Research progress of the catalysts for hydrogen production by dimethyl ether steam reforming

doi:10.16085/j.issn.1000-6613.2017-2705

Abstract

Abstract: Proton exchange membrane fuel cell (PEMFC) is considered as an ideal power source for fuel cell vehicles. However, challenges still exist for the commercialization of PEMFC, in which the supply of stable and high quality hydrogen source is the main one. The production of hydrogen by dimethyl ether steam reforming is one of the most realistic and effective solutions for hydrogen supply in the near future. The present work provides review on the progress of the catalysts for hydrogen production through dimethyl ether steam reforming, and the focus is on the modification of acid strength, acid type and structure of alumina and HZSM-5 zeolite, and the research status of Pd based noble metal catalysts and Zn based catalysts. Furthermore, related research on monolithic catalyst, and the deactivation and regeneration of catalyst are also reviewed. It is pointed out that developing the In₂O₃ catalyst; constructing of catalysts with hierarchical/nanosized structure, creating catalysts with special structure (the hierarchical zeolite/alumina core catalyst enwrapped by one layer of defect-free metallic catalyst shell), may be the future directions of dimethyl ether steam reforming.

Key words: fuel cells, multiphase reaction, hydrogen production, catalyst, deactivation

摘要： 高品质氢气的在线稳定供给是质子交换膜燃料电池（PEMFC）商业化的瓶颈和亟待解决的关键问题，以二甲醚为原料经水蒸气重整制取氢气是近中期最为现实和有效的氢源供给方案之一。本文总结和评述了近期二甲醚水蒸气重整制氢催化剂的研究进展，主要集中在固体酸催化剂中氧化铝和HZSM-5分子筛酸强度、酸类型以及结构的调变对性能的影响，同时对金属催化剂特别是Pd基贵金属催化剂和Zn基催化剂的研究现状、整体式催化剂以及催化剂的失活与再生的相关研究进行了重点介绍。根据对相关研究结果的总结，提出今后该领域的重要研究方向为：开发新型In₂O₃催化剂；构建具有多级孔、纳米结构的催化剂体系；创制具有特殊结构的催化剂（以多级孔分子筛/氧化铝为核，连续无缺陷的金属催化剂为壳）。

关键词: 燃料电池, 多相反应, 制氢, 催化剂, 失活

CLC Number:

TQ116.2

ZANG Yunhao, DANG Haifeng, HUA Kaihui, FAN Hongbo, DONG Xinfa. Research progress of the catalysts for hydrogen production by dimethyl ether steam reforming[J]. Chemical Industry and Engineering Progress, 2018, 37(12): 4662-4668.

臧云浩, 党海峰, 花开慧, 范洪波, 董新法. 二甲醚水蒸气重整制氢催化剂的研究进展[J]. 化工进展, 2018, 37(12): 4662-4668.

References

[1] COSTAMAGNA P, SRINIVASAN S. Quantum jumps in the PEMFC science and technology from the 1960s to the year 2000:Part Ⅱ. Engineering, technology development and application aspects[J]. Journal of Power Sources, 2001, 102(1):253-269.
[2] HWANG H T, VARMA A. Hydrogen storage for fuel cell vehicles[J]. Current Opinion in Chemical Engineering, 2014, 5:42-48.
[3] ZHANG Q J, DU F, HE X X, et al. Hydrogen production via partial oxidation and reforming of dimethyl ether[J]. Catalysis Today, 2009, 146(1):50-56.
[4] SEMELSBERGER T A, BORUP R L, GREENE H L. Dimethyl ether (DME) as an alternative fuel[J]. Journal of Power Sources, 2006, 156(2):497-511.
[5] SOBYANIN V A, CAVALLARO S, FRENI S. Dimethyl ether steam reforming to feed molten carbonate fuel cells (MCFCs)[J]. Energy & Fuels, 2000, 14(6):1139-1142.
[6] TANAKA Y, KIKUCHI R, TAKEGUCHI T, et al. Steam reforming of dimethyl ether over composite catalysts of γ-Al₂O₃ and Cu-based spinel[J]. Applied Catalysis B:Environmental, 2005, 57(3):211-222.
[7] FAUNGNAWAKIJ K, EGUCHI K. Dimethyl ether——reforming catalysts for hydrogen production[J]. Catalysis Surveys from Asia, 2011, 15(1):12-24.
[8] FAUNGNAWAKIJ K, TANAKA Y, SHIMODA N, et al. Influence of solid-acid catalysts on steam reforming and hydrolysis of dimethyl ether for hydrogen production[J]. Applied Catalysis A:General, 2006, 304:40-48.
[9] GALVITA V V, SEMIN G L, BELYAEV V D, et al. Production of hydrogen from dimethyl ether[J]. Applied Catalysis A:General, 2001, 216(1):85-90.
[10] SEMELSBERGER T A, OTT K C, BORUP R L, et al. Generating hydrogen-rich fuel-cell feeds from dimethyl ether (DME) using physical mixtures of a commercial Cu/Zn/Al₂O₃ catalyst and several solid-acid catalysts[J]. Applied Catalysis B:Environmental, 2006, 65(3):291-300.
[11] YANG M, MEN Y, LI S L, et al. Enhancement of catalytic activity over TiO₂-modified Al₂O₃ and ZnO-Cr₂O₃ composite catalyst for hydrogen production via dimethyl ether steam reforming[J]. Applied Catalysis A:General, 2012, 433:26-34.
[12] ZANG Y H, DONG X F, WANG C X. One-pot synthesis of mesoporous Cu-SiO₂-Al₂O₃ bifunctional catalysts for hydrogen production by dimethyl ether steam reforming[J]. Chemical Engineering Journal, 2017, 313:1583-1592.
[13] 张晓芳, 李平, 熊刚华, 等. 二甲醚蒸气重整催化制氢工艺[J]. 化工进展, 2009, 28(7):1169-1174. ZHANG X F, LI P, XIONG G H, et al. Catalytic steam reforming of dimethyl ether for hydrogen production[J]. Chemical Industry and Engineering Progress, 2009, 28(7):1169-1174.
[14] VICENTE J, GAYUBO A G, EREÑA J, et al. Improving the DME steam reforming catalyst by alkaline treatment of the HZSM-5 zeolite[J]. Applied Catalysis B:Environmental, 2013, 130:73-83.
[15] LONG X, ZHANG Q J, LIU Z T, et al. Magnesia modified H-ZSM-5 as an efficient acidic catalyst for steam reforming of dimethyl ether[J]. Applied Catalysis B:Environmental, 2013, 134:381-388.
[16] LÜ J H, ZHOU S, MA K, et al. The effect of P modification on the acidity of HZSM-5 and P-HZSM-5/CuO-ZnO-Al₂O₃ mixed catalysts for hydrogen production by dimethyl ether steam reforming[J]. Chinese Journal of Catalysis, 2015, 36(8):1295-1303.
[17] ZANG Y H, DONG X F, PING D, et al. The direct synthesis of Zn-incorporated nanosized H-ZSM-5 zeolites using ZIF-8 as a template for enhanced catalytic performance[J]. CrystEngComm, 2017, 19(23):3156-3166.
[18] IWASA N, KUDO S, TAKAHASHI H, et al. Highly selective supported Pd catalysts for steam reforming of methanol[J]. Catalysis Letters, 1993, 19(2):211-216.
[19] IWASA N, MASUDA S, TAKEZAWA N. Steam reforming of methanol over Ni, Co, Pd and Pt supported on ZnO[J]. Reaction Kinetics and Catalysis Letters, 1995, 55(2):349-353.
[20] IWASA N, MAYANAGI T, OGAWA N, et al. New catalytic functions of Pd-Zn, Pd-Ga, Pd-In, Pt-Zn, Pt-Ga and Pt-In alloys in the conversions of methanol[J]. Catalysis Letters, 1998, 54(3):119-123.
[21] LEDESMA C, OZKAN U S, LLORCA J. Hydrogen production by steam reforming of dimethyl ether over Pd-based catalytic monoliths[J]. Applied Catalysis B:Environmental, 2011, 101(3):690-697.
[22] YOSHIDA H, IWASA N, AKAMATSU H, et al. Stable and selective hydrogen production through steam reforming of dimethyl ether with an Al₂O₃ and PdZn composite catalyst[J]. International Journal of Hydrogen Energy, 2015, 40(16):5624-5627.
[23] RAMOS E, DAVIN L, ANGURELL I, et al. Improved stability of Pd/Al₂O₃ prepared from palladium nanoparticles protected with carbosilane dendrons in the dimethyl ether steam reforming reaction[J]. ChemCatChem, 2015, 7(14):2179-2187.
[24] OAR-ARTETA L, EPRON F, BION N, et al. Comparison in dimethyl ether steam reforming of conventional Cu-ZnO-Al₂O₃ and supported Pt metal catalysts[C]//International Conference On Biomass, Pts 1 and 2. 2014, 37:487-492.
[25] 黄媛媛, 巢磊, 李工, 等. Cu-ZrO₂-CeO₂/γ-Al₂O₃催化甲醇水蒸气重整制氢反应的性能[J]. 化工进展, 2017, 36(1):216-223. HUANG Y Y, CHAO L, LI G, et al. Performance of Cu-ZrO₂-CeO₂/γ-Al₂O₃ catalysts for hydrogen production from steam reforming of methanol[J]. Chemical Industry and Engineering Progress, 2017, 36(1):216-223.
[26] SHEN J P, SONG C S. Influence of preparation method on performance of Cu/Zn-based catalysts for low-temperature steam reforming and oxidative steam reforming of methanol for H₂ production for fuel cells[J]. Catalysis Today, 2002, 77(1):89-98.
[27] YAO C Z, WANG L C, LIU Y M, et al. Effect of preparation method on the hydrogen production from methanol steam reforming over binary Cu/ZrO₂ catalysts[J]. Applied Catalysis A:General, 2006, 297(2):151-158.
[28] SHISHIDO T, YAMAMOTO Y, MORIOKA H, et al. Active Cu/ZnO and Cu/ZnO/Al₂O₃ catalysts prepared by homogeneous precipitation method in steam reforming of methanol[J]. Applied Catalysis A:General, 2004, 263(2):249-253.
[29] 张新荣, 史鹏飞, 刘春涛. 甲醇水蒸气重整制氢催化剂性能的研究[J]. 化工进展, 2002, 21(7):487-489. ZHANG X R, SHI P F, LIU C T. Properties of catalysts for steam reforming of methanol[J]. Chemical Industry and Engineering Progress, 2002, 21(7):487-489.
[30] TAKEISHI K, AKAIKE Y. Hydrogen production by dimethyl ether steam reforming over copper alumina catalysts prepared using the sol-gel method[J]. Applied Catalysis A:General, 2016, 510:20-26.
[31] 王新雷, 马奎, 郭丽红, 等. 蒸氨法制备铜硅催化剂的二甲醚水蒸气重整制氢性能[J]. 物理化学学报, 2017, 33(8):1699-1708. WANG X L, MA K, GUO L H, et al. Catalytic performance for hydrogen production through steam reforming of dimethyl ether over silica supported copper catalysts synthesized by ammonia evaporation method[J]. Acta Physico-Chimica Sinica, 2017, 33(8):1699-1708.
[32] WANG X L, MA K, GUO L H, et al. Cu/ZnO/SiO₂ catalyst synthesized by reduction of ZnO-modified copper phyllosilicate for dimethyl ether steam reforming[J]. Applied Catalysis A:General, 2017, 540:37-46.
[33] AGRELL J, BIRGERSSON H, BOUTONNET M, et al. Production of hydrogen from methanol over Cu/ZnO catalysts promoted by ZrO₂ and Al₂O₃[J]. Journal of Catalysis, 2003, 219(2):389-403.
[34] YANG H M, CHAN M K. Steam reforming of methanol over copper-yttria catalyst supported on praseodymium-aluminum mixed oxides[J]. Catalysis Communications, 2011, 12(15):1389-1395.
[35] MATSUMURA Y. Durable Cu composite catalyst for hydrogen production by high temperature methanol steam reforming[J]. Journal of Power Sources, 2014, 272:961-969.
[36] LIU Y Y, HAYAKAWA T, TSUNODA T, et al. Steam reforming of methanol over Cu/CeO₂ catalysts studied in comparison with Cu/ZnO and Cu/Zn(Al)O catalysts[J]. Topics in Catalysis, 2003, 22(3/4):205-213.
[37] TSAI M C, WANG J H, SHEN C C, et al. Promotion of a copper-zinc catalyst with rare earth for the steam reforming of methanol at low temperatures[J]. Journal of Catalysis, 2011, 279(2):241-245.
[38] KNIEP B L, GIRGSDIES F, RESSLER T. Effect of precipitate aging on the microstructural characteristics of Cu/ZnO catalysts for methanol steam reforming[J]. Journal of Catalysis, 2005, 236(1):34-44.
[39] FAUNGNAWAKIJ K, TANAKA Y, SHIMODA N, et al. Hydrogen production from dimethyl ether steam reforming over composite catalysts of copper ferrite spinel and alumina[J]. Applied Catalysis B:Environmental, 2007, 74(1):144-151.
[40] FAUNGNAWAKIJ K, SHIMODA N, FUKUNAGA T, et al. Cu-based spinel catalysts CuB₂O₄ (B=Fe, Mn, Cr, Ga, Al, Fe_0.75Mn_0.25) for steam reforming of dimethyl ether[J]. Applied Catalysis A:General, 2008, 341(1):139-145.
[41] ZHANG L J, MENG M, WANG X J, et al. A series of copper-free ternary oxide catalysts ZnAlCe_x used for hydrogen production via dimethyl ether steam reforming[J]. Journal of Power Sources, 2014, 268:331-340.
[42] ZHOU S, MA K, TIAN Y, et al. Dimethyl ether steam reforming to produce H₂ over Ga-doped ZnO/γ-Al₂O₃ catalysts[J]. RSC Advances, 2016, 6(57):52411-52420.
[43] ZHANG Q, XU J J, FAN F Y, et al. Application of porous anodic alumina monolith catalyst in steam reforming of dimethyl ether:Cu/γ-Al₂O₃/Al catalyst degradation behaviors and catalytic activity improvement by pre-competition impregnation method[J]. Fuel Processing Technology, 2014, 119:52-59.
[44] ZHANG Q, WANG X, FAN F Y, et al. Preparation and catalytic behavior of second metal Ni supported on a novel conductive structured Cu/γ-Al₂O₃/Al catalysts through electrolysis on steam reforming of dimethyl ether[J]. Catalysis Communications, 2016, 76:67-71.
[45] FAN F Y, ZHANG Q, WANG X, et al. A structured Cu-based/γ-Al₂O₃/Al plate-type catalyst for steam reforming of dimethyl ether:self-activation behavior investigation and stability improvement[J]. Fuel, 2016, 186:11-19.
[46] YAN C F, YE W, GUO C Q, et al. Numerical simulation and experimental study of hydrogen production from dimethyl ether steam reforming in a micro-reactor[J]. International Journal of Hydrogen Energy, 2014, 39(32):18642-18649.
[47] YAN C F, HAI H, HU R R, et al. Effect of Cr promoter on performance of steam reforming of dimethyl ether in a metal foam micro-reactor[J]. International Journal of Hydrogen Energy, 2014, 39(32):18625-18631.
[48] YAN C F, HAI H, GUO C Q, et al. Hydrogen production by steam reforming of dimethyl ether and CO-PrO_x in a metal foam micro-reactor[J]. International Journal of Hydrogen Energy, 2014, 39(20):10409-10416.
[49] WANG X L, PAN X M, LIN R, et al. Steam reforming of dimethyl ether over Cu-Ni/γ-Al₂O₃ bi-functional catalyst prepared by deposition-precipitation method[J]. International Journal of Hydrogen Energy, 2010, 35(9):4060-4068.
[50] PATEL S, PANT K K. Activity and stability enhancement of copper-alumina catalysts using cerium and zinc promoters for the selective production of hydrogen via steam reforming of methanol[J]. Journal of Power Sources, 2006, 159(1):139-143.
[51] OAR-ARTETA L, REMIRO A, VICENTE J, et al. Stability of CuZnOAl₂O₃/HZSM-5 and CuFe₂O₄/HZSM-5 catalysts in dimethyl ether steam reforming operating in reaction-regeneration cycles[J]. Fuel Processing Technology, 2014, 126:145-154.
[52] OAR-ARTETA L, AGUAYO A T, REMIRO A, et al. Behavior of a CuFe₂O₄/γ-Al₂O₃ catalyst for the steam reforming of dimethyl ether in reaction-regeneration cycles[J]. Industrial & Engineering Chemistry Research, 2015, 54(45):11285-11294.