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CN-122006822-A - Co@S-1 (FNP) catalyst and preparation method thereof and method for preparing propylene by catalyzing propane to directly dehydrogenate

CN122006822ACN 122006822 ACN122006822 ACN 122006822ACN-122006822-A

Abstract

The invention discloses a Co@S-1 (FNP) catalyst, a preparation method thereof and a method for preparing propylene by catalyzing propane to directly dehydrogenate; the preparation method comprises the steps of (1) preparing a mixed solution of tetrapropylammonium hydroxide and pure water, (2) stirring the solution for 0.5h, (3) preparing a mixed solution of cobaltous chloride hexahydrate, ethylenediamine and pure water, (4) stirring the solution for 0.5h, (5) adding the mixed solution prepared in the step (3) into the mixed solution in the step (2), (6) stirring the solution for 0.5h, (7) adding tetraethoxysilane into the solution, (8) stirring the solution for 2h, (9) introducing the final mixed solution into a stainless steel micro-channel reactor with the temperature of 150 ℃ and the pressure of 0.55MPa by a high-pressure pump, controlling the residence time to be 32min, and obtaining a solid product, (10) washing the solid product with deionized water three times and drying the solid product, and (6) calcining the solid product in the air atmosphere at the temperature of 600 ℃ for 6 ℃ to obtain the finished product, and the thermal catalytic material belongs to the technical field of protecting the heat environment.

Inventors

  • WANG XUYU
  • JI HONGBING
  • DOU JIAQI

Assignees

  • 江苏科技大学
  • 江苏中江材料技术研究院有限公司

Dates

Publication Date
20260512
Application Date
20260326

Claims (14)

  1. 1. A preparation method of a Co@S-1 (FNP) catalyst, which is characterized by comprising the following steps of: (1) Preparing a mixed solution of tetrapropylammonium hydroxide and pure water; (2) Stirring the mixed solution for 0.5h at normal temperature; (3) Preparing a mixed solution of cobalt chloride hexahydrate, ethylenediamine and pure water; (4) Stirring the mixed solution for 0.5h at normal temperature; (5) Adding the mixed solution prepared in the step (3) into the mixed solution prepared in the step (2); (6) Stirring the mixed solution for 0.5h at normal temperature; (7) Adding ethyl orthosilicate into the mixed solution; (8) Stirring the mixed solution at 80 ℃ for 2 hours; (9) Introducing the final mixed solution into a stainless steel microchannel reactor through a high-pressure pump at a set flow rate, temperature and pressure, and controlling the residence time to obtain a solid-liquid product; (10) Centrifuging, washing with deionized water, and drying to obtain a solid product; (11) Calcining the solid product in air atmosphere to obtain the final product, which belongs to the technical field of thermocatalytic materials and environmental protection.
  2. 2. The method for preparing Co@S-1 (FNP) catalyst according to claim 1, wherein said mixed solution in step (1) is obtained by mixing 9.9g of tetrapropylammonium hydroxide with 15.5g of pure water.
  3. 3. The method for producing Co@S-1 (FNP) catalyst according to claim 1, wherein said stirring rotation speed in said step (2) is 800r/min.
  4. 4. The method for producing Co@S-1 (FNP) catalyst according to claim 1, wherein said mixed solution in step (3) is obtained by adding 0.04ml of ethylenediamine and 10g of pure water to 0.1220g of cobaltous chloride hexahydrate.
  5. 5. The method for producing Co@S-1 (FNP) catalyst according to claim 1, wherein said stirring rotation speed in said step (4) is 800r/min.
  6. 6. The method for preparing a Co@S-1 (FNP) catalyst according to claim 1, wherein the mixed solution prepared in the step (5) is obtained by adding the mixed solution prepared in the step (3) into the mixed solution prepared in the step (2) and mixing.
  7. 7. The method for producing Co@S-1 (FNP) catalyst according to claim 1, wherein said stirring rotation speed in said step (6) is 800r/min.
  8. 8. The method for producing Co@S-1 (FNP) catalyst according to claim 1, wherein 10.425g of ethyl orthosilicate is added in step (7).
  9. 9. The method for producing Co@S-1 (FNP) catalyst according to claim 1, wherein said stirring rotation speed in said step (8) is 800r/min.
  10. 10. The method for producing Co@S-1 (FNP) catalyst according to claim 1, wherein in said step (9), said set flow rate is 1.96ml/min, the temperature of the oil bath is 150 ℃, the pressure is controlled to be 0.55MPa by the pressure-preparing valve, the residence time is 32min, and the stainless steel material is 316L.
  11. 11. The method for preparing Co@S-1 (FNP) catalyst according to claim 1, wherein the centrifugation parameter in step (10) is 8000 r/min for 5min, the washing condition is deionized water washing 3 times, and the drying temperature is 80 ℃ for 12h.
  12. 12. The method for producing Co@S-1 (FNP) catalyst according to claim 1, wherein the calcination temperature in step (11) is 600℃and the calcination time is 6 hours.
  13. 13. A co@s-1 (FNP) catalyst prepared by the method of any one of claims 1 to 12.
  14. 14. The method for preparing propylene by directly dehydrogenating propane by adopting the Co@S-1 (FNP) catalyst as claimed in claim 13, wherein the catalytic condition is that the raw material gas comprises 25% of propane, the balance gas is nitrogen, the flow rate of the reaction gas is 20ml/min, and the reaction temperature is 550 ℃.

Description

Co@S-1 (FNP) catalyst and preparation method thereof and method for preparing propylene by catalyzing propane to directly dehydrogenate Technical Field The invention relates to a catalyst, in particular to a Co@S-1 (FNP) catalyst, and also relates to a preparation method of the Co@S-1 (FNP) catalyst, belonging to the technical fields of thermal catalytic materials and environmental protection. Background Propylene is an important basic organic chemical raw material, and is widely applied to the production of various chemical products such as polypropylene, acrylonitrile, epoxypropane and the like, and the market demand of the propylene is continuously increased. At present, main methods for industrially producing propylene comprise steam cracking, catalytic cracking and a propane direct dehydrogenation method, wherein the propane direct dehydrogenation method is a research hot spot in the field in recent years because of wide raw material sources, simple process route and high propylene product purity, and low-carbon alkane resources can be effectively utilized. Currently, catalysts for preparing propylene by directly dehydrogenating propane are mainly classified into three categories, namely platinum Pt-based catalysts, chromium Cr-based catalysts and non-noble metal catalysts. The Pt-based catalyst has higher catalytic activity and propylene selectivity, but the Pt resource is scarce and expensive, the catalytic stability is easy to be reduced due to agglomeration of metal particles, the industrial application cost is greatly increased, the Cr-based catalyst has lower cost and higher activity, but the Cr species has strong toxicity, the environmental pollution is easy to be caused, the development trend of green chemical industry is not met, and the application is strictly limited. Co is used as non-noble metal with rich reserves and environmental friendliness, and the oxide or the composite oxide of Co has certain dehydrogenation catalytic activity and is expected to replace Pt-based and Cr-based catalysts to be used for propane direct dehydrogenation reaction, but the cobalt-based catalysts in the prior art have the problems of low propylene selectivity and more side reactions, and the S-1 molecular sieve preparation process is long in time consumption and poor in controllability, so that active components are unevenly dispersed, the service life of the catalyst is short, and the catalyst is difficult to realize industrial amplification. Therefore, the invention focuses on the research of synthesizing and expanding the Co@S-1 catalyst, wherein the S-1 molecular sieve is of an all-silicon MFI structure, has regular micropore channels, high specific surface area and good hydrophobicity, is an excellent catalyst carrier, and Co species are loaded on the S-1 molecular sieve, so that the dispersion of the Co species can be improved and the catalytic performance can be optimized by means of the carrier effect of the Co species. Disclosure of Invention Aiming at the problems, the invention provides a preparation method of a Co@S-1 (FNP) catalyst and has higher selectivity for preparing propylene by directly dehydrogenating propane in order to save the preparation time of the catalyst and facilitate subsequent industrial amplification. In order to achieve the above object, the first technical solution provided by the present invention is as follows: The preparation method of the Co@S-1 (FNP) catalyst sequentially comprises the following steps: (1) Preparing a mixed solution of tetrapropylammonium hydroxide and pure water; (2) Stirring the mixed solution for 0.5h at normal temperature; (3) Preparing a mixed solution of cobalt chloride hexahydrate, ethylenediamine and pure water; (4) Stirring the mixed solution for 0.5h at normal temperature; (5) Adding the mixed solution prepared in the step (3) into the mixed solution prepared in the step (2); (6) Stirring the mixed solution for 0.5h at normal temperature; (7) Adding ethyl orthosilicate into the mixed solution; (8) Stirring the mixed solution at 80 ℃ for 2 hours; (9) Introducing the final mixed solution into a stainless steel microchannel reactor through a high-pressure pump at a set flow rate, temperature and pressure, and controlling the residence time to obtain a solid-liquid product; (10) Centrifuging, washing with deionized water, and drying to obtain a solid product; (11) Calcining the solid product in air atmosphere to obtain the final product, which belongs to the technical field of thermocatalytic materials and environmental protection. Further, the preparation method of the Co@S-1 (FNP) catalyst is characterized in that the mixed solution in the step (1) is obtained by adding 9.9g of tetrapropylammonium hydroxide into 15.5g of pure water and mixing. Further, the preparation method of the Co@S-1 (FNP) catalyst is characterized in that the stirring rotating speed in the step (2) is 800r/min. Further, the preparation method of the Co@S-1 (FNP) catalyst i