官能化碳纳米管负载Ru催化山梨醇氢解制备低碳二元醇

董慧焕; 郭星翠; 秦张峰; 韩生; 牟新东

官能化碳纳米管负载Ru催化山梨醇氢解制备低碳二元醇

1.
上海应用技术学院化学与环境工程学院, 上海 201418;
2.
中国科学院青岛生物能源与过程研究所生物基材料重点实验室, 山东青岛 266101;
3.
中国科学院山西煤炭化学研究所煤转化国家重点实验室, 山西太原 030001

基金项目: 国家自然科学基金(21406251,21201174)和煤转化国家重点实验室开放课题(J13-14-603)资助

详细信息

通讯作者:
韩生,E-mail:hansheng654321@sina.com;牟新东,E-mail:muxd@qibebt.ac.cn

中图分类号: O643.32
计量
- 文章访问数: 291
- HTML全文浏览量: 14
- PDF下载量: 388
- 被引次数: 0
出版历程
- 收稿日期: 2015-06-09
- 修回日期: 2015-09-14
- 刊出日期: 2015-12-30

Effect of modified groups of carbon nanotubes on catalytic properties of Ru/CNTs catalysts for hydrogenolysis of sorbitol

1.
School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai 201418, China;
2.
Key Laboratory of Bio-based Materials, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101, China;
3.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China

Funds: The project was supported by the National Natural Science Foundation of China (21406251, 21201174) and the Foundation of State Key Laboratory of Coal Conversion (J13-14-603).

摘要

摘要: 以不同官能化碳纳米管(原始MCN、氨基化AMCN和石墨化GMCN等)作为载体,通过浸渍法制备了Ru/CNTs催化剂,并应用于山梨醇氢解制1,2-丙二醇和乙二醇反应中。利用XRD、HRTEM、XPS和ICP-AES等方法对催化剂进行了表征,考察了官能团性质、碱助剂等因素对山梨醇氢解性能的影响。结果表明,与Ru/MCN或Ru/GMCN相比较,Ru/AMCN催化剂对山梨醇氢解有更高的活性,在205℃、5.0 MPa氢压条件下,以Ca(OH)₂为添加剂,山梨醇的转化率可达99.5%,1,2-丙二醇(1,2-PD)和乙二醇(EG)的总产率为47.7%。催化剂重复利用五次,催化活性无明显下降。
- 山梨醇 /
- 氢解 /
- 1,2-丙二醇 /
- 乙二醇 /
- Ru/CNTs /
- 官能化
Abstract: Ruthenium catalysts supported on carbon nanotubes with different functional groups (MCN, AMCN and GMCN) were prepared by incipient wetness impregnation with ultrasonic-assistance and used for the hydrogenolysis of sorbitol. The catalysts were characterized by X-ray diffraction (XRD), HRTEM, X-ray photoelectron spectroscopy (XPS) and ICP-AES. The effects of functional group species, and base additives on the catalytic performance of Ru/CNTs in the sorbitol hydrogenolysis reaction were investigated. Nearly 99.5% of sorbitol conversion and 47.7% total yield of ethylene glycol and 1,2-propanediol (1,2-PD) could be achieved over Ru/AMCN under mild reaction conditions (205℃, 5.0 MPa), using Ca(OH)₂ as additive. The conversion of sorbitol and the selectivity to ethylene glycol (EG) and 1,2-propanediol (1,2-PD) did not decrease over the five repeated runs, which confirmed that the Ru/AMCN catalyst exhibited high stability in the aqueous hydrogenolysis of sorbitol to glycols.
- sorbitol /
- hydrogenolysis /
- 1,2-propanediol /
- ethylene glycol /
- Ru/CNTs /
- functionalization

HTML全文

参考文献(23)

LIU Y, LUO C, LIU H. Tungsten trioxide promoted selective conversion of cellulose into propylene glycol and ethylene glycol on a ruthenium catalyst[J]. Angew Chem, 2012, 124(13):3303-3307.

PEEREBOOM L, JACKSON J E, MILLER D J. Interaction of polyols with ruthenium metal surfaces in aqueous solution[J]. Green Chem, 2009, 11:1979-1986.

MARIS E P, DAVIS R J. Hydrogenolysis of glycerol over carbon-supported Ru and Pt catalysts[J]. J Catal, 2007, 249(2):328-333.

YUE H, ZHAO Y, MA X. Ethylene glycol:Properties, synthesis, and applications[J]. Chem Soc Rev, 2012, 41(11):4218-4244.

ZARTMAN W H, ADKINS H. Hydrogenolysis of sugars[J]. J Am Chem Soc, 1933, 55(11):4559-4563.

CLARK I T. Hydrogenolysis of sorbitol[J]. Ind Eng Chem, 1958, 50:1125-1126.

POLETAEVA T I, IPATOVA T V, LEIKIN E R, MAMAEVA I A, EPISHKO G F, GOLOSMAN E Z, YAKERSON V I. Hydrogenolysis of glucose on Ni-Al₂O₃ and Ni-Cu-Al₂O₃ catalysts[J]. Rull Acad Sci VSSR, Div Chem Sci, 1976, 25(11):2412-2415.

SUN J, LIU H. Selective hydrogenolysis of biomass-derived xylitol to ethylene glycol and propylene glycol on supported Ru catalysts[J]. Green Chem, 2011, 13:135-142.

ZHAO L, ZHOU J H, SUI Z J, ZHOU X G. Hydrogenolysis of sorbitol to glycols over carbon nanofiber supported ruthenium catalyst[J]. Chem Eng Sci, 2010, 65:30-35.

PAN X L, BAO X H. Reactions over catalysts confined in carbon nanotubes[J]. Chem Commun, 2009, 47(47):6271-6281.

SERP P, CASTILLEJOS E. Catalysis in carbon nanotubes[J]. Chemcatchem, 2010, 2:41-47.

SU D S, PERATHONER S, CENTI G. Nanocarbons for the development of advanced catalysts[J]. Chem Rev, 2013, 113(8):5782-5816.

KARIMI A, NASERNEJAD B, RASHIDI A M, TAVASOLI A, POURKHALIL M. Functional group effect on carbon nanotube (CNT)-supported cobalt catalysts in Fischer-Tropsch synthesis activity, selectivity and stability[J]. Fuel, 2014, 117:1045-1051.

LEPRO X, TERRES E, TERRONES M. Efficient anchorage of Pt clusters on N-doped carbon nanotubes and their catalytic activity[J]. Chem Phys Lett, 2008, 463(1/3):124-129.

SHIDING M, ZHIMIN L, BUXING H, JUN H, ZHENYU S, JIANLING Z. Ru nanoparticles immobilized on montmorillonite by ionic liquids:A highly efficient heterogeneous catalyst for the hydrogenation of benzene[J]. Angew Chem Int Ed, 2005, 45(2):266-269.

MAURIELLO F, ARIGA H, MUSOLINO M G, PIETROPAOLO R, TAKAKUSAGI S, ASAKURA K. Exploring the catalytic properties of supported palladium catalysts in the transfer hydrogenolysis of glycerol[J]. Appl Catal B:Environ, 2015, 166-167:121-131.

卢振明,赵东林,刘云芳,沈曾民.石墨化处理对碳纳米管结构的影响[J].材料热处理学报, 2005, 26(6):9-11. (LU Zhen-ming, ZHAO Dong-lin, LIU Yun-fang, SHEN Zeng-min. Effect of graphitization on the structure of carbon nanobubes[J]. Trans Mater Heat Treat, 2005, 26(6):9-11.)

周静红,刘国才,隋志写,周兴贵,袁滑康.碱促进剂在Ru/CNFs催化梨醇氢解制备二元醇中的应用[J].催化学报, 2014, 35(5):692-702. (ZHOU Jing-hong, LIU Guo-cai, SUI Zhi-xie, ZHOU Xing-gui, YUAN Hua-kang. Hydrogenolysis of sorbitol to glycols over carbon nanofibers-supported ruthenium catalyst:The role of base promoter[J]. Chin J Catal, 2014, 35(5):692-702.)

SOHOUNLOUE D K, MONTASSIER C, BARBIER J. Catalytic hydrogenolysis of sorbitol[J]. React Kinet Catal L, 1983, 22:391-397.

ANDREWS M A, KLAEREN S A. Selective hydrocracking of monosaccharide carbon-carbon single bonds under mild conditions-ruthenium hydride catalyzed formation of glycols[J]. J Am Chem Soc, 1989, 111:4131-4133.

SCHLAF M, GHOSH P, FAGAN P J, HAUPTMAN E, BULLOCK R M. Metal-catalyzed selective deoxygenation of diols to alcohols[J]. Angew Chem Int Ed, 2001, 40:3887-3890.

KUO Y J, COCCO R A, TATARCHUK B J. Hydrogenation and hydrodesulfurization over sulfided ruthenium catalysts:ii. Impact of surface phase behavior on activity and selectivity[J]. J Catal, 1988, 112:250-266.

LI N, HUBER G W. Aqueous-phase hydrodeoxygenation of sorbitol with Pt/SiO₂-Al₂O₃:Identification of reaction intermediates[J]. J Catal, 2010, 270:48-59.

施引文献

资源附件(0)

访问统计