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CN-122006721-A - Coral copper zinc aluminum catalyst, preparation method and application thereof, and methanol preparation method

CN122006721ACN 122006721 ACN122006721 ACN 122006721ACN-122006721-A

Abstract

The invention relates to a coralloid copper-zinc-aluminum catalyst, a preparation method and application thereof, and a methanol preparation method, the catalyst comprises copper, zinc and aluminum, the microcosmic appearance of the catalyst is coral-shaped formed by thin nano rods, and can effectively reduce the temperature in the conversion process of the synthesis gas, reduce the generation of byproducts and improve the raw material conversion rate and the methanol selectivity when being applied to synthesizing the methanol from the synthesis gas. The catalyst of the invention can be used for synthesizing methanol at low temperature with high conversion rate and high selectivity by catalytic conversion.

Inventors

  • LV JIANGANG
  • SHAO YI
  • LIU BO
  • JIN PING
  • ZHOU HAICHUN
  • CHEN LONG

Assignees

  • 中国石油化工股份有限公司
  • 中石化（上海）石油化工研究院有限公司

Dates

Publication Date
20260512
Application Date
20241111

Claims (10)

  1. 1. A coral-shaped Cu-Zn-Al catalyst is characterized in that the constituent elements of the catalyst comprise Cu, zn and Al, and the microscopic morphology of the catalyst is coral-shaped formed by thin-sheet nanorods.
  2. 2. The catalyst according to claim 1, wherein the catalyst, The thin nano-rods have a width of 30-40nm, and/or Specific surface area of 85-110m 2 /g, and/or The molar ratio of aluminum to zinc is 0.3-1, and/or Copper in an amount of 50 to 70 wt.%, preferably 54 to 64 wt.%, based on the total weight of the catalyst, copper in an amount of 30 to 50 wt.%, preferably 35 to 46 wt.%, based on the total weight of the catalyst, aluminum in an amount of 30 to 50 wt.%, and zinc in an amount of 35 to 46 wt.%, and/or When the catalyst is stored, one or more of copper, zinc and aluminum exist in the form of oxide, preferably copper, zinc and aluminum exist in the form of oxide, and/or When the catalyst is used, copper exists in a reduced form, and the rest exists in an oxide form.
  3. 3. Catalyst according to claim 1 or 2, wherein the constituent elements of the catalyst further comprise a metallic M element selected from one or more of zirconium, tin, lead, lanthanum, cerium, preferably lanthanum and/or cerium; preferably, the metal M element is present in an amount of 0.01 to 20wt%, preferably 1 to 5wt%, calculated as oxide, based on the total weight of the catalyst; preferably, the metal element M is present in the form of an oxide during the storage of the catalyst, and/or When the catalyst is used, the metal element M exists in the form of oxide.
  4. 4. A process for preparing Cu-Zn-Al catalyst includes such steps as contact between Cu source, al source and Zn source under pressure, co-depositing, drying and calcining to obtain solid, and features high purity, high purity and no environmental pollution.
  5. 5. The preparation method according to claim 4, wherein, The pressure is 1-3MPa; And/or The conditions for coprecipitation include: the temperature is 50-80 ℃, and/or the time is 0.5-2h, and/or the pH value of the material after the coprecipitation is 6-8, and/or the process is carried out in a dynamic environment; And/or The drying conditions include a temperature of 60-80deg.C and/or a time of 12-36 hr; And/or The roasting conditions include a temperature of 290-330 ℃ and/or a time of 2-6 hours.
  6. 6. The process according to claim 4 or 5, wherein the copper source, the aluminum source and the zinc source are used in such an amount that the molar ratio of aluminum to zinc is 0.3 to 1 and/or the copper content is 50 to 70wt%, preferably 54 to 64wt%, calculated as oxide, based on the total weight of the catalyst, and the total content of aluminum and zinc calculated as oxide is 30 to 50wt%, preferably 35 to 46wt%; And/or The contacting is performed in the presence of a source of a metal M selected from one or more of zirconium, tin, lead, lanthanum, cerium, preferably lanthanum and/or cerium; preferably, the metal M source is used in such an amount that the metal M element is present in an amount of 0.01 to 20wt%, preferably 1 to 5wt%, calculated as oxide, based on the total weight of the catalyst.
  7. 7. The process according to any one of claim 4 to 6, wherein, The copper source is one or more selected from copper sulfate, copper chloride, copper nitrate, copper acetate, copper oxalate, and/or The aluminum source is one or more selected from aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum acetate and aluminum oxalate; the zinc source is selected from one or more of zinc sulfate, zinc chloride, zinc nitrate, zinc acetate, zinc oxalate, and/or The coprecipitate is one or more selected from alkali metal hydroxide, alkali metal carbonate and alkali metal bicarbonate, preferably alkali metal carbonate, and more preferably sodium carbonate.
  8. 8. A copper-aluminum catalyst produced by the method of any one of claims 4 to 7; Preferably, the microscopic morphology of the catalyst is coral-shaped formed by thin-sheet nanorods; The thin nano-rods have a width of 30-40nm, and/or Specific surface area of 85-110m 2 /g, and/or The molar ratio of aluminum to zinc is 0.3-1, and/or The copper content is 50-70wt%, preferably 54-64wt%, based on the total weight of the catalyst, the total content of aluminum and zinc is 30-50wt%, preferably 35-46wt%, based on the oxide; Preferably, the constituent elements of the catalyst further comprise a metal M element selected from one or more of zirconium, tin, lead, lanthanum, cerium, preferably lanthanum and/or cerium; preferably, the metal M element is present in an amount of 0.01 to 20wt%, preferably 1 to 5wt%, calculated as oxide, based on the total weight of the catalyst.
  9. 9. Use of a catalyst according to any one of claims 1-3, 8 in the field of methanol synthesis.
  10. 10. A process for preparing methanol, which comprises subjecting synthesis gas to catalytic conversion in the presence of the catalyst according to any one of claims 1 to 3 and 8 to synthesize methanol; Preferably, the synthesis gas comprises CO, CO 2 and H 2 ; The conditions for catalytic conversion include: the temperature range is 190-300 ℃; Airspeed of 2000-22000h -1 ; the pressure is 2-12MPa.

Description

Coral copper zinc aluminum catalyst, preparation method and application thereof, and methanol preparation method Technical Field The invention relates to a coral copper-zinc-aluminum catalyst, a preparation method and application thereof, and a methanol preparation method. Background Methanol is an important platform chemical, and in recent years, the demand and production capacity of methanol continue to increase, and methanol is one of the most promising alternative fuels. In industry, methanol is typically produced by reacting synthesis gas, which is a mixture of hydrogen, carbon monoxide, and carbon dioxide, at a pressure and temperature in the presence of a catalyst. At present, the methanol synthesis catalyst is generally a copper zinc aluminum system catalyst. A common method of preparation is to co-precipitate a mixed aqueous solution of Cu, zn and Al nitrates using soda ash as precipitant, then age to produce a mixed basic carbonate precursor of CuZnAl, and calcine the precipitate to an oxide mixture. Finally, cuO in the catalyst precursor is reduced prior to use. Disclosure of Invention Aiming at the defects of the prior art, one of the technical problems to be solved by the invention is to provide a coralloid copper-zinc-aluminum catalyst with novel microcosmic morphology, which is applied to methanol synthesis, particularly synthesis of methanol from synthesis gas raw materials, and can effectively improve the raw material conversion rate and the methanol selectivity at a lower working temperature. In order to achieve the above object, a first aspect of the present invention provides a coral-shaped copper-zinc-aluminum catalyst, wherein constituent elements of the catalyst include copper, zinc, and aluminum, and wherein a microstructure of the catalyst is coral-shaped by a platelet nanorod. The second aspect of the invention provides a preparation method of a coral copper-zinc-aluminum catalyst, which is characterized in that the method comprises the steps of contacting a copper source, an aluminum source and a zinc source under a solution condition under a pressure condition, and drying and roasting the obtained solid, wherein the pressure condition is higher than normal pressure. In a third aspect, the present invention provides a copper-aluminum catalyst prepared by the method of the present invention. The fourth aspect of the invention provides an application of the copper-aluminum catalyst in the field of methanol synthesis. In a fifth aspect, the invention provides a process for the preparation of methanol, which comprises subjecting synthesis gas to catalytic conversion in the presence of a catalyst according to the invention to synthesize methanol. The catalyst of the invention can effectively reduce the temperature in the synthesis process, reduce the generation of byproducts, and improve the raw material conversion rate and the methanol selectivity. The catalyst can be used for synthesizing methanol at a lower temperature with high conversion rate and high selectivity. Drawings FIG. 1 is a Scanning Electron Microscope (SEM) characterization of the CuO/ZnO/Al 2O3 catalyst CZA-1 prepared in example 1. FIG. 2 is a Scanning Electron Microscope (SEM) characterization of the CZA-a catalyst of CuO/ZnO/Al 2O3 prepared in comparative example 1. Detailed Description The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein. The following detailed description of embodiments of the invention is provided, but it should be noted that the scope of the invention is not limited by these embodiments, but is defined by the appended claims. All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the meaning commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, definitions, will control. When the specification derives materials, substances, methods, steps, devices, or elements and the like in the word "known to those skilled in the art", "prior art", or the like, such derived objects encompass those conventionally used in the art as the invention suggests, but also include those which are not currently commonly used but which would become known in the art to be suitable for similar purposes. It is specifically noted that two or more aspects (or embodiments) disclosed in the context of this specification may be arbitrarily combined with each other, and the resulti