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CN-122006720-A - Hydrogenation catalyst, preparation method and application thereof, and method for preparing 1, 3-propylene glycol by hydrogenating dialkyl malonate

CN122006720ACN 122006720 ACN122006720 ACN 122006720ACN-122006720-A

Abstract

The invention relates to a hydrogenation catalyst, a preparation method and application thereof and a method for preparing 1, 3-propylene glycol by hydrogenating dialkyl malonate, wherein the hydrogenation catalyst comprises an active component, a carrier and a modifier silicon dioxide, the active component element comprises Cu, a double reduction peak with high temperature and low temperature exists in an H 2 -TPR test spectrogram of the hydrogenation catalyst, the position range of the high temperature reduction peak comprises 200-300 ℃, and the position range of the low temperature reduction peak comprises 150-220 ℃. The catalyst is particularly suitable for catalyzing ester hydrogenation to prepare alcohol, and is particularly suitable for preparing 1, 3-propylene glycol by hydrogenating dialkyl malonate. The catalyst is applied to the preparation of alcohol by ester hydrogenation, and has the advantages of high activity at low temperature and high selectivity of target products.

Inventors

  • HUANG LE
  • ZHAO DUO
  • Lv Yuhao
  • MA WENDI

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 hydrogenation catalyst is characterized by comprising an active component, a carrier and a modifier silicon dioxide, wherein the active component comprises Cu, a high-temperature and low-temperature double reduction peak exists in an H 2 -TPR test spectrum of the hydrogenation catalyst, the position range of the high-temperature reduction peak comprises 200-300 ℃, and the position range of the low-temperature reduction peak comprises 150-220 ℃.
  2. 2. The hydrogenation catalyst according to claim 1, wherein the integrated area of the high temperature reduction peak in the H 2 -TPR test spectrum of the hydrogenation catalyst is 60% -90%, preferably 65% -85% of the integrated area of the total reduction peak; Based on the total weight of the catalyst, The content of the modifier silica is 0.01-5%, preferably 1-3.5%, and/or The active component Cu is 5-50%, preferably 15-35%, calculated as oxide, and/or The content of the carrier is 50-80%.
  3. 3. The hydrogenation catalyst according to claim 1 or 2, wherein the hydrogenation catalyst further comprises an auxiliary component, the auxiliary component element being selected from one or more of the transition metal elements; preferably, the method comprises the steps of, The auxiliary component elements are one or more of Fe, mn, zr, zn, ni, ag, and/or The content of the auxiliary component in terms of oxide is 0.1% -10%, preferably 0.5-3% based on the total weight of the catalyst; And/or The carrier is one or more of silicon oxide, aluminum oxide and manganese oxide, and/or The modifier silicon dioxide of the hydrogenation catalyst is derived from modifier source organosilane; more preferably, the modifier silica forming process of the hydrogenation catalyst comprises mixing a catalyst precursor comprising an active component, optionally an adjunct component and a support, with an organic solvent, followed by drying, calcination, wherein the organic solvent is an organosilane; Preferably, the organosilane is used in an amount such that the catalyst obtained has a content of modifier silica of 0.01 to 5%, preferably 1 to 3.5%; preferably, the solid-liquid mass ratio during the mixing process is 0.1-3, preferably 2-2.5; And/or The general formula of the organosilane is R '(CH 2 ) n Si(OR) 3 , R' is vinyl, ethoxy, alkyl and amino, preferably amino, R is alkyl functional group, preferably C1-C3 alkyl, and n is 1-3; preferably, the organosilane is selected from one or more of gamma-aminopropyl triethoxysilane and gamma-aminopropyl trimethoxysilane.
  4. 4. A method for preparing a hydrogenation catalyst, comprising: Forming a catalyst precursor comprising an active component, optionally an adjunct component, and a support, the active component element comprising Cu, the adjunct component element being selected from one or more of the transition metal elements; And mixing the catalyst precursor with an organic solvent, and then drying and roasting, wherein the organic solvent is organosilane.
  5. 5. The preparation method according to claim 4, wherein, The organosilane is used in an amount such that the catalyst obtained has a content of modifier silica of 0.01-5%, preferably 1-3.5%; preferably, the solid-liquid mass ratio during the mixing process is 0.1-3, preferably 2-2.5; And/or The general formula of the organosilane is R '(CH 2 ) n Si(OR) 3 , R' is vinyl, ethoxy, alkyl and amino, preferably amino, R is alkyl functional group, preferably C1-C3 alkyl, and n is 1-3; preferably, the organosilane is selected from one or more of gamma-aminopropyl triethoxysilane and gamma-aminopropyl trimethoxysilane.
  6. 6. The process according to claim 4 or 5, wherein, Methods of forming the catalyst precursor comprising the active component, optionally the adjunct component, and the support include one or more of co-precipitation, precipitation by deposition, impregnation, ion exchange, sol-gel; And/or In the catalyst precursor comprising an active component, optionally an auxiliary component and a support, The promoter component is present in an amount of from 0.1 to 10%, preferably from 0.5 to 3%, calculated as oxide, based on the total weight of the catalyst precursor, and/or The active component Cu is 10-50%, preferably 18-35%, calculated as oxide, and/or The content of carrier is 50-85%, preferably 60-80%, and/or The auxiliary component elements are selected from one or more of Fe, mn, zr, zn, ni, ag.
  7. 7. The production method according to any one of claims 4 to 6, wherein the production method comprises: (1) Coprecipitating Cu source, optional auxiliary agent component source and precipitant under solution condition in the presence of carrier source, aging the coprecipitated mixture, drying, roasting and optional shaping the aged solid to obtain catalyst precursor; (2) Mixing the catalyst precursor obtained in the step (1) with an organic solvent, and then drying and roasting; preferably, the method comprises the steps of, In the step (1), the step of (a), The conditions for coprecipitation include a precipitation temperature of 10-80 ℃, preferably 20-60 ℃, and/or The aging conditions include an aging temperature of 20-120deg.C, preferably 40-80deg.C, and/or an aging time of 1-24 hr, preferably 2-12 hr, and/or In the step (1) and the step (2), The drying conditions each comprise a drying temperature of 60-150deg.C, preferably 80-110deg.C, and/or a drying time of 12-24h, preferably 14-22h, and/or The conditions for calcination each include a calcination temperature of 350 to 650 ℃, preferably 450 to 550 ℃, and/or a calcination time of 2 to 6 hours, preferably 3 to 5 hours.
  8. 8. A hydrogenation catalyst obtained by the production process according to any one of claims 4 to 7, which comprises an active component, a carrier and a modifier silica, wherein the active component element comprises Cu; preferably, the H 2 -TPR test spectrogram of the hydrogenation catalyst has double reduction peaks at high temperature and low temperature, wherein the position range of the high-temperature reduction peak comprises 200-300 ℃, and the position range of the low-temperature reduction peak comprises 150-220 ℃; More preferably, in the H 2 -TPR test spectrogram of the hydrogenation catalyst, the integral area of the high-temperature reduction peak accounts for 60% -90% of the integral area of the total reduction peak, and preferably 65% -85%; more preferably, the process is carried out, based on the total weight of the catalyst, The content of the modifier silica is 0.01-5%, preferably 1-3.5%, and/or The active component Cu is 5-50%, preferably 15-35%, calculated as oxide, and/or The content of the carrier is 50-80%.
  9. 9. Use of a hydrogenation catalyst according to any one of claims 1-3, 8 for the hydrogenation of esters to produce alcohols.
  10. 10. A method for preparing 1, 3-propylene glycol by hydrogenating dialkyl malonate, which is characterized in that the hydrogenation catalyst in any one of claims 1-3 and 8 is reduced, and a hydrogen source is contacted with dialkyl malonate in the presence of the reduced hydrogenation catalyst; preferably, the method comprises the steps of, The molar ratio of the hydrogen source to the dialkyl malonate is 100-300, calculated as H 2 , and/or The contact conditions include: The temperature is 140-240 ℃, and/or the pressure is 2-8 MPa, and/or the liquid hourly space velocity is 0.1-3h -1 .

Description

Hydrogenation catalyst, preparation method and application thereof, and method for preparing 1, 3-propylene glycol by hydrogenating dialkyl malonate Technical Field The invention relates to a hydrogenation catalyst, a preparation method and application thereof, and a method for preparing 1, 3-propylene glycol by hydrogenating dialkyl malonate. Background 1, 3-Propanediol (1, 3-PDO) is an important chemical raw material, and is mainly used as a raw material for producing novel polyester polytrimethylene terephthalate (PTT). PTT has the advantages of good chemical stability, good rebound resilience, pollution resistance and the like, and has good market prospect in the textile field. In addition, the 1,3-PDO can be used as solvent, antifreeze and fine chemical raw materials such as organic synthesis intermediates. Industrial production routes of 1, 3-propanediol are mainly divided into two categories, the biological fermentation method and the chemical method. The biological fermentation method is a main flow route for producing 1,3-PDO, mainly represented by the peak groups, due to the advantages of mild conditions, less equipment investment, environmental friendliness and the like, but the method still has the route defects of long fermentation period, easy pollution, more products, difficult separation and the like. The industrial chemical process has two main production routes, including (1) acrolein hydration to obtain 3-hydroxy propionic aldehyde, hydration to obtain 1,3-PDO with Raney nickel as catalyst, and (2) ethylene oxide hydroformylation to obtain 3-hydroxy propionic aldehyde with ethylene oxide as material, further hydrogenation to obtain 1,3-PDO. The acrolein route has problems of aldehyde-containing wastewater, PTT product quality and the like, and in recent years, the technology and the scale are in a state of stagnation, while the ethylene oxide route develops a 3-hydroxy alkyl propionate instead of an intermediate product 3-hydroxy propyl aldehyde route, but the large-scale industrialization is difficult due to the defects of low selectivity of a hydrogenation catalyst, harsh reaction conditions and the like. Based on the original industrial route, the synthesis route using dialkyl malonate as raw material is reported successively. CN101134712B discloses a route for obtaining 1, 3-propanediol by hydrogenating dialkyl malonate, and the copper-based catalyst is adopted, but the conversion rate of raw materials in the method is low, about 50%. CN105435791B discloses a catalyst for preparing 1, 3-propylene glycol by hydrogenating dialkyl malonate, which comprises active component copper and carrier silicon dioxide, the conversion rate of raw material is more than 98%, and the selectivity of 1, 3-propylene glycol is up to 65%. CN113101937a discloses a doped mixed valence copper catalyst, which can be used for preparing 1, 3-propanediol by hydrogenation of malonate or 3-hydroxy propionate compounds, wherein the conversion rate of malonate is 80%, and the selectivity of 1, 3-propanediol is 47%. It can be seen that the hydrogenation route of dialkyl malonate based on copper-based catalysts has been reported correspondingly, but the selectivity of 1, 3-propanediol makes this route still a certain gap from commercial production. Disclosure of Invention The invention aims to solve the problems of poor catalyst activity and poor target product selectivity in the prior art, and provides a hydrogenation catalyst, a preparation method and application thereof, the catalyst is particularly suitable for being used as a catalyst for preparing alcohol by ester hydrogenation, is applied to the process of preparing alcohol by ester hydrogenation, and has the advantages of high activity at low temperature and high selectivity of target products. According to a first aspect of the invention, the invention provides a hydrogenation catalyst, which comprises an active component, a carrier and a modifier silicon dioxide, wherein the active component comprises Cu, a H 2 -TPR test spectrogram of the hydrogenation catalyst has a double reduction peak at high temperature and low temperature, the position range of the high-temperature reduction peak comprises 200-300 ℃, and the position range of the low-temperature reduction peak comprises 150-220 ℃. According to a second aspect of the present invention there is provided a process for the preparation of a hydrogenation catalyst according to the present invention which comprises forming a catalyst precursor comprising an active component comprising Cu and optionally an auxiliary component selected from one or more of the transition metal elements and a support, mixing the catalyst precursor with an organic solvent followed by drying and calcination, the organic solvent being an organosilane. According to a third aspect of the present invention there is provided the use of a hydrogenation catalyst according to the present invention in the hydrogenation of an ester to produce