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CN-121988327-A - Catalyst for preparing 1, 3-propanediol by hydrogenating methyl 3-hydroxypropionate and preparation method thereof

CN121988327ACN 121988327 ACN121988327 ACN 121988327ACN-121988327-A

Abstract

The invention relates to a catalyst for preparing 1, 3-propanediol by hydrogenating methyl 3-hydroxypropionate and a preparation method thereof, which mainly solve the problems of reduced activity and low selectivity of 1, 3-propanediol caused by agglomeration of active component Cu of the catalyst. The preparation method comprises (1) forming ammonia complex ion solution by one or more of main active component Cu and auxiliary Zn, ni, co, cr, pt, ag, forming composite nano particles under the action of reducing agent, (2) adding one or more of silicon source and carrier auxiliary Zr, la, ce, ga, ti, al into the solution containing composite nano particles, forming silicon dioxide supported composite catalyst under hydrothermal condition, and (3) filtering, washing, drying and roasting to obtain the catalyst. According to the invention, the active auxiliary agent and the main active component Cu are effectively formed into composite particles, the composite particles and SiO 2 are organically combined under the hydrothermal condition, and the dispersity of Cu is improved, so that the activity and stability of the catalyst are improved.

Inventors

  • ZHAI QINGGE
  • CAI JUNXIN
  • SHI SHUNXIANG
  • HUANG MINGZHI

Assignees

  • 中化泉州石化有限公司
  • 中化石油化工研究院(泉州)有限责任公司

Dates

Publication Date
20260508
Application Date
20260127

Claims (10)

  1. 1. The catalyst for preparing 1, 3-propanediol by hydrogenating methyl 3-hydroxypropionate is characterized by comprising the following components: (a) The main component is CuO; (b) One or more of the coagents Zn, ni, co, cr, pt, ag; (c) SiO 2 is used as a carrier; (d) The carrier auxiliary agent comprises one or more of Zr, la, ce, ga, ti, al.
  2. 2. The catalyst according to claim 1, wherein the main component CuO is 20-60% of the total weight of the catalyst, the active auxiliary agent is 0.01-5%, the SiO 2 carrier is 40-80%, the carrier auxiliary agent is 0.01-5%, and the sum of the weight percentages of the above components is 100%.
  3. 3. The preparation method of the catalyst for preparing 1, 3-propanediol by hydrogenating methyl 3-hydroxypropionate according to claim 1 or2 is characterized by comprising the following steps: (1) Dispersing a precursor of the main component CuO and a precursor of the active auxiliary agent in water according to the proportion of each component of the catalyst, and uniformly stirring; (2) Adding 25wt% ammonia water into the salt solution obtained in the step (1) to form a metal complex ammonia ion mixed solution; (3) Weighing a certain amount of sodium borohydride, adding the sodium borohydride into the metal complex ammonia ion mixed solution, and rapidly stirring to form nano-scale composite particles by metal; (4) Weighing a certain amount of tetraethoxysilane and a carrier auxiliary agent precursor, dissolving in ethanol, pouring the obtained solution into a reaction system obtained in the step (3), stirring for 1 hour, transferring into a hydrothermal kettle, carrying out hydrothermal treatment at 120-220 ℃ for 2-24 hours, filtering, washing, and drying in a 120 ℃ oven for 4-48 hours; (5) Roasting the solid obtained in the step (4) for 4-24 hours at 300-750 ℃; (6) Grinding, tabletting, crushing and sieving the solid obtained in the step (5) to obtain the catalyst.
  4. 4. The method according to claim 3, wherein the precursor of CuO as the main component in the step (1) is one or more of copper nitrate, copper sulfate, copper acetate and copper chloride.
  5. 5. The method of claim 3, wherein the coagent precursor in step (1) is one or more of nitrate, sulfate, acetate, chloride.
  6. 6. The method according to claim 3, wherein the ammonia water in the step (2) is used in an amount of 5 to 20 times the total molar amount of CuO as a main component and the coagent.
  7. 7. A process according to claim 3, wherein the sodium borohydride in step (3) is used in an amount of 0.05 to 5.0 times the total molar amount of the supported metal.
  8. 8. A method according to claim 3, wherein the alcohol orthosilicate in step (4) is ethyl orthosilicate or methyl orthosilicate.
  9. 9. A process according to claim 3, wherein the sieved catalyst of step (6) is of 20-60 mesh.
  10. 10. Use of the catalyst according to claim 1 or 2 for the hydrogenation of methyl 3-hydroxypropionate to 1, 3-propanediol.

Description

Catalyst for preparing 1, 3-propanediol by hydrogenating methyl 3-hydroxypropionate and preparation method thereof Technical Field The invention belongs to the field of catalytic preparations, and particularly relates to a catalyst for preparing 1, 3-propanediol by hydrogenating methyl 3-hydroxypropionate and a preparation method thereof. Background The most important use of 1, 3-propanediol (1, 3-PDO) is as a polymer monomer to synthesize PTT (polytrimethylene terephthalate) fibers with terephthalic acid (PTA). Compared with PET, PBT, PA and other fibers, the PTT has the advantages of excellent rebound resilience, dyeability and the like, and can develop personalized fashion fabric with comfortable wearing, good elasticity, rich colors and various tissue changes. The intermediate product methyl 3-hydroxypropionate is prepared from ethylene oxide through hydro-methyl esterification, and then the 1,3-PDO is prepared through catalytic hydrogenation, so that the method is a necessary way for realizing the mass production of cheap 1, 3-PDO. The method has low cost of raw materials, is easy to realize large-scale production by process amplification, and provides cheap raw materials for the mass production of PTT fibers. According to the method, the intermediate methyl 3-hydroxypropionate is hydrogenated to prepare the 1, 3-propanediol, and the beta-hydroxyl group in the methyl 3-hydroxypropionate is easier to hydrogenate and remove than the ester group, so that a more proper ester hydrogenation active site is formed, and the selectivity of the main product 1, 3-propanediol is greatly improved. The copper-based 3-hydroxy methyl propionate hydrogenation catalyst has the advantages of low production cost, high activity, high selectivity, mild reaction condition, good toxicity resistance and the like due to combination with other active auxiliary agents. According to the patent CN200610030155.5, under the condition of an alcohol solvent, organic amine is added into copper salt in advance for complexing, fatty alcohol orthosilicate and fatty alcohol aluminum are added as carrier precursors, and then a colloid forming agent is added for heating to form a sol-gel, so that the copper-based single-component catalyst with low load is prepared, the sintering resistance and the service life of the catalyst are effectively improved, and the catalytic activity of the catalyst is still to be improved due to the fact that only single-component copper is adopted in the preparation process, and in addition, the organic amine reagent is used, so that the catalyst has a pungent smell and is not friendly to people and environment. Patent CN200710045788.8 reports that copper salt, manganese salt and organosilane are mixed firstly, then dissolved in alcohol-water solvent, and then heated and stirred to form sol-gel to prepare copper-based binary catalyst, which has low-temperature hydrogenation catalytic activity, by using organosilane as precursor of carrier and manganese as active auxiliary agent. Patent CN201711465582.0 reports a copper-based catalyst for synthesizing dihydric alcohol by ester hydrogenation, a preparation method and application thereof, the catalyst consists of Cu, C60 fullerene and a carrier SiO 2, C60 and Cu are loaded on the surface of the carrier SiO 2, C60 and Cu are firmly contacted, the balance of active copper surface charge is realized through C60, and the activity of copper on the surface of the carrier is improved, so that the copper-based catalyst has higher catalytic activity. The copper-based catalyst has the problem that the Cu active component is easy to agglomerate in the use process, so that the activity of the catalyst is reduced. According to the invention, the 3-hydroxy methyl propionate hydrogenation catalyst is prepared by a nanoparticle hydrothermal cladding method, composite particles formed by multiple metals are used for enhancing interaction between an auxiliary agent and a main active component Cu, and the composite particles are clad in a carrier SiO 2 by a hydrothermal method, so that the dispersity of Cu is improved, the migration of Cu is effectively controlled, and the growth of Cu nanoparticles in the reaction process is prevented, so that the activity of the catalyst is influenced. Disclosure of Invention One of the technical problems to be solved by the invention is that the catalyst activity is low, the 1, 3-propanediol selectivity is low, and the main active component Cu is easy to agglomerate and deactivate. The second technical problem to be solved by the present invention is to provide a method for preparing the catalyst in one of the above technical problems. The third technical problem to be solved by the invention is to provide a method for preparing 1, 3-propanediol by using the catalyst for the hydrogenation of methyl 3-hydroxypropionate. In order to achieve the above purpose, the present invention adopts the following technical scheme: the catalyst for preparing 1, 3-