CN110773164A - Cu/Al for oxalate hydrogenation 2O 3/SiO 2Process for preparing catalyst - Google Patents

Cu/Al for oxalate hydrogenation 2O 3/SiO 2Process for preparing catalyst Download PDF

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CN110773164A
CN110773164A CN201910978168.2A CN201910978168A CN110773164A CN 110773164 A CN110773164 A CN 110773164A CN 201910978168 A CN201910978168 A CN 201910978168A CN 110773164 A CN110773164 A CN 110773164A
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copper
catalyst
sio
aluminum
oxalate
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李国华
黄磊
潘剑明
莫晓璐
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Zhejiang University of Technology ZJUT
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention relates to Cu/Al for oxalate hydrogenation 2O 3/SiO 2A method for preparing the catalyst. The method comprises the steps of slowly dripping copper-silicon turbid liquid into aluminum hydroxide colloid, and then drying, roasting, tabletting and grinding to obtain the oxalate hydrogenated Cu/Al 2O 3/SiO 2A catalyst. The aluminum hydroxide colloid has stronger adsorbability and can be precipitated after adsorption, so that the dispersion degree of the active component copper in the carrier is better, the sintering resistance of the copper is improved, and the stability of the catalyst is improved. The method is simple and low in cost, and when the catalyst prepared by the method is used for preparing the ethylene glycol by hydrogenating the oxalate, the selectivity of the ethylene glycol can reach 95 percent, and the conversion rate of the oxalate can reach 95 percentReaching 99 percent and being capable of continuously operating with high stability.

Description

Cu/Al for oxalate hydrogenation 2O 3/SiO 2Process for preparing catalyst
(I) technical field
The invention relates to Cu/Al for oxalate hydrogenation 2O 3/SiO 2A method for preparing the catalyst.
(II) background of the invention
Ethylene glycol is an important organic chemical raw material, and is mainly used for manufacturing products such as terylene, resin, moisture absorbent, plasticizer, surfactant and the like. Currently, the traditional route for the industrial synthesis of ethylene glycol is the petroleum route. China is a poor-oil and multi-coal country, and under the drive of increasingly exhausted petroleum resources, the oxalate hydrogenation method in the process of preparing ethylene glycol from coal becomes the hot research of the C1 chemical field. At present, the preparation method of the copper-based catalyst mainly adopts a precipitation method and an ammonia distillation method.
The use of SiO in recent years 2Research and application of a copper-based catalyst for preparing ethylene glycol by hydrogenating oxalate and prepared by a carrier become hot spots in the research field and make certain progress. Yue Hairong et al supported Cu on cordierite, increasing the stability of the catalyst. Cu-SiO to be prepared by Ye Runping et al 2In combination with a MOF material, a novel catalyst with low loading and over 95% selectivity to ethylene glycol was obtained. Zhu Ying-Ying researches the influence of the preparation method on the formation of the copper nanoparticles, and compared with the impregnation method, the copper nanoparticles prepared by the deposition precipitation method are smaller and more uniformly dispersed, the conversion rate of the oxalate is close to 100%, and the selectivity of the glycol is higher. The university of eastern China carries out model process condition experimental research on the preparation of glycol by hydrogenating oxalate, and under the conditions that the pressure is 2MPa, the temperature is 187-197 ℃, and the liquid hourly space velocity is 0.5-0.7g/gcata.h, the conversion rate of oxalate is close to 100%, and the selectivity of glycol is more than 95%.
In the long-term reaction operation process, the catalyst is not strong enough, and the active component copper is easy to sinter, so that the reaction is difficult to operate for a long time under high activity. And Cu/Al 2O 3/SiO 2The catalyst improves the dispersion degree of the active component copper, thereby improving the stability of the catalyst.
Disclosure of the invention
The invention aims to provide Cu/Al for oxalate hydrogenation with good selectivity, high stability and low cost 2O 3/SiO 2A method for preparing the catalyst.
The technical scheme adopted by the invention is as follows:
Cu/Al for oxalate hydrogenation 2O 3/SiO 2Method for preparing catalyst, active component Cu quality in the catalystThe content is 10-20%, and the method comprises the following steps:
(1) preparing aluminum hydroxide colloid: adding 0.1-2.0 mol/L ammonia water into 0.1-2.0 mol/L aluminum salt solution under stirring, controlling the pH to be 4.0-8.0, and heating and refluxing for 10-24 h to obtain aluminum hydroxide colloid;
(2) preparing copper-silicon turbid liquid: dissolving a copper salt in deionized water, adding silica sol, and stirring for 1-5 hours to obtain a copper-silicon turbid solution; the diameter of the silica sol colloidal particle is 10-50 nm, and SiO is 2The mass content is 10-40%;
(3) slowly dropwise adding the copper-silicon turbid liquid obtained in the step (2) into the aluminum hydroxide colloid obtained in the step (1), stirring for 3-6 h in a water bath at 50-60 ℃, filtering, washing, drying, roasting the dried solid for 2-6 h at 400-550 ℃, and obtaining Cu/Al 2O 3/SiO 2A catalyst precursor;
(4) Cu/Al obtained in step (3) 2O 3/SiO 2Tabletting, grinding and screening the catalyst precursor to obtain 20-40 mesh particles, and placing the particles in a fixed bed reactor to be reduced by hydrogen to obtain the Cu/Al for hydrogenation of oxalate 2O 3/SiO 2A catalyst.
The aluminum hydroxide colloid has stronger adsorbability and can be precipitated after adsorption, so that the dispersion degree of the active component copper in the carrier is better, the sintering resistance of the copper is improved, and the stability of the catalyst is improved.
The aluminum salt in the step (1) is one of the following: aluminum nitrate, aluminum sulfate, aluminum chloride, preferably aluminum chloride.
The copper salt in the step (2) is one of the following: copper nitrate, copper sulfate, copper chloride, copper acetate, preferably copper nitrate.
The reflux temperature in the step (1) is 160-240 ℃, and preferably 240 ℃.
The reduction conditions in the step (4) are as follows: the temperature is 250-350 ℃, the time is 1-4 h, and the preferred temperature is 300 ℃ and 4 h.
The invention has the following beneficial effects: the method is simple and low in cost, and when the catalyst prepared by the method is used for preparing the ethylene glycol by hydrogenating the oxalate, the selectivity of the ethylene glycol reaches 95 percent, the conversion rate of the oxalate reaches 99 percent, and the catalyst can continuously operate with high stability.
(IV) detailed description of the preferred embodiments
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
example 1:
1.Cu/Al 2O 3/SiO 2preparation of the catalyst
0.2128g of aluminum chloride solid is weighed and dissolved in 16ml of deionized water, 0.3mol/L ammonia water solution is dripped under the stirring state, the pH value is adjusted to 5.2, and the obtained solution is refluxed for 22h at 240 ℃ to obtain stable and transparent aluminum hydroxide colloid.
3.872g of copper nitrate was weighed and dissolved in 31.24ml of deionized water, and 28.9g of silica sol (JN-30, Kingjiang Delimitsu micro-nano technology Co., Ltd.) was added dropwise with stirring and stirred at room temperature for 1 hour. And dripping the obtained suspension into aluminum hydroxide colloid, placing the aluminum hydroxide colloid into a water bath at 50 ℃, heating and stirring for 5 hours, then carrying out suction filtration and washing on the obtained solid, and placing the solid in an oven at 100 ℃ for drying overnight. Roasting the dried solid in a muffle furnace at 450 ℃ for 4h to obtain a sample, tabletting, grinding and screening to obtain 20-40-mesh particles, thus obtaining the Cu/Al 2O 3/SiO 2Catalyst, in which the Cu content of the active component is 10%, is recorded as 10Cu/Al 2O 3/SiO 2。
2. Performance testing of the catalyst
0.1g of the catalyst is weighed and loaded into a fixed bed reactor, and both ends of the catalyst are filled with quartz wool. Before the reaction, 30ml/min of nitrogen is introduced into the fixed bed, the temperature of the bed layer is raised to 300 ℃ at the heating rate of 5 ℃/min, and then 25ml/min of pure hydrogen is switched to reduce for 3 h. The reactor was cooled to 270 ℃ with hydrogen, the pressure in the reactor was maintained at 2.8MPa, and a solution of oxalic ester in methanol (10% by mass) was injected into the reactor at 0.045ml/min with a constant flow pump, with the hydrogen flow rate being controlled at 8.3 ml/min. After reacting for 2h, liquid was collected and chromatographed.
Example 2:
1.Cu/Al 2O 3/SiO 2preparation of the catalyst
0.2128g of aluminum chloride solid is weighed and dissolved in 16ml of deionized water, 0.3mol/L ammonia water solution is dripped under the stirring state, the pH value is adjusted to 5.2, and the obtained solution is refluxed for 22h at 240 ℃ to obtain stable and transparent aluminum hydroxide colloid.
3.872g of copper nitrate was weighed and dissolved in 31.24ml of deionized water, and 18.32g of silica sol (JN-30, Kingjiang Delimitsu micro-nano technology Co., Ltd.) was added dropwise with stirring and stirred at room temperature for 1 hour. And dripping the obtained suspension into aluminum hydroxide colloid, placing the aluminum hydroxide colloid into a water bath at 50 ℃, heating and stirring for 5 hours, then carrying out suction filtration and washing on the obtained solid, and placing the solid in an oven at 100 ℃ for drying overnight. Roasting the dried solid in a muffle furnace at 450 ℃ for 4h to obtain a sample, tabletting, grinding and screening to obtain 20-40-mesh particles, thus obtaining the Cu/Al 2O 3/SiO 2The catalyst has an active component Cu content of 15%, and is recorded as 15Cu/Al 2O 3/SiO 2。
2. Performance testing of the catalyst
0.1g of the catalyst is weighed and loaded into a fixed bed reactor, and both ends of the catalyst are filled with quartz wool. Before the reaction, 30ml/min of nitrogen is introduced into the fixed bed, the temperature of the bed layer is raised to 300 ℃ at the heating rate of 5 ℃/min, and then 25ml/min of pure hydrogen is switched to reduce for 3 h. The reactor was cooled to 270 ℃ with hydrogen, the pressure in the reactor was maintained at 2.8MPa, and a solution of oxalic ester in methanol (10% by mass) was injected into the reactor at 0.045ml/min with a constant flow pump, with the hydrogen flow rate being controlled at 8.3 ml/min. After reacting for 2h, liquid was collected and chromatographed.
Example 3:
1.Cu/Al 2O 3/SiO 2preparation of the catalyst
0.2128g of aluminum chloride solid is weighed and dissolved in 16ml of deionized water, 0.3mol/L ammonia water solution is dripped under the stirring state, the pH value is adjusted to 5.2, and the obtained solution is refluxed for 22h at 240 ℃ to obtain stable and transparent aluminum hydroxide colloid.
3.872g of copper nitrate were weighed into 31.24ml of deionized waterWhile stirring, 12.63g of silica sol (JN-30, Kingjiang Delhi micro-nano technology Co., Ltd.) was added dropwise and stirred at room temperature for 1 hour. And dripping the obtained suspension into aluminum hydroxide colloid, placing the aluminum hydroxide colloid into a water bath at 50 ℃, heating and stirring for 5 hours, then carrying out suction filtration and washing on the obtained solid, and placing the solid in an oven at 100 ℃ for drying overnight. Roasting the dried solid in a muffle furnace at 450 ℃ for 4h to obtain a sample, tabletting, grinding and screening to obtain 20-40-mesh particles, thus obtaining the Cu/Al 2O 3/SiO 2The catalyst has an active component Cu content of 20%, and is marked as 20Cu/Al 2O 3/SiO 2。
2. Performance testing of the catalyst
0.1g of the catalyst is weighed and loaded into a fixed bed reactor, and both ends of the catalyst are filled with quartz wool. Before the reaction, 30ml/min of nitrogen is introduced into the fixed bed, the temperature of the bed layer is raised to 300 ℃ at the heating rate of 5 ℃/min, and then 25ml/min of pure hydrogen is switched to reduce for 3 h. The reactor was cooled to 270 ℃ with hydrogen, the pressure in the reactor was maintained at 2.8MPa, and a solution of oxalic ester in methanol (10% by mass) was injected into the reactor at 0.045ml/min with a constant flow pump, with the hydrogen flow rate being controlled at 8.3 ml/min. After reacting for 2h, liquid was collected and chromatographed.
Example 4:
1.Cu/Al 2O 3/SiO 2preparation of the catalyst
0.2128g of aluminum chloride solid is weighed and dissolved in 16ml of deionized water, 0.3mol/L ammonia water solution is dripped under the stirring state, the pH value is adjusted to 5.2, and the obtained solution is refluxed for 22h at 240 ℃ to obtain stable and transparent aluminum hydroxide colloid.
3.872g of copper nitrate was weighed and dissolved in 31.24ml of deionized water, and 12.63g of silica sol (JN-30, Kingjiang Delimitsu micro-nano technology Co., Ltd.) was added dropwise with stirring and stirred at room temperature for 1 hour. And dripping the obtained suspension into aluminum hydroxide colloid, placing the aluminum hydroxide colloid into a water bath at 50 ℃, heating and stirring for 5 hours, then carrying out suction filtration and washing on the obtained solid, and placing the solid in an oven at 100 ℃ for drying overnight. Roasting the dried solid in a muffle furnace at 400 ℃ for 4h to obtain a sample, tabletting, grinding and screeningObtaining 20-40 mesh particles, namely obtaining Cu/Al 2O 3/SiO 2The catalyst has an active component Cu content of 20%, and is marked as 20Cu/Al 2O 3/SiO 2-400。
2. Performance testing of the catalyst
0.1g of the catalyst is weighed and loaded into a fixed bed reactor, and both ends of the catalyst are filled with quartz wool. Before the reaction, 30ml/min of nitrogen is introduced into the fixed bed, the temperature of the bed layer is raised to 300 ℃ at the heating rate of 5 ℃/min, and then 25ml/min of pure hydrogen is switched to reduce for 3 h. The reactor was cooled to 270 ℃ with hydrogen, the pressure in the reactor was maintained at 2.8MPa, and a solution of oxalic ester in methanol (10% by mass) was injected into the reactor at 0.045ml/min with a constant flow pump, with the hydrogen flow rate being controlled at 8.3 ml/min. After reacting for 2h, liquid was collected and chromatographed.
Example 5:
1.Cu/Al 2O 3/SiO 2preparation of the catalyst
0.2128g of aluminum chloride solid is weighed and dissolved in 16ml of deionized water, 0.3mol/L ammonia water solution is dripped under the stirring state, the pH value is adjusted to 5.2, and the obtained solution is refluxed for 22h at 240 ℃ to obtain stable and transparent aluminum hydroxide colloid.
3.872g of copper nitrate was weighed and dissolved in 31.24ml of deionized water, and 12.63g of silica sol (JN-30, Kingjiang Delimitsu micro-nano technology Co., Ltd.) was added dropwise with stirring and stirred at room temperature for 1 hour. And dripping the obtained suspension into aluminum hydroxide colloid, placing the aluminum hydroxide colloid into a water bath at 50 ℃, heating and stirring for 5 hours, then carrying out suction filtration and washing on the obtained solid, and placing the solid in an oven at 100 ℃ for drying overnight. Roasting the dried solid in a muffle furnace at 500 ℃ for 4h to obtain a sample, tabletting, grinding and screening to obtain 20-40-mesh particles, thus obtaining the Cu/Al 2O 3/SiO 2The catalyst has an active component Cu content of 20%, and is marked as 20Cu/Al 2O 3/SiO 2-500。
2. Performance testing of the catalyst
0.1g of the catalyst is weighed and loaded into a fixed bed reactor, and both ends of the catalyst are filled with quartz wool. Before the reaction, 30ml/min of nitrogen is introduced into the fixed bed, the temperature of the bed layer is raised to 300 ℃ at the heating rate of 5 ℃/min, and then 25ml/min of pure hydrogen is switched to reduce for 3 h. The reactor was cooled to 270 ℃ with hydrogen, the pressure in the reactor was maintained at 2.8MPa, and a solution of oxalic ester in methanol (10% by mass) was injected into the reactor at 0.045ml/min with a constant flow pump, with the hydrogen flow rate being controlled at 8.3 ml/min. After reacting for 2h, liquid was collected and chromatographed.
Example 6:
1.Cu/Al 2O 3/SiO 2preparation of the catalyst
0.2128g of aluminum chloride solid is weighed and dissolved in 16ml of deionized water, 0.3mol/L ammonia water solution is dripped under the stirring state, the pH value is adjusted to 5.2, and the obtained solution is refluxed for 22h at 240 ℃ to obtain stable and transparent aluminum hydroxide colloid.
3.872g of copper nitrate was weighed and dissolved in 31.24ml of deionized water, and 12.63g of silica sol (JN-30, Kingjiang Delimitsu micro-nano technology Co., Ltd.) was added dropwise with stirring and stirred at room temperature for 1 hour. And dripping the obtained suspension into aluminum hydroxide colloid, placing the aluminum hydroxide colloid into a water bath at 50 ℃, heating and stirring for 5 hours, then carrying out suction filtration and washing on the obtained solid, and placing the solid in an oven at 100 ℃ for drying overnight. Roasting the dried solid in a muffle furnace at 550 ℃ for 4h to obtain a sample, tabletting, grinding and screening to obtain 20-40-mesh particles, thus obtaining the Cu/Al 2O 3/SiO 2The catalyst has an active component Cu content of 20%, and is marked as 20Cu/Al 2O 3/SiO 2-550。
2. Performance testing of the catalyst
0.1g of the catalyst is weighed and loaded into a fixed bed reactor, and both ends of the catalyst are filled with quartz wool. Before the reaction, 30ml/min of nitrogen is introduced into the fixed bed, the temperature of the bed layer is raised to 300 ℃ at the heating rate of 5 ℃/min, and then 25ml/min of pure hydrogen is switched to reduce for 3 h. The reactor was cooled to 270 ℃ with hydrogen, the pressure in the reactor was maintained at 2.8MPa, and a solution of oxalic ester in methanol (10% by mass) was injected into the reactor at 0.045ml/min with a constant flow pump, with the hydrogen flow rate being controlled at 8.3 ml/min. After reacting for 2h, liquid was collected and chromatographed.
Comparative example 1:
1.Cu/SiO 2preparation of the catalyst
3.872g of copper nitrate was weighed and dissolved in 31.24ml of deionized water, and 12.63g of silica sol (JN-30, Kingjiang Delimitsu micro-nano technology Co., Ltd.) was added dropwise with stirring and stirred at room temperature for 1 hour. Placing in 50 ℃ water bath, heating and stirring for 5h, then carrying out suction filtration and washing on the obtained solid, and placing in a 100 ℃ oven for drying overnight. Roasting the dried solid in a muffle furnace at 450 ℃ for 4h to obtain a sample, tabletting, grinding and screening to obtain 20-40-mesh particles, thus obtaining the Cu/SiO 2The catalyst has an active component Cu content of 20%, and is marked as 20Cu/SiO 2。
2. Performance testing of the catalyst
0.1g of the catalyst is weighed and loaded into a fixed bed reactor, and both ends of the catalyst are filled with quartz wool. Before the reaction, 30ml/min of nitrogen is introduced into the fixed bed, the temperature of the bed layer is raised to 300 ℃ at the heating rate of 5 ℃/min, and then 25ml/min of pure hydrogen is switched to reduce for 3 h. The reactor was cooled to 270 ℃ with hydrogen, the pressure in the reactor was maintained at 2.8MPa, and a solution of oxalic ester in methanol (10% by mass) was injected into the reactor at 0.045ml/min with a constant flow pump, with the hydrogen flow rate being controlled at 8.3 ml/min. After reacting for 2h, liquid was collected and chromatographed.
The results of comparing the reaction performance of the catalysts obtained in examples 1 to 6 and comparative example 1 in the preparation of ethylene glycol by hydrogenation of dimethyl oxalate are shown in table 1:
table 1: comparison of catalyst Performance
Figure BDA0002234338230000091
The results of the above examples show that the invention provides Cu/Al 2O 3/SiO 2The catalyst has higher catalytic activity in the reaction of preparing the ethylene glycol by catalyzing ester hydrogenation, and is compared with Cu/SiO 2The selectivity of the catalyst to glycol is close to 80%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (7)

1. Cu/Al for oxalate hydrogenation 2O 3/SiO 2The preparation method of the catalyst comprises the following steps of:
(1) preparing aluminum hydroxide colloid: adding 0.1-2.0 mol/L ammonia water into 0.1-2.0 mol/L aluminum salt solution under stirring, controlling the pH to be 4.0-8.0, and heating and refluxing for 10-24 h to obtain aluminum hydroxide colloid;
(2) preparing copper-silicon turbid liquid: dissolving a copper salt in deionized water, adding silica sol, and stirring for 1-5 hours to obtain a copper-silicon turbid solution; the diameter of the silica sol colloidal particle is 10-50 nm, and SiO is 2The mass content is 10-40%;
(3) slowly dropwise adding the copper-silicon turbid liquid obtained in the step (2) into the aluminum hydroxide colloid obtained in the step (1), stirring for 3-6 h in a water bath at 50-60 ℃, filtering, washing, drying, roasting the dried solid for 2-6 h at 400-550 ℃, and obtaining Cu/Al 2O 3/SiO 2A catalyst precursor;
(4) Cu/Al obtained in step (3) 2O 3/SiO 2Tabletting, grinding and screening the catalyst precursor to obtain 20-40 mesh particles, and placing the particles in a fixed bed reactor to be reduced by hydrogen to obtain the Cu/Al for hydrogenation of oxalate 2O 3/SiO 2A catalyst.
2. The method of claim 1, wherein the aluminum salt in step (1) is one of: aluminum nitrate, aluminum sulfate, aluminum chloride.
3. The method of claim 2, wherein the aluminum salt in step (1) is aluminum chloride.
4. The method of claim 1, wherein in step (2) the copper salt is one of: copper nitrate, copper sulfate, copper chloride and copper acetate.
5. The method of claim 4, wherein in step (2) the copper salt is copper nitrate.
6. The method according to claim 1, wherein the reflux temperature in step (1) is 160 to 240 ℃.
7. The method of claim 1, wherein the reducing conditions in step (4) are: the temperature is 250-350 ℃, and the time is 1-4 h.
CN201910978168.2A 2019-10-15 2019-10-15 Cu/Al for oxalate hydrogenation 2O 3/SiO 2Process for preparing catalyst Pending CN110773164A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101890373A (en) * 2009-05-19 2010-11-24 中国石油化工股份有限公司 Silica-alumina composite carrier and method for preparing same
CN103816908A (en) * 2014-03-20 2014-05-28 神华集团有限责任公司 Catalyst for preparing alcohol by hydrogenising acetate and preparation method of catalyst
CN104248952A (en) * 2013-06-28 2014-12-31 中国石油化工股份有限公司 Catalyst for preparation of glycol by oxalate hydrogenation and preparation method thereof
CN107303488A (en) * 2016-04-18 2017-10-31 上海浦景化工技术股份有限公司 A kind of ester through hydrogenation catalyst and preparation method and application
CN108273509A (en) * 2017-01-06 2018-07-13 平顶山市汇通达科技开发有限公司 A kind of catalyst and preparation method thereof for preparing glycol by hydrogenating oxalate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101890373A (en) * 2009-05-19 2010-11-24 中国石油化工股份有限公司 Silica-alumina composite carrier and method for preparing same
CN104248952A (en) * 2013-06-28 2014-12-31 中国石油化工股份有限公司 Catalyst for preparation of glycol by oxalate hydrogenation and preparation method thereof
CN103816908A (en) * 2014-03-20 2014-05-28 神华集团有限责任公司 Catalyst for preparing alcohol by hydrogenising acetate and preparation method of catalyst
CN107303488A (en) * 2016-04-18 2017-10-31 上海浦景化工技术股份有限公司 A kind of ester through hydrogenation catalyst and preparation method and application
CN108273509A (en) * 2017-01-06 2018-07-13 平顶山市汇通达科技开发有限公司 A kind of catalyst and preparation method thereof for preparing glycol by hydrogenating oxalate

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
刘建周等: "《工业催化工程》", 30 June 2018, 徐州：中国矿业大学出版社 *
黄彬等: "《实用化学教程》", 28 February 2018, 北京：北京邮电大学出版社 *

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