助剂对泡沫金属微反应器内二甲醚水蒸气重整制氢的影响

海航; 闫常峰; 胡蓉蓉; 郭常青; 李文博

助剂对泡沫金属微反应器内二甲醚水蒸气重整制氢的影响

1.
中国科学院广州能源研究所, 广东广州 510640;
2.
中国科学院大学, 北京 100049

基金项目: 国家自然科学基金(21276254)。

详细信息

通讯作者:
闫常峰,Tel:020-87057729,E-mail:yancf@ms.giec.ac.cn。

中图分类号: TQ032.4
计量
- 文章访问数: 1116
- HTML全文浏览量: 13
- PDF下载量: 750
- 被引次数: 0
出版历程
- 收稿日期: 2013-02-24
- 修回日期: 2013-04-12
- 刊出日期: 2013-10-30

Effect of promoter on performance of hydrogen production from steam reforming of dimethyl ether with a metal foam microreactor

1.
Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China;
2.
University of Chinese Academy of Sciences, Beijing 100049, China

摘要

摘要: 采用共沉淀耦合机械混合法制备了CuO-ZnO-Al₂O₃/HZSM-5双功能催化剂用于二甲醚水蒸气重整制氢的研究,结合BET、H₂-TPR、XRD、SEM等表征手段,在泡沫金属微反应器内考察助剂Cr、Zr、Ce、Co对双功能催化剂催化性能的影响。研究结果表明,加入Cr助剂后, 可以有效降低催化剂的平均孔径和还原温度,并抑制催化剂制备过程中氢氧化锌晶相的形成,催化剂的低温催化性能明显提高,二甲醚的转化率和氢收率在较低温度下即可分别达到99%和95%,表现出了良好的低温反应活性。考察了反应温度、空速和水醚比等条件对二甲醚水蒸气重整催化剂催化活性的影响,在250℃、空速3 884 mL/(g·h)、水醚比为5的条件下,CuO-ZnO-Al₂O₃-Cr₂O₃/ HZSM-5催化二甲醚水蒸气重整反应进行50 h,二甲醚的转化率维持在97%以上,催化剂的活性没有明显下降。
- 二甲醚水蒸气重整 /
- 泡沫金属 /
- Cr助剂 /
- 泡沫金属微反应器
Abstract: The CuO-ZnO-Al₂O₃/HZSM-5 catalyst prepared by co-precipitation and mechanical mixing with HZSM-5 was used for hydrogen production from steam reforming of dimethyl ether. The effects of Cr, Zr, Co and Ce promoters on catalyst performance were investigated by means of X-ray diffraction(XRD), temperature programmed reduction (H₂-TPR), SEM and BET. The results showed that addition of promoter Cr can reduce the average pore diameter and reduction temperature of catalyst effectively, and inhibited the form of Zn(OH)₂ in the catalyst preparation process. The conversion of dimethyl ether and hydrogen yield reaches 99% and 95% respectively at low reaction temperature. The effects of reaction termperature, space velocity and steam-to-DME ratio were investigated. At the conditions of 250℃, the space velocity of 3884mL/(g.h), H₂O/DME=5, over 97% of DME conversion was obtained over the CuO-ZnO-Al₂O₃-Cr₂O₃/HZSM-5 catalyst and the catalytic activity has no obvious deactivation during 50h durability test.
- steam reforming of dimethyl ether /
- metal foam /
- Cr promoter /
- metal foam microreactor

HTML全文

参考文献(21)

EBERLE U, FELDERHOFF M, SCHUTH F. Chemical and physical solutions for hydrogen storage[J]. Chem Int Edition, 2009, 48(36): 6608-6630.

王晓蕾, 任克威, 林瑞. 二甲醚重整制氢技术的研究进展[J]. 天然气化工, 2008, 33(03): 65-69.

(WANG Xiao-lei, REN Ke-wei, LIN Rui. Research progress in hydrogen production from the reforming of dimethyl ether[J]. Nature Gas Chemical Industry, 2008, 33(03): 65-69.)

王树东.分布式制氢与燃料电池氢源[C]. 第八届全国氢能学术会议, 西安, 2007.

(WANG Shu-dong. Distributed hydrogen production and hydrogen source of fuel cell[C]. The 8th China hydrogen energy conference, Xi'an, 2007.)

CHANG C C, HSU C C, CHANG C T, CHEN Y P, LIAW B J, CHEN Y Z. Effect of noble metal on oxidative steam reforming of methanol over CuO/ZnO/Al₂O₃ catalysts[J]. Int J Hydrogen Energy, 2012, 37(15): 11176-11184.

PAPAVASILIOU J, AVGOUROPOULOS G, IOANNIDES T. Effect of dopants on the performance of CuO-CeO₂ catalysts in methanol steam reforming[J]. App Catal B: Environ, 2007, 69(3/4): 226-234.

ALEXEY S, CHAN K. Progress in development of direct dimethyl ether fuel cells[J]. Appl Catal B: Environ, 2009, 91(1/2): 1-10.

SEMELSBERGER T A, BORUP R L, GREENE H L. Dimethyl ether (DME) as an alternative fuel[J]. J Power Sources, 2006, 156(2): 497-511.

李超, 李琢, 李建青, 杨成, 吴晋沪. 一步法合成二甲醚整体式催化剂的制备及反应性能研究[J]. 燃料化学学报, 2011, 39(4): 287-292.

(LI Chao, LI Zhuo, LI Jian-qing, YANG Cheng, WU Jin-hu. Preparation and catalytic propertiesof amonolithic catalyst for one step synthesis of dimethyl ether[J]. Journal of Fuel Chemistry and Technology, 2011, 39(4): 287-292.)

左宜赞, 张强, 安欣, 韩明汉, 王铁锋, 王金福, 金涌. 浆态床中Cu/ZnO/Al₂O₃/ZrO₂+γ-Al₂O₃双功能催化剂一步法合成二甲醚[J]. 燃料化学学报, 2010, 38(1): 102-107.

(ZUO Yi-zan, ZHANG Qiang, AN Xin, HAN Ming-han, WANG Tie-feng, WANG Jin-fu, JIN Yong. Single-step dimethyl ether synthesison a Cu/ZnO/Al₂O₃/ZrO₂+γ-Al₂O₃ bifunctional catalyst in slurry reactor[J]. Journal of Fuel Chemistry and Technology, 2010, 38(1): 102-107.)

陈卫国, 胡娟. 二甲醚(DME)的开发和应用[J]. 城市燃气, 2006, 375(5): 3-14.

(CHEN Wei-guo, HU Juan. The development and application of dimethyl ether(DME)[J]. City Gas, 2006, 375(5): 3-14.)

GALVITA V V, SEMIN G L, BELYAEV V D, YURIEVA T M, SOBYANIN V A. Production of hydrogen from dimethyl ether [J]. Appl Catal A: Gen, 2001, 216(1/2): 85-90.

PARK S, CHOI B, KIM H, KIM J H. Hydrogen production from dimethyl ether over Cu/gamma-Al₂O₃ catalyst with zeolites and its effects in the lean NO_x trap performance [J]. Int J Hydrogen Energy, 2012, 37(6): 4762-4773.

LI J, ZHANG Q J, LONG X, QI P, LIU Z T, LIU ZW. Hydrogen production for fuel cells via steam reforming of dimethyl ether over commercial Cu/ZnO/Al₂O₃ and zeolite[J]. Chem Eng J, 2012, 187: 299-305.

王晓蕾, 任克威, 潘相敏, 林瑞, 马建新.固体酸催化剂对二甲醚水蒸气重整制氢过程的影响[J]. 催化学报, 2009, 30(4): 297-304.

(WANG Xiao-lei, REN Ke-wei, PAN Xiang-min, LIN Rui, MA Jian-xin. Influence of solid acid catalysts on steam reforming of dimethyl ether for hydrogen production[J]. Chinese Journal of Catalysis, 2009, 30(4): 297-304.)

PAJAIE H S, TAGHIZADEH M. Investigation of promoted Cu/ZnO/Al₂O₃ methanol steam reforming nanocatalysts by full factorial design[J]. Chem Eng Technol, 2012, 35(10): 1857-1864.

KAWABATA T, MATSUOKA H, SHISHIDO T, LI D L, TIAN Y, SANO T, TAKEHIRA K. Steam reforming of dimethyl ether over ZSM-5 coupled with Cu/ZnO/Al₂O₃ catalyst prepared by homogeneous precipitation[J]. Appl Catal A: Gen, 2006, 32(4): 82-90.

YU H, CHEN H Q, PAN M Q, TANG Y, ZENG K, PENG F, WANG H J. Effect of the metal foam materials on the performance of methanol steam micro-reformer for fuel cells[J]. Appl Catal A: Gen, 2007, 327(1): 106-113.

李娟, 海航, 闫常峰, 胡蓉蓉, 么志伟, 罗伟民, 郭常青, 李文博. 焙烧温度对二甲醚水蒸气重整制氢Cu/ZnO/Al₂O₃/Cr₂O₃+H-ZSM-5双功能催化剂性能的影响[J]. 燃料化学学报, 2012, 40(10): 1240-1245.

(LI Juan, HAI Hang, YAN Chang-feng, HU Rong-rong, YAO Zhi-wei, LUO Wei-min, GUO Chang-qing, LI Wen-bo. Effect of calcination temperature on properties of Cu/ZnO/Al₂O₃/Cr₂O₃+HZSM-5 bi-functional catalysts for steam reforming of dimethyl ether[J]. Journal of Fuel Chemistry and Technology, 2012, 40(10): 1240-1245.)

刘智信, 李东风. 多孔金属在催化中的作用[J]. 金属功能材料, 2004, 11(2): 35-37.

(LIU Zhi-xin, LI Dong-feng. The role of the porous metal in the catalytic[J]. Metallic Function Materials, 2004, 11(2): 35-37.)

高军, 董新法, 林维明. 泡沫金属微反应器内富氢重整气中CO选择性甲烷化[J]. 燃料化学学报, 2010, 38(3): 337-342.

(GAO Jun, DONG Xin-fa, LIN Wei-ming. Selective catalytic methanation of CO in hydrogen-rich gas with a metal foam microreactor[J]. Journal of Fuel Chemistry and Technology, 2010, 38(3): 337-342.

FAUNGNAWAKIJ K, EGUCHI K. Dimethyl ether-reforming catalysts for hydrogen production[J]. Catal Surv Asia, 2011, 15(1): 12-24.

施引文献

资源附件(0)

访问统计