Synthesis of dimethylcarbonate from urea and methanol catalyzed by various metal oxides and salts
-
摘要: 在高压釜中采用金属氧化物和盐作为催化剂由尿素与甲醇合成碳酸二甲酯。结果表明,含有结晶水的金属盐比无结晶水金属盐和金属氧化物具有更好的催化活性。采用羟基化合物与硝酸锌组成的二元催化剂,其催化活性显著高于单一催化剂;羟基与硝酸锌之间具有协同催化作用。其中,硝酸锌与SiO2组成的二元催化剂活性最高;硝酸锌与SiO2的质量比为2时,DMC收率可达4.5%。Abstract: Various metal oxides and metallic salts were used as a catalyst in the synthesis of dimethyl carbonate (DMC) from urea and methanol in an autoclave. The results indicated that the hydrated metallic salt is most catalytically active in DMC synthesis among various metal oxides and salts considered in this work. Furthermore, a binary catalyst, viz, Zn(NO3)2 combined with hydroxyl containing compounds, can noticeably enhance the yield of DMC, in comparison with the single catalyst of both Zn(NO3)2 and the hydroxyl containing compound, which may be ascribed to a synergistic effect between Zn(NO3)2 and the hydroxyl group. Among various binary catalysts, Zn(NO3)2-SiO2 exhibits the best catalytic performance; the yield of DMC reaches 4.5% over Zn(NO3)2-SiO2 with a Zn(NO3)2 to SiO2 weight ratio of 2.
-
Key words:
- dimethyl carbonate /
- urea /
- methanol /
- methanolysis /
- binary catalyst /
- metallic salt /
- metal oxide /
- hydroxyl
-
SHAIKH A A, SIVARAM S. Organic carbonates[J]. Chem Rev, 1996, 96: 951-976. JESSOP P G, IKARIYA T, NOYORI R. Homogeneous catalysis in supercritical fluids[J]. Science, 1995, 269: 1065-1069. PACHECO M A, MARSHALL C L. Methanol gasoline blends: Alternative fuel for today's automobiles and cleaner burning octane for today's oil refinery[J]. Energy Fuels, 1997, 11: 2-29. YANG P, CAO Y, HU J C, DAI W L, FAN K N. Mesoporous bimetallic PdCl2-Cu-Cl2 catalysts for dimethyl carbonate synthesis by vapor phase oxidative carbonylation of methanol[J]. Appl Catal A: Gen, 2003, 241: 363-373. TOMISHIGE K, SAKAIHORI T, SAKAI S I, FUJIMOTO K. Dimethyl carbonate synthesis by oxidative carbonylation on activated carbon supported CuCl2 catalysts: Catalytic properties and sturetural change[J]. Appl Catal, 1999, 181: 95-102. ZHENG H Y, REN J, ZHOU Y, NIU Y Y, LI Z. Preparation of Cu+/SiO2-ZrO2 catalysts for oxidative carbonylation of methanol to dimethyl carbonate[J]. J Fuel Chem Technol, 2011, 39(4): 282-286. WU X M, KANG M, ZHAO N, WEI W, SUN Y H. Dimethyl carbonate synthesis over ZnO-CaO bi-functional catalysts[J]. Catal Commun, 2014, 46: 46-50. WANG D F, ZHANG X L, ZHAO W B, PENG W C, ZHAO N, XIAO F K, WEI W, SUN Y H. Synthesis of dimethyl carbonate from methyl carbamate and methanol catalyzed by mixed oxides from hydrotalcite-like compounds[J]. J Phys Chem Solids, 2010, 71(4): 427-430. ZHAO W B, PENG W C, ZHAO N, XIAO F K, WEI W, SUN Y H. Synthesis of dimethyl carbonate from methyl carbamate and methanol by acid - base catalysis[J]. Petrochem Technol, 2009, 38: 367-372. WANG M H, WANG H, ZHAO N, WEI W, SUN Y H. Synthesis of dimethyl carbonate from urea and methanol over solid base catalysts[J]. Catal Commun, 2006, 7: 6-10. WU C C, ZHAO X Q, WANG Y J. Effect of reduction treatment on catalystic performance of Zn-based catalyst for methanolysis of urea to dimethyl carbonate[J]. Catal Commun, 2005, 6: 694-698. ZHAO W B, WANG F, PENG W C, ZHAO N, LI J P, XIAO F K, WEI W, SUN Y H. Synthesis of dimethyl carbonate from methyl carbamate and methanol with zinc compounds as catalysts[J]. Ind Eng Chem Res, 2008, 47(16): 5913-5917. YANG B L, WANG D P, LIN H Y, SUN J J, WANG X P. Synthesis of dimethyl carbonate from urea and methanol catalyzed by the metallic compounds at atmospheric pressure[J]. Catal Commun, 2006, 7: 472-477. JOE W, LEE H J, HONG U G. Synthesis of dimethyl carbonate from urea and methanol over ZnOx-CeO2(1-x) catalysts prepared by a sol-gel method[J]. J Ind Eng Chem, 2012, 18: 1018-1022.J JOE W, LEE H J, HONG U G. Urea methanolysis to dimethyl carbonate over ZnO-CeO2-MO (MO: La2O3, Y2O3, Co2O3, Ga2O3, and ZrO2) catalysts[J]. J Ind Eng Chem, 2012, 18: 1730-1735. ZHAO X Q, WU C C, YANG H J, WANG Y J, ZHANG J Y. Synthesis of dimethyl carbonate from urea and methanol via homogeneous catalyst[J]. Chem React Eng Technol, 2002, 18: 200-205. FU Y, ZHU H, SHEN J. Thermal decomposition of dimethoxymethane and dimethyl carbonate catalyzed by solid acids and bases[J]. Thermochim Acta, 2005, 434: 88-92. GARCIA-GIL S, ARNAU A, GARCIA-LEKUE A. Exploring large O 1s and N 1s core level shifts due to intermolecular hydrogen bond formation in organic molecules[J]. Surf Sci, 2013, 613: 102-107.
点击查看大图
计量
- 文章访问数: 580
- HTML全文浏览量: 32
- PDF下载量: 634
- 被引次数: 0