Literature Report

Wei Li 2013.6.21

Dimethyl carbonate (DMC)

Molecular weight

Appearance Melting point/℃ Boiling point/℃ Density/g/ml

90.1 Colorless clean liquid

2~4 90 1.069~1.073

Uses of DMC

PC Pesticide industry Medicine Other fields

As a fuel additive

As a less hazardous solvent for organic or inorganic chemicals and battery electrolyte solution

etc

The world DMC consumption structure and forecast

轻化委 , 谭国林 . 碳酸二甲酯生产工艺及市场需求

Synthesis of DMC by vapor phase oxidative carbonylation of methanol

side reaction

main reaction

Preparation of methyl nitrite(MN) MN

MN

MN

MN

Methyl nitrite(MN)

PdCl2-CuCl2/ACUbe：Manada N, Murakami M, Abe K, et al. Method of producing carbonic acid diester: U.S. Patent 5,403,949[P]. 1995-4-4.Yamamoto Y. Vapor phase carbonylation reactions using methyl nitrite over Pd catalysts[J]. Catalysis surveys from Asia, 2010, 14(3-4): 103-110.Matsuzaki T, Nakamura A. Dimethyl carbonate synthesis and other oxidative reactions using alkyl nitrites[J]. Catalysis Surveys from Asia, 1997, 1(1): 77-88.

杨平复旦大学博士Yang P, Cao Y, Hu J C, et al. Mesoporous bimetallic PdCl< sub> 2</sub>-CuCl< sub> 2</sub> catalysts for dimethyl carbonate synthesis by vapor phase oxidative carbonylation of methanol[J]. Applied Catalysis A: General, 2003, 241(1): 363-373.王少成 , 曹勇 , 杨平 , 等 . TBAB 修饰的负载型 Wacker 催化剂催化甲醇羰基化合成碳酸二甲酯[J]. 高等学校化学学报 , 2002, 23(12): 2363-2365.杨平 , 曹勇 , 包信和 , 等 . 助剂对合成碳酸二甲酯用活性炭负载 Wacker 催化剂结构和性能的影响 [J]. 催化学报 , 2004, 25(2).

王延吉河北工业大学Yanji W, Xinqiang Z, Baoguo Y, et al. Synthesis of dimethyl carbonate by gas-phase oxidative carbonylation of methanol on the supported solid catalyst I. Catalyst preparation and catalytic properties[J]. Applied Catalysis A: General, 1998, 171(2): 255-260.王延吉 , 赵新强 . 甲醇气相氧化羰基化合成碳酸二甲酯的研究 [J]. 燃料化学学报 , 1997, 25(4): 323-327.岳川 , 丁晓墅 , 匡洞庭 , 等 . 硅胶包覆型催化剂在气相法合成碳酸二甲酯中的性能 [J]. 化学反应工程与工艺 , 2010, 26(5): 430r433.

曹发海华东理工大学曹发海 , 应卫勇 , 房鼎业 . 活性炭载体对甲醇氧化羰化合成碳酸二甲酯催化活性的影响 [J]. 化学世界 , 2000, 4: 195-197.

PdCl2-CuCl2/AC

PdCl2-CuCl2/AC Ube Patent

Manada N, Murakami M, Abe K, et al. Method of producing carbonic acid diester: U.S. Patent 5,403,949[P]. 1995-4-4.

0.33g PdCl2 and 0.64g CuCl2

100ml 5mol/L HCl

Heat-dissolving 80~90℃20g

AC(0.5~0.7mm)

Filter , wash with waterWater evaporation at 80℃Dry in a N2 gas

atmosphere at 200℃PdCl2-CuCl2 /C(AC)

Pd:1%Pd:Cu=1:2(atomic

ratio)

Immerse

PdCl2-CuCl2/AC Ube

Matsuzaki T, Nakamura A. Dimethyl carbonate synthesis and other oxidative reactions using alkyl nitrites[J]. Catalysis Surveys from Asia, 1997, 1(1): 77-88.

Catalyst carrier : AC

Pd : 1wt% Cu :1.2wt%

Reaction conditions : 120℃, 0.3MPa, GHSV 4000h-1

Inlet gas composition : CO 20%, MN 10%, N2 base

PdCl2-CuCl2/AC

Matsuzaki T, Nakamura A. Dimethyl carbonate synthesis and other oxidative reactions using alkyl nitrites[J]. Catalysis Surveys from Asia, 1997, 1(1): 77-88.

Catalytic activities of DMC synthesis reaction using MN

PdCl2-CuCl2/AC

Matsuzaki T, Nakamura A. Dimethyl carbonate synthesis and other oxidative reactions using alkyl nitrites[J]. Catalysis Surveys from Asia, 1997, 1(1): 77-88.

Dialkyl carbonate

PdCl2-CuCl2/AC

Matsuzaki T, Nakamura A. Dimethyl carbonate synthesis and other oxidative reactions using alkyl nitrites[J]. Catalysis Surveys from Asia, 1997, 1(1): 77-88.

Effect of catalyst carriers on DMC synthesis reaction using MN

Pd : 1wt% Cu :1.2wt% Cl : 2.0wt% /carrierReaction conditions : 120℃, 0.3MPa, GHSV 4000h-1

Inlet gas composition : CO 20%, MN 10%, HCl 100ppm, N2 base

PdCl2-CuCl2/AC

Matsuzaki T, Nakamura A. Dimethyl carbonate synthesis and other oxidative reactions using alkyl nitrites[J]. Catalysis Surveys from Asia, 1997, 1(1): 77-88.

By-products:DMO 、 MF 、 DMM etc

MF

DMM

！

PdCl2-CuCl2/AC

Yamamoto Y. Vapor phase carbonylation reactions using methyl nitrite over Pd catalysts[J]. Catalysis surveys from Asia, 2010, 14(3-4): 103-110.

Ube

Pd : 1wt% Cu :1.2wt% Cl : 2.0wt% /ACReaction conditions : 120℃, 0.4MPa, GHSV 4000h-1

Gas composition : CO 20%, MN 10%, N2 base

PdCl2-CuCl2/AC

Yamamoto Y. Vapor phase carbonylation reactions using methyl nitrite over Pd catalysts[J]. Catalysis surveys from Asia, 2010, 14(3-4): 103-110.

Pd : 1wt% Cu :1.2wt% Cl : 2.0wt% /carrierReaction conditions : 120℃, 0.4MPa, GHSV 4000h-1

Inlet gas composition : CO 20%, MN 10%, HCl 100ppm, N2 base

PdCl2-CuCl2/AC Yanji W

Yanji W, Xinqiang Z, Baoguo Y, et al. Synthesis of dimethyl carbonate by gas-phase oxidative carbonylation of methanol on the supported solid catalyst I. Catalyst preparation and catalytic properties[J]. Applied Catalysis A: General, 1998, 171(2): 255-260.

Effect of promoters:

PdCl2-CuCl2/AC Yang ping

Effect of promoters:

杨平 , 曹勇 , 包信和 , 等 . 助剂对合成碳酸二甲酯用活性炭负载 Wacker 催化剂结构和性能的影响 [J]. 催化学报 , 2004, 25(2).

PdCl2-CuCl2/AC Yang ping

杨平 , 曹勇 , 包信和 , 等 . 助剂对合成碳酸二甲酯用活性炭负载 Wacker 催化剂结构和性能的影响 [J]. 催化学报 , 2004, 25(2).

PdCl2-CuCl2-TBAB/HMS Yang ping

Yang P, Cao Y, Hu J C, et al. Mesoporous bimetallic PdCl< sub> 2</sub>-CuCl< sub> 2</sub> catalysts for dimethyl carbonate synthesis by vapor phase oxidative carbonylation of methanol[J]. Applied Catalysis A: General, 2003, 241(1): 363-373.

Cu:Pd=20:1

PdCl2-CuCl2-TBAB/HMS Yang ping

Yang P, Cao Y, Hu J C, et al. Mesoporous bimetallic PdCl< sub> 2</sub>-CuCl< sub> 2</sub> catalysts for dimethyl carbonate synthesis by vapor phase oxidative carbonylation of methanol[J]. Applied Catalysis A: General, 2003, 241(1): 363-373.

Cu:Pd:TBAB=20:1:12

Yanji W

岳川 , 丁晓墅 , 匡洞庭 , 等 . 硅胶包覆型催化剂在气相法合成碳酸二甲酯中的性能 [J]. 化学反应工程与工艺 , 2010, 26(5): 430r433.

PdCl2-CuCl2-KOAc-AC@SiO2

Yanji W

岳川 , 丁晓墅 , 匡洞庭 , 等 . 硅胶包覆型催化剂在气相法合成碳酸二甲酯中的性能 [J]. 化学反应工程与工艺 , 2010, 26(5): 430r433.

PdCl2-CuCl2-KOAc-AC@SiO2

AC pretreatment

Conventional methods: a) acid wash b) base wash c) oxidation in the gas(95%N2+5%O2) d) oxidation in the liquid (nitric acid) e) thermal treatment Modern methods: a) microwave-induced treatment b) ultrasonic treatment

AC pretreatment

曹发海 , 应卫勇 , 房鼎业 . 活性炭载体对甲醇氧化羰化合成碳酸二甲酯催化活性的影响 [J]. 化学世界 , 2000, 4: 195-197.

Conclusion

AC pretreatment Appropriate promoter

Heterogeneous catalysts

My work plan:

Thank you