CN107915639B - Method for producing dimethyl carbonate by ester exchange - Google Patents

Method for producing dimethyl carbonate by ester exchange Download PDF

Info

Publication number
CN107915639B
CN107915639B CN201610878393.5A CN201610878393A CN107915639B CN 107915639 B CN107915639 B CN 107915639B CN 201610878393 A CN201610878393 A CN 201610878393A CN 107915639 B CN107915639 B CN 107915639B
Authority
CN
China
Prior art keywords
catalyst
silica
alumina gel
dimethyl carbonate
ethylene carbonate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610878393.5A
Other languages
Chinese (zh)
Other versions
CN107915639A (en
Inventor
陈梁锋
何文军
肖含
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to CN201610878393.5A priority Critical patent/CN107915639B/en
Publication of CN107915639A publication Critical patent/CN107915639A/en
Application granted granted Critical
Publication of CN107915639B publication Critical patent/CN107915639B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
    • C07C68/065—Preparation of esters of carbonic or haloformic acids from organic carbonates from alkylene carbonates
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/182—Phosphorus; Compounds thereof with silicon
    • 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
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/49—Esterification or transesterification

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention relates to a method for producing dimethyl carbonate by ester exchange, which mainly solves the problems of poor catalyst activity and easy loss of active components in the prior art. The invention adopts the steps of contacting ethylene carbonate and methanol with a catalyst under the condition of ester exchange reaction; the catalyst is an alkali metal phosphorus catalyst M-P/SA loaded by silica-alumina gel; wherein SA is silica alumina gel SiO2‑Al2O3M is at least one of alkali metals Na, K, Rb or Cs, and P is phosphorus; in the catalyst, the weight content of M is as M2O is 1-20%, and the weight content of P is P2O5The technical scheme that the weight percentage of the SA is 5-30% and the weight percentage of the SA is 50-94% better solves the problem, and can be used in industrial production for preparing dimethyl carbonate by the transesterification of ethylene carbonate and methanol.

Description

Method for producing dimethyl carbonate by ester exchange
Technical Field
The invention relates to a method for producing dimethyl carbonate by ester exchange, in particular to a method for producing dimethyl carbonate by the ester exchange of ethylene carbonate and methanol.
Background
Dimethyl carbonate (DMC) is active in chemical property, excellent in physical property, non-toxic and easy to biodegrade, is a novel low-pollution environment-friendly green basic chemical raw material, can be used as a solvent, a gasoline additive, a lithium ion battery electrolyte and a carbonylation, methylation and carbonylmethoxylation reagent, and is widely applied to the field of chemical industry. At present, the environmental-friendly chemical process based on DMC, an environmentally-friendly chemical raw material, is actively researched in all countries. The transesterification method has mild reaction conditions and high yield, and is a method with great industrial prospects due to co-production of ethylene glycol or propylene glycol.
In general, the transesterification reaction is usually carried out using an alkali metal hydroxide, an alkali metal carbonate, an alkali metal alcohol or the like (F.Risse et al, U.S. Pat. No. 2011040117; C.P.Allas et al, WO2010063780)The catalyst is difficult to separate from the product and is difficult to reuse because the catalyst is a homogeneous catalyst. Commonly used heterogeneous catalysts include alkali or alkali metal salts, metal oxide catalysts, alkali (earth) metal exchanged zeolite or clay materials and ion exchange resins, etc. supported on a carrier. Alkali metal or alkali metal salt supported on carrier, e.g. KF/Al2O3NaOH/Chitosan and Cs2CO3/SiO2-Al2O3Etc. (H.ZHang, CN 101249452; Y.ZHao, CN 101121147; C.D.Chang et al, WO0156971A1) which have the disadvantage of being susceptible to water and CO in the air2Such that activity is reduced; metal oxide catalysts, e.g. Al2O3MgO and the like (B.M.Bhanage, et al.appl.Catal.A 219(2001) 259-266; J.S.Buchanan et al, US 2005080287; Z.Z.Jiang et al, US6207850), and alkali (earth) metal exchanged zeolite or clay materials such as Cs-ZSM-5, Mg-smitite and the like (C.D.Chang et al, WO 0073256; B.M.Bhanage et al.Cat.83 (2002)137-141), which have the disadvantage that the activity or selectivity is generally relatively low; ion exchange resins such as quaternary ammonium type or tertiary amine type resins (J.F. Knifton et al, J.mol. Cat. A67 (1991) 389-.
Disclosure of Invention
The invention aims to solve the technical problems of poor catalyst activity and easy loss of active components in the prior art, and provides a novel method for producing dimethyl carbonate by ester exchange. The method has the advantages of high activity and selectivity, and no loss of active components.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method for producing dimethyl carbonate by ester exchange comprises the steps of contacting ethylene carbonate and methanol with a catalyst under the condition of ester exchange reaction; the catalyst is an alkali metal phosphorus catalyst M-P/SA loaded by silica-alumina gel; wherein SA is silica alumina gel SiO2-Al2O3M is at least one of alkali metals Na, K, Rb or Cs, and P is phosphorus; in the presence of a catalyst comprising a metal oxide,the weight content of M is as follows2O is 1-20%, and the weight content of P is P2O55-30% in terms of weight, and the weight content of SA is 50-94%.
In the above technical solution, preferably, M is at least one of K or Cs.
In the above technical scheme, the silica alumina gel SiO2-Al2O3Middle Al2O3The content of (b) is 5 to 50% by weight, preferably 10 to 30% by weight.
In the above technical solution, preferably, in the catalyst, the weight content of M is M2O is 1-10%, and the weight content of P is P2O55-20% of SA, and 70-94% of SA.
In the technical scheme, the transesterification reaction temperature is 60-160 ℃, and preferably 80-140 ℃.
In the technical scheme, the molar ratio of the methanol to the ethylene carbonate is (2-10): 1, and preferably (2-8): 1.
In the technical scheme, the weight ratio of the catalyst to the ethylene carbonate is (0.005-0.5): 1, and preferably (0.01-0.2): 1.
The preparation method of the catalyst comprises the following steps: at room temperature, alkali metal nitrate and ammonium dihydrogen phosphate were dissolved in water to obtain a dipping solution. Adding silica-alumina gel SA into the impregnation liquid, and drying and roasting the obtained mixture to obtain the silica-alumina gel loaded alkali metal phosphorus catalyst. The drying temperature is 100-150 ℃, and the drying time is 5-24 hours. The roasting temperature is 550-650 ℃, and the roasting time is 1-24 hours. The silica-alumina gel can adopt a commercial product and can also be synthesized by the following method: 1) aluminum nitrate (Al (NO) was added at room temperature3)3·9H2O) is dissolved in alkanol, stirred for 20min and dissolved to obtain a solution A; 2) dissolving Tetraethoxysilane (TEOS) in alkanol at room temperature, adding water and nitric acid, and stirring for 20min to prehydrolyze tetraethoxysilane to obtain a mixture B; 3) and pouring the solution A into the mixture B, stirring at room temperature for a period of time, and then dropwise adding concentrated ammonia water until the pH value is 8. Aging the obtained mixture at a certain temperature for a certain period of time, and filteringAnd washing the silica-alumina gel with alkanol for a plurality of times, and drying the silica-alumina gel at 120 ℃ to obtain the silica-alumina gel SA. The alkanol used in step 1) and step 2) may be at least one of methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol and tert-butanol; the stirring time of the A, B mixture in the step 3) is 0.5-2 hours, the aging temperature is 40-90 ℃, and the aging time is 6-24 hours.
The method adopts the silica-alumina gel loaded alkali metal phosphorus catalyst which is an acid-base bifunctional catalyst, has stable property, is not easy to lose an active center, and solves the problem that the active component of the heterogeneous catalyst is easy to lose in the prior art. By adopting the method, under the conditions that the reaction temperature is 120 ℃, the molar ratio of methanol to ethylene carbonate is 4:1, and the weight ratio of the catalyst to the ethylene carbonate is 0.05:1, the reaction is carried out for 4 hours, the conversion rate of the ethylene carbonate is 71.3%, the selectivity of dimethyl carbonate is 98.4%, the selectivity of ethylene glycol is 98.5%, and after the catalyst is repeatedly used for 5 times, the activity is reduced by less than 5%, so that a better technical effect is obtained.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
Preparation of silica alumina gel SA 1: dissolving 22.1g of aluminum nitrate in 200ml of absolute ethyl alcohol at room temperature, and stirring for 20min to dissolve the aluminum nitrate to obtain a solution A1; dissolving 58.9g of tetraethoxysilane in 200ml of absolute ethyl alcohol, adding 200ml of deionized water and 5ml of concentrated nitric acid, and stirring for 20min to obtain a prehydrolysis mixture B1; the solution A1 was poured into the mixture B1 and after stirring at room temperature for 1 hour, concentrated aqueous ammonia was added dropwise until the pH was 8. Then standing and aging at 60 deg.C for 12h, filtering, washing precipitate with anhydrous ethanol for 3 times, and oven standing overnight at 120 deg.C to obtain silica-alumina gel SA1, and measuring by ICP-AES to obtain Al2O3The content of (B) is 14.9% by weight.
[ example 2 ]
Preparation of silica alumina gel SA 2: dissolving 7.3g of aluminum nitrate in 200ml of anhydrous methanol at room temperature, and stirring for 20min to dissolve the aluminum nitrate to obtain a solution A2; dissolving 65.9g of ethyl orthosilicate in 200ml of anhydrous methanol, and adding 200ml of anhydrous methanolAfter ionized water and 5ml of concentrated nitric acid are stirred for 20min, a prehydrolysis mixture B2 is obtained; the solution A2 was poured into the mixture B2 and after stirring at room temperature for 1 hour, concentrated aqueous ammonia was added dropwise until the pH was 8. Then standing and aging at 80 deg.C for 20h, filtering, washing precipitate with anhydrous methanol for 3 times, and oven standing overnight at 120 deg.C to obtain silica-alumina gel SA2, and measuring by ICP-AES to obtain Al2O3The content of (B) is 5.1% by weight.
[ example 3 ]
Preparation of silica alumina gel SA 3: the preparation procedure was identical to [ example 1 ] except that 36.8g and 52.0g of aluminum nitrate and 52.0g of ethyl orthosilicate, respectively, were used to obtain a silica-alumina gel SA3, Al measured by ICP-AES2O3The content of (B) is 24.8% by weight.
[ example 4 ]
Preparation of silica alumina gel SA 4: the preparation procedure was identical to [ example 1 ] except that 51.5g and 45.1g of aluminum nitrate and ethyl orthosilicate, respectively, were used to give a silica-alumina gel SA4, Al determined by ICP-AES2O3The content of (B) is 35.3% by weight.
[ example 5 ]
Preparation of silica alumina gel SA 5: the preparation procedure was identical to [ example 1 ] except that 66.2g and 33.1g of aluminum nitrate and ethyl orthosilicate, respectively, were used to give a silica-alumina gel SA5, Al determined by ICP-AES2O3The content of (B) is 44.6% by weight.
[ example 6 ]
Weighing 1.35g of cesium nitrate and 1.98g of diammonium hydrogen phosphate, dissolving in 50ml of deionized water, adding 10g of silica-alumina gel SA1, drying the obtained mixture at 120 ℃ overnight, and roasting at 500 ℃ for 2 hours to obtain the silica-alumina gel-loaded alkali metal phosphorus catalyst M-P/SA-1, wherein the alkali metal Cs is Cs2The weight percentage of O is 8.0 percent, and P is P2O5The weight content is 10.0 percent, and the weight content of the silica-alumina gel SA1 is 82.0 percent
[ example 7 ]
The catalyst preparation method was the same as in example 6, except that cesium nitrate and diammonium phosphate were used in amounts of 0.46g and 6.76g, respectively, to obtain a silica-alumina gel-supported alkali metal phosphorus catalyst
M-P/SA-2, wherein the alkali metal K is K2The weight percentage of O is 1.5 percent, and P is P2O5The calculated weight content is 29 percent, and the weight content of the silica-alumina gel SA1 is 69.5 percent.
[ example 8 ]
The catalyst preparation method was the same as in example 6, except that cesium nitrate and diammonium phosphate were used in amounts of 0.77g and 0.90g, respectively, to obtain a silica-alumina gel-supported alkali metal phosphorus catalyst
M-P/SA-3, wherein the alkali metal Cs is Cs2The weight percentage of O is 5.0 percent, and P is P2O5The weight content is 5.0 percent, and the weight content of the silica-alumina gel SA1 is 90.0 percent.
[ example 9 ]
The catalyst preparation method was the same as in example 6, except that cesium nitrate and diammonium phosphate were used in amounts of 1.05g and 3.08g, respectively, to obtain a silica-alumina gel-supported alkali metal phosphorus catalyst
M-P/SA-4, wherein the alkali metal Cs is Cs2The weight percentage of O is 6.0 percent, and P is P2O5The weight content is 15.0 percent, and the weight content of the silica-alumina gel SA1 is 79.0 percent.
[ example 10 ]
The catalyst preparation method was the same as in example 6, except that cesium nitrate and diammonium phosphate were used in amounts of 3.50g and 1.30g, respectively, to obtain a silica-alumina gel-supported alkali metal phosphorus catalyst M-P/SA-5 in which the alkali metal Cs was Cs2The weight percentage of O is 19.0 percent, and P is P2O5The weight content is 6.0 percent, and the weight content of the silica-alumina gel SA1 is 75.0 percent.
[ example 11 ]
The catalyst preparation method was the same as in example 6, except that cesium nitrate and diammonium phosphate were used in amounts of 5.05g and 9.03g, respectively, to obtain a silica-alumina gel-supported alkali metal phosphorus catalyst M-P/SA-6 in which the alkali metal Cs was present as Cs2The weight percentage of O is 19.0 percent, and P is P2O5The weight content is 29.0 percent, and the weight content of the silica-alumina gel SA1 is 52.0 percent.
[ example 12 ]
The catalyst preparation method was the same as [ example 6 ], except that the silica alumina gel used was SA2, yielding silica alumina gel-supported alkali metal phosphorus catalyst M-P/SA-7.
[ example 13 ]
The catalyst preparation method was the same as [ example 6 ], except that the silica-alumina gel used was SA3, yielding silica-alumina gel-supported alkali metal phosphorus catalyst M-P/SA-8.
[ example 14 ]
The catalyst preparation method was the same as [ example 6 ], except that the silica alumina gel used was SA4, yielding silica alumina gel-supported alkali metal phosphorus catalyst M-P/SA-9.
[ example 15 ]
The catalyst preparation method was the same as [ example 6 ], except that the silica-alumina gel used was SA5, yielding silica-alumina gel-supported alkali metal phosphorus catalyst M-P/SA-10.
[ example 16 ]
22.0 g of ethylene carbonate, 32.0 g of methanol and 1.1 g of catalyst M-P/SA-1 were placed in a 100 ml autoclave (molar ratio of methanol to ethylene carbonate: 4:1, weight ratio of catalyst to ethylene carbonate: 0.05: 1) and reacted at 120 ℃ for 4 hours. After the reaction was complete, the autoclave was cooled to room temperature and vented. And (3) performing gas chromatography analysis on the liquid-phase product to obtain ethylene carbonate with the conversion rate of 71.3%, the selectivity of dimethyl carbonate of 98.4% and the selectivity of ethylene glycol of 98.5%.
[ examples 17 to 25 ]
The same conditions as described in [ example 16 ] were used with varying kinds of the silica alumina gel-supported alkali metal phosphorus catalyst, and the results shown in Table 1 were obtained.
TABLE 1
Figure BDA0001126119790000061
[ example 26 ]
The same as [ example 16 ] except that the reaction temperature was 140 ℃. The conversion of ethylene carbonate was 73.2%, the selectivity to dimethyl carbonate was 95.3% and the selectivity to ethylene glycol was 94.5%.
[ example 27 ]
The same as [ example 16 ] except that the reaction temperature was 160 ℃. The conversion of ethylene carbonate was 75.2%, the selectivity to ethylene carbonate was 91.3% and the selectivity to ethylene glycol was 90.7%. [ example 28 ]
The same as [ example 16 ] except that the reaction temperature was 80 ℃. The conversion of ethylene carbonate was 31.2%, the selectivity to ethylene carbonate was 99.5% and the selectivity to ethylene glycol was 99.4%.
[ example 29 ]
The same as [ example 16 ] except that the mass of methanol was 48 g (molar ratio of methanol to ethylene carbonate was 6: 1). The conversion of ethylene carbonate was 74.5%, the selectivity to dimethyl carbonate was 97.5% and the selectivity to ethylene glycol was 96.5%.
[ example 30 ]
The same as in example 16 except that the mass of methanol was 16.0 g (molar ratio of methanol to ethylene carbonate was 2: 1). The conversion of ethylene carbonate was 56.1%, the selectivity to dimethyl carbonate was 99.1% and the selectivity to ethylene glycol was 98.4%.
[ example 31 ]
The same as in example 16, except that the mass of the catalyst was 0.55 g (the mass ratio of the catalyst to the ethylene carbonate was 0.025: 1). The conversion of ethylene carbonate was 41.2%, the selectivity for dimethyl carbonate was 98.9%, and the selectivity for ethylene glycol was 98.5%.
[ example 32 ]
The same as in example 16, except that the mass of the catalyst was 2.2 g (the weight ratio of the catalyst to the ethylene carbonate was 0.1: 1). The conversion of ethylene carbonate was 72.3%, the selectivity to dimethyl carbonate was 97.6% and the selectivity to ethylene glycol was 96.9%.
[ example 33 ]
The same as in example 16, except that the mass of the catalyst was 4.4 g (the mass ratio of the catalyst to the ethylene carbonate was 0.2: 1). The conversion of ethylene carbonate was 74.2%, the selectivity to dimethyl carbonate was 96.3% and the selectivity to ethylene glycol was 96.8%.
[ example 34 ]
After the reaction was completed [ example 16 ], the catalyst was separated by filtration and used under the same reaction conditions as in [ example 16 ] for 5 times without significant decrease in activity. The reaction results are shown in Table 2.
TABLE 2
Figure BDA0001126119790000081

Claims (7)

1. A method for producing dimethyl carbonate by ester exchange comprises the steps of contacting ethylene carbonate and methanol with a catalyst under the condition of ester exchange reaction; the catalyst is an alkali metal phosphorus catalyst M-P/SA loaded by silica-alumina gel; wherein SA is silica alumina gel SiO2-Al2O3M is at least one of alkali metals Na, K, Rb or Cs, and P is phosphorus; in the catalyst, the weight content of M is as M2O is 1-20%, and the weight content of P is P2O55-30% of SA, and 50-94% of SA;
the transesterification reaction temperature is 80-160 ℃, and does not contain 80 ℃; the mol ratio of the methanol to the ethylene carbonate is (2-10): 1, and the weight ratio of the catalyst to the ethylene carbonate is (0.05-0.5): 1.
2. The process for producing dimethyl carbonate by transesterification according to claim 1, wherein M is at least one of K or Cs.
3. The method for producing dimethyl carbonate by ester exchange according to claim 1, wherein the silica alumina gel SiO is2-Al2O3Middle Al2O3The content of (B) is 5-50 wt%.
4. The transesterification production of claim 3The method for preparing dimethyl carbonate is characterized in that the silica-alumina gel SiO2-Al2O3Middle Al2O3The content of (B) is 10-30% by weight.
5. The method for producing dimethyl carbonate by transesterification according to claim 1, wherein the weight content of M in the catalyst is M2O is 1-10%, and the weight content of P is P2O55-20% of SA, and 70-94% of SA.
6. The method for producing dimethyl carbonate through transesterification according to claim 1, wherein the transesterification reaction temperature is 80-140 ℃ and does not contain 80 ℃.
7. The method for producing dimethyl carbonate through transesterification according to claim 1, wherein the molar ratio of methanol to ethylene carbonate is (2-8): 1, and the weight ratio of the catalyst to ethylene carbonate is (0.05-0.2): 1.
CN201610878393.5A 2016-10-08 2016-10-08 Method for producing dimethyl carbonate by ester exchange Active CN107915639B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610878393.5A CN107915639B (en) 2016-10-08 2016-10-08 Method for producing dimethyl carbonate by ester exchange

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610878393.5A CN107915639B (en) 2016-10-08 2016-10-08 Method for producing dimethyl carbonate by ester exchange

Publications (2)

Publication Number Publication Date
CN107915639A CN107915639A (en) 2018-04-17
CN107915639B true CN107915639B (en) 2020-11-27

Family

ID=61892180

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610878393.5A Active CN107915639B (en) 2016-10-08 2016-10-08 Method for producing dimethyl carbonate by ester exchange

Country Status (1)

Country Link
CN (1) CN107915639B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112547037B (en) * 2019-09-24 2023-07-04 中国石油化工股份有限公司 Use of aluminosilicate compounds as catalysts in the preparation of dimethyl carbonate

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105439866A (en) * 2014-08-27 2016-03-30 中国石油化工股份有限公司 A dimethyl carbonate preparing method by transesterification

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105439866A (en) * 2014-08-27 2016-03-30 中国石油化工股份有限公司 A dimethyl carbonate preparing method by transesterification

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Synergistic hybrid catalyst for cyclic carbonate synthesis:Remarkable acceleration caused by immobilization of homogeneous catalyst on silica;Toshikazu Takahashi et al.;《Chem.Comm.》;20060308;1664-1666 *

Also Published As

Publication number Publication date
CN107915639A (en) 2018-04-17

Similar Documents

Publication Publication Date Title
CN102631930A (en) Catalyst for preparing furfuryl alcohol from furfural by vapor phase hydrogenation and preparation method thereof
CN102698811A (en) Solid basic catalyst, preparation method of solid basic catalyst and application of solid basic catalyst in ester exchange reaction
CN102391240A (en) Method for preparing cyclic carbamate by catalysis of immobilized ionic liquid
JP2010532245A5 (en)
SG175443A1 (en) Carbonylation process
CN102438747A (en) Carbonylation process
CN104549439A (en) High-activity catalyst for synthesizing dimethyl carbonate, preparation method and application of catalyst
CN107915639B (en) Method for producing dimethyl carbonate by ester exchange
KR101105460B1 (en) Method for preparing sugar alcohols using ruthenium zirconia catalyst
CN107915636B (en) Method for preparing dimethyl carbonate by ester exchange
CN105618126A (en) High-activity catalyst for synthesizing dimethyl carbonate, and preparation method and application thereof
CN107915574B (en) Method for synthesizing dimethyl carbonate
CN107915573B (en) Method for synthesizing dimethyl carbonate
CN111225742A (en) Copper-based catalyst, preparation method thereof and method for preparing ethylene glycol by using copper-based catalyst
CN107915638B (en) Method for producing dimethyl carbonate
CN112547037A (en) Use of aluminosilicate compounds as catalysts in the preparation of dimethyl carbonate
JP2016530276A (en) Manufacturing method of casting agent
CN107915572B (en) Method for synthesizing dimethyl carbonate by ester exchange
JP3592418B2 (en) Glutardialdehyde production method
CN107915714B (en) Method for synthesizing ethylene carbonate
CN107915578B (en) Method for producing ethylene glycol by ethylene carbonate hydrolysis
CN107915637B (en) Method for producing dimethyl carbonate
CN107915635B (en) Method for preparing dimethyl carbonate
CN110586187B (en) Supported phosphotungstic acid catalyst, and preparation method and application thereof
CN102294264B (en) Nuclear-shell catalyst applied to preparation of ethylene carbonate from epoxy ethane and carbon dioxide and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant