1. Literature Report Wei Li 2013.6.21

2. Dimethyl carbonate (DMC) Molecular weight Appearance Melting point/ ℃ Boiling point/ ℃ Density/g/ml 90.1Colorless clean liquid 2~4901.069~1.073

3. 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

4. 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

5. Synthesis of DMC by vapor phase oxidative carbonylation of methanol side reaction main reaction Preparation of methyl nitrite (MN) MN

6. Methyl nitrite(MN)

7. PdCl 2 -CuCl 2 /AC Ube ： 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 2 -CuCl 2 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).

8. 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. PdCl 2 -CuCl 2 /AC

9. 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 PdCl 2 and 0.64g CuCl 2 100ml 5mol/L HCl Heat-dissolving 80~90 ℃ 20g AC(0.5~0.7mm) Filter, wash with water Water evaporation at 80 ℃ Dry in a N 2 gas atmosphere at 200 ℃ PdCl 2 -CuCl 2 /C(AC) Pd:1% Pd:Cu=1:2(atomic ratio) Immerse

10. PdCl 2 -CuCl 2 /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%, N 2 base

11. PdCl 2 -CuCl 2 /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

12. PdCl 2 -CuCl 2 /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

13. PdCl 2 -CuCl 2 /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% /carrier Reaction conditions : 120 ℃, 0.3MPa, GHSV 4000h -1 Inlet gas composition : CO 20%, MN 10%, HCl 100ppm, N 2 base

14. PdCl 2 -CuCl 2 /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 ！

15. PdCl 2 -CuCl 2 /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% /AC Reaction conditions : 120 ℃, 0.4MPa, GHSV 4000h -1 Gas composition : CO 20%, MN 10%, N 2 base

16. PdCl 2 -CuCl 2 /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% /carrier Reaction conditions : 120 ℃, 0.4MPa, GHSV 4000h -1 Inlet gas composition : CO 20%, MN 10%, HCl 100ppm, N 2 base

17. PdCl 2 -CuCl 2 /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:

18. PdCl 2 -CuCl 2 /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).

19. PdCl 2 -CuCl 2 /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).

20. PdCl2-CuCl2-TBAB/HMS Yang ping Yang P, Cao Y, Hu J C, et al. Mesoporous bimetallic PdCl 2 -CuCl 2 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

21. PdCl2-CuCl2-TBAB/HMS Yang ping Yang P, Cao Y, Hu J C, et al. Mesoporous bimetallic PdCl 2 -CuCl 2 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

22. 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@SiO 2

23. 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@SiO 2

24. AC pretreatment Conventional methods: a) acid wash b) base wash c) oxidation in the gas(95%N 2 +5%O 2 ) d) oxidation in the liquid (nitric acid) e) thermal treatment Modern methods: a) microwave-induced treatment b) ultrasonic treatment

25. 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.

26. Conclusion AC pretreatment Appropriate promoter Heterogeneous catalysts My work plan:

27. Thank you