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CN-122006800-A - Cu@TS-1 molecular sieve catalyst and preparation method and application thereof

CN122006800ACN 122006800 ACN122006800 ACN 122006800ACN-122006800-A

Abstract

The invention relates to a Cu@TS-1 molecular sieve catalyst, and a preparation method and application thereof. A preparation method of a Cu@TS-1 molecular sieve catalyst comprises the following steps of (1) stirring a solution 1 and a solution 2 at 4-7 ℃ for reaction for 10-14 hours, adding a copper complex, uniformly mixing, and carrying out aging treatment, wherein the solution 1 comprises TEOS, water and TPAOH, the solution 2 comprises TBOT and IPA, cooling to room temperature after the aging treatment is finished, adding ethanol, carrying out rotary hydrothermal reaction at 160-180 ℃ for 70-74 hours, and (3) centrifuging, washing, drying, collecting solids, grinding and calcining after the reaction is finished to obtain the Cu@TS-1 molecular sieve catalyst. The Cu@TS-1 molecular sieve catalyst, the preparation method and the application thereof provided by the invention have the characteristics of high catalytic selectivity, good stability, less loss and the like.

Inventors

  • LI JIANGBING
  • LI NA
  • YAO QINGQING
  • Liao Panxue
  • WANG TINGTING
  • SUN YONGKANG
  • CHENG TIANYI
  • ZHU JIANQIANG
  • MA CAIMEI
  • XIA MING
  • Guo Panchun
  • BAI YANGYANG

Assignees

  • 石河子大学
  • 新疆石河子职业技术学院（石河子市技工学校）

Dates

Publication Date
20260512
Application Date
20260127

Claims (10)

  1. 1. The preparation method of the Cu@TS-1 molecular sieve catalyst is characterized by comprising the following steps of: (1) Stirring the solution 1 and the solution 2 at 4-7 ℃ for reaction for 10-14 hours, adding copper complex, uniformly mixing, and performing aging treatment; The solution 1 comprises TEOS, water and TPAOH; The solution 2 comprises TBOT and IPA; (2) After the aging treatment is finished, cooling to room temperature, adding ethanol, and performing rotary hydrothermal reaction for 70-74h at 160-180 ℃; (3) After the reaction is finished, the Cu@TS-1 molecular sieve catalyst is obtained by centrifugal washing, drying, collecting solids, grinding and calcining.
  2. 2. The method according to claim 1, wherein, In the step (1), the preparation method of the copper complex comprises the steps of uniformly mixing copper salt, water, 1,10 phenanthroline and ethanol, and drying.
  3. 3. The method according to claim 1, wherein, In the step (1), the molar ratio of TEOS, TBOT, TPAOH, IPA, cu to 1,10 phenanthroline is 1:0.016:0.28:0.88:0.0287-0.0717:0.0465-0.1175.
  4. 4. A process according to claim 3, wherein, In the step (1), the molar ratio of TEOS, TBOT, TPAOH, IPA, cu to 1,10 phenanthroline is 1:0.016:0.28:0.88:0.0573:0.0940.
  5. 5. The method according to claim 1, wherein, In the step (1), the aging temperature is 65-75 ℃ and the aging time is 20-24 hours.
  6. 6. The method according to claim 1, wherein, In the step (3), the calcination temperature is 450-650 ℃ and the calcination time is 5-7 h.
  7. 7. A cu@ts-1 molecular sieve catalyst characterized by the use of a preparation method according to any one of claims 1-6.
  8. 8. The use of the cu@ts-1 molecular sieve catalyst of claim 7 in the catalytic synthesis of 1,4 butynediol.
  9. 9. The use according to claim 8, wherein, Adding formaldehyde and a catalyst into a reactor, introducing acetylene, and reacting to obtain 1, 4-butynediol; The catalyst is the Cu@TS-1 molecular sieve catalyst of claim 7.
  10. 10. The use according to claim 9, wherein, The reaction temperature is 75-105 ℃ and the reaction time is 4-26h.

Description

Cu@TS-1 molecular sieve catalyst and preparation method and application thereof Technical Field The invention belongs to the technical field of catalysts for synthesis of 1, 4-butynediol, and particularly relates to a Cu@TS-1 molecular sieve catalyst, a preparation method and application thereof. Background 1, 4-Butynediol is a chemical raw material widely used in the industries of chemical industry, medicine, electroplating and the like, and can be catalytically hydrogenated into 1, 4-Butanediol (BDO) which is an important fine chemical raw material, and the 1, 4-butanediol can be used for producing tetrahydrofuran, gamma-butyrolactone, polytetrahydrofuran, polyurethane, polybutylene terephthalate, polybutylene succinate and the like, and is widely used in the fields of medicine, chemical industry, textile, papermaking, automobiles, daily chemical industry and the like. At present, the main method for industrially synthesizing 1, 4-butynediol in China is an alkynal method, formaldehyde and acetylene are used as raw materials for synthesis, and copper is used as a main active component of a catalyst. The prior art US3920759 and CN102125856A respectively disclose copper-bismuth supported catalysts with magnesium silicate and kaolin as carriers, which are used for catalytic reaction of synthesizing 1, 4-butynediol by reacting formaldehyde with acetylene. However, the catalyst has the following defects that (1) the magnesium silicate carrier is unstable, can be dissolved in a reaction system, has short service life, and (2) the catalyst has high dosage, the content of copper oxide is high, agglomeration is easy to occur, copper is easy to run off, the catalytic effect of each active center cannot be fully exerted, and the waste of copper resources is caused. (3) The traditional copper-based catalyst has higher Cu content, and can generate copper acetylide in the process of acetylene formaldehyding reaction, thereby having certain danger. Based on the method, the invention provides a novel acetylene formalization catalyst, and a preparation method and application thereof, and the Cu@TS-1 molecular sieve catalyst synthesized by the preparation method has the advantages of good stability, less Cu addition, safety guarantee, copper loss inhibition and the like. Disclosure of Invention The invention aims to provide a preparation method of a Cu@TS-1 molecular sieve catalyst, cu nano particles are encapsulated in a TS-1 molecular sieve by an in-situ synthesis method, and the preparation method has the characteristics of simplicity in operation, small Cu addition amount and the like. In order to achieve the above purpose, the technical scheme adopted is as follows: a preparation method of a Cu@TS-1 molecular sieve catalyst comprises the following steps: (1) Stirring the solution 1 and the solution 2 at 4-7 ℃ for reaction for 10-14 hours, adding copper complex, uniformly mixing, and performing aging treatment; The solution 1 comprises TEOS, water and TPAOH; The solution 2 comprises TBOT and IPA; (2) After the aging treatment is finished, cooling to room temperature, adding ethanol, and performing rotary hydrothermal reaction for 70-74h at 160-180 ℃; (3) After the reaction is finished, the Cu@TS-1 molecular sieve catalyst is obtained by centrifugal washing, drying, collecting solids, grinding and calcining. In the step (1), the copper complex is prepared by uniformly mixing copper salt, water, 1,10 phenanthroline and ethanol, and drying. Further, in the step (1), the molar ratio of TEOS, TBOT, TPAOH, IPA, cu to 1,10 phenanthroline is 1:0.016:0.28:0.88:0.0287-0.0717:0.0465-0.1175. Still further, in the step (1), the molar ratio of TEOS, TBOT, TPAOH, IPA, cu to 1,10 phenanthroline is 1:0.016:0.28:0.88:0.0573:0.0940. Further, in the step (1), the aging temperature is 65-75 ℃ and the time is 20-24 hours. Further, in the step (3), the calcination temperature is 450-650 ℃ and the calcination time is 5-7 h. The invention further aims to provide the Cu@TS-1 molecular sieve catalyst which is prepared by the preparation method and is a limited-domain copper-based titanium-silicon molecular sieve catalyst and has the characteristics of high catalytic activity, good stability, less copper loss and the like. The invention also aims to provide the application of the Cu@TS-1 molecular sieve catalyst in the catalytic synthesis of 1,4 butynediol. In order to achieve the above purpose, the technical scheme adopted is as follows: The Cu@TS-1 molecular sieve catalyst is applied to catalytic synthesis of 1,4 butynediol. Further, formaldehyde and a catalyst are added into a reactor, acetylene is introduced, and 1,4 butynediol is obtained through reaction; The catalyst is the Cu@TS-1 molecular sieve catalyst. Still further, the reaction temperature is 75-105 ℃ and the reaction time is 4-26h. Compared with the prior art, the invention has the beneficial effects that: 1. According to the technical scheme, the addition of the 1,10 phenanthroline