甲醇水蒸气重整制氢反应条件的优化

张磊; 潘立卫; 倪长军; 赵生生; 王树东; 胡永康; 王安杰; 蒋凯

甲醇水蒸气重整制氢反应条件的优化

1.
中国科学院大连化学物理研究所, 辽宁大连 116023;
2.
大连理工大学精细化工国家重点实验室, 辽宁大连 116023;
3.
抚顺石油化工研究院, 辽宁抚顺 113001

基金项目: 国家自然科学基金(21076206); 国家重点基础研究发展规划(973计划,2010CB732302); 国家高技术研究发展计划(863计划, 2011AA050706)。

详细信息

通讯作者:
潘立卫,研究员,Tel:0411-84379323;E-mail:panlw@dicp.ac.cn;王树东,研究员,Tel:0411-84379052;E-mail:wangsd@dicp.ac.cn。

中图分类号: O643.32
计量
- 文章访问数: 2283
- HTML全文浏览量: 23
- PDF下载量: 892
- 被引次数: 0
出版历程
- 收稿日期: 2012-07-05
- 修回日期: 2012-09-25
- 刊出日期: 2013-01-31

Optimization of methanol steam reforming for hydrogen production

1.
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China;
2.
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116023, China;
3.
Fushun Research Institute of Petroleum and Petrochemicals, Fushun 113001, China

摘要

摘要: 对共沉淀法制备的CuO/ZnO/CeO₂-ZrO₂催化剂在甲醇水蒸气重整制氢反应体系中的性能进行了考察,并利用统计学实验设计方法对该反应的反应条件进行了优化。选择反应温度、水醇比和甲醇气体空速为独立要因,利用全因子实验设计方法,得到反应温度对两个响应值(甲醇转化率和重整气中CO物质的量分数)的影响最为显著,甲醇气体空速对重整气中CO物质的量分数的影响最小。固定甲醇气体空速为300 h^-1,利用中心旋转组合设计实验方法对反应温度和水醇比进行优化,得出当反应温度在249~258℃、水醇比在1.76~2.00时,甲醇能全部转化,重整气中CO物质的量分数小于0.5%。此模型的计算值与实验结果较为接近,表明采用统计学实验设计方法得出的结论对甲醇水蒸气重整制氢反应条件的优化具有指导意义。
- 全因子设计 /
- 中心旋转组合设计 /
- 响应曲面 /
- 甲醇水蒸气重整 /
- 氢气 /
- 优化
Abstract: The catalytic performance of CuO/ZnO/CeO₂/ZrO₂ prepared by co-precipitation for methanol steam reforming was investigated using a statistical set of experiments in order to optimize the reaction conditions for obtaining minimal carbon monoxide in the reformed gas. The reaction temperature, steam to methanol ratio, methanol gas hourly space velocity (GHSV) were evaluated with a full factorial design experiment. The reaction temperature displayed much greater influence on the response (methanol conversion and CO concentration in reformed gas), GHSV has minimal influence on the CO concentration in reformed gas. At a fixed low methanol GHSV (300 h^-1), a central composite rotatable design was then used to approximate the optimal conditions by simultaneously considering the methanol conversion and CO concentration. The optimum theoretical conditions were found to lie within a reaction temperature of 249~258℃ and a W/M ratio of 1.76~2.00, in close agreement with the experimental results.
- full factorial design /
- central composite rotatable design (CCRD) /
- response surface /
- methanol steam reforming /
- hydrogen /
- optimization

HTML全文

参考文献(20)

LINDSTROM B, PETTERSSON L J. Hydrogen generation by steam reforming of methanol over copper-based catalysts for fuel cell applications[J]. Int J Hydrogen Energy, 2001, 26(9): 923-933.

LINDSTROM B, PETTERSSON L J, MENON P G. Activity and characterization of Cu/Zn, Cu/Cr and Cu/Zr on γ-alumina for methanol reforming for fuel cell vehicles[J]. Appl Catal A, 2002, 234(1/2): 111-125.

MATTER P H, OZKAN U S. Effect of pretreatment conditions on Cu/Zn/Zr-based catalysts for the steam reforming of methanol to H₂[J]. J Catal, 2005, 234(2): 463-475.

FUKUNAGA T, RYUMON N, ICHIKUNI N, SHIMAZU S. Characterization of CuMn-spinel catalyst for methanol steam reforming[J]. Catal Commun, 2009, 10(14): 1800-1803.

HUANG G, LIAW B-J, JHANG C-J, CHEN Y-Z. Steam reforming of methanol over CuO/ZnO/CeO₂/ZrO₂/Al₂O₃ catalysts[J]. Appl Catal A, 2009, 358(1): 7-12.

潘相敏, 宋小瑜, 余瀛, 周伟, 马建新. 湿混法制备甲醇氧化重整制氢催化剂[J]. 燃料化学学报, 2005, 33(3): 339-343. (PAN Xiang-min, SONG Xiao-yu, YU Ying, ZHOU Wei, MA Jian-xin. Wet-mixed CuZnAlZr catalysts for oxidative steam reforming of methanol[J]. Journal of Fuel Chemistry and Technology, 2005, 33(3): 339-343.)

AGRELL J, GERMANI G, JARAS S G, BOUTONNET M. Production of hydrogen by partial oxidation of methanol over ZnO-supported palladium catalysts prepared by microemulsion technique[J]. Appl Catal A, 2003, 242(2): 233-245.

CUBEIRO M L, FIERRO J L G. Selective production of hydrogen by partial oxdiation of methanol over ZnO-supported palladium catalysts[J]. J Catal, 1998, 179(1): 150-162.

MU X, PAN L, LIU N, ZHANG C, LI S, SUN G, WANG S. Autothermal reforming of methanol in a mini-reactor for miniature fuel cell[J]. Int J Hydrogen Energy, 2007, 32(15): 3327-3334.

WANG C, LIU N, PAN L, WANG S, YUAN Z, WANG S. Measurement of concentration profiles over ZnO-Cr₂O₃/CeO₂-ZrO₂ monolithic catalyst in oxidative steam reforming of methanol[J]. Fuel Process Technol, 2007, 88(1): 65-71.

LIU N, YUAN Z, WANG S, ZHANG C, WANG S, LI D. Characterization and performance of a ZnO-ZnCr₂O₄/CeO₂-ZrO₂ monolithic catalyst for hydrogen production by methanol auto-thermal reforming process[J]. Int J Hydrogen Energy, 2008, 33(6): 1643.

LIU N, YUAN Z, WANG C, WANG S, ZHANG C, WANG S. The role of CeO₂-ZrO₂ as support in the ZnO-ZnCr₂O₄ catalysts for autothermal reforming of methanol[J]. Fuel Process Technol, 2008, 89(6): 574-581.

CHEN G, YUAN Q, LI S. Microchannel reactor for methanol autothermal reforming[J]. Chin J Catal, 2002, 23(6): 491-492.

PATEL S, PANT K K. Selective production of hydrogen via oxidative steam reforming of methanol using Cu-Zn-Ce-Al oxide catalysts[J]. Chem Eng Sci, 2007, 62(18/20): 5436-5443.

PATEL S, PANT K K. Hydrogen production by oxidative steam reforming of methanol using ceria promoted copper-alumina catalysts[J]. Fuel Process Technol, 2007, 88(8): 825- 832.

ZHANG X R, SHI P. Production of hydrogen by steam reforming of methanol on CeO₂ promoted Cu/Al₂O₃ catalysts[J]. J Mol Catal A, 2003, 194(1/2): 99-105.

ZHANG X R, SHI P, ZHAO J, ZHAO M, LIU C. Production of hydrogen for fuel cells by steam reforming of methanol on Cu/ZrO₂/Al₂O₃ catalysts[J]. Fuel Process Technol, 2003, 83(1/3): 183-192.

YANG H-M, LIAO P-H. Preparation and activity of Cu/ZnO-CNTs nano-catalyst on steam reforming of methanol[J]. Appl Catal A, 2007, 317(2): 226-233.

OGUCHI H, KANAI H, UTANI K, MATSUMURA Y, IMAMURA S. Cu₂O as active species in the stram reforming of methanol by CuO/ZrO₂ catalysts[J]. Appl Catal A, 2005, 293(1/2): 64-70.

TAKAHASHI T, INOUE M, KAI T. Effect of metal composition on hydrogen selectivity in steam reforming of methanol over catalysts prepared from amorphous alloys[J]. Appl Catal A, 2001, 218(1/2): 189-195.

施引文献

资源附件(0)

访问统计