CN101143322A - Catalyst used for catalytic synthesizing dimethyl carbonate directly from methanol and carbon dioxide and preparation and using method thereof - Google Patents
Catalyst used for catalytic synthesizing dimethyl carbonate directly from methanol and carbon dioxide and preparation and using method thereof Download PDFInfo
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Abstract
The invention discloses a direct catalytic synthesis catalyst to prepare dimethyl carbonate from methanol and carbon dioxide and the preparation and application methods of the catalyst. The catalyst of the invention consists of transitional metal soluble salt, promoter and carrier, with the weight ration from 0.01to 0.5: 0.01to 0.1:1. The preparation method is that: (1) the carrier is impregnated into the transition metal soluble salt solution; (2) the promoter is added into the solution, which is stirred in room temperature, ultrasonically dispersed and stored stationarily in room temperature; (3) the solution is dried, sintered, reduced and activated to produce catalyst. The application method is that: the catalyst is put in high pressure reactor or micro reaction device with the temperature of the catalyst bed controlled between 90 degrees centigrade to 140 degrees centigrade and the reaction pressure between 0.6 to 3.0MPa. The catalyst is applicable in direct catalytic synthesis to prepare dimethyl carbonate from methanol and carbon dioxide. The raw material sources are rich, the cost is low, the preparation method is simple and the operation is easy. The catalyst is easily separated from the products, the reaction conditions are mild and the catalyst can be used repeatedly. The catalyst has high activity and selectivity.
Description
Technical field
The present invention relates to a kind of catalyst that is used for Synthesis of dimethyl carbonate, preparation method and using method.
Background technology
Dimethyl carbonate (DMC) is a kind of important organic synthesis intermediate, be described as " new template " of organic synthesis, its can replace severe toxicity or carcinogenic materials such as phosgene, methylchloroformate, dimethyl suflfate and methyl chloride as carbonylation, methylate and methoxylation reagent, can be used for the initiation material of eco-friendly intermediate and organic synthesis.In recent years, DMC obtains application more and more widely in fields such as producing high performance resin, solvent, dyestuff intermediate, medicated premix, food preservative, fuel oil additive and is subject to people's attention day by day.At present, there is the patent of producing and using about DMC in a large number to deliver both at home and abroad, and the suitability for industrialized production of existing certain scale.The synthetic method that DMC is traditional mainly contains three major types: phosgenation, oxidative carbonylation of methanol method and ester-interchange method.A, phosgenation are traditional DMC synthetic methods, and this route uses phosgene to be raw material, produces the hydrogen chloride gas of severe corrosion equipment simultaneously, and the serious environmental pollution problem is eliminated gradually because the phosgene severe toxicity causes extremely; B, oxidative carbonylation of methanol method are primary raw material with the carbon monoxide, need additional expensive gas maker, and carbon monoxide has potential explosion hazard simultaneously; C, ester-interchange method earlier carry out cycloaddition by carbon dioxide and active epoxide, prepare target product by the ester exchange with methyl alcohol again, while by-product polyalcohol.This route steps is loaded down with trivial details, and course of reaction is restive, and separation of by-products is handled trouble.Present DMC is synthetic to adopt oxidative carbonylation of methanol method and ester-interchange method usually, but cost is higher, thereby has limited the extensive use of DMC.
In recent years, utilize cheap, nontoxic carbon dioxide to have bigger research, development and application potentiality for raw material and with the synthetic DMC of the direct catalysis of methyl alcohol.Not only be significant aspect synthetic chemistry, carbon resource utilization and the environmental protection by carbon dioxide and the synthetic DMC of the direct catalysis of methyl alcohol, and production process is simplified, production cost significantly reduces, and is the new way that development DMC produces.But because synthetic being reflected on the thermodynamics of DMC of carbon dioxide and the direct catalysis of methyl alcohol is disadvantageous, there is the water that makes catalysqt deactivation to generate simultaneously in the product, the restriction of above-mentioned two aspects causes in the building-up process selectivity of conversion of raw material and target product low, so the catalyst or the design coupled reaction that need design to have higher catalytic activity change means of chemical reaction, therefore explore different reaction paths, process conditions, in the hope of the carrying out and the raising product yield of driving a reaction, become a difficult problem and the focus of subject study.At present, both at home and abroad oneself has done a large amount of research to carbon dioxide and the directly synthetic DMC of methyl alcohol.Employed catalyst system and catalyzing, comprise alkaline-earth metal alkoxy compound, alkali, acetate, organic metal tin, titanium alkoxide compound, carried metal class, zirconium dioxide class, the ceria class, organic tin and ionic liquid class etc., but subject matter is that the selectivity of the conversion ratio of reactant and target product is lower, course of reaction is restive, therefore is difficult to realize suitability for industrialized production.
Summary of the invention
The purpose of this invention is to provide a kind of catalyst that can be used for methyl alcohol and the direct catalytic synthesizing dimethyl carbonate of carbon dioxide.
It is simple that another object of the present invention provides a kind of step, the method for the above-mentioned catalyst of preparation that cost is low.
Further purpose of the present invention provides the using method of above-mentioned catalyst.
Of the present invention being used for is made up of the catalyst of methyl alcohol and the direct catalytic synthesizing dimethyl carbonate of carbon dioxide soluble salt, auxiliary agent and the carrier three by transition metal; The soluble salt of transition metal is in metal oxide, with the weight ratio of auxiliary agent, carrier be 0.01～0.5: 0.01～0.1: 1.
In above-mentioned catalyst, described transition metal is meant copper or nickel.As copper nitrate or copper sulphate or copper chloride etc., nickel nitrate or nickelous sulfate or nickel chloride etc.
In above-mentioned catalyst, described auxiliary agent is the oxide that contains rhodium, yttrium, vanadium, molybdenum, zirconium, yttrium, cerium, soluble-salt or oxysalt.
In above-mentioned catalyst, described carrier is graphite oxide, expanded graphite, CNT or active carbon.
Described graphite oxide carrier is by natural graphite powder, natural flake graphite or expansible graphite preparation, step is as follows: with natural graphite powder, natural flake graphite or expansible graphite in the presence of the concentrated sulfuric acid, potassium permanganate and sodium nitrate, in reacting below 4 ℃ 10～20 minutes, 35～38 ℃ were reacted 10～100 minutes down, reacted 15～90 minutes down at 90～100 ℃ again, product fully washs with 5% hydrochloric acid and deionized water, drying is 12～36 hours in 60～90 ℃ of vacuum drying chambers, obtains the graphite oxide carrier.
Described carbon nanotube carrier is by single wall or multi-walled carbon nano-tubes preparation, comprise the steps: SWCN or many walls nanotube in the presence of the concentrated sulfuric acid and red fuming nitric acid (RFNA), the volume ratio of the concentrated sulfuric acid and red fuming nitric acid (RFNA) is 1: 5～5: 1, in 80～120 ℃ of following back flow reaction 6～36 hours, product fully washs with deionized water, 60～90 ℃ of following vacuum drying dryings 12～36 hours, obtain carbon nanotube carrier.
Described expanded graphite carrier is prepared by expansible graphite, comprises the steps: expansible graphite to obtain the expanded graphite carrier 700～1000 ℃ of following expanding treatments 5～30 seconds.
Described active carbon comprises coal mass active carbon, the fiber-reactive charcoal of cocoanut active charcoal or other kind.Can directly use commercially available active carbon, also can carry out modification to it and handle according to instructions for use, as oxidation modification, reduction modification, soda acid modification or with metal ion-modified etc.With the dense HNO of active carbon
3Handled 8～36 hours down at 20～100 ℃, wash neutrality, in baking oven,, get the absorbent charcoal carrier of oxidation processes in 40～150 ℃ of oven dry down.
Above-mentioned Preparation of catalysts method, comprise the steps: carrier impregnation in the solution of the soluble salt that contains transition metal, add auxiliary agent again, stirring at room 0.5～24 hour, ultrasonic dispersion 0.5～24 hour, room temperature were left standstill 2～30 hours, through 40～120 ℃ of dryings, reduce to room temperature at 200～600 ℃ of following roasts after 1～8 hour, use 5%H again
2/ 95%N
2Gaseous mixture obtained catalyst in 1～8 hour 300～800 ℃ of following reduction activations.
The using method of above-mentioned catalyst, comprise the steps for: catalyst is placed reaction under high pressure axe or micro-reaction device, the temperature of control beds is 90～140 ℃, reaction pressure is 0.6～3.0MPa, and product can directly enter gas-chromatography or detect its content with gauge line taking-up in good time and with gas chromatography-mass spectrography.
Compared with prior art, the present invention has following beneficial effect:
(1) catalyst of the present invention can be used for methyl alcohol and the direct catalytic synthesizing dimethyl carbonate of carbon dioxide, and synthetic raw material sources are abundant, and are with low cost.
(2) method for preparing catalyst of the present invention is simple, and is easy to operate.
(3) catalyst of the present invention separates easily with the product dimethyl carbonate, the reaction condition gentleness, and catalyst can be reused;
(4) catalyst activity height of the present invention, and selectivity is also high.
The specific embodiment
The invention is further illustrated by the following examples.
Embodiment 1
Accurately take by weighing the 10g native graphite, under agitation slowly join in ice-water bath is cooled to the 230ml concentrated sulfuric acid (98%) below 4 ℃, slowly add 5g sodium nitrate and 28g potassium permanganate again, stirring reaction 10 minutes.Remove ice bath, reaction system forwarded in 36 ℃ the hot bath to stirring reaction after 30 minutes, 95 ℃ of following stirring reactions 1 hour in oil bath again, product fully washs with 5% hydrochloric acid and deionized water, drying is 24 hours in 90 ℃ of vacuum drying chambers, obtains the graphite oxide carrier;
Accurately take by weighing 0.822gCu (NO
3)
2.3H
2O and 0.494gNi (NO
3)
2.6H
2O is dissolved in the 30ml absolute ethyl alcohol, with 2g graphite oxide carrier impregnation in above-mentioned metal salt solution, stirring at room 2 hours, ultrasonic dispersion 1 hour is after room temperature leaves standstill 12 hours, through 40 ℃ of dryings 2 hours, drying is 4 hours under 60 ℃, descended dry 12 hours at 90 ℃ again, reduce to room temperature after 3 hours, use 5%H again through 350 ℃ of following roasts
2/ 95%N
2Gaseous mixture obtained catalyst in 1.5 hours 600 ℃ of following reduction activations.
Take by weighing the above-mentioned catalyst of 1g, add on the miniature catalytic reaction experimental rig of MRS-901 and carry out the reactivity worth evaluation.By automatic control and the measurement that computer realization is formed temperature, pressure and reactant, the timing automatic sampling of product.Catalytic reaction condition is: 100 ℃ of temperature, and pressure 1.2MPa, material molar ratio (methyl alcohol/carbon dioxide=2/1) adopts 102G-D type gas chromatograph assay products to form, and analysis result the results are shown in Table 1 by the coupling Computer Processing.
Embodiment 2
The preparing carriers method is with embodiment 1, and 2g graphite oxide carrier impregnation is to 0.4116gCu (NO
3)
2.3H
2O and 0.2476gNi (NO
3)
2.6H
2In the metal salt solution of O, all the other preparations and test condition the results are shown in Table 1 with embodiment 1.
Embodiment 3
The Preparation of Catalyst condition is with embodiment 1, and catalytic reaction condition is; 120 ℃ of temperature, pressure 1.2MPa, material molar ratio (methyl alcohol/carbon dioxide=2/1), all the other test conditions the results are shown in Table 1 with embodiment 1.
Embodiment 4
The Preparation of Catalyst condition is with embodiment 1, and catalytic reaction condition is; 100 ℃ of temperature, pressure 1.4MPa, material molar ratio (methyl alcohol/carbon dioxide=2/1), all the other test conditions the results are shown in Table 1 with embodiment 1.
Embodiment 5
The preparing carriers method is with embodiment 1, and 2g graphite oxide carrier impregnation is to 0.822gCu (NO
3)
2.3H
2O and 0.494gNi (NO
3)
2.6H
2In the metal salt solution of O, add 0.06gV again
2O
5, catalytic reaction condition is; 120 ℃ of temperature, pressure 1.3MPa, material molar ratio (methyl alcohol/carbon dioxide=2/1), all the other test conditions the results are shown in Table 1 with embodiment 1.
Embodiment 6
Add the 30ml concentrated sulfuric acid and 30ml red fuming nitric acid (RFNA) in many walls of 5g nanotube, in 90 ℃ of following back flow reaction 24 hours, product fully washed with deionized water, dry 24 hours of 80 ℃ of following vacuum drying, obtains carbon nanotube carrier.
Accurately take by weighing 0.822gCu (NO
3)
2.3H
2O and 0.494gNi (NO
3)
2.6H
2O is dissolved in the 30ml absolute ethyl alcohol, many walls of 2g nano-tube support is impregnated in the above-mentioned metal salt solution, stirring at room 1 hour, ultrasonic dispersion is after 2 hours, after room temperature leaves standstill 12 hours, through 40 ℃ of dryings 2 hours, drying is 6 hours under 60 ℃, descended dry 12 hours at 90 ℃ again, reduce to room temperature after 3 hours, use 5%H again through 350 ℃ of following roasts
2/ 95%N
2Gaseous mixture obtained catalyst in 2 hours 600 ℃ of following reduction activations.The catalytic performance test of catalyst and the analytical method of product the results are shown in Table 1 with embodiment 1.
Embodiment 7
The preparing carriers method is with embodiment 6, and many walls of 2g nano-tube support is impregnated into 1.234gCu (NO
3)
2.3H
2O and 0.742gNi (NO
3)
2.6H
2In the metal salt solution of O, all the other preparations and test condition the results are shown in Table 1 with embodiment 6.
Embodiment 8
The preparing carriers method is with embodiment 6, and many walls of 2g nano-tube support is impregnated into 0.4116gCu (NO
3)
2.3H
2O and 0.2476gNi (NO
3)
2.6H
2In the metal salt solution of O, add 0.06gV again
2O
5, all the other preparations and test condition the results are shown in Table 1 with embodiment 6.
Embodiment 9
Expansible graphite 900 ℃ of following expanding treatments 10 seconds, is obtained the expanded graphite carrier.
Accurately take by weighing 0.411gCu (NO
3)
2.3H
2O and 0.247gNi (NO
3)
2.6H
2O is dissolved in the 30ml absolute ethyl alcohol, with 1g expanded graphite carrier impregnation in above-mentioned metal salt solution, stirring at room 2 hours, ultrasonic dispersion is after 1 hour, after room temperature leaves standstill 12 hours, through 40 ℃ of dryings 2 hours, drying is 6 hours under 60 ℃, descended dry 8 hours at 90 ℃ again, reduce to room temperature after 3 hours, use 5%H again through 350 ℃ of following roasts
2/ 95%N
2Gaseous mixture obtained catalyst in 4 hours 600 ℃ of following reduction activations.
The catalytic performance test of catalyst and the analytical method of product the results are shown in Table 1 with embodiment 1.
Embodiment 10
The preparing carriers method accurately takes by weighing 0.617gCu (NO with embodiment 9
3)
2.3H
2O and 0.371g Ni (NO
3)
2.6H
2O is dissolved in the 30ml absolute ethyl alcohol, and in above-mentioned metal salt solution, all the other preparation conditions are with embodiment 9 with 1g expanded graphite carrier impregnation.The catalytic performance test of catalyst and the analytical method of product the results are shown in Table 1 with embodiment 1.
Embodiment 11
The preparing carriers method is with embodiment 9, and 1g expanded graphite carrier impregnation is to 0.617gCu (NO
3)
2.3H
2O and 0.371gNi (NO
3)
2.6H
2In the salting liquid of O, add 0.03gV again
2O
5, all the other preparation conditions are with embodiment 9.The catalytic performance test of catalyst and the analytical method of product the results are shown in Table 1 with embodiment 1.
Embodiment 12
The preparing carriers method is with embodiment 9, and catalytic reaction condition is; 120 ℃ of temperature, pressure 1.4MPa, material molar ratio (methyl alcohol/carbon dioxide=2/1), all the other test conditions the results are shown in Table 1 with embodiment 1.
Table 1
| Embodiment | Methanol conversion (%) | DMC yield (%) | DMC selectivity (%) |
| 1 | 10.14 | 9.15 | 90.2 |
| 2 | 5.26 | 4.63 | 88.1 |
| 3 | 3.13 | 2.58 | 82.4 |
| 4 | 10.22 | 9.33 | 91.3 |
| 5 | 6.46 | 5.64 | 87.3 |
| 6 | 3.44 | 2.98 | 86.8 |
| 7 | 1.17 | 1.45 | 89.6 |
| 8 | 4.27 | 3.64 | 85.3 |
| 9 | 2.50 | 2.14 | 85.7 |
| 10 | 2.63 | 2.20 | 83.8 |
| 11 | 4.26 | 3.73 | 87.6 |
| 12 | 3.31 | 2.93 | 88.5 |
Claims (10)
1. a catalyst that is used for by methyl alcohol and the direct catalytic synthesizing dimethyl carbonate of carbon dioxide is characterized in that being made up of soluble salt, auxiliary agent and the carrier three of transition metal; The soluble salt of transition metal is in metal oxide, with the weight ratio of auxiliary agent, carrier be 0.01～0.5: 0.01～0.1: 1.
2. catalyst as claimed in claim 1 is characterized in that described transition metal is meant copper or nickel.
3. catalyst as claimed in claim 1 is characterized in that described auxiliary agent is the oxide that contains rhodium, yttrium, vanadium, molybdenum, zirconium, yttrium, cerium, soluble-salt or oxysalt.
4. catalyst as claimed in claim 1 is characterized in that described carrier is graphite oxide, expanded graphite, CNT or active carbon.
5. catalyst as claimed in claim 4, it is characterized in that described graphite oxide carrier is by natural graphite powder, natural flake graphite or expansible graphite preparation, step is as follows: with natural graphite powder, natural flake graphite or expansible graphite are at the concentrated sulfuric acid, potassium permanganate and sodium nitrate exist down, in reacting below 4 ℃ 10～20 minutes, 35～38 ℃ were reacted 10～100 minutes down, reacted 15～90 minutes down at 90～100 ℃ again, product fully washs with 5% hydrochloric acid and deionized water, drying is 12～36 hours in 60～90 ℃ of vacuum drying chambers, obtains the graphite oxide carrier.
6. catalyst as claimed in claim 4, it is characterized in that described carbon nanotube carrier is by single wall or multi-walled carbon nano-tubes preparation, comprise the steps: SWCN or many walls nanotube in the presence of the concentrated sulfuric acid and red fuming nitric acid (RFNA), the volume ratio of the concentrated sulfuric acid and red fuming nitric acid (RFNA) is 1: 5～5: 1, in 80～120 ℃ of following back flow reaction 6～36 hours, product fully washs with deionized water, 60～90 ℃ of following vacuum drying dryings 12～36 hours, obtains carbon nanotube carrier.
7. catalyst as claimed in claim 4 is characterized in that described expanded graphite carrier is prepared by expansible graphite, comprises the steps: expansible graphite to obtain the expanded graphite carrier 700～1000 ℃ of following expanding treatments 5～30 seconds.
8. catalyst as claimed in claim 4 is characterized in that described active carbon is a coal mass active carbon, the fiber-reactive charcoal of cocoanut active charcoal or other kind.
9. Preparation of catalysts method according to claim 1 is characterized in that comprising the steps:
Carrier impregnation in the solution of the soluble salt that contains transition metal, is added auxiliary agent again, stirring at room 0.5～24 hour, ultrasonic dispersion 0.5～24 hour, room temperature were left standstill 2～30 hours, through 40～120 ℃ of dryings, reduce to room temperature at 200～600 ℃ of following roasts after 1～8 hour, use 5%H again
2/ 95%N
2Gaseous mixture obtained catalyst in 1～8 hour 300～800 ℃ of following reduction activations.
10. the using method of the described catalyst of claim 1, it is characterized in that comprising the steps for: catalyst is placed reaction under high pressure axe or micro-reaction device, the temperature of control beds is 90～140 ℃, reaction pressure is 0.6～3.0MPa, and product can directly enter gas-chromatography or detect its content with gauge line taking-up in good time and with gas chromatography-mass spectrography.
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|---|---|---|---|
| CNB2007100310065A CN100531904C (en) | 2007-10-23 | 2007-10-23 | Catalyst used for catalytic synthesis for dimethyl carbonate directly from methanol and carbon dioxide, and preparation and using method thereof |
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|---|---|---|---|
| CNB2007100310065A CN100531904C (en) | 2007-10-23 | 2007-10-23 | Catalyst used for catalytic synthesis for dimethyl carbonate directly from methanol and carbon dioxide, and preparation and using method thereof |
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Cited By (13)
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| CN101947425A (en) * | 2010-08-24 | 2011-01-19 | 中山大学 | Method for directly synthesizing dimethyl carbonate from methanol and carbon dioxide and special electrical assisted catalytic reactor |
| CN102659601A (en) * | 2012-06-05 | 2012-09-12 | 东北石油大学 | Synthesis method of dimethyl carbonate, catalyst and preparation method |
| CN101632932B (en) * | 2009-08-28 | 2012-12-19 | 中山大学 | Dimethyl carbonate supported catalyst directly synthesized by methanol and carbon dioxide |
| CN102872879A (en) * | 2012-09-26 | 2013-01-16 | 太原理工大学 | Chlorine-free bimetallic catalyst for gas phase synthesis of dimethyl carbonate and preparation and application |
| CN103007940A (en) * | 2012-12-21 | 2013-04-03 | 云南大学 | Preparation method of catalyst in microwave-assisted catalytic oxidation treating process for imidacloprid pesticide waste water |
| CN103521266A (en) * | 2013-08-30 | 2014-01-22 | 重庆大学 | Composite catalyst for synthesizing dimethyl carbonate and preparation method of dimethyl carbonate |
| CN107652182A (en) * | 2017-09-18 | 2018-02-02 | 西北大学 | A kind of method using rare earth oxide as catalyst preparation dimethyl carbonate |
| CN109926056A (en) * | 2019-01-25 | 2019-06-25 | 浙江师范大学 | It is a kind of using carbon nanotube as the catalyst of carrier, preparation method and application |
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Family Cites Families (3)
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| CN85103556A (en) * | 1985-04-29 | 1986-10-29 | 化学工业部西南化工研究院 | Low steam carbon ratio hydrocarbon gas conversion catalyst and manufacturing thereof and purposes |
| CN1024536C (en) * | 1988-10-19 | 1994-05-18 | 中国科学院大连化学物理研究所 | Active non-uniform catalyzer for ordinary pressure water-gas methanides and its making method |
| CN1269567C (en) * | 2003-07-15 | 2006-08-16 | 四川大学 | Novel catalyst for methanol cracking reaction to produce CO and H2 |
-
2007
- 2007-10-23 CN CNB2007100310065A patent/CN100531904C/en not_active Expired - Fee Related
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| CN101947425A (en) * | 2010-08-24 | 2011-01-19 | 中山大学 | Method for directly synthesizing dimethyl carbonate from methanol and carbon dioxide and special electrical assisted catalytic reactor |
| CN101947425B (en) * | 2010-08-24 | 2013-05-08 | 中山大学 | Method for directly synthesizing dimethyl carbonate from methanol and carbon dioxide and special electrical assisted catalytic reactor |
| CN102659601B (en) * | 2012-06-05 | 2014-06-11 | 东北石油大学 | Synthesis method of dimethyl carbonate, catalyst and preparation method |
| CN102659601A (en) * | 2012-06-05 | 2012-09-12 | 东北石油大学 | Synthesis method of dimethyl carbonate, catalyst and preparation method |
| CN102872879A (en) * | 2012-09-26 | 2013-01-16 | 太原理工大学 | Chlorine-free bimetallic catalyst for gas phase synthesis of dimethyl carbonate and preparation and application |
| CN102872879B (en) * | 2012-09-26 | 2014-11-19 | 太原理工大学 | Chlorine-free bimetallic catalyst for gas phase synthesis of dimethyl carbonate and preparation and application |
| CN103007940A (en) * | 2012-12-21 | 2013-04-03 | 云南大学 | Preparation method of catalyst in microwave-assisted catalytic oxidation treating process for imidacloprid pesticide waste water |
| CN103521266A (en) * | 2013-08-30 | 2014-01-22 | 重庆大学 | Composite catalyst for synthesizing dimethyl carbonate and preparation method of dimethyl carbonate |
| CN107652182A (en) * | 2017-09-18 | 2018-02-02 | 西北大学 | A kind of method using rare earth oxide as catalyst preparation dimethyl carbonate |
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| CN110479287A (en) * | 2019-09-12 | 2019-11-22 | 西南石油大学 | A kind of integral catalyzer for Synthesis of dimethyl carbonate and preparation method thereof, application method |
| CN112642481A (en) * | 2019-10-10 | 2021-04-13 | 中国石油化工股份有限公司 | Catalyst for preparing dialkyl carbonate from dialkyl oxalate, preparation method thereof and method for preparing dialkyl carbonate |
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