Search

CN-122006741-A - Preparation method of high-activity bisphenol A hydrogenation catalyst

CN122006741ACN 122006741 ACN122006741 ACN 122006741ACN-122006741-A

Abstract

The invention discloses a preparation method of a high-activity bisphenol A hydrogenation catalyst, which comprises the following steps of weighing transition metal salt in the fourth period of the periodic table of elements, adding a mixed solvent of alcohol and deionized water, stirring uniformly to prepare a uniformly mixed solution, weighing a ruthenium-containing compound, adding an accelerator, adding deionized water to prepare a uniform solution, uniformly mixing the solutions, reacting to obtain a reaction solution, weighing aluminum oxide, adding the reaction solution into the aluminum oxide to complete an impregnation process, then performing heat treatment to obtain a hydrogenation catalyst precursor, and reducing the hydrogenation catalyst precursor to obtain a reduced high-activity bisphenol A hydrogenation catalyst. The preparation method improves the metal utilization rate of Ru and is beneficial to the catalytic activity of the catalyst.

Inventors

  • GUO RONG
  • ZHAO FAN
  • LI RONGGUAN
  • WANG YAN
  • ZHANG ZHANQUAN
  • Hou yuandong
  • LEI JUNWEI
  • ZHANG RUOLIN
  • Sun Xinchan
  • QIAN JUNFENG

Assignees

  • 中国石油天然气股份有限公司

Dates

Publication Date
20260512
Application Date
20241108

Claims (10)

  1. 1. The preparation method of the high-activity bisphenol A hydrogenation catalyst is characterized by comprising the following steps: Step 1, weighing transition metal salt in the fourth period of the periodic table, adding a mixed solvent of alcohol and deionized water, and uniformly stirring to prepare a uniformly mixed solution; Step 2, weighing ruthenium-containing compounds, adding an accelerator, and adding deionized water to prepare a uniform solution; step 3, uniformly mixing the solutions in the step 1 and the step 2, and reacting to obtain a reaction solution; step 4, weighing the alumina, and adding the reaction liquid obtained in the step 3 into the alumina to complete the impregnation process; Step 5, carrying out heat treatment on the sample obtained in the step 4 to obtain a hydrogenation catalyst precursor; And 6, reducing the hydrogenation catalyst precursor obtained in the step 5 to obtain the reduced high-activity bisphenol A hydrogenation catalyst.
  2. 2. The method according to claim 1, wherein the transition metal salt of the fourth period of the periodic table is an iron salt and/or a zinc salt.
  3. 3. The preparation method of claim 2, wherein the iron salt is one or more of ferric nitrate, ethylene diamine tetraacetic acid monosodium ferric salt hydrate, ammonium ferric salt, ferrous fumarate and ferric acetylacetonate, and the zinc salt is one or more of zinc nitrate, zinc diethyl dithiocarbamate, zinc acetate and zinc N-ethyl-N-phenyl dithiocarbamate.
  4. 4. The preparation method according to claim 1, wherein the alcohol comprises methanol and/or ethanol, and the alcohol in the mixed solvent of the alcohol and deionized water accounts for 25-80 wt% of the total solvent.
  5. 5. The method according to claim 1, wherein the ruthenium-containing compound comprises one or both of ruthenium nitrosylnitrate and ruthenium trichloride, and the ratio of ruthenium to the high-activity bisphenol A hydrogenation catalyst is 0.1wt% to 0.3wt%.
  6. 6. The preparation method of claim 1, wherein the accelerator is one or more of isopropanol, n-butanol, sorbitol and glucose, and the molar amount of the accelerator is in the range of 0.0020 to 0.0056mol.
  7. 7. The method according to claim 1, wherein the content of the transition metal salt in the fourth period of the periodic table is 5 to 20 in terms of molar ratio of the metal element M to the ruthenium element Ru.
  8. 8. The method according to claim 1, wherein in step 3, the reaction is carried out at a temperature of 25 to 60 ℃ for a time of 2 to 8 hours; in the step 4, the temperature of the drying is 20-100 ℃ and the time is 4-24 hours, and the soaking is carried out under the ultrasonic condition for 10-30 minutes.
  9. 9. The method according to claim 1, wherein the heat treatment temperature is 150 to 350 ℃ for 2 to 6 hours, and the atmosphere is air or N 2 .
  10. 10. The method according to claim 1, wherein the reduction is carried out in an atmosphere of H 2 at a temperature of 150-300 ℃ for 1-6 hours.

Description

Preparation method of high-activity bisphenol A hydrogenation catalyst Technical Field The invention belongs to the field of chemical monomer hydrogenation catalysts, and particularly relates to a preparation method of a high-activity bisphenol A hydrogenation catalyst. Background The hydrogenated bisphenol A can be used for replacing the hydrogenated bisphenol A which is a hydrogenated product of bisphenol A in the fields of producing high polymer materials such as polycarbonate, epoxy resin and the like. Under the action of a catalyst, bisphenol A molecules are subjected to continuous hydrogenation to fully saturate two benzene rings, so that hydrogenated bisphenol A is obtained. For this reaction, a noble metal supported catalyst such as ruthenium is often used. With the continuous improvement of the requirements of the industry on the catalytic process and the product quality, the performance requirements of the catalyst are continuously updated. Noble metals raise the cost of the catalyst due to scarcity and high value, and noble metal atoms are easy to agglomerate on the catalyst due to high surface energy to form larger-particle metal clusters, so that the metal utilization rate is reduced, and the activity of the catalyst is seriously influenced. In the prior art, the catalyst can be modified to meet the use requirements of the catalyst, including optimizing metal active centers, modifying and improving carrier materials, introducing new functional components and the like. Therefore, the ruthenium-based catalyst can still show higher reaction activity under lower load by modifying and modifying, and has important significance and practical application value. Chinese patent CN202111345207.9, mixing zinc-aluminum hydrotalcite dispersion liquid with ruthenium source solution and alkali liquor, crystallizing, and reducing the obtained precursor in reducing gas atmosphere to obtain Ru-Zn hydrogenation catalyst. In the process of preparing cyclohexylbenzene by catalytic benzene hydroalkylation, the benzene conversion rate can reach 76.65 percent, and the selectivity of cyclohexylbenzene can reach 80.39 percent. However, the ruthenium hydroxide precipitate formed under alkaline conditions tends to form larger metal clusters without protection, and the metal particles deposit on the support by physical action, which is weak and detrimental to the stability of the catalyst. Chinese patent CN201710760364.3, adding organic modifier into Ru and Ni metal precursor alcohol solution, regulating pH with NaOH, adding hydrogen peroxide aluminum lithium hydride alcohol solution at a certain temperature to react and obtain ruthenium/nickel alloy nano catalyst. The catalyst has higher activity and stability in the reaction of catalyzing the hydrogenation of 1-nitroanthraquinone to prepare 1-aminoanthraquinone. The method takes NaOH as a pH regulator, can generate certain alkaline waste liquid, and is not friendly to the environment. Chinese patent CN201310080626.3, respectively preparing ruthenium and palladium metal solutions, soaking on an alumina carrier, and roasting to obtain a supported ruthenium-palladium bimetallic hydrogenation catalyst, and applying the supported ruthenium-palladium bimetallic hydrogenation catalyst to the reaction of preparing 1, 4-cyclohexanedicarboxylic acid dimethyl ester by selective hydrogenation of dimethyl terephthalate, and showing better activity and high CHDM yield. The metal components of the catalyst are ruthenium and palladium noble metals, so that the cost is high, the metal components are not subjected to protection treatment before roasting, and the metal is easy to agglomerate. Chinese patent CN202211652631.2, ni (NO 3)2·6H2 O and (NH 4)H2W12O40·xH2 O) solution are added into NH 4HCO3 solution to be deposited on an Al 2O3 carrier and then baked, ruthenium metal is soaked, then baked and reduced to obtain a hydrogenation catalyst of three metals, and the hydrogenation catalyst is applied to the catalytic hydrogenation of tetramethyl pyromellitate. Disclosure of Invention The invention aims to provide a preparation method of a high-activity bisphenol A hydrogenation catalyst, which improves the metal utilization rate of Ru and is beneficial to the catalytic activity of the catalyst. In order to achieve the above purpose, the invention provides a preparation method of a high-activity bisphenol A hydrogenation catalyst, which comprises the following steps: Step 1, weighing transition metal salt in the fourth period of the periodic table, adding a mixed solvent of alcohol and deionized water, and uniformly stirring to prepare a uniformly mixed solution; Step 2, weighing ruthenium-containing compounds, adding an accelerator, and adding deionized water to prepare a uniform solution; step 3, uniformly mixing the solutions in the step 1 and the step 2, and reacting to obtain a reaction solution; step 4, weighing the alumina, and adding the reaction liquid obtained in the step 3 into t