tetrapropyl ammonium hydroxide according to the core/shell mass ratio 5/1 by taking/HZ 5(12) as a core, and adding a certain amount of ZnCr into the mother liquor₂Mn₂O_x/HZ5(12), carrying out hydrothermal treatment on the obtained mixed system to finally obtain a mixed system with ZnCr core₂Mn₂O_xThe inner shell layer is HZSM-5(Si/Al ═ 12), the outer shell layer is Silicalite-1 (full-silicon ZSM-5, Si/Al ═ infinity) core-shell structure molecular sieve, and the molecular sieve is expressed as ZnCr₂Mn₂O_x(ii)/HZ 5 (12)/S1; ZnCr is mixed with₂Mn₂O_xGranulating and crushing the/HZ 5(12)/S1 to obtain 20-40 mesh catalyst particles, and weighing 1.5g of the catalyst particles to fill the reactor. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 2000h^-1The catalyst was evaluated under the conditions of (1). The catalyst is reacted at 395 ℃ with H₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 1.

[ example 24 ]

Preparing Zn-In-Cr-Mn oxide, noted as Zn, by a coprecipitation method according to a Zn/In/Cr/Mn molar ratio of 4:1:10:10_0.8In_0.2Cr₂Mn₂O_x(ii) a Preparing mother liquor containing sodium silicate, aluminium sulfate and tetrapropylammonium hydroxide according to shell layer Si/Al of 12 and core/shell mass ratio 2/3, and adding a certain quantity of Zn into the mother liquor_0.8In_0.2Cr₂Mn₂O_xThe obtained mixed system is subjected to hydrothermal treatment to obtain a mixed system with Zn as a core_0.8In_0.2Cr₂Mn₂O_xAnd a core-shell structure molecular sieve with a shell layer of HZSM-5(Si/Al ═ 12), and is marked as Zn_0.8In_0.2Cr₂Mn₂O_x/HZ5 (12); with Zn_0.8In_0.2Cr₂Mn₂O_xPreparing mother liquor containing ethyl orthosilicate and tetrapropyl ammonium hydroxide according to a core/shell mass ratio of 5/1 by taking/HZ 5(12) as a core, and adding a certain amount of Zn into the mother liquor_0.8In_0.2Cr₂Mn₂O_x/HZ5(12), hydrothermal treatment of the resulting mixed systemTreating to obtain Zn core_0.8In_0.2Cr₂Mn₂O_xThe inner shell layer is HZSM-5(Si/Al ═ 12), the outer shell layer is Silicalite-1 (full-silicon ZSM-5, Si/Al ═ infinity) core-shell structure molecular sieve, and is marked as Zn_0.8In_0.2Cr₂Mn₂O_x(ii)/HZ 5 (12)/S1; zn is added_0.8In_0.2Cr₂Mn₂O_xGranulating and crushing the/HZ 5(12)/S1 to obtain 20-40 mesh catalyst particles. 1.5g of catalyst particles were weighed and charged in the reactor. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 2000h^-1The catalyst was evaluated under the conditions of (1). The pre-reaction catalyst was reacted with H at 395 deg.C₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 1.

[ example 25 ]

Preparing Zn-Ga-Cr oxide by a coprecipitation method according to the Zn/Ga/Cr molar ratio of 0.9:0.1:3, and recording the Zn-Ga-Cr oxide as Zn_0.9Ga_0.1Cr₃O_x(ii) a Preparing mother liquor containing sodium silicate, aluminium sulfate and tetrapropylammonium hydroxide according to shell layer Si/Al of 12 and core/shell mass ratio 2/3, and adding a certain quantity of Zn into the mother liquor_0.9Ga_0.1Cr₃O_xThe obtained mixed system is subjected to hydrothermal treatment to obtain Zn serving as a core_0.9Ga_0.1Cr₃O_xAnd the shell layer is HZSM-5(Si/Al 12) core-shell structure molecular sieve, and is marked as Zn_0.9Ga_0.1Cr₃O_x/HZ5 (12); with Zn_0.9Ga_0.1Cr₃O_xPreparing mother liquor containing ethyl orthosilicate and tetrapropyl ammonium hydroxide according to a core/shell mass ratio of 5/1 by taking/HZ 5(12) as a core, and adding a certain amount of Zn into the mother liquor_0.9Ga_0.1Cr₃O_xThe core of/HZ 5(12) is obtained, and the obtained mixed system is subjected to hydrothermal treatment to finally obtain the core Zn_0.9Ga_0.1Cr₃O_xThe inner shell layer is HZSM-5(Si/Al ═ 12), the outer shell layer is Silicalite-1 (full-silicon ZSM-5, Si/Al ═ infinity) core-shell structure molecular sieve, and is marked as Zn_0.9Ga_0.1Cr₃O_x(ii)/HZ 5 (12)/S1; zn is added_0.9Ga_0.1Cr₃O_xGranulating and crushing the/HZ 5(12)/S1 to obtain 20-40 mesh catalyst particles, and weighing 1.5g of the catalyst particles to fill the reactor. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 2000h^-1The catalyst was evaluated under the conditions of (1). The pre-reaction catalyst was reacted with H at 395 deg.C₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 1.

[ example 26 ]

Preparing Ga-Cr-Mn oxide by a coprecipitation method according to the Ga/Cr/Mn molar ratio of 1:2:3, and recording the Ga-Cr-Mn oxide as GaCr₂Mn₃O_x(ii) a Preparing mother liquor containing sodium silicate, aluminium sulfate and tetrapropylammonium hydroxide according to shell layer Si/Al 12 and core/shell mass ratio 2/3, and adding a certain quantity of GaCr₂Mn₃O_xThe obtained mixed system is subjected to hydrothermal treatment to obtain the product with the core of GaCr₂Mn₃O_xAnd a core-shell structure molecular sieve with a shell layer of HZSM-5(Si/Al 12), which is marked as GaCr₂Mn₃O_x/HZ5 (12); with GaCr₂Mn₃O_xPreparing mother liquor containing ethyl orthosilicate and tetrapropylammonium hydroxide according to a core/shell mass ratio of 5/1 by taking/HZ 5(12) as a core, and adding a certain amount of GaCr into the mother liquor₂Mn₃O_xThe core of/HZ 5(12) is obtained by hydrothermal treatment of the obtained mixed system, and the obtained core is GaCr₂Mn₃O_xThe inner shell layer is HZSM-5(Si/Al ═ 12), and the outer shell layer is Silicalite-1 (full-silicon ZSM-5, Si/Al ═ infinity) core-shell structure molecular sieve, which is denoted as GaCr₂Mn₃O_x(ii)/HZ 5 (12)/S1; mixing GaCr₂Mn₃O_xGranulating and crushing the/HZ 5(12)/S1 to obtain 20-40 mesh catalyst particles, and weighing 1.5g of the catalyst particles to be filled in a reactor. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 2000h^-1The catalyst was evaluated under the conditions of (1). The pre-reaction catalyst was reacted with H at 395 deg.C₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity, and aromatics product distribution are shown in table 1.

Comparative example 1

Preparing Zn-Cr oxide by coprecipitation method according to Zn/Cr molar ratio of 1:3, and recording the Zn-Cr oxide as ZnCr₃O_x(ii) a Synthesizing an HZSM-5 molecular sieve with the Si/Al ratio of 12 by adopting a hydrothermal method, wherein the obtained molecular sieve is recorded as HZ5 (12); ZnCr is mixed with₃O_xAnd mechanically mixing the HZ5(12) powder according to the mass ratio of 1:1, and then granulating and crushing to obtain 20-40-mesh catalyst particles. 1.5g of catalyst particles were weighed out and loaded into the reactor. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 2000h^-1The catalyst was evaluated under the conditions of (1). The pre-reaction catalyst was reacted with H at 395 deg.C₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 1.

Comparative example 2

Preparing Fe-Mn oxide by a coprecipitation method according to the Fe/Mn molar ratio of 2:3, and recording the Fe₂Mn₃O_x(ii) a Synthesizing an HZSM-5 molecular sieve with the Si/Al ratio of 12 by a hydrothermal method, and recording the molecular sieve as HZ5 (12); mixing Fe₂Mn₃O_xAnd HZ5(12) are respectively granulated and crushed to obtain particles of 20-40 meshes. 0.75g of Fe was weighed₂Mn₃O_x0.75g of HZ5(12) granules and mixed homogeneously. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 2000h^-1The catalyst was evaluated under the conditions of (1). Catalyst at 395 ℃ H before reaction₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 1.

Comparative example 3

Preparing Zn-Cr oxide by a coprecipitation method according to the Zn/Cr molar ratio of 2:1, and recording the Zn as Zn₂CrO_x(ii) a Synthesizing an H beta molecular sieve with Si/Al ratio of 40 by a hydrothermal method, and recording the H beta molecular sieve as H beta (40); zn is added₂CrO_xAnd H beta (40) are respectively granulated and crushed to obtain particles of 20-40 meshes. 0.75g of Zn was weighed₂CrO_x0.75g H beta (40) granules and mixed homogeneously. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 2000h^-1The catalyst was evaluated under the conditions of (1). Catalyst at 395 deg.C H before reaction₂And (4) pretreating for 2 h. CO conversionThe results of conversion, aromatics selectivity and aromatics product distribution are shown in Table 1.

Comparative example 4

Weighing Zr (NO) according to the Zn/Zr molar ratio of 0.02:1₃)₄·5H₂Adding O into ethanol, stirring at 50 deg.C for 2 hr, adding polyvinyl alcohol, stirring for 3 hr, and adding ZnCl₂Stirring was continued for 2h at 50 ℃. To the resulting solution was added a 10 wt% NaOH solution, the pH of the system was adjusted to 9.5, and the mixture was stirred under reflux at 70 ℃ for 5 hours. The obtained sample is filtered, washed, dried and roasted to obtain the catalyst Zn_0.02ZrO_x(ii) a Synthesizing a USY molecular sieve with the Si/Al ratio of 40 by a hydrothermal method, and recording the USY molecular sieve as USY (40); weighing Zn in a mass ratio of 2:3_0.02ZrO_xAnd USY (40) powder is added into an ethanol solvent for ultrasonic dispersion, the mixture is subjected to suction filtration, ethanol washing, vacuum drying and mortar grinding, then the mixture is moved into a tube furnace and roasted for 12 hours at 550 ℃ in a flowing air atmosphere, and the obtained sample is granulated and crushed to obtain 20-40 mesh catalyst particles. 1.5g of catalyst particles were weighed out and loaded into the reactor. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 2000h^-1The catalyst was evaluated under the conditions of (1). Catalyst at 395 ℃ H before reaction₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 1.

Comparative example 5

Weighing Zr (NO) according to the Zn/Zr molar ratio of 0.02:1₃)₄·5H₂Adding O into ethanol, stirring at 50 deg.C for 2 hr, adding polyvinyl alcohol, stirring for 3 hr, and adding ZnCl₂Stirring was continued for 2h at 50 ℃. To the resulting solution was added a 10 wt% NaOH solution, the pH of the system was adjusted to 9.5, and the mixture was stirred under reflux at 70 ℃ for 5 hours. The obtained sample is filtered, washed, dried and roasted to obtain the catalyst Zn_0.02ZrO_x(ii) a Synthesizing a USY molecular sieve with the Si/Al ratio of 12 by a hydrothermal method, and recording the USY molecular sieve as USY (12); zn is added_0.02ZrO_xAnd mechanically mixing the USY (12) powder according to the mass ratio of 1:1, and then granulating and crushing to obtain 20-40-mesh catalyst particles. 1.5g of catalyst particles were weighed out and loaded into the reactor. At the reaction temperature of 395 ℃ and the pressure of 2.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 2000h^-1The catalyst was evaluated under the conditions of (1). Catalyst at 395 ℃ H before reaction₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 1.

[ example 27 ] A method for producing a polycarbonate

Preparing Zn-Cr oxide by coprecipitation method according to Zn/Cr molar ratio of 1:3, and recording the Zn-Cr oxide as ZnCr₃O_x(ii) a Preparing mother liquor containing ethyl orthosilicate, pseudo-boehmite and tetrapropylammonium hydroxide according to shell layer Si/Al being 12 and core/shell mass ratio 2/3, and adding a certain amount of ZnCr into the mother liquor₃O_xThe obtained mixed system is subjected to hydrothermal treatment to obtain ZnCr as a core₃O_xAnd a core-shell structure molecular sieve with a shell layer of HZSM-5(Si/Al ═ 12), and is marked as ZnCr₃O_xHZ5 (12); with ZnCr₃O_xPreparing mother liquor containing sodium silicate and tetrapropylammonium hydroxide according to a core/shell mass ratio of 5/1 by taking/HZ 5(12) as a core, and adding a certain amount of ZnCr into the mother liquor₃O_x/HZ5(12), the obtained mixed system is subjected to hydrothermal treatment to obtain a mixed system with ZnCr core₃O_xThe inner shell layer is HZSM-5(Si/Al ═ 12), the outer shell layer is Silicalite-1 (full-silicon ZSM-5, Si/Al ═ infinity) core-shell structure molecular sieve, and the molecular sieve is expressed as ZnCr₃O_x(ii) HZ5(12)/S1(2:3: 1); ZnCr is mixed with₃O_xGranulating and crushing the/HZ 5(12)/S1(2:3:1) to obtain 20-40 mesh catalyst particles, and weighing 1.5g of the catalyst particles to fill the reactor. At the reaction temperature of 350 ℃, the pressure of 8.0MPa and the feed gas H₂The ratio of/CO is 1.0, and the space velocity is 8000h^-1The catalyst was evaluated under the conditions of (1). Catalyst at 395 ℃ H before reaction₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 2.

[ example 28 ]

Preparing Zn-Cr oxide by coprecipitation method according to Zn/Cr molar ratio of 1:3, and recording the Zn-Cr oxide as ZnCr₃O_x(ii) a Preparing mother liquor containing ethyl orthosilicate, pseudo-boehmite and tetrapropylammonium hydroxide according to shell layer Si/Al being 12 and core/shell mass ratio 2/3, and adding a certain amount of ZnCr into the mother liquor₃O_xThe obtained mixed system is heated by waterTreating to obtain ZnCr core₃O_xAnd a core-shell structure molecular sieve with a shell layer of HZSM-5(Si/Al ═ 12), and is marked as ZnCr₃O_x/HZ5 (12); with ZnCr₃O_xPreparing mother liquor containing sodium silicate and tetrapropylammonium hydroxide according to a core/shell mass ratio of 5/1 by taking/HZ 5(12) as a core, and adding a certain amount of ZnCr into the mother liquor₃O_x/HZ5(12), the obtained mixed system is subjected to hydrothermal treatment to obtain a mixed system with ZnCr core₃O_xThe inner shell layer is HZSM-5(Si/Al ═ 12), the outer shell layer is Silicalite-1 (full-silicon ZSM-5, Si/Al ═ infinity) core-shell structure molecular sieve, and the molecular sieve is expressed as ZnCr₃O_x(ii) HZ5(12)/S1(2:3: 1); ZnCr is mixed with₃O_xGranulating and crushing the/HZ 5(12)/S1(2:3:1) to obtain 20-40 mesh catalyst particles, and weighing 1.5g of the catalyst particles to fill the reactor. At the reaction temperature of 395 ℃ and the pressure of 8.0MPa, the raw material gas H₂The ratio of/CO is 0.25, and the space velocity is 10000h^-1The catalyst was evaluated under the conditions of (1). Catalyst at 395 ℃ H before reaction₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 2.

[ example 29 ]

Preparing Zn-Cr oxide by coprecipitation method according to Zn/Cr molar ratio of 1:3, and recording the Zn-Cr oxide as ZnCr₃O_x(ii) a Preparing mother liquor containing ethyl orthosilicate, pseudo-boehmite and tetrapropylammonium hydroxide according to shell layer Si/Al being 12 and core/shell mass ratio 2/3, and adding a certain amount of ZnCr into the mother liquor₃O_xThe obtained mixed system is subjected to hydrothermal treatment to obtain ZnCr as a core₃O_xAnd a core-shell structure molecular sieve with a shell layer of HZSM-5(Si/Al ═ 12), and is marked as ZnCr₃O_x/HZ5 (12); with ZnCr₃O_xPreparing mother liquor containing sodium silicate and tetrapropylammonium hydroxide according to a core/shell mass ratio of 5/1 by taking/HZ 5(12) as a core, and adding a certain amount of ZnCr into the mother liquor₃O_x/HZ5(12), the obtained mixed system is subjected to hydrothermal treatment to obtain a mixed system with ZnCr core₃O_xThe inner shell layer is HZSM-5(Si/Al ═ 12), the outer shell layer is Silicalite-1 (full-silicon ZSM-5, Si/Al ═ infinity) core-shell structure molecular sieve, and the molecular sieve is expressed as ZnCr₃O_x(ii) HZ5(12)/S1(2:3: 1); ZnCr is mixed with₃O_xGranulating and crushing the/HZ 5(12)/S1(2:3:1) to obtain 20-40 mesh catalyst particles, and weighing 1.5g of the catalyst particles to fill the reactor. At the reaction temperature of 350 ℃, the pressure of 5.0MPa and the feed gas H₂The ratio of/CO is 4.0, and the space velocity is 18000h^-1The catalyst was evaluated under the conditions of (1). Catalyst at 395 ℃ H before reaction₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 2.

[ example 30 ]

Preparing Zn-Cr oxide by coprecipitation method according to Zn/Cr molar ratio of 1:3, and recording the Zn-Cr oxide as ZnCr₃O_x(ii) a Preparing mother liquor containing ethyl orthosilicate, pseudo-boehmite and tetrapropylammonium hydroxide according to shell layer Si/Al being 12 and core/shell mass ratio 2/3, and adding a certain amount of ZnCr into the mother liquor₃O_xThe obtained mixed system is subjected to hydrothermal treatment to obtain ZnCr as a core₃O_xAnd a core-shell structure molecular sieve with a shell layer of HZSM-5(Si/Al ═ 12), and is marked as ZnCr₃O_x/HZ5 (12); with ZnCr₃O_xPreparing mother liquor containing sodium silicate and tetrapropylammonium hydroxide according to a core/shell mass ratio of 5/1 by taking/HZ 5(12) as a core, and adding a certain amount of ZnCr into the mother liquor₃O_x/HZ5(12), the obtained mixed system is subjected to hydrothermal treatment to obtain a mixed system with ZnCr core₃O_xThe inner shell layer is HZSM-5(Si/Al ═ 12), the outer shell layer is Silicalite-1 (full-silicon ZSM-5, Si/Al ═ infinity) core-shell structure molecular sieve, and the molecular sieve is expressed as ZnCr₃O_x(ii) HZ5(12)/S1(2:3: 1); ZnCr is mixed with₃O_xGranulating and crushing the/HZ 5(12)/S1(2:3:1) to obtain 20-40 mesh catalyst particles, and weighing 1.5g of the catalyst particles to be filled in a reactor. At the reaction temperature of 395 ℃ and the pressure of 5.0MPa, the raw material gas H₂The ratio of/CO is 1.0, and the space velocity is 18000h^-1The catalyst was evaluated under the conditions of (1). Catalyst at 395 deg.C H before reaction₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 2.

[ example 31 ] A method for producing a polycarbonate

Preparing Zn-Cr oxide, namely ZnCr oxide by adopting a coprecipitation method according to the Zn/Cr molar ratio of 1:3₃O_x(ii) a Si/Al as shell 12Preparing mother liquor containing ethyl orthosilicate, pseudo-boehmite and tetrapropyl ammonium hydroxide according to the core/shell mass ratio of 2/3, and adding a certain amount of ZnCr into the mother liquor₃O_xThe obtained mixed system is subjected to hydrothermal treatment to obtain ZnCr as a core₃O_xAnd a core-shell structure molecular sieve with a shell layer of HZSM-5(Si/Al ═ 12), and is marked as ZnCr₃O_x/HZ5 (12); with ZnCr₃O_xPreparing mother liquor containing sodium silicate and tetrapropylammonium hydroxide according to a core/shell mass ratio of 5/1 by taking/HZ 5(12) as a core, and adding a certain amount of ZnCr into the mother liquor₃O_x/HZ5(12), the obtained mixed system is subjected to hydrothermal treatment to obtain a mixed system with ZnCr core₃O_xThe inner shell layer is HZSM-5(Si/Al ═ 12), the outer shell layer is Silicalite-1 (full-silicon ZSM-5, Si/Al ═ infinity) core-shell structure molecular sieve, and the molecular sieve is expressed as ZnCr₃O_x(ii)/HZ 5(12)/S1(2:3: 1); ZnCr is mixed with₃O_xGranulating and crushing the/HZ 5(12)/S1(2:3:1) to obtain 20-40 mesh catalyst particles, and weighing 1.5g of the catalyst particles to fill the reactor. At the reaction temperature of 450 ℃, the pressure of 5.0MPa and the feed gas H₂The ratio of/CO is 1.0, and the space velocity is 18000h^-1The catalyst was evaluated under the conditions of (1). Catalyst at 395 ℃ H before reaction₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity and aromatics product distribution are shown in table 2.

[ example 32 ]

Preparing Zn-Cr oxide by coprecipitation method according to Zn/Cr molar ratio of 1:3, and recording the Zn-Cr oxide as ZnCr₃O_x(ii) a Preparing mother liquor containing ethyl orthosilicate, pseudo-boehmite and tetrapropylammonium hydroxide according to shell layer Si/Al being 12 and core/shell mass ratio 2/3, and adding a certain amount of ZnCr into the mother liquor₃O_xThe obtained mixed system is subjected to hydrothermal treatment to obtain a mixed system with ZnCr as a core₃O_xAnd a core-shell structure molecular sieve with a shell layer of HZSM-5(Si/Al ═ 12), and is marked as ZnCr₃O_x/HZ5 (12); with ZnCr₃O_xThe preparation method comprises the steps of taking/HZ 5(12) as a core, preparing mother liquor containing sodium silicate and tetrapropylammonium hydroxide according to the core/shell mass ratio of 5/1, and adding a certain amount of ZnCr into the mother liquor₃O_x/HZ5(12), the obtained mixed system is subjected to hydrothermal treatment to obtain a mixed system with ZnCr core₃O_xThe inner shell layer is HZSM-5(Si/Al ═ 12), the outer shell layer is Silicalite-1 (full-silicon ZSM-5, Si/Al ═ infinity) core-shell structure molecular sieve, and the molecular sieve is expressed as ZnCr₃O_x(ii) HZ5(12)/S1(2:3: 1); ZnCr is mixed with₃O_x/HZ5(12)/S1(2:3:1)、P₂O₅Mechanically mixing the powder according to the mass ratio of 1:0.02, granulating, crushing to obtain 20-40-mesh catalyst particles, and weighing 1.5g of the catalyst particles to fill the catalyst particles into a reactor. At the reaction temperature of 395 ℃ and the pressure of 4.0MPa, the raw material gas H₂The ratio of/CO is 0.5, and the space velocity is 5000h^-1The catalyst was evaluated under the conditions of (1). Catalyst at 395 ℃ H before reaction₂And (4) pretreating for 2 h. The results of CO conversion, aromatics selectivity, and aromatics product distribution are shown in table 2.

[ examples 1 to 26 ]

TABLE 1

[ examples 27 to 32 ]

The catalyst prepared in example 15 was used in the reaction of producing aromatic hydrocarbons and light hydrocarbons from synthesis gas, and the reaction conditions and evaluation results are shown in table 2.

TABLE 2

Claims (16)

1. A multifunctional catalyst system with a core-shell structure is characterized in that the catalyst is an integral multifunctional catalyst with a core-shell structure, a core layer is a metal oxide, and a shell layer is a molecular sieve;

the silicon-aluminum ratio of the shell layer molecular sieve is 12-infinity;

the shell layer molecular sieve is selected from one or more of MFI or MEL structure molecular sieves;

the core-shell structure catalyst at least comprises 2 layers of shell layer molecular sieves.

2. Core-shell structured multifunctional catalyst system according to claim 1, characterized in that the metal component of the metal oxide is selected from one or at least one of the elements of groups IVB, VIII, IB, IIB, IIIA or alkali metals, alkaline earth metals, rare earth metals.

3. Core-shell structured multifunctional catalyst system according to claim 2, characterized In that the metal component of the metal oxide is selected from one or at least one of Cr, Zr, Mn, Ce, La, Mo, Ti, In, Ga, Zn.

4. Core-shell structured multifunctional catalyst system according to claim 2 or 3, characterized In that the metal component of the metal oxide is selected from one or at least one of Cr, Zr, Mn, In, Ga, Zn.

5. 4-core-shell structured multifunctional catalyst system according to claim 2 or 3, characterized in that the metal component of the metal oxide is selected from one or at least one of Zn, Ce, La, Mo, Ti.

6. The multifunctional catalyst system with core-shell structure of claim 2, wherein the metal oxide is a single metal oxide or a double metal oxide or a multi-metal oxide.

7. The multifunctional catalyst system with core-shell structure of claim 1, wherein the shell layer molecular sieve is selected from one or at least one of ZSM-5, ZSM-11, Silicalite-1 and Silicalite-2.

8. The multifunctional catalyst system with core-shell structure of claim 1, wherein the silica-alumina ratio of the shell molecular sieve is 12-250.

9. The multifunctional catalyst system with core-shell structure of claim 1, wherein the catalyst with core-shell structure comprises at least 3 layers of shell molecular sieves.

10. The multifunctional catalyst system with core-shell structure of claim 1, wherein the mass ratio of the metal oxide in the core layer to the molecular sieve in the shell layer is in the range of (8: 1) - (1: 8).

11. The multifunctional catalyst system with core-shell structure of claim 1, wherein the mass ratio of the metal oxide in the core layer to the molecular sieve in the shell layer is in the range of (3: 1) - (1: 3).

12. A method for producing aromatic hydrocarbon and light hydrocarbon by converting synthesis gas, which takes the synthesis gas as a raw material, and the raw material is in contact reaction with the core-shell structure multifunctional catalyst of any one of claims 1 to 11 to obtain a material flow containing the aromatic hydrocarbon and the light hydrocarbon.

13. The method for producing aromatic hydrocarbons and light hydrocarbons by conversion of synthesis gas according to claim 12, wherein the raw synthesis gas comprises 10-50% by volume of H₂。

14. The method of claim 12, wherein the synthesis gas conversion process produces aromatics and light hydrocarbons in the presence of H₂The molar ratio/CO ranges from 0.25 to 5.0.

15. The method of claim 12, wherein the synthesis gas conversion process produces aromatics and light hydrocarbons in the presence of H₂The molar ratio/CO ranges from 0.25 to 1.0.

16. The method for producing aromatic hydrocarbons and light hydrocarbons by conversion of synthesis gas according to claim 12, wherein the reaction conditions are as follows: the reaction temperature is 300 ℃ and 500 ℃; and/or the reaction pressure is 0.5-10.0 MPa; and/or the volume space velocity is 1000-^-1。