CN-122006688-A - Modified composite oxide carrier, preparation method and application thereof, selective hydrogenation catalyst containing carrier, preparation method and application thereof

CN122006688ACN 122006688 ACN122006688 ACN 122006688ACN-122006688-A

Abstract

The invention provides a modified composite oxide carrier, which is a metal composite oxide modified by organic cation quaternary ammonium salt and silane reagents, wherein metal elements in the metal composite oxide comprise aluminum and titanium. According to the invention, the organic cationic quaternary ammonium salt and the silane reagent are introduced into the surface of the composite oxide, so that the defect of low crushing strength of the composite oxide caused by Ti introduction is overcome, the higher crushing strength can effectively avoid the pulverization problem of the catalyst in long-period operation, the catalyst can be produced in a strip extrusion mode, the contact area between the outer surface of the catalyst and the physical contact area is improved by utilizing the special-shaped surface, and the activity of the catalyst can be further improved. The invention also provides a preparation method and application of the modified composite oxide carrier, a selective hydrogenation catalyst containing the carrier, and a preparation method and application of the selective hydrogenation catalyst.

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 modified composite oxide carrier is characterized in that the carrier is a metal composite oxide modified by organic cation quaternary ammonium salt and silane reagents, and metal elements in the metal composite oxide comprise aluminum and titanium.
2. The carrier according to claim 1, wherein the organic cationic quaternary ammonium salt comprises a hydrocarbyl quaternary ammonium salt, preferably of the formula 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 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 alkaryl, at least one R, preferably 1 to 2R is selected from the group consisting of C6 and higher alkyl, preferably from the group consisting of C6 to C20 alkyl, the remaining R is preferably selected from the group consisting of C1 to C4 alkyl, C7 to C11 aralkyl; Preferably, the organic cation 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 organic cation quaternary ammonium salt is used in an amount of 1% -50%, preferably 30% -50%, more preferably 35% -50% of the mass of the metal composite oxide, and/or The silane reagent is used in an amount of 0.5-30%, preferably 0.5-15%, more preferably 0.5-10% by mass of the metal composite oxide, and/or The metal composite oxide is TiO 2 -Al 2 O 3 composite oxide, preferably, based on the TiO 2 -Al 2 O 3 composite oxide, the content of Ti in the TiO 2 -Al 2 O 3 composite oxide is 5-30wt%, preferably 8-25wt%, the content of Al in the TiO 2 composite oxide is 70-95wt%, preferably 75-92 wt%, and/or the content of Al in the Al 2 O 3 composite oxide is The carrier is SiO 2 -TiO 2 -Al 2 O 3 composite oxide, preferably, based on the carrier, the carrier contains 5-25wt% of Ti, 65-90wt% of Al, preferably 80-90wt% of Al, and 0.5-15wt% of Si, based on SiO 2 , based on TiO 2 , and/or The specific surface of the carrier is 30-150 m 2 /g, preferably 50-90 m 2 /g, and/or The pore volume of the carrier is 0.2-0.8 mL/g, preferably 0.3-0.5 mL/g.
3. A method for preparing the modified composite oxide carrier according to claim 1 or 2, which is characterized by comprising the steps of carrying out a first treatment on a metal composite oxide by using an organic cation quaternary ammonium salt solution, and then carrying out a second treatment on the metal composite oxide by using a silane reagent to obtain the carrier; Preferably, the first treatment comprises sequentially performing first impregnation and first drying, and/or the second treatment comprises dropwise adding a solution containing a silane reagent into the metal composite oxide subjected to the first treatment, and then stirring, performing second drying and first roasting, wherein the stirring time is preferably 1 min-60 min.
4. The method according to claim 3, wherein the solvent in the organic cationic quaternary ammonium salt solution is at least one of water, methanol, ethanol, benzene, toluene, ethyl chloride, isopropyl alcohol, acetone, hydrochloric acid, sulfuric acid, nitric acid, sodium hydroxide, potassium hydroxide, and/or The concentration of the organic cation quaternary ammonium salt solution is 0.1-10wt%, preferably 0.2-10wt%, more preferably 1-5wt%, and/or The solution containing the silane reagent is an aqueous solution containing the silane reagent, the concentration of the aqueous solution is 0.1-10wt%, preferably 1-10wt%, and/or The first impregnation condition comprises an impregnation temperature of 10-50 ℃ and an impregnation time of 1-12 hours, preferably 1-8 hours, and/or 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 hours, preferably 4-12 hours, and/or The first roasting condition comprises a roasting temperature of 300-1100 ℃, preferably 500-900 ℃ and a roasting time of 4-12 hours.
5. The use of the modified composite oxide carrier according to claim 1 or 2 or the modified composite oxide carrier produced by the production method according to claim 3 or 4 in 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 comprises a main active component which is Cu and optionally a co-active component selected from at least one of Ni and Ru.
6. A selective hydrogenation catalyst comprising the modified composite oxide support of claim 1 or 2 or the modified composite oxide support produced by the production method of claim 3 or 4 and an active component supported on the support, the active component comprising a main active component and optionally a co-active component, the main active component being Cu, the co-active component being selected from at least one of Ni and Ru; Preferably, the content of the carrier in the selective hydrogenation catalyst is 70wt% to 95wt%, the content of the main active component is 5wt% to 25wt%, preferably 10wt% to 25wt%, and the content of the auxiliary active component is 0wt% to 15wt%, preferably 0.1wt% to 15wt%, and/or based on the selective hydrogenation catalyst The active component is distributed on the carrier in the form of nanoclusters, wherein the nanoclusters have a particle size of 5nm or less.
7. A process for preparing a selective hydrogenation catalyst according to claim 6, comprising the steps of subjecting the support to a second impregnation with a copper-containing solution and optionally a solution containing a co-active component, followed by a third drying and a second calcination.
8. The method according to claim 7, wherein the copper source in the copper-containing solution comprises a sulfate, a nitrate, a soluble carboxylate, a hypophosphite and a 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, The concentration of the copper-containing solution is 0.1mol/L to 0.6mol/L, and/or, The solvent of the copper-containing solution and the auxiliary active component-containing solution is respectively and independently selected from at least one of water, methanol, ethanol, benzene, toluene and chloroethane, and/or, The salt of the co-active ingredient-containing solution is selected from at least one of a nitrate, a hydrochloride, a soluble carboxylate and a halide, preferably at least one of a nitrate, a hydrochloride, an oxalate and an acetate, more preferably nickel nitrate and/or ruthenium nitrate, and/or, The concentration of the auxiliary active component-containing solution is 0.1mol/L to 0.6mol/L, preferably 0.1mol/L to 0.3mol/L, and/or, The second impregnation condition comprises an impregnation temperature of 10-50 ℃ and an impregnation time of 1-12 hours, preferably 1-8 hours, and/or, The third drying condition comprises a drying temperature of 60-150 ℃, preferably 60-110 ℃ and a drying time of 1-12 h, and/or, The second roasting condition comprises that the temperature is 300-1100 ℃, preferably 500-900 ℃ and the time is 4-12 hours.
9. The selective hydrogenation catalyst of claim 6 or the application of the selective hydrogenation catalyst prepared by the preparation method of any one of claims 7-8 in preparing dimethyl succinate by selective hydrogenation of dimethyl maleate, preferably, the selective hydrogenation condition comprises that raw material dimethyl maleate and hydrogen are mixed and then enter a reactor, the reaction temperature is 80-200 ℃, the pressure is 0.5-3 MPa, the volume ratio of hydrogen to the catalyst is 200-2000:1, and the volume space velocity of the raw material dimethyl maleate is 0.1-3 h -1 .
10. A method for preparing dimethyl succinate by selectively hydrogenating dimethyl maleate is characterized by comprising the step of carrying out selective hydrogenation reaction on dimethyl maleate and hydrogen in the presence of a selective hydrogenation catalyst prepared by the selective hydrogenation catalyst according to claim 6 or a selective hydrogenation catalyst prepared by the preparation method according to any one of claims 7-8, wherein the selective hydrogenation reaction condition preferably comprises the steps of mixing raw material dimethyl maleate and hydrogen and then entering a reactor, wherein the reaction temperature is 80-200 ℃, the pressure is 0.5-3 MPa, the volume ratio of hydrogen to the catalyst is 200-2000:1, and the volume airspeed of dimethyl maleate raw materials is 0.1-3 h -1 .

Description

Modified composite oxide carrier, preparation method and application thereof, selective hydrogenation 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 selective hydrogenation catalyst containing the carrier, a preparation method and application thereof, and the carrier is particularly suitable for being used as a carrier of a non-noble metal dimethyl maleate selective hydrogenation catalyst. Background 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. Many specialists remain questionable about the biodegradability of PBAT (polybutylene terephthalate) due to the presence of benzene rings in terephthalic acid monomers in PBAT. PBS is therefore advantageous over PBAT in terms of environmental benefits. PBS is one of hot spot materials for general-purpose complete biodegradable plastic research, has the characteristics of low price, excellent mechanical property and the like compared with PCL, PHB, PHA and other degradable plastics, has the characteristics of convenient processing, adaptability to conventional plastic processing technology and good heat resistance compared with PLA with close price, and has the heat deformation temperature of more than 100 ℃ (the heat resistance temperature of PLA is only about 60 ℃). And the raw material source for PBS synthesis can be petroleum resources or biomass resources, so that the PBS synthesis is obtained through fermentation, and therefore, great attention is paid to science and technology and industry. Among these fully degradable aliphatic polyesters, PBS is one of the most promising general-purpose degradable plastics for industrialization. Current PBS processes use dimethyl succinate (DMS) as a polymerizing monomer to polymerize with 1, 4-butanediol to produce PBS. Dimethyl succinate (DMS) is mainly used for synthesizing perfume and food additives, is an important chemical intermediate, and is widely used for preparing various chemicals, such as 1, 4-butanediol, gamma-butyrolactone (GBL), tetrahydrofuran (THF) and the like, or is subjected to transesterification polymerization with 1, 4-butanediol to generate a biodegradable material polybutylene succinate (PBS) with wide application prospect. 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. For example, a company of Italy Kang Se (CONSER) uses a noble metal selective hydrogenation catalyst, the noble metal hydrogenation catalyst is easy to lose active components after long-term use, the impurity resistance is insufficient, and the non-noble metal hydrogenation catalyst is researched and developed to carry out selective hydrogenation on dimethyl maleate to prepare dimethyl succinate, so that the production cost can be reduced, and the running stability of the device is improved. In addition, development of non-noble metal hydrogenation catalysts, using readily available dimethyl maleate (DMM) for selective hydrogenation to prepare dimethyl succinate (DMS) as a polymeric monomer, will further promote the development of PBS. Disclosure of Invention Based on the foregoing, it is an object of the present invention to provide a modified composite oxide support which is suitable for use as a support for a catalyst for the selective hydrogenation of non-noble metal dimethyl maleate to dimethyl succinate (DMS). The second object of the present invention is to provide a method for producing a modified composite oxide carrier. The invention also provides an application of the modified composite oxide