CN111298791B - Preparation method of composite carrier catalyst for preparing ethylene glycol by dimethyl oxalate hydrogenation - Google Patents

Preparation method of composite carrier catalyst for preparing ethylene glycol by dimethyl oxalate hydrogenation Download PDF

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CN111298791B
CN111298791B CN201911180980.7A CN201911180980A CN111298791B CN 111298791 B CN111298791 B CN 111298791B CN 201911180980 A CN201911180980 A CN 201911180980A CN 111298791 B CN111298791 B CN 111298791B
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catalyst
solution
adjusting
preparation
ethylene glycol
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CN111298791A (en
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乔川
周焕文
曲雪琴
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Dalian Ruike Technology Co ltd
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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
    • B01J35/615—
    • B01J35/635—
    • B01J35/647—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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

Abstract

A preparation method of a composite carrier catalyst for preparing ethylene glycol by dimethyl oxalate hydrogenation belongs to the technical field of preparation of coal chemical catalysts. The method comprises the following steps: adding urea into aqueous solution of copper nitrate, and then using HNO 3 Adjusting the pH value of the solution; adding silica sol and titanium sol into the solution, adjusting the pH value with nitric acid, and adding the reaction mixture into a hydrothermal kettle for reaction; then the solid obtained by filtering is washed, dried, roasted and formed. Finally reducing to obtain the composite carrier TiO 2 ‑SiO 2 Catalyst of (2), tiO in the catalyst 2 The mass fraction is 5-40%, and the loading capacity of copper is 10-50%. TiO2 2 The catalyst effectively improves the pore structure of the catalyst, improves the selectivity of the glycol, reduces the coverage of active center polymer and carbon deposition, and is beneficial to prolonging the service life.

Description

Preparation method of composite carrier catalyst for preparing ethylene glycol by dimethyl oxalate hydrogenation
Technical Field
The invention relates to the technical field of preparation of catalysts in coal chemical industry, and relates to a preparation method of a catalyst for preparing ethylene glycol by hydrogenation of dimethyl oxalate.
Background
Ethylene glycol is an important organic chemical raw material in petrochemical industry. It not only reacts with terephthalic acid to produce polyethylene terephthalate (PET), but also is an important raw material for producing alkyd resin, polyester fiber and polyester plastics. It can also be used to prepare moisture absorbent, plasticizer, surfactant, cosmetics and explosive, and used as solvent for dye and ink, and used to prepare antifreezing agent of engine.
Traditional industrial preparation route-hydration or pressurized hydration process industrial route: ethylene glycol is synthesized in a fixed bed reactor by an ethylene oxide hydration method under certain pressure and temperature. The raw material ethylene oxide is obtained by oxidizing ethylene obtained by petroleum cracking. In view of the national situation that China has more coal and less oil, and the cost of the hydration method depends on the price of petroleum and downstream products, the cost of the route is greatly increased. The preparation route of synthesizing dimethyl oxalate by carbonylation of synthesis gas and preparing ethylene glycol by hydrogenation is in line with the advantage of abundant coal resources in China. The industrial production of dimethyl oxalate through carbon monoxide coupling synthesis is mature at home and abroad, and the ethylene glycol prepared by hydrogenating dimethyl oxalate can obtain better yield under necessary control conditions.
At present, most of catalysts used for preparing ethylene glycol by hydrogenating dimethyl oxalate are Cu/SiO2 catalysts, such as patents CN 101411990A and CN101648134A, and the catalysts have high conversion rate of dimethyl oxalate and good EG selectivity. However, how to prolong the service life of the catalyst is an important problem in industrial production. The catalyst deactivation process index shows that the activity is reduced, the selectivity is reduced, and the EG yield is reduced; the catalyst is characterized by sintering, carbon deposition and Cu valence change of an active component. According to the analysis of the reaction mechanism, cu crystal grains of the catalyst grow, the intermediate product of the reaction, namely methyl glycolate, is enriched on the catalyst to generate polymers with reaction raw materials or products, or carbon deposition substances, such as polyethylene glycol, diethylene glycol and other polymers generated by the polymerization of ethylene glycol, can cover the active center of the catalyst to block the pore channel, so that the activity of the catalyst is reduced, and even the catalyst is coked. Therefore, analysis of the catalyst internal and external diffusion from a kinetic perspective is one of the factors affecting coking. The industrial process indexes are adjusted as follows: such as increasing the H2/ester ratio, increasing the reaction temperature, decreasing the liquid hourly space velocity, etc., to extend the catalyst life. The pore structure of the catalyst is improved from the microstructure, so that the reaction product can be timely diffused out of the pore channel, and the problems of the generated polymer covering the active center of the catalyst, the activity reduction and the coking of the catalyst can be essentially solved, so that the service life of the catalyst is prolonged.
Disclosure of Invention
In order to overcome the defects of the technology, the aperture of the catalyst is increased, and the diffusion speed of the material is improved, the invention fully considers that the catalyst developed by taking TiO2 as a carrier by a sol-gel method has the characteristics of high activity, good low-temperature activity, good thermal stability, strong resistance to poisoning and the like, can promote the reduction and vulcanization of metal oxide loaded on the surface of the catalyst, has the advantages of larger specific surface area, aperture and pore volume, can effectively improve the pore structure when being used in an oxalate hydrogenation Cu/SiO2 catalyst, increases the Cu dispersibility, prevents Cu grains from growing, accelerates the reaction diffusion speed, reduces the polymer covered by the active center of the catalyst, and avoids carbon deposition and coking; the effective active specific surface area is improved, so that the activity of the catalyst, the DMO conversion rate and the EG selectivity are improved, and the service life of the catalyst is prolonged.
The technical scheme of the invention is a preparation method of a Cu/TiO2-SiO2 catalyst, and the sol-gel-hydrothermal method comprises the following steps:
1. under the condition of normal temperature, dissolving copper nitrate in water to prepare copper nitrate aqueous solution with the concentration of 0.05-0.5 mol/L, wherein the mass ratio of urea to copper nitrate is 3-12: 1, adding urea solid and using HNO 3 Adjusting the pH of the solution, adjusting the corresponding pH of the silica sol and the titanium sol, adding the solution into the copper liquid respectively while stirring, continuing to stir for 1-3 hours, adding the reaction mixture into a hydrothermal kettle, keeping the temperature at 50-150 ℃ until the pH is = 6-8, and reacting for 20-40 hours; then filtering, washing, drying, roasting and forming the solid obtained by filtering. Finally reducing to obtain the composite carrier TiO 2 -SiO 2 Catalyst of (2), tiO in the catalyst 2 The mass fraction is 5-25% (wt), and the load of CuO in the catalyst is 10-50%.
2. With HNO 3 Regulating the pH value of the copper solution, the silica sol and the titanium sol to be less than or equal to 2.
3. The mass ratio of urea to copper nitrate is 3-12: 1, preferably in a ratio of 5-10.
4. The reaction temperature of the reaction solution is 50-150 ℃, and the preferable reaction temperature is 70-120 ℃;
5. the reaction time of the reaction solution is 20-40h, and the preferable reaction time is 25-35h;
6. in the catalyst TiO 2 The mass fraction is 5-40% (wt), the preferred proportion is 15-30%; the supported amount of CuO in the catalyst is 10-50%, preferably 25%.
7. The roasting temperature of the catalyst is 300-600 ℃, and the preferred roasting temperature is 350-550 ℃.
The invention relates to a preparation method of a catalyst for preparing ethylene glycol by hydrogenating dimethyl oxalate, which takes copper nitrate as a copper source, silica sol as a silicon source, titanium sol as a titanium source and urea as a precipitator, prepares a Cu/TiO2-SiO2 catalyst by a uniform precipitation method, and obtains the preferable mass content of TiO2 of 15-30%, the mass content of CuO of 25%, the DMO conversion rate of more than 99% and the EG selectivity of 98.5% by observing the catalyst ratio, the pore size distribution and the corresponding performance by adjusting the TiO2 proportion in a catalyst carrier. TiO2 2 The addition of the catalyst effectively improves the pore structure of the catalyst, improves the selectivity of the ethylene glycol, reduces the coverage of active center polymers and carbon deposition, and is beneficial to prolonging the service life.
The catalyst developed by taking TiO2 as a carrier by a sol-gel method has the characteristics of high activity, good low-temperature activity, good thermal stability, strong resistance to poisoning and the like, can promote the reduction and vulcanization of metal oxide loaded on the surface of the catalyst, has the advantages of large specific surface area, pore diameter and pore volume, can effectively improve the pore structure when being used in an oxalate hydrogenation Cu/SiO2 catalyst, increases the Cu dispersibility, prevents Cu crystal grains from growing up, accelerates the reaction diffusion speed, reduces the polymer covering of the active center of the catalyst, and avoids carbon deposition and coking; the effective active specific surface area is improved, so that the activity of the catalyst, the DMO conversion rate and the EG selectivity are improved, and the service life of the catalyst is prolonged.
Detailed Description
Comparative example
Weighing 40.4g of copper nitrate (Cu (NO 3) 2.3H 2O) solid, dissolving in 1300ml of deionized water, adding 51g of urea, adjusting the pH of the solution to be less than or equal to 2 by using HNO3 after dissolving, dropwise adding 157.7g of silica sol (25 percent of SiO2 and pH of the HNO3 adjusting solution to be less than or equal to 2), stirring for 2H, transferring the mixture into a hydrothermal kettle, stirring for 2H, heating to 90 ℃, keeping for 30H, filtering, washing with water, drying at 120 ℃, and roasting at 360 ℃ for 3H to obtain the catalyst precursor; reducing the catalyst precursor (20-40 mesh) in a fixed bed reactor with 30% of H2-N2 at 230 ℃ for 4h at 420mL/min to obtain the CuO catalyst with the load of 25%, and the rest SiO2 =75% (wt%). The physical properties and evaluation results of the catalyst are shown in Table 1.
Example 1
Weighing 40.4g of copper nitrate (Cu (NO 3) 2.3H 2O) solid, dissolving the solid in 1280ml of deionized water, adding 51g of urea, adjusting the pH of the solution to be less than or equal to 2 by using HNO3 after dissolution, respectively dropwise adding 141.9g of silica sol (SiO 2 with the mass fraction of 25% and the pH of the HNO3 adjusting solution to be less than or equal to 2) and 26.3g of titanium sol (TiO 2 with the mass fraction of 15% and the pH of the HNO3 adjusting solution to be less than or equal to 2), stirring for 2h, transferring the mixture into a hydrothermal kettle, stirring for 2h, heating to 90 ℃, keeping for 30h, then filtering, washing, drying at 120 ℃, and roasting for 3h at 360 ℃ to obtain the catalyst precursor; reducing the catalyst precursor (20-40 mesh) in a fixed bed reactor by using 420mL/min 30% of H2-N2 at 230 ℃ for 4h to obtain the CuO catalyst with the load of 25%, wherein the mass fraction of TiO2 on the catalyst is 7.5wt%. The physical properties and evaluation results of the catalyst are shown in Table 1.
Example 2
Weighing 40.4g of copper nitrate (Cu (NO 3) 2.3H 2O) solid, dissolving in 1260ml of deionized water, adding 51g of urea, adjusting the pH of the solution to be less than or equal to 2 by HNO3 after dissolution, respectively dropwise adding 126.2g of silica sol (25% of SiO2, the pH of the solution to be adjusted by HNO3 to be less than or equal to 2) and 52.6g of titanium sol (15% of TiO2 and the pH of the solution to be adjusted by HNO3 to be less than or equal to 2), stirring for 2h, transferring the mixture into a hydrothermal kettle, stirring for 2h, heating to 90 ℃, keeping for 30h, then filtering, washing with water, drying at 120 ℃, and roasting for 3h at 360 ℃ to obtain the catalyst precursor; reducing a catalyst precursor (20-40 meshes) in a fixed bed reactor by using 420mL/min 30 percent of H2-N2 at 230 ℃ for 4 hours to obtain the CuO catalyst with the load of 25 percent, wherein the mass fraction of TiO2 on the catalyst is 15wt percent, and the physical properties and evaluation results of the catalyst are shown in Table 1.
Example 3
Weighing 40.4g of copper nitrate (Cu (NO 3) 2.3H 2O) solid, dissolving in 1240ml of deionized water, adding 51g of urea, adjusting the pH of the solution to be less than or equal to 2 by HNO3 after dissolution, respectively dropwise adding 110.4g of silica sol (25% of SiO2, the pH of the solution to be adjusted by HNO3 to be less than or equal to 2) and 78.9g of titanium sol (15% of TiO2 and the pH of the solution to be adjusted by HNO3 to be less than or equal to 2), stirring for 2h, transferring the mixture into a hydrothermal kettle, stirring for 2h, heating to 90 ℃, keeping for 30h, then filtering, washing with water, drying at 120 ℃, and roasting for 3h at 360 ℃ to obtain the catalyst precursor; reducing the catalyst precursor (20-40 mesh) in a fixed bed reactor by using 420mL/min 30% of H2-N2 at 230 ℃ for 4h to obtain the CuO catalyst with the load of 25%, wherein the mass fraction of TiO2 on the catalyst is 22.5wt%. The physical properties and evaluation results of the catalyst are shown in Table 1.
Example 4
Weighing 40.4g of copper nitrate (Cu (NO 3) 2.3H 2O) solid, dissolving in 1220ml of deionized water, adding 51g of urea, adjusting the pH of the solution to be less than or equal to 2 by using HNO3 after dissolving, respectively dropwise adding 94.6g of silica sol (25% of SiO2, the pH of the solution to be adjusted by using HNO3 to be less than or equal to 2) and 105.1g of titanium sol (15% of TiO2 and the pH of the solution to be adjusted by using HNO3 to be less than or equal to 2), stirring for 2h, transferring the mixture into a hydrothermal kettle, stirring for 2h, heating to 90 ℃, keeping for 30h, then filtering, washing with water, drying at 120 ℃, and roasting for 3h at 360 ℃ to obtain the catalyst precursor; reducing catalyst precursor (20-40 mesh) in fixed bed reactor with 30% of H2-N2 at 230 deg.C of 420mL/min for 4 hr to obtain 25% CuO catalyst, and adding TiO to the catalyst 2 The mass fraction ratio is 30wt%. The physical properties and evaluation results of the catalyst are shown in Table 1.
Example 5
Weighing 40.4g of copper nitrate (Cu (NO 3) 2.3H 2O) solid, dissolving in 1200ml of deionized water, adding 51g of urea, adjusting the pH of the solution to be less than or equal to 2 by HNO3 after dissolution, respectively dropwise adding 78.9g of silica sol (25% of SiO2, the pH of the solution to be adjusted by HNO3 to be less than or equal to 2) and 131.4g of titanium sol (15% of TiO2 and the pH of the solution to be adjusted by HNO3 to be less than or equal to 2), stirring for 2h, transferring the mixture into a hydrothermal kettle, stirring for 2h, heating to 90 ℃, keeping for 30h, then filtering, washing with water, drying at 120 ℃, and roasting for 3h at 360 ℃ to obtain the catalyst precursor; reducing a catalyst precursor (20-40 meshes) in a fixed bed reactor by using 420mL/min 30 percent of H2-N2 at 230 ℃ for 4 hours to obtain the CuO catalyst with the load of 25 percent, wherein the mass fraction of TiO2 on the catalyst is 37.5 percent by weight, and the physical properties and evaluation results of the catalyst are shown in Table 1.
The specific surface area of the catalyst is determined by a V-Sorb 2008P specific surface area and pore size analyzer.
The catalyst performance evaluation conditions were temperature: 180 ℃, pressure: 3MPa, the oxalate feed is a methanol solution containing 20 percent of dimethyl oxalate, the mass ratio of hydrogen to the dimethyl oxalate is 75, and the space velocity of the oxalate is 1.0g/ml.h -1 . The evaluation results of the respective catalysts are shown in the table.
TABLE 1 comparison of support composition with catalyst characterization and Performance
Catalyst and process for producing the same BET m2/g D BJH nm Vp ml/g X DMO % S EG %
Comparative example 1 425 6.9 0.79 95.7 88.3
Case 1 395 8.0 0.83 98.9 97.4
Case 2 387 8.3 0.87 99.3 98.7
Case 3 381 8.9 0.92 99.8 99.6
Case 4 376 9.2 0.95 99.7 98.5
Case 5 366 9.4 0.97 99.5 98.1
According to the evaluation result of the catalyst, the addition of the titanium oxide improves the aperture of the catalyst, so that the reaction materials can enter and exit the inside of the catalyst particles, and the reaction performance of the catalyst is improved.

Claims (1)

1. TiO for preparing ethylene glycol by dimethyl oxalate hydrogenation 2 -SiO 2 The preparation method of the composite carrier catalyst is characterized by comprising the following steps:
weighing 40.4g Cu (NO) 3 ) 2 •3H 2 Dissolving O solid in 1240mL deionized water, adding 51g urea, dissolving, and adding HNO 3 Adjusting the pH of the solution to 2 or less, adding 110.4g 25% SiO dropwise 2 Of silica sol, HNO 3 Adjusting the solution pH to 2 or less, and 78.9g 15% 2 Titanium sol of (2), HNO 3 Adjusting the pH value of the solution to be less than or equal to 2, stirring for 2h, transferring the solution into a hydrothermal kettle, stirring for 2h, heating to 90 ℃, keeping the temperature for 30h, then filtering, washing with water, drying at 120 ℃, and roasting at 360 ℃ for 3h to obtain a catalyst precursor;
subjecting a 20-40 mesh catalyst precursor to a fixed bed reactor with a 30% H of 420mL/min 2 -N 2 Reducing for 4 hours at 230 ℃ to obtain 25 percent CuO catalyst, and adding TiO on the catalyst 2 The mass fraction ratio is 22.5wt%.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5801115A (en) * 1995-09-05 1998-09-01 Kataleuna Gmbh Catalyst composition and methods for using and preparing same
CN101342489A (en) * 2007-07-12 2009-01-14 上海焦化有限公司 Hydrogenation reaction catalyst, preparation and application thereof
CN102125843A (en) * 2010-12-07 2011-07-20 浙江大学 Method for preparing catalyst for hydrogenation reaction of dimethyl oxalate and product
CN102225338A (en) * 2011-04-29 2011-10-26 上海浦景化工技术有限公司 Composite carrier catalyst used for glycol and synthesized from hydrogenation of alkyl oxalate, and preparation method thereof
CN104923228A (en) * 2014-03-17 2015-09-23 中国石油化工股份有限公司 Catalyst for preparing ethylene glycol by hydrogenation of oxalate and preparation method thereof
CN108722408A (en) * 2017-12-26 2018-11-02 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) A kind of catalyst and preparation method thereof of dimethyl oxalate gas phase hydrogenation synthesizing glycol

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5801115A (en) * 1995-09-05 1998-09-01 Kataleuna Gmbh Catalyst composition and methods for using and preparing same
CN101342489A (en) * 2007-07-12 2009-01-14 上海焦化有限公司 Hydrogenation reaction catalyst, preparation and application thereof
CN102125843A (en) * 2010-12-07 2011-07-20 浙江大学 Method for preparing catalyst for hydrogenation reaction of dimethyl oxalate and product
CN102225338A (en) * 2011-04-29 2011-10-26 上海浦景化工技术有限公司 Composite carrier catalyst used for glycol and synthesized from hydrogenation of alkyl oxalate, and preparation method thereof
CN104923228A (en) * 2014-03-17 2015-09-23 中国石油化工股份有限公司 Catalyst for preparing ethylene glycol by hydrogenation of oxalate and preparation method thereof
CN108722408A (en) * 2017-12-26 2018-11-02 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) A kind of catalyst and preparation method thereof of dimethyl oxalate gas phase hydrogenation synthesizing glycol

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
"Cu／SiO2催化剂的制备、表征及其对草酸二乙酯加氢制乙二醇的催化性能";王保伟等;《催化学报》;20080331;第29卷(第3期);275-280 *
"Enhanced catalytic performance for SiO2-TiO2 binary oxide supported Cu-based catalyst in the hydrogenation of dimethyloxalate";Wen Chao et al.;《Applied Catalysis A: General》;20130510;第458卷;82-89 *
SiO_2/TiO_2复合气凝胶的孔道结构研究;傅颖怡等;《材料科学与工艺》;20150415(第02期);6-12 *
脂肪酸酯催化加氢制醇研究进展;张峻炜等;《化工进展》;20091115;第28卷;62-65 *

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