Citation: GU Chuan-tao, LI Guang-jun, HU Yun-qing, QING Shao-jun, HOU Xiao-ning, GAO Zhi-xian. Effect of calcination temperature of starch-modified silica on the performance of silica supported Cu catalyst in methanol conversion[J]. Journal of Fuel Chemistry and Technology, ;2012, 40(11): 1328-1335. shu

Effect of calcination temperature of starch-modified silica on the performance of silica supported Cu catalyst in methanol conversion

1.
1. State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China;

Corresponding author: GAO Zhi-xian,
Received Date: 8 February 2012
Available Online: 16 April 2012
Fund Project: 煤转化国家重点实验室开放基金(11-12-308)。 (11-12-308)

A series of starch-modified SiO₂ (SSi-T) were obtained by calcining the extrudate of SiO₂ and starch at different temperatures (T) and used as the support to prepare Cu catalysts (Cu/SSi-T, 10%) by the impregnation method. The Cu catalysts were characterized by N₂ sorption, FT-IR, TG, XRD, SEM and H₂-TPR; their catalytic performance in methanol conversion was investigated in a fixed bed reactor. The results indicated that starch can reduce the removal rate of silanol groups (Si-OH) from the surface of the support during calcination and the surface silanol groups are beneficial to the dispersion of Cu species. The calcination temperature of starch-modified SiO₂ exhibits a significant influence on the surface silanol (Si-OH) concentration, the surface area and porous structure of the support; as a result, it may be used to adjust the size of supported CuO crystal grains and dispersion of Cu species, which determine the performance of the silica supported Cu catalysts in methanol conversion.
- silica,
- starch-modification,
- Cu-based catalyst,
- calcination temperature,
- methanol conversion,
- methyl formate
1. [1]
  [1] 朱洪法. 催化剂载体制备与应用技术[M]. 北京: 石油工业出版社, 2003: 6-17. (ZHU Hong-fa. Preparation and application of catalyst carrier[M]. Beijing: Petroleum Industry Press, 2003: 6-17.)
2. [2]
  [2] ILER R K. The Chemistry of silica, solubility, polymerization, colloid, and surface properties and biochemistry[M]. New York: Wiley-Interscience, 1979: 622-654.
3. [3]
  [3] 史泰尔斯A B. 催化剂载体与负载型催化剂[M]. 李大东, 钟孝湘译. 北京: 中国石化出版社, 1992: 59-65. (STILES A B. Catalytic support and supported catalyst[M]. trans LI Da-zhong, ZHONG Xiao-xiang. Beijing: Chemical Industry Press, 1992: 59-65.)
4. [4]
  [4] POLSHETTIWAR V, MOLNAR A. Silica-supported Pd catalysts for Heck coupling reactions[J]. Tetrahedron, 2007, 63(30): 6949-6976.
5. [5]
  [5] POLSHETTIWAR V, LEN C. Silica-supported palladium: Sustainable catalysts for cross-coupling reactions[J]. Coord Chem Rev, 2009, 253(21/22): 2599-2626.
6. [6]
  [6] PULLUKAT T J, HOFF R E. Silica-based Ziegler-Natta catalysts: A patent review[J]. Catal Rev-Sci Eng, 1999, 41(3/4): 389-428.
7. [7]
  [7] 潘履让. 固体催化剂的设计与制备[M]. 天津: 南开大学出版社, 1993: 89-91. (PAN Lv-rang. Design and preparation of solid catalysts[M]. Tianjin: Nankai University Press, 1993: 89-91.)
8. [8]
  [8] KRIJN P. Synthesis of solid catalysts[M]. Weinheim: WILEY-VCH Verlag GmbH & Co.KGaA, 2009: 7-10.
9. [9]
  [9] OLAH G A. Beyond oil and gas: The methanol economy[J]. Angew Chem Int Ed, 2005, 44(18): 2636-2639.
10. [10]
  [10] SÁ S, SILVA H, BRANDO L, SOUSA J M, MENDES A. Catalysts for methanol steam reforming-A review[J]. Appl Catal B, 2010, 99(1/2): 43-57.
11. [11]
  [11] SCHRADER J, SCHILLING M, HOLTMANN D, SELL D, FILHO M V, MARX A, VORHOLT J A. Methanol-based industrial biotechnology: current status and future perspectives of methylotrophic bacteria[J]. Trends Biotechnol, 2009, 27(2): 107-115.
12. [12]
  [12] BASRI S, KAMARUDIN S K, DAUD W R W, YAAKUB Z. Nanocatalyst for direct methanol fuel cell (DMFC) [J]. In J Hydrogen Energy, 2010, 35(15): 7957-7970.
13. [13]
  [13] KIM H Y, LEE H M, PALA R G S, METIU H. Oxidative dehydrogenation of methanol to formaldehyde by isolated vanadium, molybdenum, and chromium oxide clusters supported on rutile TiO₂(110)[J]. J Physi Chem C, 2009, 113(36): 16083-16093.
14. [14]
  [14] MINYUKOVA T P, SIMENTSOVA I I, KHASIN A V, SHTERTSER N V, BARONSKAYA N A, KHASSIN A A, YURIEVA T M. Dehydrogenation of methanol over copper-containing catalysts[J]. Appl Catal, A, 2002, 237(1/2): 171-180.
15. [15]
  [15] AI M. Dehydrogenation of methanol to methyl formate over copper-based catalysts[J]. Appl Catal, 1984, 11(2): 259-270.
16. [16]
  [16] SODESAWA T, NAGACHO M, ONODERA A, NOZAKI F. Dehydrogenation of methanol to methyl formate over Cu-SiO₂ catatysts prepared by ion exchange method[J]. J Catal, 1986, 102(2): 460-463.
17. [17]
  [17] ZHURAVLEV L T. Concentration of hydroxyl-groups on the surface of amorphous silicas[J]. Langmuir, 1987, 3(3): 316-318.
18. [18]
  [18] ZHURAVLEV L T. Characterization of amorphous silica surface[J]. React Kinet Catal Lett, 1993, 50(1/2): 15-25.
19. [19]
  [19] WU C C. Adsorption property of silican dioxidehybrid starch material to dyes[J]. Environ Sci Technol, 2011, 34(9): 162-165.
20. [20]
  [20] 阮建明, 王亚东, 伍秋美, 周忠诚. 单分散球形SiO₂的制备及其分散体系的流变性能[J]. 中南大学学报自然科学版, 2007, 38(5): 825-829. (UAN Jian-ming, WANG Ya-dong, WU Qiu-mei, ZHOU Zhong-cheng. Preparation of monodisperse spherical SiO₂ and rheological property of its suspension[J]. Journal of Central South University(Science and Technology), 2007, 38(5): 825-829.)
21. [21]
  [21] WILLIAMS D H, FLEMING I. 有机化学中的光谱方法[M]. 王剑波, 施卫峰译. 北京: 北京大学出版社, 2001: 23-44. (WILLIAMS D H, FLEMING I. Spectroscopic methods in organic chemistry[M]. trans WANG Jian-bo, SHI Wei-feng. Beijing: Peking University Press, 2001: 23-44)
22. [22]
  [22] GUERREIRO E D, GORRIZ O F, RIVAROLA J B, ARRUA L A. Characterization of Cu/SiO₂catalysts prepared by ion exchange for methanol dehydrogenation[J]. Appl Catal A, 1997, 165(1/2): 259-271.
23. [23]
  [23] GUERREIRO E D, GORRIZ O F, Larsen G, ARRUA L A. Cu/SiO₂ catalysts for methanol to methyl formate dehydrogenation -A comparative study using different preparation techniques[J]. Appl Catal A, 2000, 204(1): 33-48.
24. [24]
  [24] ZHANG R, SUN Y H, PENG S Y. Dehydrogenation of methanol to methyl formate over CuO-SiO₂ gel catalyst[J]. React Kinet Catal Lett, 1999, 67(1): 95-102.
25. [25]
  [25] 张荣. 铜基催化剂的表面结构和甲醇脱氢反应选择性的调控. 太原: 中国科学院山西煤炭化学研究所, 1999 (ZHANG Rong. Surface properties of copper catalysts and control of the selectivity of methanol dehydrogenation. Taiyuan: Institute of Coal Chemistry, CAS, 1999)
26. [26]
  [26] TAKAHASHI K, TAKEZAWA N, KOBAYASHI H. Mechanism of formation of methyl formate from formaldehyde over copper catalysts[J]. Chem Lett, 1983, 7: 1061-1064.
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