WO2019062815A1 - 用于合成气直接制备对二甲苯的催化剂及其制备和应用 - Google Patents

用于合成气直接制备对二甲苯的催化剂及其制备和应用 Download PDF

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WO2019062815A1
WO2019062815A1 PCT/CN2018/107966 CN2018107966W WO2019062815A1 WO 2019062815 A1 WO2019062815 A1 WO 2019062815A1 CN 2018107966 W CN2018107966 W CN 2018107966W WO 2019062815 A1 WO2019062815 A1 WO 2019062815A1
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catalyst
molecular sieve
zsm
core
shell
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English (en)
French (fr)
Chinese (zh)
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杨国辉
椿范立
高潮
柴剑宇
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Highchem Technology Co Ltd
Mohan Co Ltd
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Highchem Technology Co Ltd
Mohan Co Ltd
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Priority to EA202090904A priority Critical patent/EA202090904A1/ru
Priority to JP2020539126A priority patent/JP7232836B2/ja
Publication of WO2019062815A1 publication Critical patent/WO2019062815A1/zh
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Definitions

  • the present invention relates to a core-shell type catalyst and its preparation.
  • the invention further relates to a composite catalyst comprising the core-shell catalyst and its preparation, and to the use of the core-shell catalyst and composite catalyst of the invention for the direct preparation of para-xylene from syngas.
  • Paraxylene is an important organic synthetic raw material widely used in the field of textiles and packaging materials. Para-xylene is mainly used to prepare terephthalic acid and terephthalic acid, and the latter is used as an intermediate for plastics and polyester fibers, as well as raw materials for coatings, dyes and pesticides.
  • terephthalic acid and terephthalic acid are used as an intermediate for plastics and polyester fibers, as well as raw materials for coatings, dyes and pesticides.
  • terephthalic acid and terephthalic acid is used as an intermediate for plastics and polyester fibers, as well as raw materials for coatings, dyes and pesticides.
  • terephthalic acid and terephthalic acid is used as an intermediate for plastics and polyester fibers, as well as raw materials for coatings, dyes and pesticides.
  • p-xylene is typically only obtained at a concentration of about 24% by weight due to the thermodynamic equilibrium of the para-xylene content of the product.
  • the paraxylene concentration is required to be 60% by weight or more, so the concentration is far from meeting the needs of industrial production, such as the production of polyester materials.
  • a series of subsequent treatments are required.
  • the difference in boiling points between the three isomers of xylene is small, and high-purity para-xylene cannot be obtained by the usual distillation technique, and an expensive adsorption separation process must be employed, which brings about loss of raw materials and Cost increase.
  • the development of new aromatics synthesis process routes is of great value, both in terms of market demand and oil substitution.
  • syngas can convert coal, natural gas and biomass into clean oil, which is considered to be one of the most potential alternatives to petroleum.
  • the composite catalyst combined with a metal catalyst and a suitable molecular sieve can effectively regulate the distribution of the Fischer-Tropsch reaction product, and such research has made great progress in recent years.
  • Fischer-Tropsch synthesis to prepare oils with different carbon number intervals, more and more scientists have turned their attention to the direct and highly selective preparation of high value-added chemicals, including low-carbon olefins and low-carbon alcohols.
  • the key to improving the selectivity of syngas to produce para-xylene is the development and development of high performance catalysts.
  • the use of a bifunctional composite catalyst consisting of a methanol synthesis catalyst and a molecular sieve has better catalytic performance.
  • the reaction scheme comprises a series of series reactions: synthesis gas hydrogenation to methanol, methanol hydrodehydration reaction, aromatization reaction, xylene isomerization reaction and the like.
  • This route has great benefits for the development of syngas conversion technology, which not only promotes the national energy strategy security, but also is one of the solutions to the potential threat of globalized petroleum energy depletion. Therefore, improving the selectivity of p-xylene, reducing process complexity and cost is a technical difficulty in the direct preparation of para-xylene from syngas.
  • a synthesis gas is passed through a mixed catalyst of methanol synthesis and methanol dehydration, and a mixture of an aromatization catalyst and a catalyst is mixed in a two-stage reactor for aromatization to finally obtain an aromatic hydrocarbon product.
  • the above two-stage method for preparing p-xylene from syngas not only has many steps, the second-stage reaction process is long, the energy consumption is high, and the preparation method of the catalyst is complicated, and the selectivity of p-xylene is less than 30 weight in the hydrocarbon product. %.
  • the above catalysts can all obtain aromatic hydrocarbons in one step from the synthesis gas, the selectivity to para-xylene is often not high, and the isomerization reaction of xylene cannot be effectively suppressed.
  • the present invention aims to provide a catalyst for directly preparing p-xylene from a synthesis gas with high selectivity, a preparation method and application thereof.
  • the designed catalyst has simple preparation method, high synthesis gas conversion rate and high selectivity to para-xylene, and is expected to be applied in industry.
  • the catalyst is used in combination with a catalyst for catalyzing the conversion of synthesis gas to methanol, not only the selectivity to p-xylene and the conversion rate of synthesis gas are high, but also the selectivity of p-xylene in xylene is high.
  • Another object of the present invention is to provide a process for preparing the core-shell type catalyst of the present invention.
  • It is still another object of the present invention to provide a composite catalyst for the direct preparation of para-xylene from a synthesis gas comprising a catalyst for catalyzing the conversion of synthesis gas to methanol and a core-shell catalyst of the present invention.
  • the composite catalyst not only makes the p-xylene selectivity high and the conversion rate of the synthesis gas, but also has high selectivity to p-xylene in xylene when the catalytic synthesis gas is converted into a hydrocarbon.
  • a final object of the invention is to provide the use of the core-shell catalyst of the invention or the composite catalyst of the invention in the direct preparation of para-xylene from synthesis gas.
  • the use of the core-shell catalyst or composite catalyst of the present invention as a catalyst for directly preparing para-xylene from syngas not only makes the p-xylene selectivity high and the conversion rate of the synthesis gas high, but also the selectivity of p-xylene in xylene. Also high.
  • a modified ZSM-5 molecular sieve substituted with an element M of Ce, Co, La, Rh, Pd, Pt, Ni, Cu, K, Ca, Ba, Fe, Mn and B, or any mixture thereof, the shell being selected from carbon Membrane, Silicalite-1, MCM-41, SBA-15, KIT-6, MSU series, silica, graphene, carbon nanotubes, metal organic framework MOF, graphite, activated carbon, metal oxide film (such as MgO, P One or more of 2 O 5 , CaO).
  • the core is a H-type ZSM-5 molecular sieve, a modified ZSM-5 molecular sieve in which H is partially or completely replaced by Zn in the H-type ZSM-5 molecular sieve, or any mixture thereof;
  • the shell is one or more selected from the group consisting of a silicon dioxide film, a Silicalite-1, a metal oxide film (such as MgO, P 2 O 5 , CaO), MCM-41, SBA-15, and KIT
  • the element M modified M-ZSM-5 molecular sieve comprises from 0.5 to 15% by weight, preferably from 1 to 10% by weight based on the total weight of the M-ZSM-5 molecular sieve % is particularly preferably from 1 to 5% by weight.
  • the core-shell type catalyst according to Item 1 or 2 wherein the weight ratio of core to shell is from 100:1 to 1:100, preferably from 10:1 to 1:10, more preferably from 5:1 to 1:5. It is particularly preferably 5:1 to 1:1.
  • H-type ZSM-5 molecular sieve a core in the form of particles, which is an H-type ZSM-5 molecular sieve, and all or part of H in the H-type ZSM-5 molecular sieve is one or more selected from the group consisting of Sn, Ga, Ti, Zn, Mg, Li, a modified ZSM-5 molecular sieve substituted with an element M of Ce, Co, La, Rh, Pd, Pt, Ni, Cu, Na, K, Ca, Ba, Fe, Mn, and B, or any mixture thereof;
  • a composite catalyst for the direct preparation of para-xylene from syngas comprising:
  • Catalyst B for catalyzing the formation of xylene which is a core-shell type catalyst according to any one of items 1 to 3,
  • the composite catalyst is in the form of a mixture of catalyst A and catalyst B, the form of catalyst A physically or chemically encapsulated catalyst B, or the form of catalyst B physically or chemically encapsulated catalyst A.
  • the catalyst A comprises or consists of a first metal component and a second metal component, the first metal component being selected from the group consisting of Cr, An element of Fe, Zr, In, Ga, Co, Cu, an oxide thereof, a composite oxide thereof, or any mixture thereof, and the second metal component is selected from the group consisting of Zn, Na, Al, Ag, Ce, K, Mn, An element of Pd, Ni, La, V, an oxide thereof, a composite oxide thereof, or any mixture thereof; preferably, the first metal component is an element selected from the group consisting of Cr, Co, Cu, Zr, an oxide thereof, a composite oxide thereof or any mixture thereof; and/or the second metal component is an element selected from the group consisting of Zn, Al, an oxide thereof, a composite oxide thereof, or any mixture thereof; it is particularly preferred that the catalyst A is ZnO-Cr 2 O 3 .
  • the catalyst A is prepared by any one or more selected from the group consisting of a sequential impregnation method, a co-impregnation method, a urea method, and a coprecipitation method; preferably, in the sequential impregnation method, co-impregnation
  • the process conditions are as follows:
  • the firing atmosphere is air; and/or,
  • the calcination temperature is 200-700 ° C, preferably 400-600 ° C; and / or
  • the calcination time is from 3 to 8 h, preferably from 4 to 6 h.
  • the core-shell catalyst according to any one of items 1 to 3, the core-shell catalyst prepared according to the method of item 4, the composite catalyst according to any one of items 5 to 8 or according to items 9-10 The composite catalyst prepared by the process of any of the above uses as a catalyst in the direct preparation of p-xylene from syngas.
  • the reducing gas is pure hydrogen
  • the pretreatment temperature is 300-700 ° C, preferably 400-600 ° C;
  • the pretreatment pressure is 0.1-1 MPa, preferably 0.1-0.5 MPa;
  • the pretreatment hydrogen gas volume velocity is 500-8000 h -1 , preferably 1000-4000 h -1 ; and/or
  • the pretreatment reduction time is 2-10 h, preferably 4-6 h.
  • FIG. 1 is a SEM photograph of Zn/ZSM-5 and Zn/ZSM-5@S1 molecular sieves involved in Example 2, wherein FIG. a is an SEM photograph of Zn/ZSM-5 molecular sieve, and FIG. b is Zn/ZSM-5@ SEM photograph of S1 molecular sieve.
  • Example 2 is a STEM image of the Zn/ZSM-5@S1 molecular sieve prepared in Example 2 and a corresponding element EDS surface scan.
  • a core-shell type catalyst wherein the core is a H-type ZSM-5 molecular sieve, and all or part of H in the H-type ZSM-5 molecular sieve is selected from one or more selected from the group consisting of Sn, Modified ZSM-5 molecular sieves replaced by elements M of Ga, Ti, Zn, Mg, Li, Ce, Co, La, Rh, Pd, Pt, Ni, Cu, K, Ca, Ba, Fe, Mn and B or Any mixture of shells selected from the group consisting of carbon film, Silicalite-1, MCM-41, SBA-15, KIT-6, MSU series, silica, graphene, carbon nanotubes, metal organic framework MOF, graphite, activated carbon, One or more of metal oxide films (such as MgO, P 2 O 5 , CaO).
  • metal oxide films such as MgO, P 2 O 5 , CaO
  • the core-shell type catalyst of the present invention has a core/shell structure.
  • the core is H-type ZSM-5 molecular sieve (hereinafter sometimes referred to as HZSM-5), and all or part of H in the H-type ZSM-5 molecular sieve is one or more selected from the group consisting of Sn, Ga, Ti, Zn, Mg, Li.
  • Modified ZSM-5 molecular sieve replaced by element M of Ce, Co, La, Rh, Pd, Pt, Ni, Cu, Na, K, Ca, Ba, Fe, Mn and B (hereinafter sometimes referred to as M/ZSM) -5 molecular sieves) or any mixture thereof.
  • M/ZSM Modified ZSM-5 molecular sieve replaced by element M of Ce, Co, La, Rh, Pd, Pt, Ni, Cu, Na, K, Ca, Ba, Fe, Mn and B
  • ZSM-5 molecular sieves are capable of catalyzing the conversion to hydrocarbons in a one-step synthesis of hydrocarbons from syngas.
  • the present inventors have found that these catalytically active components can significantly improve para-xylene selectivity, especially in para-xylene, in xylene, after being covered according to the present invention, before being used for surface gas formation, without prior surface coverage. Selectivity while maintaining high CO conversion.
  • the core-shell type catalyst of the present invention can also significantly improve the selectivity of p-xylene, especially the paraxylene in xylene, compared to the mixed catalyst obtained by physically mixing the core material and the shell material under the same conditions. While maintaining a high CO conversion rate.
  • both the H-type ZSM-5 molecular sieve and the M/ZSM-5 molecular sieve are commercially available or can be obtained by a conventional method in the art, for example, by hydrothermal synthesis, impregnation, ion exchange, Prepared by vapor deposition, liquid deposition, or the like.
  • HZSM-5 molecular sieves and Na/ZSM-5 can be prepared by hydrothermal synthesis, and then M/ZSM-5 molecular sieves are prepared from HZSM-5 molecular sieves and Na/ZSM-5 by ion exchange.
  • the hydrothermal synthesis method of HZSM-5 zeolite molecular sieve is taken as an example.
  • a silicon source TEOS, ethyl orthosilicate
  • an aluminum source Al(NO 3 ) 3 . 9H 2 O
  • an organic templating agent TPAOH, tetrapropylammonium hydroxide
  • ethanol and deionized water 2TEOS: xAl 2 O 3 : 0.68
  • M/ZSM-5 molecular sieve when element M is a metal element, M/ZSM-5 molecular sieve can be prepared by using ion exchange method, impregnation method, vapor deposition method and liquid phase deposition method as HZSM-5 as raw material;
  • M is a non-metallic element B
  • the M/ZSM-5 molecular sieve can be prepared by using a HZSM-5 as a raw material by a dipping method, a vapor deposition method, a liquid phase deposition method, or the like.
  • the element M in the element M modified M/ZSM-5 molecular sieve, comprises from 0.5 to 15% by weight, preferably from 1 to 10% by weight, based on the total weight of the M/ZSM-5 molecular sieve, in particular It is preferably 1-5% by weight.
  • the Si/Al molar ratio is usually from 10 to 1,000, preferably from 20 to 800.
  • These molecular sieves usually have a particle size of from 0.01 to 20 ⁇ m, preferably from 0.1 to 15 ⁇ m.
  • the shell of the core-shell type catalyst of the present invention is selected from the group consisting of carbon film, Silicalite-1, MCM-41, SBA-15, KIT-6, MSU series (pure silicon molecular sieve), silicon dioxide, graphene, carbon nanotubes, metal One or more of organic framework MOF (such as ZIF-8, ZIF-11), graphite, activated carbon, metal oxide film (such as MgO, P2O5, CaO). These materials are coated on the outer surface of the core to form a shell. These shell materials themselves are not active for the aromatization of hydrocarbons into dimethylbenzene, but their coating on the ZSM-5 molecular sieve core affects the bare acid sites on the outer surface of ZSM-5, which can cover these bare acid sites.
  • the shell material one or more selected from the group consisting of a silica film, a Silicalite-1, a metal oxide film (such as MgO, P 2 O 5 , CaO), MCM-41, SBA-15, and KIT-6 is preferable.
  • the core to shell weight ratio is from 100:1 to 1:100, preferably from 10:1 to 1:10, more preferably from 5:1 to 1:5, in particular Preferably 5:1-1:1.
  • a method of preparing a core-shell type catalyst of the present invention comprising:
  • H-type ZSM-5 molecular sieve a core in the form of particles, which is an H-type ZSM-5 molecular sieve, and all or part of H in the H-type ZSM-5 molecular sieve is one or more selected from the group consisting of Sn, Ga, Ti, Zn, Mg, Li, a modified ZSM-5 molecular sieve substituted with an element M of Ce, Co, La, Rh, Pd, Pt, Ni, Cu, Na, K, Ca, Ba, Fe, Mn, and B, or any mixture thereof;
  • Both the core material and the shell material of the core-shell type catalyst of the present invention are conventional.
  • the core material In order to provide the core in step 1), when the core material itself is already a suitably sized particle, the core material is used directly; when the size of the core material is large, it is used in step 2) after pulverization. Coating of the core particles is achieved in step 2).
  • the coating of core particles by different shell materials is common knowledge in the art.
  • the coating method there may be mentioned hydrothermal synthesis method, vapor deposition method, dipping method, sputtering method, This method can be routinely selected depending on the nature of the coating material.
  • the coating of the molecular sieve shell material can be carried out by hydrothermal synthesis
  • the coating of carbon film, graphene and carbon nanotubes can be carried out by vapor deposition
  • the coating of metal oxide can be carried out by dipping and sputtering. Coating of silica can be used law.
  • Zn/ZSM-5@Silicalite-1 core-shell catalyst was obtained by coating Zn/ZSM-5 by hydrothermal synthesis with Silicalite-1.
  • a silicon source (TEOS), an organic templating agent (TPAOH), ethanol and deionized water molar ratio (1.00 SiO 2 : 0.06 TPA OH: 16.0 EtOH: 240 H 2 O) were mixed into a mixture, and stirred at room temperature for 4-6 h to obtain Silicalite- 1 molecular sieve precursor solution.
  • the one-step synthesis of aromatic hydrocarbons in syngas can be broadly divided into two stages, one in which the synthesis gas is converted to methanol and the other in which the methanol is further reacted to finally obtain an aromatic hydrocarbon such as p-xylene.
  • the core-shell type catalyst of the present invention is very effective for improving the selectivity of p-xylene in the second stage, and can not only significantly improve the selectivity of para-xylene, especially the selectivity of para-xylene in xylene, while still maintaining high selectivity. CO conversion rate.
  • a composite catalyst for the direct preparation of para-xylene from a synthesis gas comprising:
  • Catalyst B for catalyzing the formation of xylene which is a core-shell type catalyst of the present invention.
  • Catalyst A it can be any catalyst capable of promoting the conversion of synthesis gas to methanol.
  • the catalyst A comprises a first metal component and a second metal component, or the catalyst A consists of a first metal component and a second metal component, wherein the first metal component is selected An element from Cr, Fe, Zr, In, Ga, Co, Cu, an oxide thereof, a composite oxide thereof, or any mixture thereof, the second metal component being selected from the group consisting of Zn, Na, Al, Ag, Ce, An element of K, Mn, Pd, Ni, La, V, an oxide thereof, a composite oxide thereof, or any mixture thereof.
  • the first metal component is an element selected from the group consisting of Cr, Fe, Co, Zr, Cu, an oxide thereof, a composite oxide thereof, or any mixture thereof; and/or the second metal component is selected from the group consisting of An element of Zn, Al, an oxide thereof, a composite oxide thereof, or any mixture thereof. It is particularly preferred that the catalyst A is ZnO-Cr 2 O 3 .
  • Catalyst A is commercially available or can be prepared by any conventional method, such as sequential impregnation, co-impregnation, urea, and coprecipitation, preferably coprecipitation.
  • the catalyst A comprising the first metal component and the second metal component
  • the calcination atmosphere is air; and/or, the calcination temperature is from 200 to 700 ° C, preferably from 400 to 600 ° C; and/or, the calcination time is from 3 to 8 h, preferably from 4 to 6 h.
  • the ZnO-Cr 2 O 3 as the catalyst A was prepared by a coprecipitation method as an example.
  • the respective nitrate precursors of chromium and zinc are usually formulated into a mixed nitrate aqueous solution having a concentration of 1 mol/L with deionized water according to the chromium/zinc ratio required for the catalyst A; this solution is combined with 1 mol/L.
  • Ammonium carbonate aqueous solution other precipitants such as sodium carbonate, sodium hydroxide, ammonium hydroxide
  • the precipitation temperature is 50-90 ° C, pH
  • the value is controlled between 6-8, which is controlled by the relative addition speed of the two solutions; after the addition is completed, the obtained precipitate is continuously stirred and maintained at 50-90 ° C for 60-240 minutes for aging; the precipitate after filtration aging
  • the product is washed with deionized water; the washed product is dried in an oven at 80-120 ° C for 8-12 h; and then placed in a muffle furnace and calcined at 350-550 ° C for 3-6 h to obtain ZnO-Cr. 2 O 3 catalyst.
  • the molar ratio of the first metal component and the second metal component in the catalyst A to the metal element is from 1000:1 to 1:100, preferably from 100:1 to 1: 50, more preferably 10:1 to 1:10, particularly preferably 3:1 to 1:3.
  • the weight ratio of catalyst A to catalyst B is from 1:99 to 99:1, preferably from 20:80 to 80:20, more preferably from 30:70 to 70:30, particularly preferably 50:50. 75:25.
  • the composite catalyst may be in the form of a mixture of catalyst A and catalyst B, in the form of catalyst A physically or chemically encapsulated catalyst B, or in the form of catalyst B physical or chemical encapsulated catalyst A.
  • a method of preparing a composite catalyst of the invention comprising:
  • the technique of compounding catalyst A with catalyst B is conventional.
  • Catalyst A and Catalyst B are usually prepared in powder form.
  • the Catalyst A powder is mixed with the Catalyst B powder and the optional binder and then formed into a composite catalyst.
  • the binder water, alumina, silica or the like can be mentioned.
  • the powder of the catalyst A is mixed with the catalyst B powder and an optional binder, and the resulting powder mixture can be molded into the form of tablets, pellets, granules and the like.
  • the catalyst A is used as the core and the catalyst B is in the form of a physical or chemical encapsulation.
  • the catalyst B is used as the core and the catalyst A is used as the shell to form a physical or chemical cyst. form.
  • the method of forming the encapsulated form is conventional.
  • Catalyst B Encapsulated Catalyst A A@B Catalyst by Physical Encapsulation: First, the binder liquid is immersed in the surface of the granular catalyst A having a certain size, and then the excess binder is removed, and then Catalyst A in a surface wet state was placed in a round bottom flask containing powdered catalyst B, and the round bottom flask was quickly and vigorously rotated to ensure that the surface of the catalyst A was entirely covered with the catalyst B. This process can be repeated 2-3 times.
  • the catalyst was dried overnight, and calcined in a muffle furnace at 350-550 ° C for 3-6 h to prepare an A@B catalyst, wherein the catalyst A was a core and the catalyst B was a shell.
  • the catalyst A and the catalyst B in the above method may be reversed.
  • the A@B catalyst for preparing catalyst B encapsulated catalyst A by chemical method firstly, the granular catalyst A having a certain size is hydrothermally synthesized together with the ZSM-5 synthetic liquid, and the specific operation steps can be referred to the above ZSM. -5 molecular sieve preparation method.
  • the obtained A@ZSM-5 catalyst was collected after the end of the water heat.
  • the A@ZSM-5 catalyst was then hydrothermally synthesized with Silicalite-1 molecular sieve.
  • the catalyst B is first prepared by hydrothermal synthesis. The specific operation steps can be referred to the above preparation method of Zn/HZSM5@S1 molecular sieve, and then the granular form.
  • a core-shell catalyst of the invention a core-shell catalyst prepared according to the process of the invention, a composite catalyst of the invention or a composite catalyst prepared by the process of the invention in the direct preparation of para-xylene from synthesis gas
  • the use of the catalyst since these catalysts of the present invention are used, not only the selectivity to p-xylene and the conversion rate of synthesis gas are high, but also the selectivity of p-xylene in xylene is high while maintaining high conversion of synthesis gas.
  • the process conditions of the reduction pretreatment are as follows: the reducing gas is pure hydrogen; the pretreatment temperature is 300-700 ° C, preferably 400-600 ° C; the pretreatment pressure is 0.1-1 MPa, preferably 0.1-0.5 MPa; The treatment gas has a volumetric space velocity of 500 to 8000 h -1 , preferably 1000 to 4000 h -1 ; and/or a pretreatment reduction time of 2 to 10 h, preferably 4 to 6 h.
  • the synthesis gas is passed through to carry out a reaction to convert to obtain p-xylene.
  • the molar ratio of hydrogen to carbon monoxide in the synthesis gas used for this purpose is from 0.1 to 5, preferably from 1 to 4.
  • the reaction pressure is 1-10 MPa, preferably 2-8 MPa.
  • the reaction temperature is from 150 to 600 ° C, preferably from 250 to 500 ° C.
  • the space velocity is 200-8000 h -1 , preferably 500-5000 h -1 .
  • the synthesis catalyst of the invention can be used for the conversion of synthesis gas, the conversion rate of synthesis gas can reach more than 55%, the selectivity of p-xylene in the xylene isomer can reach more than 70%, and the selectivity of p-xylene is equal to the same condition. Significantly improved.
  • the synthesis catalyst of the present invention can be used to convert the synthesis gas into p-xylene in one step without the need to pass through a multi-stage reactor containing a mixture of a plurality of different types of catalysts, and the reaction process is simpler and easier to handle.
  • the syngas conversion process carried out on the catalyst of the present invention enables higher p-xylene selectivity while maintaining a higher CO conversion.
  • the mixture was aged at 70 ° C for 3 h.
  • the precipitate was filtered and then washed with deionized water.
  • the washed precipitate was baked in an oven at 120 ° C for 12 h and then calcined in a muffle furnace at 400 ° C for 5 h.
  • a methanol synthesis catalyst was obtained, which was designated as a Cr/Zn catalyst in which the chromium/zinc molar ratio in terms of the element was 2:1.
  • a silicon source (TEOS), an aluminum source (Al(NO 3 ) 3 ⁇ 9H 2 O), an organic templating agent (TPAOH), ethanol and deionized water molar ratio (2TEOS: 0.02Al 2 O 3 :0.68 TPAOH:8EtOH :120H 2 O)
  • TEOS silicon source
  • Al(NO 3 ) 3 ⁇ 9H 2 O aluminum source
  • TPAOH organic templating agent
  • ethanol and deionized water molar ratio (2TEOS: 0.02Al 2 O 3 :0.68 TPAOH:8EtOH :120H 2 O)
  • the molar ratio of Si/Al in the HZSM-5 molecular sieve was 46.
  • the prepared Cr/Zn catalyst and HZSM-5 molecular sieve powder were physically mixed, ground for 10 min, and then tableted to obtain a bifunctional catalyst prepared by mechanical mixing, which was recorded as Cr/Zn-HZSM-5, wherein Cr/Zn catalyst
  • the mass ratio to the HZSM-5 molecular sieve is 2:1.
  • 0.5g Cr/Zn-HZSM-5 catalyst was packed in a fixed bed high-pressure reactor in a fixed bed form, and a synthesis gas with a volume ratio of H 2 to CO of 2.1 was continuously introduced, and the reaction pressure was controlled to 5 MPa.
  • the temperature was 1200 h -1 and the reaction temperature was 400 °C.
  • the reaction product and the raw material gas were analyzed by gas chromatography on-line, and the reaction performance is shown in Table 1.
  • a silicon source (TEOS), an organic templating agent (TPAOH), ethanol and deionized water molar ratio (1.0 SiO 2 : 0.06 TPA OH: 16.0 EtOH: 240H 2 O) were mixed into a mixture, and stirred at room temperature for 4 h to obtain a Silicalite-1 molecular sieve.
  • the HZSM-5 molecular sieve prepared above was pulverized and transferred to a polytetrafluoroethylene crystallizer together with the obtained Silicalite-1 molecular sieve precursor solution, and then sealed, and crystallized at a rotation rate of 2 rpm for 24 hours at a temperature of 180 °C.
  • HZSM-5@Silicalite-1 molecular sieve recorded as HZSM-5@S1 catalyst, wherein HZSM-5 molecular sieve is the core, Silicalite-1 molecular sieve is the shell, and the weight ratio of HZSM-5 molecular sieve to Silicalite-1 molecular sieve is 3:1.
  • Zn/ZSM-5@Silicalite-1 molecular sieve recorded as Zn/ZSM-5@S1 catalyst, in which Zn/ZSM-5 molecular sieve is core, Silicalite-1 molecular sieve is shell, Zn/ZSM-5 molecular sieve and Silicalite-1 molecular sieve
  • the weight ratio is 3:1.
  • Figure 1 is a SEM photograph of Zn/ZSM-5 and Zn/ZSM-5@S1 involved in this example, wherein Figure a is a SEM photograph of Zn/ZSM-5, and Figure b is a Zn/ZSM-5@S1 SEM photo. It can be seen from Fig. 1 that the size of the Zn/ZSM-5 molecular sieve is 0.5-1 ⁇ m before the Silicalite-1 molecular sieve coating, and the Zn/ZSM-5@S1 is obtained after the Silicalite-1 molecular sieve is coated with Zn/ZSM-5. The size of the molecular sieve becomes 1.5-2 ⁇ m. It can be concluded that Silicalite-1 molecular sieve is grown in situ on the Zn/ZSM-5 molecular sieve core to form a shell.
  • a is a STEM image of Zn/ZSM-5@S1 molecular sieve prepared in Example 2 and a corresponding EDS surface scan of the element, wherein: a is a STEM image of Zn/ZSM-5@S1, and b is a Si Figure of the element; c is a diagram of the Al element; d is a diagram of the O element; e is a diagram of the Zn element; and f is a mixture of the elements. It can be seen from Fig. 2 that most of Zn is supported on the ZSM-5 molecular sieve, so the Zn/ZSM-5@S1 molecular sieve is a core-shell molecular sieve with Zn/ZSM-5 as the core and Silicalite-1 as the shell.
  • Zn/ZSM-5@S1 molecular sieve Zn/ZSM-5 is the core
  • Silicalite-1 molecular sieve is the shell of the coated core.
  • Silicon source SiO 2
  • aluminum source isopropoxide aluminum
  • organic template TEAOH
  • NaOH sodiumOH
  • deionized water molar ratio (1SiO 2 :0.023Al 2 O 3 :0.0425TEAOH:0.049NaOH:6.8H 2 O)
  • the ⁇ molecular sieve has a Si/Al molar ratio of 20.
  • Example 1 The "preparation of HZSM-5@S1 catalyst" in Example 1 was repeated, but the HZSM-5 molecular sieve and the Silicalite-1 molecular sieve were physically mixed to obtain a bifunctional catalyst, which was designated as HZSM-5 & S1 catalyst, wherein HZSM-5 molecular sieve and The weight ratio of Silicalite-1 molecular sieve is 3:1.
  • Example 1 The "catalytic experiment” in Example 1 was repeated, but the Cr/Zn-HZSM-5 & S1 catalyst was used to replace the Cr/Zn-HZSM-5 catalyst.
  • the reaction results are shown in Table 1.
  • Example 2 The preparation of "Preparation of Cr/Zn catalyst” and "Zn/ZSM-5@S1 molecular sieve” in Example 2 was repeated to obtain a Cr/Zn catalyst and a Zn/ZSM-5@S1 catalyst, respectively.
  • Example 2 The "catalytic experiment" in Example 2 was repeated, but the Cr/Zn catalyst and the Zn/ZSM-5@S1 catalyst were not mixed together, but the two catalysts were each fixed in a fixed bed in a fixed bed high pressure reaction. In the two sections of the apparatus, the middle is separated by quartz wool, wherein along the direction of the gas stream, the Cr/Zn catalyst section is in front and the Zn/ZSM-5@S1 catalyst section is in the back. The reaction results are shown in Table 1.
  • Example 2 The "preparation of Zn/ZSM-5@S1 molecular sieve" in Example 2 was repeated to obtain a Zn/ZSM-5@S1 molecular sieve.
  • the prepared Fe/Zn/Cu catalyst and Zn/ZSM-5@S1 molecular sieve powder were physically mixed, ground for 10 min, and then tableted to obtain a bifunctional catalyst prepared by mechanical mixing, which was recorded as Fe/Zn/Cu-Zn. /ZSM-5@S1, wherein the mass ratio of Fe/Zn/Cu catalyst to Zn/ZSM-5@S1 molecular sieve is 2:1.
  • ZrO 2 -ZnO catalyst which was designated as Zr/Zn.
  • Example 2 The "preparation of Zn/ZSM-5@S1 molecular sieve" in Example 2 was repeated to obtain a Zn/ZSM-5@S1 molecular sieve.
  • the prepared Zr/Zn catalyst and Zn/ZSM-5@S1 molecular sieve powder were physically mixed, ground for 10 min, and then tableted to obtain a bifunctional catalyst prepared by mechanical mixing, which was recorded as Zr/Zn-Zn/ZSM-5. @S1, wherein the mass ratio of Zr/Zn catalyst to Zn/ZSM-5@S1 molecular sieve is 2:1.
  • Example 2 The "preparation of Zn/ZSM-5@S1 molecular sieve" in Example 2 was repeated to obtain a Zn/ZSM-5@S1 molecular sieve.
  • the prepared Cr/Zn/Al catalyst and Zn/ZSM-5@S1 molecular sieve powder were physically mixed, ground for 10 min, and then tableted to obtain a bifunctional catalyst prepared by mechanical mixing, which was recorded as Cr/Zn/Al-Zn. /ZSM-5@S1, wherein the mass ratio of Cr/Zn/Al catalyst to Zn/ZSM-5@S1 molecular sieve is 3:1.
  • Example 2 The "preparation of HZSM-5@S1 catalyst" in Example 1 was repeated, but Ag/ZSM-5 was used instead of HZSM-5 molecular sieve.
  • Ag/ZSM-5@Silicalite-1 molecular sieve was obtained, which was recorded as Ag/ZSM-5@S1 catalyst, in which Ag/ZSM-5 molecular sieve was core, Silicalite-1 molecular sieve was shell, Ag/ZSM-5 molecular sieve and Silicalite-1
  • the molecular sieve has a weight ratio of 3:1.
  • the prepared Cr/Zn catalyst and Ag/ZSM-5@S1 molecular sieve powder were physically mixed, ground for 10 min, and then tableted to obtain a bifunctional catalyst prepared by mechanical mixing, which was recorded as Cr/Zn-Ag/ZSM-5. @S1, wherein the mass ratio of Cr/Zn catalyst to Ag/ZSM-5@S1 molecular sieve is 1:1.
  • HZSM-5 molecular sieve The "preparation of HZSM-5 molecular sieve" in Comparative Example 1 was repeated to obtain an HZSM-5 molecular sieve.
  • 2.0 g of HZSM-5 molecular sieve was impregnated with a 1 mol/L aqueous solution of magnesium nitrate, followed by drying at 120 ° C overnight, then calcined in a muffle furnace at 500 ° C, and calcined for 4 h to obtain HZSM-5@MgO molecular sieve, which was recorded as HZSM-5@MgO, in which HZSM-5 molecular sieve is a core and MgO is a shell.
  • the content of MgO is 1% by weight based on the total weight of the HZSM-5@MgO molecular sieve.
  • the prepared Cr/Zn catalyst and the HZSM-5@MgO catalyst powder were physically mixed, ground for 10 min, and then tableted to obtain a bifunctional catalyst prepared by mechanical mixing, which was recorded as Cr/Zn-HZSM-5@MgO, wherein The mass ratio of the Cr/Zn catalyst to the HZSM-5@MgO catalyst was 2:1.
  • HZSM-5@SiO 2 catalyst which was designated as HZSM-5@SiO. 2 .
  • the system can be carried out 2-3 times.
  • the content of SiO 2 was 1% by weight based on the total weight of the HZSM-5@SiO 2 molecular sieve.
  • the prepared Cr/Zn catalyst and the HZSM-5@SiO 2 catalyst powder were physically mixed, ground for 10 min, and then tableted to obtain a bifunctional catalyst prepared by mechanical mixing, which was recorded as Cr/Zn-HZSM-5@SiO 2 .
  • the mass ratio of the Cr/Zn catalyst to the HZSM-5@SiO 2 catalyst is 2:1.

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