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CN-122006709-A - Catalyst for preparing methyl isobutyl ketone and diisobutyl ketone by acetone condensation-hydrogenation and preparation method thereof

CN122006709ACN 122006709 ACN122006709 ACN 122006709ACN-122006709-A

Abstract

The invention belongs to the field of catalyst preparation, and provides a catalyst for preparing methyl isobutyl ketone (MIBK) and diisobutyl ketone (DIBK) by acetone condensation-hydrogenation and a preparation method thereof. Mixing the prepared aqueous solution containing aluminum compound and the aqueous solution containing lanthanide compound, stirring at a certain temperature for a period of time to obtain a solution A, proportionally adding a surfactant, stirring at a certain temperature for a period of time to obtain a solution B, regulating the pH of the solution B with an alkaline solution with a certain concentration to obtain a suspension C, stirring at a certain temperature for a period of time, filtering, washing, drying and roasting to obtain a solid D, preparing an aqueous solution containing palladium compound with a certain concentration, slowly dripping the aqueous solution into the solid D, standing at room temperature for a period of time, drying and roasting to obtain an oxidation state catalyst E, and reducing the oxidation state catalyst E to obtain a catalyst for preparing MIBK and DIBK by acetone condensation-hydrogenation. The catalyst prepared by the invention is suitable for preparing MIBK and DIBK by acetone condensation-hydrogenation, and has good acetone conversion rate and MIBK and DIBK selectivity.

Inventors

  • XU JUNDONG
  • YUAN YONGBING
  • LI LIJUN
  • HUANG WEN
  • HUANG RONG
  • YANG ZAN
  • ZENG YIQING
  • ZHANG CEN
  • ZHOU CONGSHAN
  • ZHENG SHUQIN
  • LI AN

Assignees

  • 湖南理工学院

Dates

Publication Date
20260512
Application Date
20260127

Claims (10)

  1. 1. The preparation method of the catalyst for preparing methyl isobutyl ketone and diisobutyl ketone by condensing and hydrogenating acetone is characterized by comprising the following steps: (1) Mixing the prepared aluminum-containing compound aqueous solution and lanthanide compound aqueous solution, and stirring for a period of time at a certain temperature to obtain a solution A; (2) Adding a surfactant according to a proportion, and stirring for a period of time at a certain temperature to obtain a solution B; (3) Regulating the pH value of the solution B by using an alkaline solution with a certain concentration to obtain a suspension C; (4) Stirring the suspension C for a period of time at a certain temperature, and then filtering, washing, drying and roasting to obtain a solid D; (5) Preparing an aqueous solution containing a palladium compound with a certain concentration, slowly dripping the aqueous solution into the solid D, standing for 24 hours at room temperature, and drying and roasting to obtain an oxidation state catalyst E; (6) The oxidation state catalyst E is reduced in a hydrogen atmosphere to obtain the catalyst for preparing MIBK and DIBK by acetone condensation-hydrogenation.
  2. 2. The method according to claim 1, wherein the aluminum-containing compound is aluminum sulfate, aluminum chloride or aluminum nitrate, the lanthanide compound is lanthanum nitrate, cerium nitrate, praseodymium nitrate, neodymium nitrate, europium nitrate, lanthanum acetate, cerium acetate, praseodymium acetate, neodymium acetate or europium acetate, the concentration of the aqueous solution of the aluminum-containing compound is 0.20 mol/L to 0.60 mol/L, the concentration of the aqueous solution of the lanthanide-containing compound is 0.10 mol/L to 0.65 mol/L, and the molar ratio of aluminum atoms to lanthanide atoms is 1 (0.1 to 5).
  3. 3. The process according to claim 1, wherein in step (1), the temperature of the stirring reaction is 50 to 80℃and the reaction time is 1 to 10 h.
  4. 4. The method of claim 1, wherein the surfactant is cetyl trimethylammonium bromide, fatty acid methyl ester ethoxylate sulfonate, cocamide propyl betaine or glyceryl monostearate, and the molar ratio of aluminum atoms to surfactant is 1 (0.01-0.1).
  5. 5. The process according to claim 1, wherein the alkaline solution for adjusting the pH is a sodium acetate solution, a sodium carbonate solution or a sodium hydroxide solution, and the pH of the suspension C is in the range of 8 to 12.
  6. 6. The method according to claim 1, wherein in the step (4), the drying temperature is 80-150 ℃ and the time is 8-24 h, the roasting reaction temperature is 450-650 ℃, the roasting atmosphere is air, the heating rate is 1-10 ℃ per minute, and the temperature is kept 2-8 h.
  7. 7. The method according to claim 1, wherein the palladium compound is palladium chloride or palladium oxide, the aqueous solution of the palladium compound has a concentration of 0.015 mol/L to 0.865/mol/L and a molar ratio of palladium atoms to aluminum atoms of 1 (10 to 1000).
  8. 8. The method according to claim 1, wherein in the step (5), the drying temperature is 120-150 ℃ and the time is 12-24 h, the baking temperature is 550-650 ℃, the baking atmosphere is air, the heating rate is 1-10 ℃ per minute, and the temperature is kept 2-8 h.
  9. 9. The method according to claim 1, wherein in the step (6), the reducing conditions are such that the hydrogen atmosphere is at a temperature rise rate of 1 to 4 ℃ per minute, the temperature is 200 to 300 ℃, the hydrogen flow rate is 10 to 30 mL per minute, the hydrogen pressure is 1 to 3 MPa, and 1 to 6h is maintained.
  10. 10. A catalyst for preparing methyl isobutyl ketone and diisobutyl ketone by condensing and hydrogenating acetone prepared by the method according to any one of claims 1-8, wherein the catalyst is used for condensing and hydrogenating acetone under the reaction conditions of 100-250 ℃, 1-15 h -1 of liquid volume space velocity, 1-4 MPa of pressure and 100-600 of hydrogen-ketone ratio.

Description

Catalyst for preparing methyl isobutyl ketone and diisobutyl ketone by acetone condensation-hydrogenation and preparation method thereof Technical Field The invention belongs to the field of catalyst preparation, and relates to a catalyst for preparing methyl isobutyl ketone (MIBK) and diisobutyl ketone (DIBK) by acetone condensation-hydrogenation and a preparation method thereof. Background Methyl isobutyl ketone (MIBK) and diisobutyl ketone (DIBK) are important chemical products in the fields of paint, medicine and petrochemical industry. In addition, it can be used as a chemical intermediate for synthesizing surfactants, rubber antioxidants and fragrances. With the development of the automotive industry and high solid coating materials, the demand for MIBK and DIBK will further increase in asian countries such as china, korea, etc. The process route for preparing MIBK is industrially divided into an isopropyl alcohol method and an acetone method according to the production raw materials. The process route for preparing MIBK by the isopropanol method is to take isopropanol as a raw material, firstly generate acetone under the action of a dehydrogenation catalyst, then carry out dehydration reaction on the acetone and the isopropanol under the catalysis of an acid-base catalyst, and finally obtain the target product MIBK. The process for preparing MIBK from isopropanol has the advantages of mild conditions, low equipment investment and the like, so that the isopropanol method becomes the main process for early production of MIBK. However, with the oxidation of cumene to phenol produces a large amount of acetone and the yield of acetone is excessive, a process route for preparing MIBK using acetone as a raw material is gradually selected. The acetone is used as a raw material, and the acetone method can be divided into two preparation routes of an acetone one-step method and an acetone three-step method according to different reaction processes. The process for preparing MIBK by the three-step method of acetone comprises the following three steps of (1) stretching a carbon chain of Acetone (ACE) under the action of acid or alkali catalysis to prepare diacetone alcohol, (2) releasing H 2 O molecules to convert into isopropylidene acetone under the action of acid catalysis, and (3) taking Pd as a hydrogenation active component to induce the isopropylidene acetone to perform reduction reaction, so that the target product MIBK is finally produced. The three-step acetone preparation process has the advantages of high flexibility, mild reaction conditions and the like, and becomes the main stream for producing MIBK in the middle and earlier stages of the 20 th century. However, the process uses a plurality of reactors and treatment units due to the traditional preparation process, so that the problems of high investment cost, serious corrosion of strong acid and strong alkali to equipment and the like are caused. In view of the problems of atom economy and environment, the one-step method for preparing MIBK by acetone is a promising synthetic process route. The key of the process is the preparation of a multifunctional catalyst, and the catalyst needs to have the functions of condensation, dehydration and selective hydrogenation. According to the different supported metals, the catalyst is divided into a noble metal catalyst and a non-noble metal catalyst, wherein the non-noble metal catalyst (Cu, ni and the like) has low price and higher conversion rate, but a large amount of byproducts are generated, and the noble metal catalyst (Pd, pt and the like) has high conversion rate and selectivity though expensive, so that the catalyst is widely applied to the research of preparing MIBK by an acetone one-step method. Pd/resin is the only commercial catalyst for preparing MIBK, however, the problems of poor thermal stability, short service life and the like of the resin still cannot be thoroughly solved. Zhao Dongmei et Al prepared a Pd/Al 2O3 catalyst with an acetone conversion of 35% and a MIBK selectivity of 89% at 140-160 oC, 4-5 MPa and a hydroketone ratio of 2. Higashio et al developed a Pd/Nb 2O5·nH2 O multifunctional catalyst with an acetone conversion of 45.6% and MIBK selectivity of 92.5% at a reaction temperature of 160 ℃ and a pressure of 2MPa, but with poor stability. For DIBK, there is no production process directly using it as a main product in industry, and it is common to use a production process in which DIBK is produced as a by-product when MIBK is produced. At present, the industry has large MIBK yield and relatively saturated market, but the DIBK yield is low, the demand of China for the DIBK is increased increasingly, and the productivity can not meet the market demand far. There is therefore a need in the art to develop an acetone condensation-hydrogenation catalyst with high activity, high stability and selectivity to achieve the regulated production of MIBK and DIBK. Disclosure of Invention In