WO2019062815A1 - Catalyst for directly preparing p-xylene by using syngas, preparation thereof, and applications thereof - Google Patents

Catalyst for directly preparing p-xylene by using syngas, preparation thereof, and applications thereof 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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PCT/CN2018/107966
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French (fr)
Chinese (zh)
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杨国辉
椿范立
高潮
柴剑宇
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株式会社模范
高化学技术株式会社
杨国辉
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Priority to JP2020539126A priority Critical patent/JP7232836B2/en
Priority to EA202090904A priority patent/EA202090904A1/en
Publication of WO2019062815A1 publication Critical patent/WO2019062815A1/en
Priority to JP2022187184A priority patent/JP7443474B2/en

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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.

Abstract

A core-shell type catalyst. The core of the core-shell type catalyst is a HZSM-5 molecular sieve, a modified HZSM-5 molecular whose parts or all of Hs in the HZSM-5 molecular are replaced by metal (non-metal) elements defined in the specification, or a mixture thereof. The shell is selected from a carbon film, Silicalite-l, MCM-41, SBA-15, KIT-6, MSU series, silicon dioxide, graphene, a carbon nanotube, a metal-organic framework (MOF), graphite, activated carbon, and a metal oxide film. When a composite catalyst consisting of the catalyst and a methanol catalyst for syngas conversion is used for converting syngas in a one-step method, the selectivity of the p-xylene is high and the conversion rate of the syngas is high, and the selectivity of xylene in the p-xylene is also high.

Description

用于合成气直接制备对二甲苯的催化剂及其制备和应用Catalyst for direct preparation of para-xylene from syngas and preparation and application thereof 技术领域Technical field
本发明涉及一种核壳型催化剂及其制备。本发明还涉及包含该核壳型催化剂的复合催化剂及其制备，以及本发明核壳型催化剂和复合催化剂的应用，用于由合成气直接制备对二甲苯。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.
背景技术Background technique
对二甲苯作为重要的有机合成原料，广泛应用于纺织和包装材料领域。对二甲苯主要用于制取对苯二甲酯及对苯二甲酸等，后者用作塑料和聚酯纤维的中间体，以及涂料、染料和农药的原料。目前，工业上最常用的对二甲苯生产方法为甲苯歧化与碳九芳烃烷基转移。在该方法中，由于产物中对二甲苯含量受热力学平衡限制，通常仅能得到浓度约为24重量％的对二甲苯。然而，二甲苯需求市场上，要求对二甲苯浓度为60重量％以上，因此该浓度远不能满足工业生产的需求，比如聚酯材料的生产。而为了得到高浓度对二甲苯以及提高对二甲苯收率，需要经过一系列后续处理。特别是，二甲苯的三个异构体间的沸点相差很小，采用通常的蒸馏技术不能得到高纯度的对二甲苯，而必须采用昂贵的吸附分离工艺，这就带来了原料的损耗与成本的提升。随着石油能源的日益短缺，无论是从市场需求还是从石油替代的角度出发，开发新的芳烃合成工艺路线都具有极高的价值。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. Currently, the most common paraxylene production process in the industry is toluene disproportionation and carbon nonarene alkyl transfer. In this process, 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. However, in the xylene demand market, 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. In order to obtain high concentrations of p-xylene and increase the yield of p-xylene, a series of subsequent treatments are required. In particular, 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. With the increasing shortage of petroleum energy, the development of new aromatics synthesis process routes is of great value, both in terms of market demand and oil substitution.
合成气作为能源转化的桥梁，可以将煤炭、天然气、生物质转化为清洁油品，被认为是最有潜力的石油替代途径之一。其中，以金属催化剂与合适的分子筛组合的复合催化剂能有效地调控费托反应产物的分布，此类研究在近些年取得了很大的进展。在成功利用费托合成制备不同碳数区间的油品之后，越来越多的科学工作者将目光转向合成气直接高选择性制备高附加值化学品，包括低碳烯烃、低碳醇等。虽然合成气一步法制芳烃如苯、甲苯、二甲苯的方法已有相关的研究报道，但产物中对二甲苯的选择性通常不高且该技术尚未实现产业化。主要存在问题是，产物选择性的调控难以取得突破。此外，催化剂易于 失活，催化性能的稳定性难以保持。As a bridge for energy conversion, syngas can convert coal, natural gas and biomass into clean oil, which is considered to be one of the most potential alternatives to petroleum. Among them, 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. After the successful use of 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. Although there have been reports on the synthesis of aromatic hydrocarbons such as benzene, toluene and xylene in one-step synthesis of syngas, the selectivity of p-xylene in the product is generally not high and the technology has not yet been industrialized. The main problem is that it is difficult to achieve breakthroughs in product selectivity regulation. In addition, the catalyst is easily deactivated and the stability of the catalytic performance is difficult to maintain.
提高合成气一步法制备对二甲苯的选择性关键在于，高性能催化剂的研制和开发。其中，使用由甲醇合成催化剂与分子筛组成的双功能复合催化剂具有较好的催化性能。该反应路线包含一些列的串联反应：合成气加氢制甲醇，甲醇加氢脱水反应，芳香化反应，二甲苯异构化反应等等。该路线对发展合成气转化工艺有很大的益处，不仅能促进国家的能源战略安全，也是应对世界化石油能源枯竭潜在威胁的解决方案之一。因此，提高对二甲苯的选择性，降低工艺复杂性和成本，是合成气直接制备对二甲苯急需解决的技术难点。The key to improving the selectivity of syngas to produce para-xylene is the development and development of high performance catalysts. Among them, 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.
研究表明，合成气直接制芳烃一般需经历两步过程，即，先将合成气转化为甲醇或二甲醚，再由甲醇或二甲醚制芳烃(MTA)。例如，山西煤化所采用的两段反应器分别装有两种类型催化剂，可将合成气经二甲醚转化为芳烃(CN101422743A)。采用的合成气芳构化催化剂为：HNKF-5：磷酸铝分子筛:Ga 2O 3:ZnO:BaO。该专利将合成气通过一段的甲醇合成和甲醇脱水的混合催化剂后，在二段反应器中装入芳构化催化剂与一段催化剂的混合催化剂进行芳构化，最终得到芳烃产物。 Studies have shown that direct synthesis of aromatics from syngas generally involves a two-step process, namely conversion of synthesis gas to methanol or dimethyl ether followed by methanol or dimethyl ether to aromatics (MTA). For example, the two-stage reactor used in Shanxi Coalification is equipped with two types of catalysts, which convert syngas to dianlocarbons (CN101422743A). The synthesis gas aromatization catalyst used was: HNKF-5: aluminum phosphate molecular sieve: Ga 2 O 3 : ZnO: BaO. In the patent, 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.
上述两段法由合成气制备对二甲苯不仅存在步骤多，二段反应流程较长，能耗高以及催化剂制备方法复杂等问题，而且对二甲苯的选择性在碳氢化合物产物中不足30重量％。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. %.
Lasa等人早期报道了在Cr-Zn/ZSM-5催化剂上由合成气制芳烃的性能(Ind.Eng.Chem.Res.,1991,30,1448-1455)，其中芳烃在碳氢化合物中选择性可达到70.8％，但未提及芳烃的具体产物分布。后续又报道了在Cr-Zn/ZSM-5复合催化剂上的由合成气制芳烃的性能(Appl.Catal.A,1995,125,81-98)，其中在356-410℃，3.6-4.5MPa的反应条件下，碳氢化合物中芳烃选择性达到75％，但二甲苯的选择性不超过20％。王德生等人(催化化学学报,2002,23(4),333-335)采用F-T合成Fe基催化剂与芳构化分子筛混合的Fe/MnO-ZnZSM-5复合催化剂，使合成气在费托反应中生成低碳烃中间体并在分子筛上转化为芳烃，其中的CO转化率在270℃时达到98.1％，然而苯、甲苯等芳烃选择性较低。最近，马丁与樊卫斌团队(Chem,2017,3,323-333)将铁基催化剂Na-Zn-Fe 5C 2(FeZnNa) 与改性处理后的介孔HZSM-5分子筛混合，有效地实现了以烯烃为中间体的合成气直接制备芳烃。在340℃、2MPa的条件下在烃类产物中最多可以得到51重量％的芳烃，其中以轻质芳烃为主。然而并未提及芳烃中的对二甲苯的选择性。厦门大学王野团队(Chem,2017,3,334-347)基于发展耦合反应的学术思想，巧妙设计出Zn掺杂ZrO 2/H-ZSM-5双功能催化剂，实现了合成气一步高选择性、高稳定性制备芳烃。为了提高轻质芳烃BTX(苯，甲苯，二甲苯)的含量，作者通过对H-ZSM-5分子筛外表面进行硅烷化处理从而达到毒化
Figure PCTCN2018107966-appb-000001
酸性位的目的，成功地提高了最终芳烃产物中的BTX选择性。BTX在芳烃中的比例可提高至60重量％，然而其中二甲苯和对二甲苯的含量也不曾提及。 Lasa et al. earlier reported the performance of aromatic hydrocarbons from synthesis gas on Cr-Zn/ZSM-5 catalysts (Ind. Eng. Chem. Res., 1991, 30, 1448-1455), in which aromatic hydrocarbons are selected among hydrocarbons. The property can reach 70.8%, but the specific product distribution of the aromatic hydrocarbon is not mentioned. The performance of aromatic hydrocarbons from syngas on Cr-Zn/ZSM-5 composite catalysts was subsequently reported (Appl. Catal. A, 1995, 125, 81-98), which was 356-410 ° C, 3.6-4.5 MPa. Under the reaction conditions, the aromatics selectivity in hydrocarbons reaches 75%, but the selectivity of xylene does not exceed 20%. Wang Desheng et al. (Acta Physica Sinica, 2002, 23(4), 333-335) used Fe/MnO-ZnZSM-5 composite catalyst mixed with Fe-based catalyst and aromatized molecular sieve to synthesize syngas in Fischer-Tropsch reaction. The lower hydrocarbon intermediate is formed and converted to an aromatic hydrocarbon on a molecular sieve, wherein the CO conversion rate reaches 98.1% at 270 ° C, whereas the aromatic hydrocarbons such as benzene and toluene are less selective. Recently, Martin and Fan Weibin (Chem, 2017, 3, 323-333) mixed iron-based catalyst Na-Zn-Fe 5 C 2 (FeZnNa) with modified mesoporous HZSM-5 molecular sieve to effectively achieve olefins. The aromatic hydrocarbon is directly produced as a synthesis gas for the intermediate. At the 340 ° C, 2 MPa condition, up to 51% by weight of aromatic hydrocarbons can be obtained in the hydrocarbon product, among which light aromatic hydrocarbons are dominant. However, the selectivity to para-xylene in aromatics is not mentioned. The Wang Ye team of Xiamen University (Chem, 2017, 3, 334-347) based on the academic idea of developing coupling reaction, cleverly designed the Zn-doped ZrO 2 /H-ZSM-5 bifunctional catalyst to achieve a high selectivity and high synthesis gas. Stability preparation of aromatic hydrocarbons. In order to improve the content of light aromatic BTX (benzene, toluene, xylene), the authors achieved poisoning by silanizing the outer surface of H-ZSM-5 molecular sieve.
Figure PCTCN2018107966-appb-000001
For the purpose of the acid site, the BTX selectivity in the final aromatic product is successfully increased. The proportion of BTX in the aromatic hydrocarbon can be increased to 60% by weight, however the contents of xylene and para-xylene are not mentioned.
尽管上述催化剂均可由合成气一步得到芳烃，但对二甲苯的选择性往往不高，并且不能有效地抑制二甲苯的异构化反应。Although 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.
发明内容Summary of the invention
本发明旨在提供一种以高选择性由合成气直接制备对二甲苯的催化剂及其制备方法和应用。所设计的催化剂制备方法简单、合成气转化率高、对二甲苯选择性高，有望在工业上应用。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.
本发明的一个目的是提供一种核壳型催化剂。当该催化剂与用于催化合成气转化为甲醇的催化剂复合使用时，不仅使得对二甲苯选择性高和合成气的转化率高，而且对二甲苯在二甲苯中的选择性也高。It is an object of the present invention to provide a core-shell type catalyst. When 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.
本发明另一个目的是提供一种制备本发明核壳型催化剂的方法。Another object of the present invention is to provide a process for preparing the core-shell type catalyst of the present invention.
本发明的再一目的是提供一种用于由合成气直接制备对二甲苯的复合催化剂，该催化剂包含用于催化合成气转化为甲醇的催化剂和本发明核壳型催化剂。该复合催化剂在催化合成气转化为烃时，不仅使得对二甲苯选择性高和合成气的转化率高，而且对二甲苯在二甲苯中的选择性也高。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.
本发明的又一目的是提供一种制备本发明复合催化剂的方法。It is still another object of the present invention to provide a process for preparing the composite catalyst of the present invention.
本发明的最后一个目的是提供本发明核壳型催化剂或本发明复合催化剂在由合成气直接制备对二甲苯中的用途。采用本发明的核壳型催化剂或复合催化剂作为由合成气直接制备对二甲苯的催化剂，不仅使得对二甲苯选择性高和合 成气的转化率高，而且对二甲苯在二甲苯中的选择性也高。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.
解决本发明上述技术问题采用的技术方案可以概括如下：The technical solutions adopted to solve the above technical problems of the present invention can be summarized as follows:
1.一种核壳型催化剂，其中核为H型ZSM-5分子筛，H型ZSM-5分子筛中的H全部或部分被一种或多种选自Sn、Ga、Ti、Zn、Mg、Li、Ce、Co、La、Rh、Pd、Pt、Ni、Cu、K、Ca、Ba、Fe、Mn和B的元素M替换的改性ZSM-5分子筛或者它们的任意混合物，壳为选自碳膜、Silicalite-1、MCM-41、SBA-15、KIT-6、MSU系列、二氧化硅、石墨烯、碳纳米管、金属有机框架MOF、石墨、活性炭、金属氧化物膜(如MgO、P 2O 5、CaO)中的一种或多种。 A core-shell type catalyst in which a core is a 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, 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).
2.根据第1项的核壳型催化剂，其中核为H型ZSM-5分子筛，H型ZSM-5分子筛中的H部分或全部被Zn替换的改性ZSM-5分子筛或它们的任意混合物；和/或，壳为选自二氧化硅膜、Silicalite-1、金属氧化物膜(如MgO、P 2O 5、CaO)、MCM-41、SBA-15、KIT-6中的一种或多种，优选为Silicalite-1；特别优选的是，在元素M改性的M-ZSM-5分子筛中，元素M占M-ZSM-5分子筛总重量的0.5-15重量％，优选1-10重量％，特别优选1-5重量％。 2. The core-shell catalyst according to item 1, wherein 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; And/or, 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-6. , preferably Silicalite-1; it is particularly preferred that in the element M modified M-ZSM-5 molecular sieve, the element M 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.
3.根据第1或2项的核壳型催化剂，其中核与壳的重量比为100:1-1:100，优选为10:1-1:10，更优选为5:1-1:5，特别优选5:1-1:1。3. 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.
4.一种制备根据第1-3项中任一项的核壳型催化剂的方法，包括：A method of preparing a core-shell type catalyst according to any one of items 1 to 3, comprising:
1)提供呈颗粒形式的核，其为H型ZSM-5分子筛，H型ZSM-5分子筛中的H全部或部分被一种或多种选自Sn、Ga、Ti、Zn、Mg、Li、Ce、Co、La、Rh、Pd、Pt、Ni、Cu、Na、K、Ca、Ba、Fe、Mn和B的元素M替换的改性ZSM-5分子筛或者它们的任意混合物；以及1) providing 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;
2)将选自碳膜、Silicalite-1、MCM-41、SBA-15、KIT-6、MSU系列、二氧化硅、石墨烯、碳纳米管、金属有机框架MOF、石墨、活性炭、金属氧化物膜(如MgO、P 2O 5、CaO)中的一种或多种材料包覆在呈颗粒形式的核表面上。 2) Will be 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, metal oxide One or more of the films (e.g., MgO, P 2 O 5 , CaO) are coated on the surface of the core in the form of particles.
5.一种用于由合成气直接制备对二甲苯的复合催化剂，其包含：5. A composite catalyst for the direct preparation of para-xylene from syngas comprising:
A)用于催化合成气转化为甲醇的催化剂A；和A) Catalyst A for catalyzing the conversion of synthesis gas to methanol;
B)用于催化形成二甲苯的催化剂B，该催化剂B为如第1-3项中任一项的核壳型催化剂，B) Catalyst B for catalyzing the formation of xylene, which is a core-shell type catalyst according to any one of items 1 to 3,
优选的是，复合催化剂呈催化剂A与催化剂B的混合物形式，催化剂A物理性或化学性包囊催化剂B的形式，或者催化剂B物理性或化学性包囊催化剂A的形式。Preferably, 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.
6.根据第5项的复合催化剂，其中催化剂A包含第一金属组分和第二金属组分或者由第一金属组分和第二金属组分组成，第一金属组分为选自Cr、Fe、Zr、In、Ga、Co、Cu的元素、其氧化物、其复合氧化物或它们的任意混合物，第二金属组分为选自Zn、Na、Al、Ag、Ce、K、Mn、Pd、Ni、La、V的元素、其氧化物、其复合氧化物或它们的任意混合物；优选的是，第一金属组分为选自Cr、Co、Cu、Zr的元素、其氧化物、其复合氧化物或它们的任意混合物；和/或，第二金属组分为选自Zn、Al的元素、其氧化物、其复合氧化物或它们的任意混合物；特别优选催化剂A是ZnO-Cr 2O 3。 6. The composite catalyst according to item 5, wherein 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 .
7.根据第5或6项的复合催化剂，其中催化剂A中的第一金属组分与第二金属组分以金属元素计的摩尔比为1000:1-1:100，优选100:1-1:50,更优选为10:1-1:10，特别优选为3:1-1:3。7. The composite catalyst according to item 5 or 6, wherein the molar ratio of the first metal component to the second metal component in the catalyst A in terms of the metal element is from 1000:1 to 1:100, preferably from 100:1 to 1-1. : 50, more preferably 10:1 to 1:10, particularly preferably 3:1 to 1:3.
8.根据第5-7项中任一项的复合催化剂，其中催化剂A与催化剂B的重量比为1:99-99:1，优选20:80-80:20，更优选为30:70-70:30，特别优选50:50-75:25。The composite catalyst according to any one of items 5 to 7, wherein the weight ratio of the catalyst A to the catalyst B is from 1:99 to 99:1, preferably from 20:80 to 80:20, more preferably from 30:70. 70:30, particularly preferably 50:50-75:25.
9.一种制备根据第5-8项中任一项的复合催化剂的方法，包括：A method of producing a composite catalyst according to any one of items 5-8, comprising:
1)分别制备催化剂A粉末和催化剂B粉末；和1) separately preparing a catalyst A powder and a catalyst B powder;
2a)将催化剂A粉末与催化剂B粉末和任选的粘合剂混合在一起，然后成型为复合催化剂；2a) mixing the catalyst A powder with the catalyst B powder and the optional binder, and then forming into a composite catalyst;
2b)将催化剂A粉末和催化剂B粉末分别成型，得到催化剂A成型体和催化剂B成型体，然后将这些成型体混合在一起；2b) separately molding the catalyst A powder and the catalyst B powder to obtain a catalyst A molded body and a catalyst B molded body, and then mixing the molded bodies together;
2c)以催化剂A为核、催化剂B为壳形成物理性或化学性包囊形式；或2c) forming a physical or chemical encapsulation form with Catalyst A as the core and Catalyst B as the shell; or
2d)以催化剂B为核、催化剂A为壳形成物理性或化学性包囊形式。2d) Forming physical or chemical encapsulation in the form of catalyst B as the core and catalyst A as the shell.
10.根据第9项的方法，其中催化剂A通过选自顺序浸渍法、共浸渍法、尿素法和共沉淀法中的任何一种或多种制备；优选的是，在顺序浸渍法、共浸渍法、尿素法和/或共沉淀法制催化剂A的焙烧工艺中，工艺条件如下：10. The method according to item 9, wherein 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 In the roasting process of the catalyst A by the method, the urea method and/or the coprecipitation method, the process conditions are as follows:
焙烧气氛为空气；和/或，The firing atmosphere is air; and/or,
焙烧温度为200-700℃，优选400-600℃；和/或The calcination temperature is 200-700 ° C, preferably 400-600 ° C; and / or
焙烧时间为3-8h，优选4-6h。The calcination time is from 3 to 8 h, preferably from 4 to 6 h.
11.根据第1-3项中任一项的核壳催化剂、根据第4项的方法制备的核壳催化剂、根据第5-8项中任一项的复合催化剂或者通过根据第9-10项中任一项的方法制备的复合催化剂在由合成气直接制备对二甲苯中作为催化剂的用途。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.
12.根据第11项的用途，其中合成气中的氢气与一氧化碳的摩尔比为0.1-5，优选为1-4；反应压力为1-10MPa，优选为2-8MPa；反应温度为150-600℃，优选为250-500℃；和/或，空速为200-8000h -1，优选为500-5000h -1。 12. The use according to item 11, wherein the molar ratio of hydrogen to carbon monoxide in the synthesis gas is from 0.1 to 5, preferably from 1 to 4; the reaction pressure is from 1 to 10 MPa, preferably from 2 to 8 MPa; and the reaction temperature is from 150 to 600. °C, preferably 250-500 ° C; and / or, the space velocity is 200-8000 h -1 , preferably 500-5000 h -1 .
13.根据第12项的用途，其中在通入合成气反应之前，将复合催化剂先还原预处理，优选还原预处理的工艺条件下如下：13. The use according to item 12, wherein the composite catalyst is first subjected to a reduction pretreatment prior to the introduction of the synthesis gas reaction, preferably under the conditions of the reduction pretreatment:
还原气为纯氢气；The reducing gas is pure hydrogen;
预处理温度为300-700℃，优选为400-600℃；The pretreatment temperature is 300-700 ° C, preferably 400-600 ° C;
预处理压力为0.1-1MPa，优选为0.1-0.5MPa；The pretreatment pressure is 0.1-1 MPa, preferably 0.1-0.5 MPa;
预处理氢气体积空速为500-8000h -1，优选为1000-4000h -1；和/或 The pretreatment hydrogen gas volume velocity is 500-8000 h -1 , preferably 1000-4000 h -1 ; and/or
预处理还原时间为2-10h，优选为4-6h。The pretreatment reduction time is 2-10 h, preferably 4-6 h.
附图说明DRAWINGS
图1是实施例2中涉及的Zn/ZSM-5和Zn/ZSM-5@S1分子筛的SEM照片，其中图a是Zn/ZSM-5分子筛的SEM照片，图b是Zn/ZSM-5@S1分子筛的SEM照片。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.
图2是实施例2中制备的Zn/ZSM-5@S1分子筛的STEM图和相对应的元素EDS面扫图。2 is a STEM image of the Zn/ZSM-5@S1 molecular sieve prepared in Example 2 and a corresponding element EDS surface scan.
具体实施方式Detailed ways
根据本发明的第一个方面，提供了一种核壳型催化剂，其中核为H型ZSM-5分子筛，H型ZSM-5分子筛中的H全部或部分被一种或多种选自Sn、Ga、Ti、Zn、Mg、Li、Ce、Co、La、Rh、Pd、Pt、Ni、Cu、K、Ca、Ba、Fe、Mn和B的元素M替换的改性ZSM-5分子筛或者它们的任意混合物，壳为选自碳膜、 Silicalite-1、MCM-41、SBA-15、KIT-6、MSU系列、二氧化硅、石墨烯、碳纳米管、金属有机框架MOF、石墨、活性炭、金属氧化物膜(如MgO、P 2O 5、CaO)中的一种或多种。 According to a first aspect of the present invention, there is provided 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).
本发明的核壳型催化剂具有核/壳结构。核为H型ZSM-5分子筛(下文中有时表示为HZSM-5)，H型ZSM-5分子筛中的H全部或部分被一种或多种选自Sn、Ga、Ti、Zn、Mg、Li、Ce、Co、La、Rh、Pd、Pt、Ni、Cu、Na、K、Ca、Ba、Fe、Mn和B的元素M替换的改性ZSM-5分子筛(下文中有时表示为M/ZSM-5分子筛)或者它们的任意混合物。这些分子筛在本发明中统称为ZSM-5分子筛。ZSM-5分子筛能够在合成气一步法制备烃类化合物的反应中催化促进转换为烃类。本发明人发现，这些催化活性成分在按照本发明覆盖后比未经表面覆盖前，在用于合成气制烃时，能够明显提高对二甲苯的选择性，尤其是二甲苯中对二甲苯的选择性，同时保持高的CO转化率。而且，相比于同等条件下将核材料和壳材料物理混合得到的混合催化剂，本发明的核壳型催化剂也能够明显提高对二甲苯的选择性，尤其是二甲苯中对二甲苯的选择性，同时保持高的CO转化率。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. These molecular sieves are collectively referred to herein as ZSM-5 molecular sieves. 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. Moreover, 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.
作为核组分，H型ZSM-5分子筛和M/ZSM-5分子筛都既可市购获得，也可通过本领域的常规方法制得，例如通过水热合成法、浸渍法、离子交换法、气相沉积法、液相沉积法等制备。通常，可通过水热合成法制备HZSM-5分子筛和Na/ZSM-5，然后再通过离子交换法由HZSM-5分子筛和Na/ZSM-5制备M/ZSM-5分子筛。As the core component, 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. In general, 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.
以HZSM-5沸石分子筛的水热合成法为例。将硅源(TEOS，正硅酸乙酯)、铝源(Al(NO 3) 3 .9H 2O)、有机模板剂(TPAOH，四丙基氢氧化铵)、乙醇和去离子水按摩尔比(2TEOS:xAl 2O 3:0.68TPAOH:8EtOH:120H 2O,x＝0.002-0.2)配制成混合物，室温搅拌4-6h得到溶胶，然后将搅拌好的溶胶转移入聚四氟乙烯晶化釜中，尔后密封，在160-200℃的温度下以2-5rpm的旋转速度晶化24-72h。晶化结束后冷却至室温，将所得的产物洗涤至滤液pH＝7-8，干燥过夜，然后置于马弗炉中以1℃-3℃/min升温速率升至550-650℃，焙烧4-8h后，得到ZSM-5分子筛，其为HZSM-5。所述ZSM-5分子筛中SiO 2/Al 2O 3为10-1000。 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 TPAOH: 8EtOH: 120H 2 O, x = 0.002-0.2) is formulated into a mixture, stirred at room temperature for 4-6 hours to obtain a sol, and then the stirred sol is transferred into a polytetrafluoroethylene crystallizer. Medium and then sealed, crystallized at a rotational speed of 2-5 rpm for 24-72 h at a temperature of 160-200 °C. After the crystallization is completed, it is cooled to room temperature, and the obtained product is washed until the filtrate pH=7-8, dried overnight, and then placed in a muffle furnace at a temperature increase rate of 1 ° C - 3 ° C / min to 550-650 ° C, roasting 4 After -8 h, a ZSM-5 molecular sieve was obtained which was HZSM-5. The ZSM-5 molecular sieve has a SiO 2 /Al 2 O 3 of 10-1000.
为了制备M/ZSM-5分子筛，当元素M为金属元素时，可以以HZSM-5为 原料采用离子交换法、浸渍法、气相沉积法和液相沉积法等制备M/ZSM-5分子筛；当M为非金属元素B时，可以以HZSM-5为原料采用浸渍法、气相沉积法和液相沉积法等制备M/ZSM-5分子筛。In order to prepare 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; When 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.
以离子交换方法制备Zn/ZSM-5分子筛为例。例如，将1.5g的HZSM-5分子筛加入到1mol/L的硝酸锌水溶液中，在80-100℃下不断搅拌10-15h，进行离子交换。离子交换结束后冷却至室温，将所得产物洗涤至滤液pH＝7-8，干燥过夜，然后置于马弗炉中焙烧500℃，焙烧4-6h后，得到Zn/ZSM-5分子筛。The Zn/ZSM-5 molecular sieve was prepared by ion exchange method as an example. For example, 1.5 g of HZSM-5 molecular sieve is added to a 1 mol/L zinc nitrate aqueous solution, and stirring is continued for 10-15 hours at 80-100 ° C for ion exchange. After the end of the ion exchange, the mixture was cooled to room temperature, and the obtained product was washed until the filtrate pH = 7-8, dried overnight, then placed in a muffle furnace and calcined at 500 ° C, and calcined for 4-6 hours to obtain a Zn/ZSM-5 molecular sieve.
在本发明的一个优选实施方案中，在元素M改性的M/ZSM-5分子筛中，元素M占M/ZSM-5分子筛总重量的0.5-15重量％，优选1-10重量％，特别优选1-5重量％。In a preferred embodiment of the invention, in the element M modified M/ZSM-5 molecular sieve, the element M 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.
在本发明的HZSM-5分子筛或者由M改性的M/ZSM-5分子筛中，Si/Al摩尔比通常为10-1000，优选为20-800。这些分子筛的粒径大小通常为0.01-20μm，优选为0.1-15μm。In the HZSM-5 molecular sieve of the present invention or the M/ZSM-5 molecular sieve modified by M, 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 μm, preferably from 0.1 to 15 μm.
本发明核壳型催化剂的壳为选自碳膜、Silicalite-1、MCM-41、SBA-15、KIT-6、MSU系列(纯硅分子筛)、二氧化硅、石墨烯、碳纳米管、金属有机框架MOF(比如ZIF-8、ZIF-11)、石墨、活性炭、金属氧化物膜(如MgO、P2O5、CaO)中的一种或多种。这些材料包覆在核的外表面，形成壳。这些壳材料本身对烃芳构化成二甲基苯不具有活性，但是通过它们对ZSM-5分子筛核的包覆，影响了ZSM-5外表面的裸露酸性位，能把这些裸露的酸性位覆盖或处理掉，从而可以减少副反应，最终提高目标产物对二甲苯的选择性。作为壳材料，优选为选自二氧化硅膜、Silicalite-1、金属氧化物膜(如MgO、P 2O 5、CaO)、MCM-41、SBA-15、KIT-6中的一种或多种，尤其为Silicalite-1。 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. Or disposed of, thereby reducing side reactions and ultimately improving the selectivity of the target product to xylene. As 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. Species, especially Silicalite-1.
壳的用量没有特别的选择，只要能够将核包覆起来即可。在本发明核壳型催化剂的一个实施方案中，核与壳的重量比为100:1-1:100，优选为10:1-1:10，更优选为5:1-1:5，特别优选5:1-1:1。There is no particular choice as to the amount of shell used, as long as the core can be coated. In one embodiment of the core-shell catalyst of the present invention, 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.
根据本发明的第二方面，提供了一种制备本发明核壳型催化剂的方法，包括：According to a second aspect of the present invention, there is provided a method of preparing a core-shell type catalyst of the present invention, comprising:
1)提供呈颗粒形式的核，其为H型ZSM-5分子筛，H型ZSM-5分子筛中 的H全部或部分被一种或多种选自Sn、Ga、Ti、Zn、Mg、Li、Ce、Co、La、Rh、Pd、Pt、Ni、Cu、Na、K、Ca、Ba、Fe、Mn和B的元素M替换的改性ZSM-5分子筛或者它们的任意混合物；以及1) providing 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;
2)将选自碳膜、Silicalite-1、MCM-41、SBA-15、KIT-6、MSU系列、二氧化硅、石墨烯、碳纳米管、金属有机框架MOF、石墨、活性炭、金属氧化物膜(如MgO、P 2O 5、CaO)中的一种或多种材料包覆在呈颗粒形式的核表面上。 2) Will be 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, metal oxide One or more of the films (e.g., MgO, P 2 O 5 , CaO) are coated on the surface of the core in the form of particles.
本发明核壳型催化剂的核材料和壳材料都是常规的。为了提供步骤1)中的核，当核材料本身已经是尺寸合适的颗粒时，则直接使用该核材料；当核材料的尺寸较大时，粉碎后用于步骤2)。在步骤2)中实现对核颗粒的包覆。不同壳材料对核颗粒的包覆，这在本领域中属于常识。作为包覆方法，可以提及水热合成法、气相沉积法、浸渍法、溅射法、
Figure PCTCN2018107966-appb-000002
法等，这可以根据包覆材料的性质进行常规选择。例如，分子筛类壳材料的包覆，可采用水热合成法，碳膜、石墨烯及碳纳米管的包覆可采用气相沉积法，金属氧化物的包覆可采用浸渍法和溅射法，二氧化硅的包覆可采用
Figure PCTCN2018107966-appb-000003
法。 Both the core material and the shell material of the core-shell type catalyst of the present invention are conventional. 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. As the coating method, there may be mentioned hydrothermal synthesis method, vapor deposition method, dipping method, sputtering method,
Figure PCTCN2018107966-appb-000002
This method can be routinely selected depending on the nature of the coating material. For example, 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, and the coating of metal oxide can be carried out by dipping and sputtering. Coating of silica can be used
Figure PCTCN2018107966-appb-000003
law.
以Silicalite-1通过水热合成法包覆Zn/ZSM-5得到Zn/ZSM-5@Silicalite-1核壳型催化剂为例。将硅源(TEOS)、有机模板剂(TPAOH)、乙醇和去离子水按摩尔比(1.00SiO 2:0.06TPAOH:16.0EtOH:240H 2O)配制成混合物，室温搅拌4-6h，得到Silicalite-1分子筛前体溶液。将上述制备的Zn/ZSM-5沸石分子筛粉碎后同所得Silicalite-1分子筛前体溶液一起转移入聚四氟乙烯晶化釜中，然后密封，在180℃的温度下以2-5rmp的旋转速度晶化24-72h。晶化结束后冷却至室温，将所得产物用去离子水洗涤至滤液pH＝7-8，干燥过夜，然后置于马弗炉中以1 °-3 °/min升温速率升至550-650℃，焙烧4-8h后，得到Zn/ZSM-5@Silicalite-1核壳型催化剂，其中Zn/ZSM-5为核，Silicalite-1为壳。 An example of 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 Zn/ZSM-5 zeolite molecular sieve prepared above is pulverized and transferred to a polytetrafluoroethylene crystallization tank together with the obtained Silicalite-1 molecular sieve precursor solution, and then sealed, and rotated at a temperature of 180 ° C at a rotation speed of 2-5 rpm. Crystallization for 24-72h. After the end of crystallization, it was cooled to room temperature, and the obtained product was washed with deionized water until the filtrate pH=7-8, dried overnight, and then placed in a muffle furnace at a heating rate of 1 ° -3 ° /min to 550-650 ° C. After calcination for 4-8 h, a Zn/ZSM-5@Silicalite-1 core-shell catalyst was obtained, in which Zn/ZSM-5 was a core and Silicalite-1 was a shell.
合成气一步法制备芳族烃可大致划分为两个阶段，一个阶段是合成气转化成甲醇的阶段，另一个阶段是甲醇进一步反应最终得到芳烃比如对二甲苯的阶段。本发明的核壳型催化剂对于第二个阶段提高对二甲苯的选择性非常有效，不仅能够明显提高对二甲苯的选择性，尤其是二甲苯中对二甲苯的选择性，同时还保持高的CO转化率。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.
因此，根据本发明的第三方面，提供了一种用于由合成气直接制备对二甲苯的复合催化剂，其包含：Therefore, according to a third aspect of the present invention, there is provided a composite catalyst for the direct preparation of para-xylene from a synthesis gas, comprising:
A)用于催化合成气转化为甲醇的催化剂A；和A) Catalyst A for catalyzing the conversion of synthesis gas to methanol;
B)用于催化形成二甲苯的催化剂B，该催化剂B为本发明的核壳型催化剂。B) Catalyst B for catalyzing the formation of xylene, which is a core-shell type catalyst of the present invention.
作为催化剂A，它可以是任何能够促进合成气转化为甲醇的催化剂。在本发明的一个优选实施方案中，催化剂A包含第一金属组分和第二金属组分，或者催化剂A由第一金属组分和第二金属组分组成，其中第一金属组分为选自Cr、Fe、Zr、In、Ga、Co、Cu的元素、其氧化物、其复合氧化物或它们的任意混合物，第二金属组分为选自Zn、Na、Al、Ag、Ce、、K、Mn、Pd、Ni、La、V的元素、其氧化物、其复合氧化物或它们的任意混合物。优选的是，第一金属组分为选自Cr、Fe、Co、Zr、Cu的元素、其氧化物、其复合氧化物或它们的任意混合物；和/或，第二金属组分为选自Zn、Al的元素、其氧化物、其复合氧化物或它们的任意混合物。特别优选的是，催化剂A为ZnO-Cr 2O 3。 As Catalyst A, it can be any catalyst capable of promoting the conversion of synthesis gas to methanol. In a preferred embodiment of the invention, 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. Preferably, 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 .
催化剂A可市购获得，或者通过任何常规方法制备，例如顺序浸渍法、共浸渍法、尿素法和共沉淀法，优选共沉淀法。对于包含第一金属组分和第二金属组分的催化剂A，当该催化剂通过前述方法制备时，最后都会涉及将包含第一金属组分和第二金属组分的前体混合物进行焙烧。有利的是，焙烧气氛为空气；和/或，焙烧温度为200-700℃，优选400-600℃；和/或，焙烧时间为3-8h，优选4-6h。Catalyst A is commercially available or can be prepared by any conventional method, such as sequential impregnation, co-impregnation, urea, and coprecipitation, preferably coprecipitation. For the catalyst A comprising the first metal component and the second metal component, when the catalyst is prepared by the aforementioned method, it is finally involved in the calcination of the precursor mixture comprising the first metal component and the second metal component. Advantageously, 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.
以共沉淀法制备作为催化剂A的ZnO-Cr 2O 3为例。为了制备该催化剂，通常将铬、锌各自的硝酸盐前体用去离子水按催化剂A所需的铬/锌比例配成浓度为1mol/L的混合硝酸盐水溶液；将此溶液与1mol/L的碳酸铵水溶液(也可使用其它沉淀剂，比如碳酸钠、氢氧化钠、氢氧化铵)同时滴加到烧杯中进行共沉淀，共沉淀过程中不断搅拌，沉淀温度为50-90℃，pH值控制在6-8之间，这由两种溶液相对添加速度进行控制；加料完毕后，继续搅拌所得沉淀物并于50-90℃下保持60-240分钟以进行老化；过滤老化后的沉淀物并用去离子水洗涤；将洗涤后的产物放入烘箱中在80-120℃下干燥8-12h；再放入马弗炉中于350-550℃下煅烧3-6h，即得ZnO-Cr 2O 3催化剂。 The ZnO-Cr 2 O 3 as the catalyst A was prepared by a coprecipitation method as an example. In order to prepare the catalyst, 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) can also be added dropwise to the beaker for coprecipitation. Stirring during the coprecipitation process, 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.
在本发明复合催化剂的一个优选实施方案中，催化剂A中的第一金属组分和第二金属组分以金属元素计的摩尔比为1000:1-1:100，优选100:1-1:50，更优选为10:1-1:10，特别优选为3:1-1:3。In a preferred embodiment of the composite catalyst of the present invention, 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.
在另一个实施方案中，催化剂A与催化剂B的重量比为1:99-99:1，优选20:80-80:20，更优选为30:70-70:30，特别优选50:50-75:25。In another embodiment, 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.
对本发明而言，复合催化剂可以呈催化剂A与催化剂B的混合物形式，催化剂A物理性或化学性包囊催化剂B的形式，或者催化剂B物理性或化学性包囊催化剂A的形式。For the purposes of the present invention, 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.
根据本发明的第四个方面，提供了一种制备本发明复合催化剂的方法，包括：According to a fourth aspect of the invention, there is provided a method of preparing a composite catalyst of the invention comprising:
1)分别制备催化剂A粉末和催化剂B粉末；和1) separately preparing a catalyst A powder and a catalyst B powder;
2a)将催化剂A粉末与催化剂B粉末和任选的粘合剂混合在一起，然后成型为复合催化剂；2a) mixing the catalyst A powder with the catalyst B powder and the optional binder, and then forming into a composite catalyst;
2b)将催化剂A粉末和催化剂B粉末分别成型，得到催化剂A成型体和催化剂B成型体，然后将这些成型体混合在一起；2b) separately molding the catalyst A powder and the catalyst B powder to obtain a catalyst A molded body and a catalyst B molded body, and then mixing the molded bodies together;
2c)以催化剂A为核、催化剂B为壳形成物理性或化学性包囊形式；或2c) forming a physical or chemical encapsulation form with Catalyst A as the core and Catalyst B as the shell; or
2d)以催化剂B为核、催化剂A为壳形成物理性或化学性包囊形式。2d) Forming physical or chemical encapsulation in the form of catalyst B as the core and catalyst A as the shell.
在本发明中，将催化剂A与催化剂B复合在一起的技术是常规的。催化剂A和催化剂B通常以粉末制得。然后，在方案2a)中，将催化剂A粉末与催化剂B粉末和任选的粘合剂混合在一起，然后成型为复合催化剂。作为粘合剂，可以提及水、氧化铝、氧化硅等。将催化剂A粉末与催化剂B粉末和任选的粘合剂混合在一起，可以将所得粉末混合物成型为片剂、丸粒、颗粒状等形式。在方案2c)中，以催化剂A为核、催化剂B为壳形成物理性或化学性包囊形式，在方案2d)中，以催化剂B为核、催化剂A为壳形成物理性或化学性包囊形式。形成包囊形式的方法是常规的。In the present invention, the technique of compounding catalyst A with catalyst B is conventional. Catalyst A and Catalyst B are usually prepared in powder form. Then, in Scheme 2a), the Catalyst A powder is mixed with the Catalyst B powder and the optional binder and then formed into a composite catalyst. As 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. In Scheme 2c), the catalyst A is used as the core and the catalyst B is in the form of a physical or chemical encapsulation. In the scheme 2d), 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.
例如，1.采用物理包膜法制备催化剂B包囊催化剂A的A@B催化剂：首先将粘合剂液体浸渍在具有一定尺寸的颗粒状催化剂A表面，随后将多余的粘结剂除去，然后将表面湿润状态的催化剂A放入盛有粉末状催化剂B的圆底烧 瓶中，快速有力的旋转圆底烧瓶，保证催化剂A表面全部被催化剂B包覆。此过程可重复2-3次。最后将催化剂干燥过夜，在马弗炉中于350-550℃下煅烧3-6h制得A@B催化剂，其中催化剂A为核，催化剂B为壳。当要制备催化剂A物理包囊催化剂B的B@A催化剂时，将上述方法中的催化剂A和催化剂B对调即可。For example, 1. Preparation of 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. Finally, 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. When the B@A catalyst of the catalyst A physical encapsulation catalyst B is to be prepared, the catalyst A and the catalyst B in the above method may be reversed.
例如，2.采用化学法制备催化剂B包囊催化剂A的A@B催化剂：首先将具有一定尺寸的颗粒状催化剂A与ZSM-5合成液一起进行水热合成，具体操作步骤可参照上文ZSM-5分子筛的制备方法。水热结束后收集得到的A@ZSM-5催化剂。然后将A@ZSM-5催化剂与Silicalite-1分子筛一起进行水热合成。最后水热结束后将催化剂用去离子水冲洗至pH＝7，干燥过夜，在马弗炉中于500-600℃，焙烧4-6h后，得到A@B催化剂，其中催化剂A为核，催化剂B为壳。当要制备催化剂A化学包囊催化剂B的B@A催化剂时，首先采用水热合成的方法制备催化剂B，具体操作步骤可参考上文Zn/HZSM5@S1分子筛的制备方法，然后将颗粒状的催化剂B与催化剂A的前体溶液一起进行水热合成，在220℃的温度下以2-5rmp的旋转速度晶化24-72h。晶化结束后冷却至室温，将所得产物用去离子水洗涤至滤液pH＝7-8，干燥过夜，然后置于马弗炉中以1°-3°/min升温速率升至550-650℃，焙烧4-8h后，得到B@A催化剂，其中催化剂B为核，催化剂A为壳。For example, 2. 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. After the end of the water heat, the catalyst is rinsed with deionized water to pH=7, dried overnight, and calcined in a muffle furnace at 500-600 ° C for 4-6 h to obtain A@B catalyst, wherein the catalyst A is a core, the catalyst B is a shell. When preparing the B@A catalyst of Catalyst A Chemical Encapsulated Catalyst B, 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. Catalyst B was hydrothermally synthesized with the precursor solution of Catalyst A, and crystallized at a rotation speed of 2 to 5 rpm at a temperature of 220 ° C for 24-72 h. After the end of crystallization, it was cooled to room temperature, and the obtained product was washed with deionized water until the filtrate pH=7-8, dried overnight, and then placed in a muffle furnace at a heating rate of 1°-3°/min to 550-650 °C. After calcination for 4-8 h, a B@A catalyst was obtained in which the catalyst B was a core and the catalyst A was a shell.
根据本发明的最后一个方面，提供了本发明核壳催化剂、根据本发明方法制备的核壳催化剂、本发明复合催化剂或者通过本发明方法制备的复合催化剂在由合成气直接制备对二甲苯中作为催化剂的用途。由于使用了本发明的这些催化剂，不仅使得对二甲苯选择性高和合成气的转化率高，而且对二甲苯在二甲苯中的选择性也高，同时保持合成气的高转化率。According to a final aspect of the invention there is provided 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.
在本发明的复合催化剂用于催化合成气制对二甲苯之前，有利的是，将复合催化剂先还原预处理。有利的是，还原预处理的工艺条件如下：还原气为纯氢气；预处理温度为300-700℃，优选为400-600℃；预处理压力为0.1-1MPa，优选为0.1-0.5MPa；预处理氢气体积空速为500-8000h -1，优选为1000-4000h -1；和/或，预处理还原时间为2-10h，优选为4-6h。还原预处理之后，通入合成气 进行反应以转化制得对二甲苯。为此使用的合成气中的氢气与一氧化碳的摩尔比为0.1-5，优选为1-4。反应压力为1-10MPa，优选为2-8MPa。反应温度为150-600℃，优选为250-500℃。空速为200-8000h -1，优选为500-5000h -1。 Before the composite catalyst of the present invention is used to catalyze the synthesis gas to produce para-xylene, it is advantageous to subject the composite catalyst to a reduction pretreatment. Advantageously, 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. After the reduction pretreatment, 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 .
采用本发明的复合催化剂进行合成气的转化，合成气转化率可以达到55％以上，对二甲苯在二甲苯异构体中的选择性可达到70％以上，对二甲苯的选择性比同等条件下明显提高。使用本发明的复合催化剂可将合成气一步转化为对二甲苯，无需经过包含多种不同类型催化剂混合使用的多段反应器，反应流程更为简单，易于操作。在本发明所述催化剂上进行的合成气转化过程，能够得到更高的对二甲苯选择性，同时保持较高的CO转化率。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.
实施例Example
对比例1Comparative example 1
a.Cr/Zn催化剂的制备a. Preparation of Cr/Zn catalyst
将23.6g的Cr(NO 3) 3·9H 2O和9.0g的Zn(NO 3) 2·6H 2O溶于100ml去离子水中。将所得的混合硝酸盐水溶液与1mol/L的(NH 4) 2CO 3水溶液(将9.6g的(NH 4) 2CO 3溶于100ml去离子水中制得)同时滴加到盛有少量去离子水的烧杯中进行共沉淀。共沉淀过程中不断搅拌，在70℃下恒温，pH值保持在7左右，这由两种溶液的相对流速来控制。共沉淀结束后在70℃下静置老化3h。将沉淀物过滤，然后用去离子水洗涤。将洗净的沉淀物在烘箱中于120℃烘12h，再在马弗炉中于400℃下煅烧5h。得甲醇合成催化剂，记为Cr/Zn催化剂，其中以元素计的铬/锌摩尔比为2:1。 23.6 g of Cr(NO 3 ) 3 ·9H 2 O and 9.0 g of Zn(NO 3 ) 2 ·6H 2 O were dissolved in 100 ml of deionized water. The obtained mixed nitrate aqueous solution was added dropwise with a 1 mol/L aqueous solution of (NH 4 ) 2 CO 3 (prepared by dissolving 9.6 g of (NH 4 ) 2 CO 3 in 100 ml of deionized water) with a small amount of deionized Coprecipitation was carried out in a water beaker. Stirring was continued during the coprecipitation, and the temperature was kept constant at 70 ° C, and the pH was maintained at about 7, which was controlled by the relative flow rates of the two solutions. After the completion of the coprecipitation, 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.
b.HZSM-5分子筛的制备b. Preparation of HZSM-5 molecular sieve
将硅源(TEOS)、铝源(Al(NO 3) 3·9H 2O)、有机模板剂(TPAOH)、乙醇和去离子水按摩尔比(2TEOS:0.02Al 2O 3:0.68TPAOH:8EtOH:120H 2O)配制成混合物，室温搅拌6h，得到溶胶。然后将搅拌好的溶胶转移入聚四氟乙烯晶化釜中，尔后密封，在180℃的温度下以2rmp速度旋转晶化24h。晶化结束后冷却至室温，将所得产物用去离子水洗涤至滤液pH＝7，干燥过夜，然后置于马弗炉中以1℃/min升温速率升至550℃，焙烧6h后得到ZSM-5分子筛，为HZSM-5。所述 HZSM-5分子筛中Si/Al摩尔比为46。 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) Prepared as a mixture and stirred at room temperature for 6 h to give a sol. The stirred sol was then transferred to a polytetrafluoroethylene crystallization vessel, sealed, and crystallized at a temperature of 180 ° C for 2 h at 2 rpm. After crystallization, the mixture was cooled to room temperature, and the obtained product was washed with deionized water until the filtrate pH=7, dried overnight, then placed in a muffle furnace at a temperature increase rate of 1 ° C/min to 550 ° C, and calcined for 6 h to obtain ZSM- 5 molecular sieves, HZSM-5. The molar ratio of Si/Al in the HZSM-5 molecular sieve was 46.
c.双功能催化剂的制备c. Preparation of a bifunctional catalyst
将制备的Cr/Zn催化剂和HZSM-5分子筛粉末物理混合，研磨10min，再压片成型，即得到机械混合法制备的双功能催化剂，记为Cr/Zn-HZSM-5，其中Cr/Zn催化剂与HZSM-5分子筛的质量比为2:1。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.
d.催化实验d. Catalytic experiment
将0.5g Cr/Zn-HZSM-5催化剂以固定床形式填充在固定床高压反应器中，连续通入H 2与CO的体积比为2.1的合成气，控制反应压力为5MPa，合成气空速为1200h -1，反应温度为400℃。反应4h后对反应产物和原料气用气相色谱在线分析，反应性能见表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. After 4 hours of reaction, the reaction product and the raw material gas were analyzed by gas chromatography on-line, and the reaction performance is shown in Table 1.
对比例2Comparative example 2
a.Cr/Zn催化剂的制备a. Preparation of Cr/Zn catalyst
重复对比例1中的“Cr/Zn催化剂的制备”，得到Cr/Zn催化剂。The "preparation of Cr/Zn catalyst" in Comparative Example 1 was repeated to obtain a Cr/Zn catalyst.
b.Zn/ZSM-5分子筛的制备b. Preparation of Zn/ZSM-5 molecular sieve
重复对比例1中的“HZSM-5分子筛的制备”，得到HZSM-5分子筛。然后，将1.5g的HZSM-5分子筛加入到1mol/L的硝酸锌水溶液中，在80℃下不断搅拌15h，进行离子交换。离子交换结束后冷却至室温，将所得的产物洗涤至滤液pH＝7-8，干燥过夜，然后置于500℃马弗炉中焙烧，焙烧4h后，得到Zn/ZSM-5分子筛。基于Zn/ZSM-5分子筛的总重量，Zn的含量为1重量％。The "preparation of HZSM-5 molecular sieve" in Comparative Example 1 was repeated to obtain an HZSM-5 molecular sieve. Then, 1.5 g of HZSM-5 molecular sieve was added to a 1 mol/L zinc nitrate aqueous solution, and stirring was continued at 80 ° C for 15 hours to carry out ion exchange. After completion of the ion exchange, the mixture was cooled to room temperature, and the obtained product was washed until the filtrate pH = 7-8, dried overnight, and then calcined in a muffle furnace at 500 ° C, and calcined for 4 hours to obtain a Zn/ZSM-5 molecular sieve. The content of Zn was 1% by weight based on the total weight of the Zn/ZSM-5 molecular sieve.
c.双功能催化剂的制备c. Preparation of a bifunctional catalyst
重复对比例1中的“双功能催化剂的制备”，但是将HZSM-5分子筛替换为Zn/ZSM-5分子筛，即得到机械混合法制备的双功能催化剂，记为Cr/Zn-Zn/ZSM-5催化剂，其中Cr/Zn催化剂与Zn/ZSM-5分子筛的质量比为2:1。The "preparation of the bifunctional catalyst" in Comparative Example 1 was repeated, but the HZSM-5 molecular sieve was replaced with the Zn/ZSM-5 molecular sieve to obtain a bifunctional catalyst prepared by mechanical mixing, which was recorded as Cr/Zn-Zn/ZSM- 5 catalyst, wherein the mass ratio of the Cr/Zn catalyst to the Zn/ZSM-5 molecular sieve is 2:1.
d.催化实验d. Catalytic experiment
重复对比例1中的“催化实验”，但是使用Cr/Zn-Zn/ZSM-5催化剂代替Cr/Zn-HZSM-5催化剂。反应结果见表1。The "catalytic experiment" in Comparative Example 1 was repeated, but a Cr/Zn-Zn/ZSM-5 catalyst was used instead of the Cr/Zn-HZSM-5 catalyst. The reaction results are shown in Table 1.
实施例1Example 1
a.Cr/Zn催化剂的制备a. Preparation of Cr/Zn catalyst
重复对比例1中的“Cr/Zn催化剂的制备”，得到Cr/Zn催化剂。The "preparation of Cr/Zn catalyst" in Comparative Example 1 was repeated to obtain a Cr/Zn catalyst.
b.HZSM-5@S1催化剂的制备b. Preparation of HZSM-5@S1 catalyst
重复对比例1中的“HZSM-5分子筛的制备”，得到HZSM-5分子筛。The "preparation of HZSM-5 molecular sieve" in Comparative Example 1 was repeated to obtain an HZSM-5 molecular sieve.
将硅源(TEOS)、有机模板剂(TPAOH)、乙醇和去离子水按摩尔比(1.0SiO 2:0.06TPAOH:16.0EtOH:240H 2O)配制成混合物，室温搅拌4h，得到Silicalite-1分子筛前体溶液。将上述制备的HZSM-5分子筛粉碎后同所得Silicalite-1分子筛前体溶液一起转移入聚四氟乙烯晶化釜中，尔后密封，在180℃的温度下以2rmp旋转速度晶化24h。晶化结束后冷却至室温，将所得产物用去离子水洗涤至滤液pH＝7，干燥过夜，然后置于马弗炉中以1℃/min升温速率升至550℃，焙烧4h后，得到HZSM-5@Silicalite-1分子筛，记为HZSM-5@S1催化剂，其中HZSM-5分子筛为核，Silicalite-1分子筛为壳，HZSM-5分子筛与Silicalite-1分子筛的重量比为3:1。 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. Precursor solution. 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. After the crystallization was completed, it was cooled to room temperature, and the obtained product was washed with deionized water until the filtrate pH=7, dried overnight, and then placed in a muffle furnace at a heating rate of 1 ° C/min to 550 ° C, and calcined for 4 h to obtain 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.
c.双功能催化剂的制备c. Preparation of a bifunctional catalyst
重复对比例1中的“双功能催化剂的制备”，但是使用HZSM-5@S1催化剂代替HZSM-5分子筛，即得到机械混合法制备的双功能催化剂，记为Cr/Zn-HZSM-5@S1催化剂，其中Cr/Zn催化剂与HZSM-5@S1催化剂的质量比为2:1。The "preparation of the bifunctional catalyst" in Comparative Example 1 was repeated, but the HZSM-5@S1 catalyst was used instead of the HZSM-5 molecular sieve to obtain a bifunctional catalyst prepared by mechanical mixing, which was recorded as Cr/Zn-HZSM-5@S1. A catalyst wherein the mass ratio of the Cr/Zn catalyst to the HZSM-5@S1 catalyst is 2:1.
d.催化实验d. Catalytic experiment
重复对比例1中的“催化实验”，但是使用Cr/Zn-HZSM-5@S1催化剂代替Cr/Zn-HZSM-5催化剂。反应结果见表1。The "catalytic experiment" in Comparative Example 1 was repeated, but the Cr/Zn-HZSM-5@S1 catalyst was used instead of the Cr/Zn-HZSM-5 catalyst. The reaction results are shown in Table 1.
实施例2Example 2
a.Cr/Zn催化剂的制备a. Preparation of Cr/Zn catalyst
重复对比例1中的“Cr/Zn催化剂的制备”，得到Cr/Zn催化剂。The "preparation of Cr/Zn catalyst" in Comparative Example 1 was repeated to obtain a Cr/Zn catalyst.
b.Zn/ZSM-5@S1分子筛的制备b. Preparation of Zn/ZSM-5@S1 molecular sieve
重复对比例2中的“Zn/ZSM-5分子筛的制备”，得到Zn/ZSM-5分子筛。然 后将硅源(TEOS)、有机模板剂(TPAOH)、乙醇和去离子水按摩尔比(1.0SiO 2:0.06TPAOH:16.0EtOH:240H 2O)配制成混合物，室温搅拌4h，得到Silicalite-1分子筛前体溶液。将上述制备的Zn/ZSM-5分子筛粉碎后同所得Silicalite-1分子筛前体溶液一起转移入聚四氟乙烯晶化釜中，尔后密封，在180℃的温度下以2rmp速度旋转晶化24h。晶化结束后冷却至室温，将所得产物用去离子水洗涤至滤液pH＝7，干燥过夜，然后置于马弗炉中以1℃/min升温速率升至550℃，焙烧4h后，得到Zn/ZSM-5@Silicalite-1分子筛，记为Zn/ZSM-5@S1催化剂，其中Zn/ZSM-5分子筛为核，Silicalite-1分子筛为壳，Zn/ZSM-5分子筛与Silicalite-1分子筛的重量比为3:1。 The "preparation of Zn/ZSM-5 molecular sieve" in Comparative Example 2 was repeated to obtain a Zn/ZSM-5 molecular sieve. Then, a silicon source (TEOS), an organic templating agent (TPAOH), ethanol and deionized water molar ratio (1.0 SiO 2 : 0.06 TPAOH: 16.0 EtOH: 240 H 2 O) were mixed into a mixture, and stirred at room temperature for 4 hours to obtain Silicalite-1. Molecular sieve precursor solution. The Zn/ZSM-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 rotated at a temperature of 180 ° C for 2 hours at a rate of 2 rpm. After the crystallization was completed, it was cooled to room temperature, and the obtained product was washed with deionized water until the filtrate pH=7, dried overnight, and then placed in a muffle furnace at a heating rate of 1 ° C/min to 550 ° C, and calcined for 4 h to obtain 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.
图1是该实施例中涉及的Zn/ZSM-5和Zn/ZSM-5@S1的SEM照片，其中图a是Zn/ZSM-5的SEM照片，图b是Zn/ZSM-5@S1的SEM照片。由图1可见，在Silicalite-1分子筛包覆之前，Zn/ZSM-5分子筛的尺寸大小为0.5-1μm，当Silicalite-1分子筛包覆Zn/ZSM-5之后，所得Zn/ZSM-5@S1分子筛的尺寸大小变为1.5-2μm。由此可以得出，Silicalite-1分子筛原位生长在Zn/ZSM-5分子筛核上，形成壳。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 μm 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 μm. 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.
为了进一步直观地表明Zn/ZSM-5@S1分子筛为核壳型结构，为此采用了STEM及EDS面扫图进行证明。In order to further visually show that the Zn/ZSM-5@S1 molecular sieve is a core-shell structure, STEM and EDS surface scans are used to prove this.
图2是实施例2中制备的Zn/ZSM-5@S1分子筛的STEM图和相对应的元素EDS面扫图，当中：a图为Zn/ZSM-5@S1的STEM图，b图为Si元素的图；c图为Al元素的图；d为O元素的图；e为Zn元素的图；f为各个元素的混合图。由图2可见，Zn大部分负载在ZSM-5分子筛上面，因此Zn/ZSM-5@S1分子筛为以Zn/ZSM-5为核、Silicalite-1为壳的核壳型分子筛。2 is a STEM image of the 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.
综上，在Zn/ZSM-5@S1分子筛中，Zn/ZSM-5为核，Silicalite-1分子筛为包覆核的壳。In summary, in Zn/ZSM-5@S1 molecular sieve, Zn/ZSM-5 is the core, and Silicalite-1 molecular sieve is the shell of the coated core.
c.双功能催化剂的制备c. Preparation of a bifunctional catalyst
重复对比例1中的“双功能催化剂的制备”，但是使用Zn/ZSM-5@S1催化剂代替HZSM-5分子筛，即得到机械混合法制备的双功能催化剂，记为Cr/Zn-Zn/ZSM-5@S1，其中Cr/Zn催化剂与Zn/ZSM-5@S1催化剂的质量比为2:1。The "preparation of the bifunctional catalyst" in Comparative Example 1 was repeated, but the Zn/ZSM-5@S1 catalyst was used instead of the HZSM-5 molecular sieve to obtain a bifunctional catalyst prepared by mechanical mixing, which was recorded as Cr/Zn-Zn/ZSM. -5@S1, wherein the mass ratio of the Cr/Zn catalyst to the Zn/ZSM-5@S1 catalyst is 2:1.
d.催化实验d. Catalytic experiment
重复对比例1中的“催化实验”，但是使用Cr/Zn-Zn/ZSM-5@S1代替Cr/Zn-HZSM-5催化剂。反应结果见表1。The "catalytic experiment" in Comparative Example 1 was repeated, but Cr/Zn-Zn/ZSM-5@S1 was used instead of the Cr/Zn-HZSM-5 catalyst. The reaction results are shown in Table 1.
对比例3Comparative example 3
重复对比例1的“催化实验”，但是催化剂仅仅采用其中的Cr/Zn催化剂，不采用分子筛。反应结果见表1。The "catalytic experiment" of Comparative Example 1 was repeated, but the catalyst used only the Cr/Zn catalyst therein, and no molecular sieve was used. The reaction results are shown in Table 1.
对比例4Comparative example 4
a.Cr/Zn催化剂的制备a. Preparation of Cr/Zn catalyst
重复对比例1中的“Cr/Zn催化剂的制备”，得到Cr/Zn催化剂。The "preparation of Cr/Zn catalyst" in Comparative Example 1 was repeated to obtain a Cr/Zn catalyst.
b.β分子筛的制备b. Preparation of β molecular sieve
将硅源(SiO 2)、铝源(异丙醇铝)、有机模板剂(TEAOH)、NaOH和去离子水按摩尔比(1SiO 2:0.023Al 2O 3:0.0425TEAOH:0.049NaOH:6.8H 2O)配制成混合物，室温搅拌6h，得到溶胶。然后将搅拌好的溶胶转移入聚四氟乙烯晶化釜中，尔后密封，在150℃的温度下以2rmp速度旋转晶化时间72h。晶化结束后冷却至室温，将所得产物用去离子水洗涤至滤液pH＝7，干燥过夜，然后置于马弗炉中以1℃/min升温速率升至550℃，焙烧6h后得到β分子筛。所述β分子筛中Si/Al摩尔比为20。 Silicon source (SiO 2 ), aluminum source (isopropoxide aluminum), organic template (TEAOH), NaOH and deionized water molar ratio (1SiO 2 :0.023Al 2 O 3 :0.0425TEAOH:0.049NaOH:6.8H 2 O) A mixture was prepared and stirred at room temperature for 6 h to give a sol. The stirred sol was then transferred to a polytetrafluoroethylene crystallization vessel, and then sealed, and the crystallization time was rotated at a temperature of 150 ° C at a rate of 2 rpm for 72 h. After crystallization, the mixture was cooled to room temperature, and the obtained product was washed with deionized water until the filtrate pH=7, dried overnight, then placed in a muffle furnace at a temperature increase rate of 1 ° C/min to 550 ° C, and calcined for 6 h to obtain a β molecular sieve. . The β molecular sieve has a Si/Al molar ratio of 20.
c.双功能催化剂的制备c. Preparation of a bifunctional catalyst
重复对比例1中的“双功能催化剂的制备”，但是将HZSM-5分子筛替换为β分子筛，即得到机械混合法制备的双功能催化剂，记为Cr/Zn-β催化剂，其中Cr/Zn催化剂与β分子筛的质量比为2:1。The "preparation of the bifunctional catalyst" in Comparative Example 1 was repeated, but the HZSM-5 molecular sieve was replaced with the β molecular sieve to obtain a bifunctional catalyst prepared by mechanical mixing, which was recorded as a Cr/Zn-β catalyst, wherein the Cr/Zn catalyst The mass ratio to the beta molecular sieve is 2:1.
d.催化实验d. Catalytic experiment
重复对比例1中的“催化实验”，但是使用Cr/Zn-β催化剂代替Cr/Zn-HZSM-5催化剂。反应结果见表1。The "catalytic experiment" in Comparative Example 1 was repeated, but a Cr/Zn-β catalyst was used instead of the Cr/Zn-HZSM-5 catalyst. The reaction results are shown in Table 1.
对比例5Comparative example 5
b.HZSM-5&S1物理混合催化剂的制备b. Preparation of HZSM-5&S1 physical mixed catalyst
重复实施例1中的“HZSM-5@S1催化剂的制备”，但是将HZSM-5分子筛和Silicalite-1分子筛物理混合，即得到双功能催化剂，记为HZSM-5&S1催化剂，其中HZSM-5分子筛与Silicalite-1分子筛的重量比为3:1。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.
c.双功能催化剂的制备c. Preparation of a bifunctional catalyst
重复对比例1中的“双功能催化剂的制备”，但是使用HZSM-5&S1催化剂代替HZSM-5分子筛，即得到机械混合法制备的双功能催化剂，记为Cr/Zn-HZSM-5&S1物理混合催化剂，其中Cr/Zn催化剂与HZSM-5&S1催化剂的质量比为2:1。The "preparation of the bifunctional catalyst" in Comparative Example 1 was repeated, but the HZSM-5 & S1 catalyst was used instead of the HZSM-5 molecular sieve to obtain a bifunctional catalyst prepared by mechanical mixing, which was recorded as a Cr/Zn-HZSM-5 & S1 physical mixed catalyst. The mass ratio of the Cr/Zn catalyst to the HZSM-5&S1 catalyst is 2:1.
d.催化实验d. Catalytic experiment
重复实施例1中的“催化实验”，但是使用Cr/Zn-HZSM-5&S1催化剂代Cr/Zn-HZSM-5催化剂。反应结果见表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.
对比例6Comparative example 6
重复实施例2中的“Cr/Zn催化剂的制备”和“Zn/ZSM-5@S1分子筛”的制备，分别得到Cr/Zn催化剂和Zn/ZSM-5@S1催化剂。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.
重复实施例2中的“催化实验”，但是将Cr/Zn催化剂和Zn/ZSM-5@S1催化剂不混合在一起，而是将这两种催化剂各自以固定床形式分开固定在固定床高压反应器的两段中，中间用石英棉隔开，其中沿着气体料流方向，Cr/Zn催化剂段在前，Zn/ZSM-5@S1催化剂段在后。反应结果见表1。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.
实施例3Example 3
a.Fe/Zn/Cu催化剂的制备a. Preparation of Fe/Zn/Cu catalyst
将9.0g的Fe(NO 3) 3·9H 2O、3.8g的Zn(NO 3) 2·6H 2O和1.3g的Cu(NO 3) 2·3H 2O溶于200mL去离子水中得到含铁锌铜的混合水溶液。取10.0g的Na 2CO 3溶于100mL去离子水中得到碳酸钠水溶液。将这两种溶液同时滴加在盛有少量去离子水的烧杯中进行共沉淀。共沉淀过程中不断搅拌，并保持温度在85℃，pH＝8-8.5，这由两种溶液的相对流速来控制。沉淀结束后在85℃下静置老化2h。将 沉淀物过滤，然后用去离子水洗涤。将洗净的沉淀物在烘箱中于120℃烘12h，再在马弗炉中于320℃下焙烧5小时，得到甲醇合成催化剂，记为Fe/Zn/Cu催化剂。该催化剂中的金属以元素计的摩尔比为：Fe/Zn/Cu＝55∶32∶13。 9.0 g of Fe(NO 3 ) 3 ·9H 2 O, 3.8 g of Zn(NO 3 ) 2 ·6H 2 O and 1.3 g of Cu(NO 3 ) 2 ·3H 2 O were dissolved in 200 mL of deionized water to obtain A mixed aqueous solution of iron, zinc and copper. 10.0 g of Na 2 CO 3 was dissolved in 100 mL of deionized water to obtain an aqueous sodium carbonate solution. The two solutions were simultaneously added dropwise to a co-precipitate in a beaker containing a small amount of deionized water. Stirring was continued during the coprecipitation and the temperature was maintained at 85 ° C, pH = 8-8.5, which was controlled by the relative flow rates of the two solutions. After the end of the precipitation, the mixture was allowed to stand at 85 ° C for 2 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 further calcined in a muffle furnace at 320 ° C for 5 hours to obtain a methanol synthesis catalyst, which was designated as Fe/Zn/Cu catalyst. The molar ratio of the metal in the catalyst to the element is: Fe/Zn/Cu = 55:32:13.
b.Zn/ZSM-5@S1分子筛的制备b. Preparation of Zn/ZSM-5@S1 molecular sieve
重复实施例2中的“Zn/ZSM-5@S1分子筛的制备”，得到Zn/ZSM-5@S1分子筛。The "preparation of Zn/ZSM-5@S1 molecular sieve" in Example 2 was repeated to obtain a Zn/ZSM-5@S1 molecular sieve.
c.双功能催化剂的制备c. Preparation of a bifunctional catalyst
将制备的Fe/Zn/Cu催化剂和Zn/ZSM-5@S1分子筛粉末物理混合，研磨10min，再压片成型，即得到机械混合法制备的双功能催化剂，记为Fe/Zn/Cu-Zn/ZSM-5@S1，其中Fe/Zn/Cu催化剂与Zn/ZSM-5@S1分子筛的质量比为2:1。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.
d.催化实验d. Catalytic experiment
重复实施例2中的“催化实验”，但是使用Fe/Zn/Cu-Zn/ZSM-5@S1催化剂代Cr/Zn-Zn/ZSM-5@S1催化剂。反应结果见表1。The "catalytic experiment" in Example 2 was repeated, but the Fe/Zn/Cu-Zn/ZSM-5@S1 catalyst was used to replace the Cr/Zn-Zn/ZSM-5@S1 catalyst. The reaction results are shown in Table 1.
实施例4Example 4
a.Zr/Zn催化剂的制备a. Preparation of Zr/Zn catalyst
用1mol/L的硝酸锌水溶液浸渍2.0g的ZrO 2，随后在120℃温度下干燥过夜，然后置于400℃马弗炉中焙烧，焙烧3h后得到ZrO 2-ZnO催化剂，记为Zr/Zn催化剂，其中以元素计的锆/锌摩尔比为13.5:1。 2.0 g of ZrO 2 was impregnated with a 1 mol/L zinc nitrate aqueous solution, followed by drying at 120 ° C overnight, and then calcined in a 400 ° C muffle furnace, and calcined for 3 h to obtain a ZrO 2 -ZnO catalyst, which was designated as Zr/Zn. A catalyst in which the zirconium/zinc molar ratio in terms of the element is 13.5:1.
b.Zn/ZSM-5@S1分子筛的制备b. Preparation of Zn/ZSM-5@S1 molecular sieve
重复实施例2中的“Zn/ZSM-5@S1分子筛的制备”，得到Zn/ZSM-5@S1分子筛。The "preparation of Zn/ZSM-5@S1 molecular sieve" in Example 2 was repeated to obtain a Zn/ZSM-5@S1 molecular sieve.
c.双功能催化剂的制备c. Preparation of a bifunctional catalyst
将制备的Zr/Zn催化剂和Zn/ZSM-5@S1分子筛粉末物理混合，研磨10min,再压片成型，即得到机械混合法制备的双功能催化剂，记为Zr/Zn-Zn/ZSM-5@S1,其中Zr/Zn催化剂与Zn/ZSM-5@S1分子筛的质量比为2:1。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.
d.催化实验d. Catalytic experiment
重复实施例2中的“催化实验”，但是使用Zr/Zn-Zn/ZSM-5@S1催化剂代Cr/Zn-Zn/ZSM-5@S1催化剂。反应结果见表1。The "catalytic experiment" in Example 2 was repeated, but the Cr/Zn-Zn/ZSM-5@S1 catalyst was substituted using Zr/Zn-Zn/ZSM-5@S1 catalyst. The reaction results are shown in Table 1.
实施例5Example 5
a.Cr/Zn/Al催化剂的制备a. Preparation of Cr/Zn/Al catalyst
将23.6g的Cr(NO 3) 3·9H 2O，9.0g的Zn(NO 3) 2·6H 2O和5.4g的Al(NO 3) 3·9H 2O溶于100ml去离子水。后续共沉淀方法与对比例1中的“Cr/Zn催化剂的制备”相同，得到Cr/Zn/Al催化剂，其中以元素记的Cr/Zn/Al摩尔比为:4:2:1。 23.6 g of Cr(NO 3 ) 3· 9H 2 O, 9.0 g of Zn(NO 3 ) 2· 6H 2 O and 5.4 g of Al(NO 3 ) 3· 9H 2 O were dissolved in 100 ml of deionized water. The subsequent coprecipitation method was the same as the "preparation of Cr/Zn catalyst" in Comparative Example 1, to obtain a Cr/Zn/Al catalyst in which the molar ratio of Cr/Zn/Al in the element was: 4:2:1.
b.Zn/ZSM-5@S1分子筛的制备b. Preparation of Zn/ZSM-5@S1 molecular sieve
重复实施例2中的“Zn/ZSM-5@S1分子筛的制备”，得到Zn/ZSM-5@S1分子筛。The "preparation of Zn/ZSM-5@S1 molecular sieve" in Example 2 was repeated to obtain a Zn/ZSM-5@S1 molecular sieve.
c.双功能催化剂的制备c. Preparation of a bifunctional catalyst
将制备的Cr/Zn/Al催化剂和Zn/ZSM-5@S1分子筛粉末物理混合，研磨10min,再压片成型，即得到机械混合法制备的双功能催化剂，记为Cr/Zn/Al-Zn/ZSM-5@S1,其中Cr/Zn/Al催化剂与Zn/ZSM-5@S1分子筛的质量比为3:1。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.
d.催化实验d. Catalytic experiment
重复实施例2中的“催化实验”，但是使用Cr/Zn/Al-Zn/ZSM-5@S1催化剂代Cr/Zn-Zn/ZSM-5@S1催化剂。反应结果见表1。The "catalytic experiment" in Example 2 was repeated, but the Cr/Zn/Al-Zn/ZSM-5@S1 catalyst was used to replace the Cr/Zn-Zn/ZSM-5@S1 catalyst. The reaction results are shown in Table 1.
实施例6Example 6
a.Cr/Zn催化剂的制备a. Preparation of Cr/Zn catalyst
重复对比例1中的“Cr/Zn催化剂的制备”，得到Cr/Zn催化剂。The "preparation of Cr/Zn catalyst" in Comparative Example 1 was repeated to obtain a Cr/Zn catalyst.
b.Ag/ZSM-5@S1分子筛的制备b. Preparation of Ag/ZSM-5@S1 molecular sieve
重复对比例1中的“HZSM-5分子筛的制备”，得到HZSM-5分子筛。然后，将1.5g的HZSM-5分子筛加入到1mol/L的硝酸银水溶液中，在80℃下不断搅拌15h，进行离子交换。离子交换结束后冷却至室温，将所得的产物洗涤至滤液pH＝7-8，干燥过夜，然后置于500℃马弗炉中焙烧，焙烧4h后，得到Ag/ZSM-5 分子筛。基于Ag/ZSM-5分子筛的总重量，Ag的含量为重量1％。The "preparation of HZSM-5 molecular sieve" in Comparative Example 1 was repeated to obtain an HZSM-5 molecular sieve. Then, 1.5 g of HZSM-5 molecular sieve was added to a 1 mol/L aqueous solution of silver nitrate, and stirring was continued at 80 ° C for 15 hours to carry out ion exchange. After the end of the ion exchange, the mixture was cooled to room temperature, and the obtained product was washed until the filtrate pH = 7-8, dried overnight, and then calcined in a muffle furnace at 500 ° C, and calcined for 4 hours to obtain Ag/ZSM-5 molecular sieve. The content of Ag was 1% by weight based on the total weight of the Ag/ZSM-5 molecular sieve.
重复实施例1中的“HZSM-5@S1催化剂的制备”，但是使用Ag/ZSM-5代替HZSM-5分子筛。得到Ag/ZSM-5@Silicalite-1分子筛，记为Ag/ZSM-5@S1催化剂，其中Ag/ZSM-5分子筛为核，Silicalite-1分子筛为壳，Ag/ZSM-5分子筛与Silicalite-1分子筛的重量比为3:1。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.
c.双功能催化剂的制备c. Preparation of a bifunctional catalyst
将制备的Cr/Zn催化剂和Ag/ZSM-5@S1分子筛粉末物理混合，研磨10min，再压片成型，即得到机械混合法制备的双功能催化剂，记为Cr/Zn-Ag/ZSM-5@S1，其中Cr/Zn催化剂与Ag/ZSM-5@S1分子筛的质量比为1:1。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.
d.催化实验d. Catalytic experiment
重复实施例2中的“催化实验”，但是使用Cr/Zn-Ag/ZSM-5@S1催化剂代Cr/Zn-Zn/ZSM-5@S1催化剂。反应结果见表1。The "catalytic experiment" in Example 2 was repeated, but the Cr/Zn-Ag/ZSM-5@S1 catalyst was used to replace the Cr/Zn-Zn/ZSM-5@S1 catalyst. The reaction results are shown in Table 1.
实施例7Example 7
a.Cr/Zn催化剂的制备a. Preparation of Cr/Zn catalyst
重复对比例1中的“Cr/Zn催化剂的制备”相同，得到Cr/Zn催化剂。The same procedure as in the preparation of "Cr/Zn catalyst" in Comparative Example 1 was repeated to obtain a Cr/Zn catalyst.
b.HZSM-5@MgO催化剂的制备b. Preparation of HZSM-5@MgO catalyst
重复对比例1中的“HZSM-5分子筛的制备”，得到HZSM-5分子筛。用1mol/L的硝酸镁水溶液浸渍2.0g的HZSM-5分子筛，随后在120℃温度下干燥过夜，然后置于500℃马弗炉中焙烧，焙烧4h后得到HZSM-5@MgO分子筛，记为HZSM-5@MgO，其中HZSM-5分子筛为核，MgO为壳。基于HZSM-5@MgO分子筛的总重量，MgO的含量为重量1％。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.
c.双功能催化剂的制备c. Preparation of a bifunctional catalyst
将制备的Cr/Zn催化剂和HZSM-5@MgO催化剂粉末物理混合，研磨10min，再压片成型，即得到机械混合法制备的双功能催化剂，记为Cr/Zn-HZSM-5@MgO，其中Cr/Zn催化剂与HZSM-5@MgO催化剂的质量比为2:1。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.
d.催化实验d. Catalytic experiment
将0.5g Cr/Zn-HZSM-5@MgO催化剂以固定床形式填充在固定床高压反应器中，连续通入H 2与CO的体积比为2.1的合成气，控制反应压力为3MPa，合成气空速为1200h -1，反应温度为400℃。反应4h后对反应产物和原料气用气相色谱在线分析，反应性能见表1。 0.5g of Cr/Zn-HZSM-5@MgO 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 3 MPa. The space velocity is 1200 h -1 and the reaction temperature is 400 °C. After 4 hours of reaction, the reaction product and the raw material gas were analyzed by gas chromatography on-line, and the reaction performance is shown in Table 1.
实施例8Example 8
a.Cr/Zn催化剂的制备a. Preparation of Cr/Zn catalyst
重复对比例1中的“Cr/Zn催化剂的制备”相同，得到Cr/Zn催化剂。The same procedure as in the preparation of "Cr/Zn catalyst" in Comparative Example 1 was repeated to obtain a Cr/Zn catalyst.
b.HZSM-5@SiO 2分子筛的制备 b. Preparation of HZSM- 5 @SiO 2 molecular sieve
重复对比例1中的“HZSM-5分子筛的制备”，得到HZSM-5分子筛。采用
Figure PCTCN2018107966-appb-000004
方法制备SiO 2膜，将1.0g的HZSM-5分子筛、5-10μL的TEOS和15ml的乙醇放于20ml的烧杯中，随后滴加2.3ml的25重量％氨水溶液，然后搅拌2h。反应结束后，将所得的产物用乙醇洗涤直至滤液pH＝7，干燥过夜，然后置于500℃马弗炉中焙烧，焙烧4h后得到HZSM-5@SiO 2催化剂,记为HZSM-5@SiO 2。为了使SiO 2膜包覆均匀，此体系可以进行2-3次。最终，基于HZSM-5@SiO 2分子筛的总重量，SiO 2的含量为1重量％。 The "preparation of HZSM-5 molecular sieve" in Comparative Example 1 was repeated to obtain an HZSM-5 molecular sieve. use
Figure PCTCN2018107966-appb-000004
Method A SiO 2 film was prepared, and 1.0 g of HZSM-5 molecular sieve, 5-10 μL of TEOS and 15 ml of ethanol were placed in a 20 ml beaker, followed by dropwise addition of 2.3 ml of a 25 wt% aqueous ammonia solution, followed by stirring for 2 h. After completion of the reaction, the obtained product was washed with ethanol until the filtrate pH=7, dried overnight, and then calcined in a muffle furnace at 500 ° C, and calcined for 4 h to obtain HZSM-5@SiO 2 catalyst, which was designated as HZSM-5@SiO. 2 . In order to coat the SiO 2 film uniformly, the system can be carried out 2-3 times. Finally, the content of SiO 2 was 1% by weight based on the total weight of the HZSM-5@SiO 2 molecular sieve.
c.双功能催化剂的制备c. Preparation of a bifunctional catalyst
将制备的Cr/Zn催化剂和HZSM-5@SiO 2催化剂粉末物理混合，研磨10min，再压片成型，即得到机械混合法制备的双功能催化剂，记为Cr/Zn-HZSM-5@SiO 2，其中Cr/Zn催化剂与HZSM-5@SiO 2催化剂的质量比为2:1。 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 . Wherein the mass ratio of the Cr/Zn catalyst to the HZSM-5@SiO 2 catalyst is 2:1.
d.催化实验d. Catalytic experiment
重复实施例2中的“催化实验”，但是使用Cr/Zn-HZSM-5@SiO 2催化剂代Cr/Zn-Zn/ZSM-5@S1催化剂。反应结果见表1。 The "catalytic experiment" in Example 2 was repeated, but the Cr/Zn-HZSM-5@SiO 2 catalyst was used to replace the Cr/Zn-Zn/ZSM-5@S1 catalyst. The reaction results are shown in Table 1.
对比例7Comparative example 7
重复实施例3的“催化实验”，但是催化剂仅仅采用其中的Fe/Zn/Cu催化剂，不采用分子筛。反应结果见表1。The "catalytic experiment" of Example 3 was repeated, but the catalyst used only the Fe/Zn/Cu catalyst therein, and no molecular sieve was used. The reaction results are shown in Table 1.
对比例8Comparative example 8
重复实施例4的“催化实验”，但是催化剂仅仅采用其中的Zr/Zn催化剂，不采用分子筛。反应结果见表1。The "catalytic experiment" of Example 4 was repeated, but the catalyst used only the Zr/Zn catalyst therein, and no molecular sieve was used. The reaction results are shown in Table 1.
表1Table 1
Figure PCTCN2018107966-appb-000005
Figure PCTCN2018107966-appb-000005
注：Note:
MeOH：甲醇MeOH: methanol
DME：二甲醚DME: dimethyl ether
C 2-C 5：C 2-C 5烃 C 2 -C 5 :C 2 -C 5 hydrocarbon
其余：所有其余产物The rest: all the rest of the product
MX：间二甲苯MX: m-xylene
OX:邻二甲苯OX: o-xylene
PX:对二甲苯PX: p-xylene
PX/X:对二甲苯在二甲苯中的选择性PX/X: Selectivity of p-xylene in xylene

Claims (13)

  1. 一种核壳型催化剂，其中核为H型ZSM-5分子筛，H型ZSM-5分子筛中的H全部或部分被一种或多种选自Sn、Ga、Ti、Zn、Mg、Li、Ce、Co、La、Rh、Pd、Pt、Ni、Cu、K、Ca、Ba、Fe、Mn和B的元素M替换的改性ZSM-5分子筛或者它们的任意混合物，壳为选自碳膜、Silicalite-1、MCM-41、SBA-15、KIT-6、MSU系列、二氧化硅、石墨烯、碳纳米管、金属有机框架MOF、石墨、活性炭、金属氧化物膜(如MgO、P 2O 5、CaO)中的一种或多种。 A core-shell type catalyst in which 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 one or more selected from the group consisting of Sn, Ga, Ti, Zn, Mg, Li, Ce a modified ZSM-5 molecular sieve substituted with an element M of Co, La, Rh, Pd, Pt, Ni, Cu, K, Ca, Ba, Fe, Mn, and B, or any mixture thereof, the shell being selected from the group consisting of carbon films, 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 2 O One or more of 5 , CaO).
  2. 根据权利要求1的核壳型催化剂，其中核为H型ZSM-5分子筛，H型ZSM-5分子筛中的H部分或全部被Zn替换的改性ZSM-5分子筛或它们的任意混合物；和/或，壳为选自二氧化硅膜、Silicalite-1、金属氧化物膜(如MgO、P 2O 5、CaO)、MCM-41、SBA-15、KIT-6中的一种或多种，优选为Silicalite-1；特别优选的是，在元素M改性的M-ZSM-5分子筛中，元素M占M-ZSM-5分子筛总重量的0.5-15重量％，优选1-10重量％，特别优选1-5重量％。 The core-shell type catalyst according to claim 1, wherein the core is a H-type ZSM-5 molecular sieve, a modified ZSM-5 molecular sieve partially or wholly replaced by Zn in the H-type ZSM-5 molecular sieve, or any mixture thereof; and / Or the shell is one or more selected from the group consisting of a silica film, Silicalite-1, a metal oxide film (such as MgO, P 2 O 5 , CaO), MCM-41, SBA-15, and KIT-6. Preferred is Silicalite-1; it is particularly preferred that in the element M modified M-ZSM-5 molecular sieve, the element M 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, It is particularly preferably from 1 to 5% by weight.
  3. 根据权利要求1或2的核壳型催化剂，其中核与壳的重量比为100:1-1:100，优选为10:1-1:10，更优选为5:1-1:5，特别优选5:1-1:1。The core-shell type catalyst according to claim 1 or 2, wherein the weight ratio of the core to the shell is from 100:1 to 1:100, preferably from 10:1 to 1:10, more preferably from 5:1 to 1:5, particularly Preferably 5:1-1:1.
  4. 一种制备根据权利要求1-3中任一项的核壳型催化剂的方法，包括：A method of preparing a core-shell type catalyst according to any one of claims 1 to 3, comprising:
    1)提供呈颗粒形式的核，其为H型ZSM-5分子筛，H型ZSM-5分子筛中的H全部或部分被一种或多种选自Sn、Ga、Ti、Zn、Mg、Li、Ce、Co、La、Rh、Pd、Pt、Ni、Cu、Na、K、Ca、Ba、Fe、Mn和B的元素M替换的改性ZSM-5分子筛或者它们的任意混合物；以及1) providing 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;
    2)将选自碳膜、Silicalite-1、MCM-41、SBA-15、KIT-6、MSU系列、二氧化硅、石墨烯、碳纳米管、金属有机框架MOF、石墨、活性炭、金属氧化物膜(如MgO、P 2O 5、CaO)中的一种或多种材料包覆在呈颗粒形式的核表面上。 2) Will be 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, metal oxide One or more of the films (e.g., MgO, P 2 O 5 , CaO) are coated on the surface of the core in the form of particles.
  5. 一种用于由合成气直接制备对二甲苯的复合催化剂，其包含：A composite catalyst for the direct preparation of para-xylene from syngas, comprising:
    A)用于催化合成气转化为甲醇的催化剂A；和A) Catalyst A for catalyzing the conversion of synthesis gas to methanol;
    B)用于催化形成二甲苯的催化剂B，该催化剂B为如权利要求1-3中任一项的核壳型催化剂，B) Catalyst B for catalyzing the formation of xylene, the catalyst B being a core-shell type catalyst according to any one of claims 1 to 3,
    优选的是，复合催化剂呈催化剂A与催化剂B的混合物形式，催化剂A物理性或化学性包囊催化剂B的形式，或者催化剂B物理性或化学性包囊催化剂A的形式。Preferably, 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.
  6. 根据权利要求5的复合催化剂，其中催化剂A包含第一金属组分和第二金属组分或者由第一金属组分和第二金属组分组成，第一金属组分为选自Cr、Fe、Zr、In、Ga、Co、Cu的元素、其氧化物、其复合氧化物或它们的任意混合物，第二金属组分为选自Zn、Na、Al、Ag、Ce、K、Mn、Pd、Ni、La、V的元素、其氧化物、其复合氧化物或它们的任意混合物；优选的是，第一金属组分为选自Cr、Co、Cu、Zr的元素、其氧化物、其复合氧化物或它们的任意混合物；和/或，第二金属组分为选自Zn、Al的元素、其氧化物、其复合氧化物或它们的任意混合物；特别优选催化剂A是ZnO-Cr 2O 3。 The composite catalyst according to claim 5, wherein 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, Fe, An element of 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, Pd, An element of 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, and a composite thereof An oxide 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; and particularly preferably the catalyst A is ZnO-Cr 2 O 3 .
  7. 根据权利要求5或6的复合催化剂，其中催化剂A中的第一金属组分与第二金属组分以金属元素计的摩尔比为1000:1-1:100，优选100:1-1:50,更优选为10:1-1:10，特别优选为3:1-1:3。The composite catalyst according to claim 5 or 6, wherein the molar ratio of the first metal component to the second metal component in the catalyst A in terms of the metal element is from 1000:1 to 1:100, preferably from 100:1 to 1:50. More preferably, it is 10:1-1:10, and it is especially preferable that it is 3:1-1:3.
  8. 根据权利要求5-7中任一项的复合催化剂，其中催化剂A与催化剂B的重量比为1:99-99:1，优选20:80-80:20，更优选为30:70-70:30，特别优选50:50-75:25。The composite catalyst according to any one of claims 5 to 7, wherein the weight ratio of the catalyst A to the 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.
  9. 一种制备根据权利要求5-8中任一项的复合催化剂的方法，包括：A method of preparing a composite catalyst according to any one of claims 5-8, comprising:
    1)分别制备催化剂A粉末和催化剂B粉末；和1) separately preparing a catalyst A powder and a catalyst B powder;
    2a)将催化剂A粉末与催化剂B粉末和任选的粘合剂混合在一起，然后成型为复合催化剂；2a) mixing the catalyst A powder with the catalyst B powder and the optional binder, and then forming into a composite catalyst;
    2b)将催化剂A粉末和催化剂B粉末分别成型，得到催化剂A成型体和催化剂B成型体，然后将这些成型体混合在一起；2b) separately molding the catalyst A powder and the catalyst B powder to obtain a catalyst A molded body and a catalyst B molded body, and then mixing the molded bodies together;
    2c)以催化剂A为核、催化剂B为壳形成物理性或化学性包囊形式；或2c) forming a physical or chemical encapsulation form with Catalyst A as the core and Catalyst B as the shell; or
    2d)以催化剂B为核、催化剂A为壳形成物理性或化学性包囊形式。2d) Forming physical or chemical encapsulation in the form of catalyst B as the core and catalyst A as the shell.
  10. 根据权利要求9的方法，其中催化剂A通过选自顺序浸渍法、共浸渍法、尿素法和共沉淀法中的任何一种或多种制备；优选的是，在顺序浸渍法、共浸渍法、尿素法和/或共沉淀法制催化剂A的焙烧工艺中，工艺条件如下：The method according to claim 9, wherein 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, the co-impregnation method, In the roasting process of the catalyst A by the urea method and/or the coprecipitation method, the process conditions are as follows:
    焙烧气氛为空气；和/或，The firing atmosphere is air; and/or,
    焙烧温度为200-700℃，优选400-600℃；和/或The calcination temperature is 200-700 ° C, preferably 400-600 ° C; and / or
    焙烧时间为3-8h，优选4-6h。The calcination time is from 3 to 8 h, preferably from 4 to 6 h.
  11. 根据权利要求1-3中任一项的核壳催化剂、根据权利要求4的方法制备的核壳催化剂、根据权利要求5-8中任一项的复合催化剂或者通过根据权利要求9-10中任一项的方法制备的复合催化剂在由合成气直接制备对二甲苯中作为催化剂的用途。A core-shell catalyst according to any one of claims 1 to 3, a core-shell catalyst prepared according to the process of claim 4, a composite catalyst according to any one of claims 5-8 or by any of claims 9-10 The composite catalyst prepared by the method of the invention is used as a catalyst in the direct preparation of p-xylene from synthesis gas.
  12. 根据权利要求11的用途，其中合成气中的氢气与一氧化碳的摩尔比为0.1-5，优选为1-4；反应压力为1-10MPa，优选为2-8MPa；反应温度为150-600℃，优选为250-500℃；和/或，空速为200-8000h -1，优选为500-5000h -1。 The use according to claim 11, wherein the molar ratio of hydrogen to carbon monoxide in the synthesis gas is from 0.1 to 5, preferably from 1 to 4; the reaction pressure is from 1 to 10 MPa, preferably from 2 to 8 MPa; and the reaction temperature is from 150 to 600 ° C. Preferably, it is from 250 to 500 ° C; and/or, the space velocity is from 200 to 8000 h -1 , preferably from 500 to 5000 h -1 .
  13. 根据权利要求12的用途，其中在通入合成气反应之前，将复合催化剂先还原预处理，优选还原预处理的工艺条件下如下：The use according to claim 12, wherein the composite catalyst is first subjected to a reduction pretreatment prior to the introduction of the synthesis gas, preferably under the conditions of the reduction pretreatment:
    还原气为纯氢气；The reducing gas is pure hydrogen;
    预处理温度为300-700℃，优选为400-600℃；The pretreatment temperature is 300-700 ° C, preferably 400-600 ° C;
    预处理压力为0.1-1MPa，优选为0.1-0.5MPa；The pretreatment pressure is 0.1-1 MPa, preferably 0.1-0.5 MPa;
    预处理氢气体积空速为500-8000h -1，优选为1000-4000h -1；和/或 The pretreatment hydrogen gas volume velocity is 500-8000 h -1 , preferably 1000-4000 h -1 ; and/or
    预处理还原时间为2-10h，优选为4-6h。The pretreatment reduction time is 2-10 h, preferably 4-6 h.
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