CN110227451A - Dimethyl oxalate and dimethyl carbonate joint production process catalyst and preparation method thereof - Google Patents

Dimethyl oxalate and dimethyl carbonate joint production process catalyst and preparation method thereof Download PDF

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Publication number
CN110227451A
CN110227451A CN201910557112.XA CN201910557112A CN110227451A CN 110227451 A CN110227451 A CN 110227451A CN 201910557112 A CN201910557112 A CN 201910557112A CN 110227451 A CN110227451 A CN 110227451A
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catalyst
hours
carrier
sodium
potassium
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Inventor
梁旭
赵立红
蒋元力
李丰
崔发科
魏灵朝
曹洪刚
张国锋
丁蕊
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HENAN ENERGY CHEMICAL GROUP RESEARCH INSTITUTE Co Ltd
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HENAN ENERGY CHEMICAL GROUP RESEARCH INSTITUTE 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Abstract

The invention proposes a kind of dimethyl oxalates and dimethyl carbonate joint production process catalyst and preparation method thereof, and wherein catalyst includes the carrier of active component and load active component；Wherein carrier is Al2O3With TiO2Or ZrO2Composite oxides；TiO2Or ZrO2Content is Al2O3The 5 ~ 15% of quality；Active component includes palladium and metal hydroxides or metal salt；Palladium content is 0.001 ~ 0.2w% of carrier quality；Metal hydroxides or metal salt are 0.1 ~ 2w% of carrier quality.The advantages that active constituent content of catalyst disclosed by the invention is low, and feed stock conversion is high, selectivity of product is adjustable, while there is superperformance stability, can flexible modulation synthesis gas downstream product structure, enterprise's ability to ward off risks is provided.

Description

Dimethyl oxalate and dimethyl carbonate joint production process catalyst and preparation method thereof
Technical field
The present invention relates to chemical field catalyst technical fields, in particular to a kind of dimethyl oxalate and carbonic acid two Methyl esters joint production process catalyst and preparation method thereof.
Background technique
Coal based synthetic gas is the gas using coal as waste, and the carbon monoxide and hydrogen in coal gas are important chemical industry original Material.Traditional coal chemical process can prepare a variety of chemical products, such as synthesis ammonia, methanol using synthesis gas.Due to Modern Coal-based Chemical Rise, developing coal based synthetic gas or coke oven tail gas is the multiple chemical products of feedstock downstream, wherein dimethyl carbonate (DMC) and Dimethyl oxalate (DMO) is important Organic Chemicals.Dimethyl oxalate is mainly for the production of medicine, pesticide intermediate and second Glycol.The major product that emerging coal chemical industry is had become using synthesis gas coupling synthesizing dimethyl oxalate, because of raw material of synthetic gas source Extensively, the advantages that reaction condition is mild, energy saving, and raw material is can be recycled has realized industrialized production.
Dimethyl oxalate is subsequently used for the production of polyester material mainly for the production of ethylene glycol at present.And dimethyl carbonate As a kind of green chemical products, belong to nontoxic or micro- poison, be expected to from its structural behaviour numerous areas substitute comprehensively phosgene, The severe toxicity such as dimethyl suflfate (DMS), chloromethanes and methylchloroformate or carcinogenic substance be carbonylated, methylated, esterification and ester The reactions such as exchange produce a variety of chemical products, therefore the new foundation stone of referred to as 21 century organic synthesis.If can be from synthesis gas Raw material realize two kinds of chemical products production undoubtedly can for manufacturing enterprise structural adjustment and it is anti-risk on sound assurance is provided. 200610118543.9 disclose it is a kind of using synthesis gas as Material synthesis dimethyl oxalate and the method for by-product dimethyl carbonate, should Method provides the production process route of a kind of synthesizing dimethyl oxalate and by-product dimethyl carbonate, announce content from it is found that Dimethyl carbonate is only because a kind of catalyst not high and generation by-product selective to principal product dimethyl oxalate. CN101830806A equally discloses the method and apparatus of a kind of co-producing dimethyl carbonate and dimethyl oxalate, this method provides A kind of separation method and device of dimethyl carbonate and dimethyl oxalate.The above patent of invention is not directed to specific catalyst.
Provide thus it is a kind of can modulation dimethyl oxalate and dimethyl carbonate product proportion catalyst and its preparation side Method, can flexible modulation synthesis gas downstream product structure, providing enterprise's ability to ward off risks is those skilled in the art's urgent need to resolve Technical problem.
Summary of the invention
The present invention is based at least one above-mentioned technical problem, proposes a kind of dimethyl oxalate and dimethyl carbonate connection The active constituent content of catalyst of production. art catalyst and preparation method thereof, this method preparation is low, feed stock conversion height, The advantages that selectivity of product is adjustable, while there is superperformance stability.
In view of this, the invention proposes a kind of dimethyl oxalate and dimethyl carbonate joint production process catalyst, catalysis Agent includes the carrier of active component and load active component；Wherein carrier is Al2O3With TiO2Or ZrO2Composite oxides；TiO2 Or ZrO2Content is Al2O3The 5 ~ 15% of quality；Active component includes palladium and metal hydroxides or metal salt；Palladium content is carrier 0.001 ~ 0.2w% of quality；Metal hydroxides or metal salt are 0.1 ~ 2w% of carrier quality.
Further, metal is selected from one or more of sodium, potassium, calcium or magnesium.
Second direction according to the present invention proposes the method for preparing catalyst, includes the following steps:
(1) carrier is roasted 3 ~ 12 hours at 400 ~ 900 DEG C, is cooled to room temperature；
(2) compound concentration is the metal hydroxides or metal salt solution of 0.001 ~ 0.02g/mL, step (1) carrier is added molten Place 1 ~ 8 hour in liquid, 60 ~ 120 DEG C drying 1 ~ 6 hour, roast 2 ~ 12 hours under 200 ~ 800 DEG C of air atmospheres；
(3) preparing palladium ion concentration is 0.001 ~ 0.02g/mL palladium chloride solution, is added in step (2), and it is small to place 0.5 ~ 5 When, then 60 ~ 120 DEG C drying 1 ~ 6 hour roasts 2 ~ 24 hours under 150 ~ 500 DEG C of nitrogen atmospheres；
(4) by the material in step (3), 2 ~ 12 hours are handled under 150 ~ 400 DEG C of reducing atmospheres up to catalyst.
Further, step (1) roasting rear bearing surface area per unit volume product is 150 ~ 380m20.5 ~ 2.5cm of/g, Kong Rongwei3/ g is put down Equal aperture is 10 ~ 35nm.
Further, maturing temperature is 500 ~ 750 DEG C in step (1), and calcining time is 3 ~ 6 hours.
Further, metal hydroxides or metal salt are selected from sodium hydroxide, potassium hydroxide, potassium carbonate, nitre in step (2) Sour potassium, sodium carbonate, saleratus, sodium bicarbonate, sodium nitrate, calcium nitrate, magnesium nitrate, magnesium chloride, sodium chloride, potassium chloride, chlorination In calcium, one or more of sodium formate, sodium acetate, potassium formate or potassium acetate.
Further, calcination process temperature is 200 ~ 600 DEG C in step (2), is roasted 3 ~ 6 hours in air atmosphere.
Further, roasting described in step (3) roasts 3 ~ 8 hours at 180 ~ 300 DEG C.
Further, reducing atmosphere is carbon monoxide/nitrogen mixture in step (4), and volume ratio is 5 ~ 50v%.
By above technical scheme, the invention proposes a kind of dimethyl oxalates and dimethyl carbonate joint production process to be catalyzed The active constituent content of catalyst of agent and preparation method thereof, this method preparation is low, active temperature is low, feed stock conversion is high, The advantages that selectivity of product can be adjusted by raw material proportioning and reaction temperature, while there is superperformance stability.The catalyst It is reacted for carbon monoxide and methyl nitrite synthesizing dimethyl oxalate co-producing dimethyl carbonate, reaction condition is mild, operates bullet Property big, adjusting easy to produce, it is ensured that methyl nitrite conversion ratio be greater than 80%, dimethyl oxalate/dimethyl carbonate proportion of products For 1 ~ 19:1, and 1000 hours activity of continuous operation are held essentially constant.
Specific embodiment
To better understand the objects, features and advantages of the present invention, With reference to embodiment The present invention is further described in detail.It should be noted that in the absence of conflict, the embodiment of the present invention and reality The feature applied in example can be combined with each other.
In the following description, numerous specific details are set forth in order to facilitate a full understanding of the present invention, still, the present invention may be used also To be implemented using other than the one described here other modes, therefore, protection scope of the present invention is not by described below Specific embodiment limitation.
Embodiment 1
Catalyst includes the carrier of active component and load active component in the present embodiment；Wherein carrier is Al2O3With TiO2Or ZrO2Composite oxides；TiO2Or ZrO2Content is Al2O3The 5 ~ 15% of quality；Active component includes palladium and metal hydroxides Or metal salt；Metal is selected from one or more of sodium, potassium, calcium or magnesium；Palladium content is 0.001 ~ 0.2w% of carrier quality；Gold Belong to hydroxide or metal salt is 0.1 ~ 2w% of carrier quality.
Wherein the name of carrier is with TiO2Or ZrO2Mass percentage name.Wherein catalyst the preparation method is as follows:
(1) carrier is roasted 3 ~ 12 hours at 400 ~ 900 DEG C, is cooled to room temperature, carrier specific surface area is 150 ~ 380m2/ g, Kong Rong For 0.5 ~ 2.5cm3/ g, average pore size are 10 ~ 35nm；
(2) compound concentration is the metal hydroxides or metal salt solution of 0.001 ~ 0.02g/mL, step (1) carrier is added molten Place 1 ~ 8 hour in liquid, 60 ~ 120 DEG C drying 1 ~ 6 hour, roast 2 ~ 12 hours under 200 ~ 800 DEG C of air atmospheres；Wherein metal Hydroxide or metal salt solution are selected from sodium hydroxide, potassium hydroxide, potassium carbonate, potassium nitrate, sodium carbonate, saleratus, carbonic acid Hydrogen sodium, sodium nitrate, calcium nitrate, magnesium nitrate, magnesium chloride, sodium chloride, potassium chloride, in calcium chloride, sodium formate, sodium acetate, potassium formate Or one or more of potassium acetate；
(3) preparing palladium ion concentration is 0.001 ~ 0.02g/mL palladium chloride solution, is added in step (2), and it is small to place 0.5 ~ 5 When, then 60 ~ 120 DEG C drying 1 ~ 6 hour roasts 2 ~ 24 hours under 150 ~ 500 DEG C of nitrogen atmospheres；
(4) by the material in step (3), at 150 ~ 400 DEG C, volume ratio is in carbon monoxide/nitrogen mixture of 5 ~ 50v% Reason 2 ~ 12 hours up to catalyst.
Embodiment 2
Choose 5%TiO2-Al2O3Composite oxides, 650 DEG C roast 5 hours, are cooled to room temperature.Preparation potassium concentration is 0.01 g/ ML potassium nitrate aqueous solution 60mL, be added 100g processing after carrier, place 1 hour, 120 DEG C drying 4 hours, 350 DEG C of air atmospheres Lower roasting 2 hours.0.002 g/mL palladium chloride solution of 55mL is taken, is added after roasting in material, places 2 hours, 110 DEG C of dryings 5 Hour, it is roasted 4 hours under 250 DEG C of nitrogen atmospheres.It is passed through the carbon monoxide and 150 DEG C of nitrogen mixture reduction that volume ratio is 5v% 5 hours are handled under atmosphere up to catalyst.
Gained catalyst is anti-for carbon monoxide and methyl nitrite synthesizing dimethyl oxalate and dimethyl carbonate Ying Shiwei 4CH3ONO+3CO=CO(OCH3)2 (DMC)+(COOCH3)2(DMO)+4NO ↑, wherein air speed 3000h-1, methyl nitrite Concentration 15%, carbonomonoxide concentration 30%, 120 DEG C of reaction temperature, methyl nitrite conversion ratio 85%, dimethyl oxalate/carbonic acid two Methyl esters ratio is 90/10, and the two overall selectivity is 99%.
Embodiment 3
Choose 5%ZrO2-Al2O3Composite oxides, 550 DEG C roast 7 hours, are cooled to room temperature.Preparation magnesium ion concentration is 0.02 g/ ML magnesium nitrate aqueous solution 60mL, be added 100g processing after carrier, place 2 hours, 100 DEG C drying 5 hours, 320 DEG C of air atmospheres Lower roasting 2 hours.0.001 g/mL palladium chloride solution of 55mL is taken, is added after roasting in material, places 3 hours, 120 DEG C of dryings 5 Hour, it is roasted 4 hours under 200 DEG C of nitrogen atmospheres.It is passed through the carbon monoxide and 180 DEG C of nitrogen mixture reduction that volume ratio is 10v% 4 hours are handled under atmosphere up to catalyst.
Gained catalyst is for carbon monoxide and methyl nitrite synthesizing dimethyl oxalate and dimethyl carbonate, air speed 3000h-1, methyl nitrite concentration 15%, carbonomonoxide concentration 40%, 115 DEG C of reaction temperature, methyl nitrite conversion ratio 81%, Dimethyl oxalate/dimethyl carbonate ratio is 95/5, and the two overall selectivity is 99.5%.
Embodiment 4
Choose 15%ZrO2-Al2O3Composite oxides, 800 DEG C roast 3 hours, are cooled to room temperature.Preparing calcium ion concentration is 0.01 G/mL calcium nitrate aqueous solution 60mL, be added 100g processing after carrier, place 3 hours, 110 DEG C drying 5 hours, 200 DEG C of air gas It is roasted 3 hours under atmosphere.0.004 g/mL palladium chloride solution of 50mL is taken, is added after roasting in material, is placed 3 hours, 120 DEG C dry It dry 5 hours, roasts 4 hours under 250 DEG C of nitrogen atmospheres.It is passed through the carbon monoxide and 210 DEG C of nitrogen mixture that volume ratio is 15v% 4 hours are handled under reducing atmosphere up to catalyst.
Gained catalyst is for carbon monoxide and methyl nitrite synthesizing dimethyl oxalate and dimethyl carbonate, air speed 3000h-1, methyl nitrite concentration 15%, carbonomonoxide concentration 23%, 120 DEG C of reaction temperature, methyl nitrite conversion ratio 83%, Dimethyl oxalate/dimethyl carbonate ratio is 85/15, and the two overall selectivity is 99.2%.
Embodiment 5
Choose 10%TiO2-Al2O3Composite oxides, 700 DEG C roast 5 hours, are cooled to room temperature.Preparation Na ion concentration is 0.02g/ ML sodium hydrate aqueous solution 60mL, be added 100g processing after carrier, place 3 hours, 110 DEG C drying 5 hours, 550 DEG C of air gas It is roasted 3 hours under atmosphere.0.002 g/mL palladium chloride solution of 50mL is taken, is added after roasting in material, is placed 3 hours, 120 DEG C dry It dry 5 hours, roasts 3 hours under 300 DEG C of nitrogen atmospheres.It is passed through the carbon monoxide and 170 DEG C of nitrogen mixture that volume ratio is 30v% 5 hours are handled under reducing atmosphere up to catalyst.
Gained catalyst is for carbon monoxide and methyl nitrite synthesizing dimethyl oxalate and dimethyl carbonate, air speed 3000h-1, methyl nitrite concentration 15%, carbonomonoxide concentration 18%, 125 DEG C of reaction temperature, methyl nitrite conversion ratio 82%, Dimethyl oxalate/dimethyl carbonate ratio is 80/20, and the two overall selectivity is 99.5%.
Embodiment 6
Choose 15%TiO2-Al2O3Composite oxides, 750 DEG C roast 4 hours, are cooled to room temperature.Preparation potassium concentration is 0.02g/ ML potassium hydroxide aqueous solution 70mL, be added 100g processing after carrier, place 3 hours, 120 DEG C drying 4 hours, 450 DEG C of air gas It is roasted 3 hours under atmosphere.0.001 g/mL palladium chloride solution of 60mL is taken, is added after roasting in material, is placed 4 hours, 120 DEG C dry It dry 5 hours, roasts 3 hours under 450 DEG C of nitrogen atmospheres.It is passed through the carbon monoxide and 300 DEG C of nitrogen mixture that volume ratio is 20v% 6 hours are handled under reducing atmosphere up to catalyst.
Gained catalyst is for carbon monoxide and methyl nitrite synthesizing dimethyl oxalate and dimethyl carbonate, air speed 3000h-1, methyl nitrite concentration 15%, carbonomonoxide concentration 14%, 130 DEG C of reaction temperature, methyl nitrite conversion ratio 84%, Dimethyl oxalate/dimethyl carbonate ratio is 60/40, and the two overall selectivity is 99.1%.
Embodiment 7
Choose 10%ZrO2-Al2O3Composite oxides, 600 DEG C roast 6 hours, are cooled to room temperature.Preparation magnesium ion concentration is 0.02g/ ML magnesium chloride brine 65mL, be added 100g processing after carrier, place 3 hours, 110 DEG C drying 5 hours, 550 DEG C of air atmospheres Lower roasting 4 hours.60mL 0.003g/mL palladium chloride solution is taken, is added after roasting and is placed 4 hours in material, 110 DEG C of dryings 5 are small When, it roasts 3 hours under 300 DEG C of nitrogen atmospheres.It is passed through volume ratio and goes back Primordial Qi for the carbon monoxide of 15v% and 200 DEG C of nitrogen mixture 8 hours are handled under atmosphere up to catalyst.
Gained catalyst is for carbon monoxide and methyl nitrite synthesizing dimethyl oxalate and dimethyl carbonate, air speed 3000h-1, methyl nitrite concentration 15%, carbonomonoxide concentration 20%, 115 DEG C of reaction temperature, methyl nitrite conversion ratio 81%, Dimethyl oxalate/dimethyl carbonate ratio is 85/15, and the two overall selectivity is 99.6%.
Comparative example 1
By 10%ZrO in embodiment 72-Al2O3Composite oxides replace with ZrO2Carrier, remaining parameter constant.
Gained catalyst is for carbon monoxide and methyl nitrite synthesizing dimethyl oxalate and dimethyl carbonate, air speed 3000h-1, methyl nitrite concentration 15%, carbonomonoxide concentration 20%, 115 DEG C of reaction temperature, methyl nitrite conversion ratio 43%, Dimethyl oxalate/dimethyl carbonate ratio is 40/51, and the two overall selectivity is 85.2%.
Comparative example 2
By 10%ZrO in embodiment 72-Al2O3Composite oxides replace with Al2O carrier, remaining parameter constant.
Gained catalyst is for carbon monoxide and methyl nitrite synthesizing dimethyl oxalate and dimethyl carbonate, air speed 3000h-1, methyl nitrite concentration 15%, carbonomonoxide concentration 20%, 115 DEG C of reaction temperature, methyl nitrite conversion ratio 64%, Dimethyl oxalate/dimethyl carbonate ratio is 96/3, and the two overall selectivity is 92.7%.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.

Claims (9)

1. a kind of dimethyl oxalate and dimethyl carbonate joint production process catalyst, which is characterized in that the catalyst includes living Property component and load the carrier of the active component；Wherein the carrier is Al2O3With TiO2Or ZrO2Composite oxides；Institute State TiO2Or ZrO2Content is the Al2O3The 5 ~ 15% of quality；The active component includes palladium and metal hydroxides or described Metal salt；The palladium content is 0.001 ~ 0.2w% of the carrier quality；The metal hydroxides or the metal salt are institute State 0.1 ~ 2w% of carrier quality.
2. a kind of dimethyl oxalate according to claim 1 and dimethyl carbonate joint production process catalyst, feature exist In the metal is selected from one or more of sodium, potassium, calcium or magnesium.
3. the method for preparing catalyst as claimed in claim 1 or 2, which comprises the steps of:
(1) carrier is roasted 3 ~ 12 hours at 400 ~ 900 DEG C, is cooled to room temperature；
(2) compound concentration is the metal hydroxides or the metal salt solution of 0.001 ~ 0.02g/mL, and step (1) is carried Body is added in solution and places 1 ~ 8 hour, 60 ~ 120 DEG C drying 1 ~ 6 hour, roast 2 ~ 12 hours under 200 ~ 800 DEG C of air atmospheres；
(3) preparing palladium ion concentration is 0.001 ~ 0.02g/mL palladium chloride solution, is added in step (2), and it is small to place 0.5 ~ 5 When, then 60 ~ 120 DEG C drying 1 ~ 6 hour roasts 2 ~ 24 hours under 150 ~ 500 DEG C of nitrogen atmospheres；
(4) by the material in step (3), 2 ~ 12 hours are handled under 150 ~ 400 DEG C of reducing atmospheres up to catalyst.
4. the method according to claim 3 for preparing the catalyst, which is characterized in that institute after step (1) roasting Stating carrier specific surface area is 150 ~ 380m20.5 ~ 2.5cm of/g, Kong Rongwei3/ g, average pore size are 10 ~ 35nm.
5. the method according to claim 3 for preparing the catalyst, which is characterized in that roast temperature described in step (1) Degree is 500 ~ 750 DEG C, and calcining time is 3 ~ 6 hours.
6. the method according to claim 3 for preparing the catalyst, which is characterized in that metallic hydrogen described in step (2) Oxide or the metal salt are selected from sodium hydroxide, potassium hydroxide, potassium carbonate, potassium nitrate, sodium carbonate, saleratus, bicarbonate Sodium, sodium nitrate, calcium nitrate, magnesium nitrate, magnesium chloride, sodium chloride, potassium chloride, in calcium chloride, sodium formate, sodium acetate, potassium formate or One or more of potassium acetate.
7. the method according to claim 3 for preparing the catalyst, which is characterized in that at roasting described in step (2) Managing temperature is 200 ~ 600 DEG C, is roasted 3 ~ 6 hours in air atmosphere.
8. the method according to claim 3 for preparing the catalyst, which is characterized in that described in the step (3) Roasting roasts 3 ~ 8 hours at 180 ~ 300 DEG C.
9. the method according to claim 3 for preparing the catalyst, which is characterized in that reproducibility in the step (4) Atmosphere is carbon monoxide/nitrogen mixture, and wherein carbon monoxide volume ratio is 5 ~ 50v%.
CN201910557112.XA 2019-06-25 2019-06-25 Dimethyl oxalate and dimethyl carbonate joint production process catalyst and preparation method thereof Pending CN110227451A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101993361A (en) * 2009-08-31 2011-03-30 中国石油化工股份有限公司上海石油化工研究院 Method for producing oxalic ester
US20110196167A1 (en) * 2010-02-09 2011-08-11 Almusaiteer Khalid A Synthesis of dimethyl carbonate from carbon dioxide and methanol
CN102649755A (en) * 2011-02-25 2012-08-29 中国石油化工股份有限公司 Method for preparing dimethyl carbonate by CO gaseous-phase coupling
CN102962060A (en) * 2012-11-22 2013-03-13 北京北大先锋科技有限公司 Catalyst for synthetizing dimethyl oxalate and preparation method thereof
CN103962130A (en) * 2014-04-28 2014-08-06 河南能源化工集团研究院有限公司 Catalyst for oxalate ester synthetic reaction and preparation method of catalyst
CN105597743A (en) * 2016-03-01 2016-05-25 中国科学院福建物质结构研究所 Preparation method of catalyst for CO gas-phase catalyzed synthesis of dimethyl oxalate

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101993361A (en) * 2009-08-31 2011-03-30 中国石油化工股份有限公司上海石油化工研究院 Method for producing oxalic ester
US20110196167A1 (en) * 2010-02-09 2011-08-11 Almusaiteer Khalid A Synthesis of dimethyl carbonate from carbon dioxide and methanol
CN102649755A (en) * 2011-02-25 2012-08-29 中国石油化工股份有限公司 Method for preparing dimethyl carbonate by CO gaseous-phase coupling
CN102962060A (en) * 2012-11-22 2013-03-13 北京北大先锋科技有限公司 Catalyst for synthetizing dimethyl oxalate and preparation method thereof
CN103962130A (en) * 2014-04-28 2014-08-06 河南能源化工集团研究院有限公司 Catalyst for oxalate ester synthetic reaction and preparation method of catalyst
CN105597743A (en) * 2016-03-01 2016-05-25 中国科学院福建物质结构研究所 Preparation method of catalyst for CO gas-phase catalyzed synthesis of dimethyl oxalate

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