CN-122006689-A - Modified composite oxide carrier, preparation method and application thereof, catalyst containing carrier, preparation method and application thereof

CN122006689ACN 122006689 ACN122006689 ACN 122006689ACN-122006689-A

Abstract

The invention provides a preparation method of a modified composite oxide carrier, which comprises the following steps of mixing and coprecipitating an aluminum salt solution, a titanium salt solution and an organic cation quaternary ammonium salt solution, treating obtained precipitate particles with a silane reagent, and then carrying out second drying and first roasting. According to the preparation method of the selective hydrogenation catalyst carrier, provided by the invention, the organic cation quaternary ammonium salt is added as the structure directing agent, and the obtained precipitate particles are treated by using the silane reagent, so that the dispersion of the active components on the surface of the carrier can be obviously improved, the particle size of nanoclusters formed by the active components on the surface of the carrier can be controlled to be less than 5nm, and the low-temperature activity of the catalyst containing the carrier is obviously improved. The invention also provides a modified composite oxide carrier prepared by the preparation method and application thereof, a catalyst containing the carrier, and a preparation method and application thereof.

Inventors

DU ZHOU
LIU YANHUI
YANG GUANG
ZHANG FUCHUN
DONG LIXIA
REN YUMEI

Assignees

中国石油化工股份有限公司
中石化(北京)化工研究院有限公司

Dates

Publication Date: 20260512
Application Date: 20241111

Claims (10)

1. A preparation method of a modified composite oxide carrier is characterized by comprising the following steps of mixing and coprecipitating an aluminum salt solution, a titanium salt solution and an organic cation quaternary ammonium salt solution, treating obtained precipitate particles with a silane reagent, and then carrying out second drying and first roasting.
2. The preparation method according to claim 1, wherein the organic cationic quaternary ammonium salt comprises a hydrocarbyl quaternary ammonium salt, preferably the hydrocarbyl quaternary ammonium salt has a general formula of R 4 N + X - , wherein X - is selected from the group consisting of halogen ions, acid ions, preferably the halogen ions comprise F - 、Cl - 、Br - and I - , the acid ions comprise nitrate ions and carboxylate ions, each R in the general formula R 4 N + X - is the same or different and is each independently selected from the group consisting of alkyl, cycloalkyl, aryl, aralkyl and alkylaryl groups, at least one R, preferably 1 to 2R is selected from the group consisting of C6 and higher alkyl groups, preferably from the group consisting of C6 to C20 alkyl groups, the remaining R is preferably selected from the group consisting of C1 to C4 alkyl groups, C7 to C11 aralkyl groups; Preferably, the organic cationic quaternary ammonium salt comprises at least one of dioctadecyl dimethyl quaternary ammonium salt, cetyl trimethyl quaternary ammonium salt and C12-C18 alkyl dimethyl benzyl quaternary ammonium salt; more preferably, the organic cationic quaternary ammonium salt is selected from at least one of dioctadecyl dimethyl ammonium chloride, cetyl trimethyl ammonium bromide, dodecyl dimethyl benzyl ammonium chloride, tetradecyl dimethyl benzyl ammonium chloride, hexadecyl dimethyl benzyl ammonium chloride and octadecyl dimethyl benzyl ammonium chloride, and/or The general formula of the silane reagent is SiR 1 x (OR 2 ) y , wherein x and y are respectively and independently selected from integers of 1-3, x+y=4, R 1 is selected from hydrogen, C1-C6 alkyl and C2-C6 alkenyl, and R 2 is selected from C1-C6 alkyl; Preferably, the silane-based reagent comprises at least one of triethoxysilane, trimethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and/or The mass ratio of the aluminum salt, the titanium salt and the organic cation quaternary ammonium salt is (30-45): 1.5-5): 1, and/or The mass ratio of the silane-based reagent to the aluminum salt is 1 (5-70), and/or The mass ratio of the silane-based reagent to the titanium salt is 1 (0.5-5), and/or The aluminum salt comprises at least one of aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum acetate, aluminum fluoride, and/or The titanium salt comprises at least one of metatitanic acid, titanium sulfate, titanium tetrachloride, tetraethyl titanate, titanium nitrate, titanium oxalate, titanium fluoride, titanium acetate and titanium isopropoxide, and/or The solvents in the aluminum salt solution and the titanium salt solution are the same or different, and are at least one of water, methanol, ethanol, benzene, toluene and chloroethane respectively and independently The solvent in the organic cation quaternary ammonium salt solution is at least one selected from water, methanol, ethanol, benzene, toluene, chloroethane, isopropanol, acetone, hydrochloric acid, sulfuric acid, nitric acid, sodium hydroxide and potassium hydroxide, and/or The concentration of the aluminum salt solution is 0.1moL/L to 2.5moL/L, and/or The concentration of the titanium salt solution is 0.1moL/L to 1.5moL/L, and/or The concentration of the organic cation quaternary ammonium salt solution is 0.1-10wt%, preferably 0.2-10wt%, and more preferably 1-5wt%.
3. The method according to claim 1 or 2, wherein the conditions of the mixed coprecipitation include a temperature of 20 to 80 ℃ for 1 to 8 hours under stirring, and/or The precipitate particles are first dried before being treated with the silane-based agent, and/or The treatment of the silane-based reagent comprises the steps of dripping a solution of the silane-based reagent into the precipitate particles, and stirring, wherein the solution of the silane-based reagent is preferably an aqueous solution of the silane-based reagent, and the concentration of the aqueous solution is 0.1-10wt%, preferably 1-10wt%, and/or Preferably, the conditions of the first drying and the second drying are the same or different, and each independently comprises a drying temperature of 60-150 ℃, preferably 60-110 ℃, a drying time of 1-12 h, preferably 4-12 h, and/or Preferably, the first roasting condition comprises a roasting temperature of 300-1100 ℃, preferably 500-900 ℃ and a roasting time of 4-12 h.
4. A modified composite oxide carrier produced by the production method according to any one of claims 1 to 3, preferably the carrier is a SiO 2 -TiO 2 -Al 2 O 3 composite oxide, preferably the carrier contains 5 to 25 wt.% of Ti in terms of TiO 2 , 65 to 90 wt.% of Al in terms of Al 2 O 3 , preferably 80 to 90 wt.% and 0.5 to 15 wt.% of Si in terms of SiO 2 , and/or The specific surface of the support is 30m 2 /g～150m 2 /g, preferably 65m 2 /g～150m 2 /g, and/or The pore volume of the carrier is 0.2 mL/g-0.8 mL/g, preferably 0.35 mL/g-0.5 mL/g.
5. The use of the modified composite oxide support produced by the production method according to any one of claims 1 to 3 or the modified composite oxide support according to claim 4 for producing a non-noble metal selective hydrogenation catalyst, Preferably, the non-noble metal selective hydrogenation catalyst is used for catalyzing the selective hydrogenation of dimethyl maleate to prepare dimethyl succinate; Preferably, the non-noble metal selective hydrogenation catalyst comprises a carrier and an active component supported on the carrier, wherein the active component comprises a main active component Cu and an optional auxiliary active component, and the auxiliary active component is selected from at least one of Ni and Ru.
6. A selective hydrogenation catalyst comprising the modified composite oxide support produced by the production method according to any one of claims 1 to 3 or the modified composite oxide support according to claim 4 and an active component supported on the support, the active component comprising a main active component Cu and optionally a co-active component selected from at least one of Ni and Ru.
7. The catalyst according to claim 6, wherein the selective hydrogenation catalyst comprises Cu in an amount of 5 to 25wt% in terms of CuO, ni and/or Ru in an amount of 0 to 5wt% in terms of its oxide, preferably 0.1 to 5wt%, and the carrier in an amount of 70 to 95wt%, based on the selective hydrogenation catalyst, and/or The active component is distributed on the carrier in the form of nanoclusters, wherein the nanoclusters have a particle size of 5nm or less.
8. A process for preparing a selective hydrogenation catalyst according to claim 6 or7, comprising the steps of impregnating the modified composite oxide support prepared by the preparation process according to any one of claims 1 to 3 or the modified composite oxide support according to claim 4 with a copper salt solution, an optional nickel salt solution, and an optional ruthenium salt solution, respectively, followed by third drying and second calcination to obtain the catalyst; Preferably, the impregnation conditions comprise an impregnation temperature of 10-50 ℃ and an impregnation time of 1-12 hours, preferably 1-8 hours, and/or Preferably, the third drying condition comprises a drying temperature of 60-150 ℃, preferably 100-150 ℃, a drying time of 1-12 h, preferably 4-12 h, and/or Preferably, the second roasting condition comprises a roasting temperature of 300-1100 ℃, preferably 500-900 ℃ and a roasting time of 4-12 h, and/or Preferably, the copper source in the copper salt solution comprises at least one of a sulfate, nitrate, soluble carboxylate, hypophosphite and halide of copper, preferably the copper source is selected from at least one of copper sulfate, copper nitrate, copper chloride and copper acetate, and/or Preferably, the concentration of the copper salt solution is 0.1moL/L to 0.6moL/L, and/or Preferably, the solvents of the copper salt solution, the nickel salt solution and the ruthenium salt solution each independently comprise at least one of water, methanol, ethanol, benzene, toluene and chloroethane, and/or Preferably, the nickel salt solution and the ruthenium salt solution each independently comprise at least one of a corresponding nitrate, soluble carboxylate and halide, preferably at least one of a corresponding nitrate, hydrochloride, oxalate and acetate, more preferably nickel nitrate and/or ruthenium nitrate; Preferably, the concentration of the nickel salt solution and the ruthenium salt solution is 0.1moL/L to 0.6moL/L, preferably 0.1moL/L to 0.3moL/L, respectively.
9. The selective hydrogenation catalyst according to claim 6 or 7 or the use of the selective hydrogenation catalyst according to claim 8 in the preparation of dimethyl succinate by selective hydrogenation of dimethyl maleate, preferably, the selective hydrogenation conditions comprise a reaction temperature of 80-200 ℃, a pressure of 0.5-3 mpa, a volume ratio of hydrogen to catalyst of 200-2000:1, and a volume space velocity of the dimethyl maleate raw material of 0.1-3 h -1 .
10. A method for preparing dimethyl succinate by selectively hydrogenating dimethyl maleate comprises the step of carrying out selective hydrogenation reaction on dimethyl maleate and hydrogen in the presence of a selective hydrogenation catalyst according to claim 6 or 7 or a selective hydrogenation catalyst prepared by a preparation method according to claim 8, wherein the condition of the selective hydrogenation reaction preferably comprises the reaction temperature of 80-200 ℃, the pressure of 0.5-3 MPa, the volume ratio of hydrogen to the catalyst of 200-2000:1, and the volume space velocity of dimethyl maleate raw materials of 0.1h -1 ～3h -1 .

Description

Modified composite oxide carrier, preparation method and application thereof, catalyst containing carrier, preparation method and application thereof Technical Field The invention relates to the technical field of selective hydrogenation catalysts, in particular to a modified composite oxide carrier, a preparation method and application thereof, a catalyst containing the carrier, a preparation method and application thereof, and the carrier is particularly suitable for preparing a non-noble metal dimethyl maleate selective hydrogenation catalyst. Background Dimethyl succinate (DMS) is mainly used for synthesizing perfume and food additives, and is also an important chemical intermediate, and is widely used for preparing various chemicals. Further hydrogenating dimethyl succinate to produce 1, 4-butanediol, gamma-butyrolactone (GBL), tetrahydrofuran (THF) and the like, or performing transesterification polymerization with 1, 4-butanediol to produce the biodegradable material poly (butylene succinate) (PBS) with wide application prospect. PBS is short for poly (butylene succinate) and similar copolymers, and is aliphatic polyester mainly prepared by polycondensation of succinic acid and butanediol and copolymerization of the poly (butylene succinate) and other straight-chain dibasic acid or dihydric alcohol. PBS is milky white in appearance, odorless and tasteless, has excellent biodegradability, and can be 100% decomposed into CO 2 and H 2 O under natural conditions. PBS is one of hot spot materials for research of general type complete biodegradable plastics, has the characteristics of low price, excellent mechanical property and the like compared with PCL, PHB, PHA and other degradable plastics, and has the advantages of convenient processing and heat resistance compared with PLA with close price, and can adapt to the conventional plastic processing technology. The source of raw materials for PBS synthesis can be petroleum resources or biomass resources obtained by fermentation, and therefore, great attention is paid to science and industry. The current new PBS process uses dimethyl succinate (DMS) as a polymerizing monomer to polymerize with 1, 4-butanediol to produce PBS. Dimethyl succinate (DMS) is currently mainly prepared from succinic acid and methanol as raw materials through esterification reaction under the catalysis of a concentrated sulfuric acid catalyst. The process adopting the concentrated sulfuric acid catalyst for esterification has the advantages of multiple side reactions, low yield, complex post-treatment, serious equipment corrosion, and serious environmental pollution, and the byproduct dimethyl sulfate is a highly toxic substance. The Dimethyl Maleate (DMS) is prepared by using the selective hydrogenation of dimethyl maleate (also called dimethyl maleate DMM), so that concentrated sulfuric acid can be avoided, the environment is protected, and the fixed bed hydrogenation continuous production can be realized. Therefore, the use of dimethyl maleate (DMM) selective hydrogenation to prepare dimethyl succinate is a key to the whole new PBS manufacturing technology, in which noble metal hydrogenation catalysts are used abroad. The non-noble metal hydrogenation catalyst is researched and developed to prepare dimethyl succinate by selectively hydrogenating dimethyl maleate, so that the production cost can be reduced, and the running stability of the device can be improved. The development of non-noble metal hydrogenation catalysts, the preparation of dimethyl succinate (DMS) as a polymeric monomer by selective hydrogenation of readily available dimethyl maleate (DMM), will further promote the development of PBS. Disclosure of Invention In order to overcome at least one of the above problems in the prior art, it is an object of the present invention to provide a method for preparing a modified composite oxide carrier, which is suitable for preparing a catalyst for preparing dimethyl succinate (DMS) by selective hydrogenation of non-noble metal dimethyl maleate. The second object of the present invention is to provide a modified composite oxide carrier produced by the above production method. The invention also provides an application of the modified composite oxide carrier or the modified composite oxide carrier prepared by the preparation method in preparing a non-noble metal selective hydrogenation catalyst. It is a fourth object of the present invention to provide a selective hydrogenation catalyst comprising the above-mentioned carrier. The fifth object of the present invention is to provide a method for preparing the selective hydrogenation catalyst. The invention also provides an application of the selective hydrogenation catalyst or the selective hydrogenation catalyst prepared by the preparation method in preparing dimethyl succinate by selective hydrogenation of dimethyl maleate. The invention aims at providing a method for preparing dimethyl succinate by selectively hydrogenating d