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

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

中国科学院广州能源研究所, 广东广州 510640

基金项目: 国家自然科学基金(20806082, 50306026); 广东省自然科学基金(10151007006000016)。

详细信息

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

中图分类号: TQ032
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出版历程
- 收稿日期: 2012-02-20
- 修回日期: 2012-05-04
- 刊出日期: 2012-10-31

Effect of calcination temperature on properties of Cu/ZnO/Al₂O₃/ Cr₂O₃+H-ZSM-5 bi-functional catalysts for steam reforming of dimethyl ether

Guangzhou Insititute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China

摘要

摘要: 采用共沉淀耦合机械混合法制备了Cu/ZnO/Al₂O₃/Cr₂O₃+H-ZSM-5双功能催化剂,并用于二甲醚水蒸气重整制氢反应,结合热重、傅里叶红外光谱、XRD、BET、H₂-TPR表征,考察了焙烧温度对Cu/ZnO/Al₂O₃/Cr₂O₃催化剂物理化学性质及双功能催化剂催化性能的影响。研究结果表明,400℃焙烧时,析出CuO粒子的同时伴有尖晶石相,进而在反应过程中对金属铜粒子起到良好的隔离作用。而焙烧温度较低时,催化剂分解不完全,催化剂活性位较少。焙烧温度大于500℃时,CuO粒子发生二次团聚,同时尖晶石相大量生成,造成催化剂活性位减少,活性较低。合适的焙烧温度为400℃,此时二甲醚转化率为92.9%,氢气收率可达到76.5%,具有较好的反应效果。
- Cu/ZnO/Al₂O₃/Cr₂O₃+H-ZSM-5催化剂 /
- 焙烧温度 /
- 水蒸气重整 /
- 二甲醚 /
- 氢
Abstract: The Cu/ZnO/Al₂O₃/Cr₂O₃+H-ZSM-5 performances for hydrogen production during dimethyl ether steam reforming (DME SR) were investigated,which was prepared by the co-precipitation coupling with mechanical mixing method.Meanwhile, the effect of calcination temperature on the physicochemical properties of catalysts were studied by thermogravimetry, Fourier transform infrared spectroscopy, X-ray diffraction, Brunauer-Emmett-Teller, and H₂ temperature-programmed reduction.It was revealed that Cu/ZnO/Al₂O₃/Cr₂O₃ catalyst was decomposed at 400℃ to form CuO and sponel phase that played a key role in separating the Cu during the reaction.Under lower calcination temperatures,the catalyst was incompeletely decomposed.Increasing the calcination temperature to over 500℃ caused severe sintering of CuO and facilitated the formation of spinel phase, which led to a significant decrease in the number of active sites.When the calcination temperature was controlled at 400℃, the biggest DME conversion rate of 92.9% and hydrogen yield of 76.5% was reached.
- Cu/ZnO/Al₂O₃/Cr₂O₃+H-ZSM-5 catalysts /
- calcination temperature /
- steam reforming /
- dimethyl ether /
- hydrogen

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参考文献(29)

DELUGA G A, SALGE J R, SCHMIDT L D, VERYKIO X E. Renewable hydrogen from ethanol by autothermal reforming[J]. Science, 2004, 303(5660): 993-997.

WINTER C J. Hydrogen energy- abundant, efficient, clean: A debate over the energy-system-of-change[J]. Int J Hydrogen Energy, 2009, 34(14): s1-s52.

ARCOUMANIS C, BAE C, CROOKES R, KINOSHITA E. The potential of dimethyl ether (DME) as an alternative fuel for compression-ignition engines: A review[J]. Fuel, 2008, 87(7): 1014-1030.

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

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.)

钱伯章. 二甲醚的技术进展与市场分析 [J]. 石油与天然气化工, 2004, 33(5): 324-332. (QIAN Bo-zhang. Technology progress and market analysis of dimethyl ether [J]. Chemical Engineering of Oil & Gas, 2004, 33(5): 324-332.)

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 properties of a monolithic catalyst for one step synthesis of dimethyl ether [J]. Journal of Fuel Chemistry and Technology, 2011, 39(4): 287-292.)

TOMOAKI M, TOSHIVA N, HIROVOSHI K, KAZUNORI U, YASUVUKI M, SEIICHIRO I. Steam reforming of dimethyl ether over H-mordenite-Cu/CeO₂ catalysts[J]. Appl Catal A, 2006, 276(1/2): 267-273.

SEMELSBERGER T A, OTT K C, BORUP R L, GREENE H L. Role of acidity on the hydrolysis of dimethyl ether (DME) to methanol [J]. Appl Catal B, 2005, 61(3/4): 281-287.

FAUNGNAWAKIJ K, TANAKA Y, SHIMODA N. Influence of solid-acid catalysts on steam reforming and hydrolysis of dimethyl ether for hydrogen production [J]. Appl Catal A, 2006, 304(1): 40-48.

冯冬梅, 王金福, 王德峥. 二甲醚水蒸气重整制氢催化剂的研究[J]. 中国科技论文在线, 2007, 2(8): 567-571. (FENG Dong-mei, WANG Jin-fu, WANG De-zheng. Production of hydrogen from dimethyl ether over catalysts[J]. Sciencepaper Online, 2007, 2(8): 567-571.)

FUKUNAGA T, RYUMON N, SHIMAZU S. The influence of metals and acidic oxide species on the steam reforming of dimethyl ether (DME)[J]. Appl Catal A, 2008, 348(2): 193-200.

LEDESMA C, OZKAN U S, LIORCA J. Hydrogen production by steam reforming of dimethyl ether over Pd-based catalytic monoliths [J]. Appl Catal B, 2011, 101(3/4): 690-697.

WANG X, PAN X, LIN R, KOU S, ZOU W, MA J. Steam reforming of dimethyl ether over Cu-Ni/γ-Al₂O₃ bi-functional catalyst prepared by deposition-precipitation method[J]. Int J Hydrogen Energy, 2010, 35(9): 4060-4068.

FENG D, ZUO Y, WANG D, WANG J. Steam reforming of dimethyl ether over coupled catalysts of CuO-ZnO-Al₂O₃-ZrO₂ and solid-acid catalyst[J]. Chin J Chem Eng, 2009, 17(1): 64-71.

FENG D, ZUO Y, WANG D, WANG J. steam reforming of dimethyl ether over coupled zsm-5 and cu-zn-based catalysts [J]. Chin J Catal, 2009, 30(3): 223-229.

SHIMODA N, MUROYAMA H, MATSUI T, FAUNGNAWAKIJ K, KIKUCHI R, EGUCHI K. Dimethyl ether steam reforming under daily start-up and shut-down (DSS)-like operation over CuFe₂O₄ spinel and alumina composite catalysts [J]. Appl Catal A, 2011, 409: 91-98.

KUDO S, MAKI T, MIURA K, MAE K. High porous carbon with Cu/ZnO nanoparticles made by the pyrolysis of carbon material as a catalyst for steam reforming of methanol and dimethyl ether[J]. Carbon, 2010, 48(4): 1186-1195.

SEMELSBERGER T A, OTT K C, BORUP R L, GREENE H L. Generating hydrogen-rich fuel-cell feeds from dimethyl ether(DME) using Cu/Zn supported on various solid-acid substrates[J]. Appl Catal A, 2006, 309(2): 210-223.

SEMELSBERGER T A, OTT K C, BORUP R L, GREENE H L. 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]. Appl Catal B, 2006, 65(3/4): 291-300.

KAWABATA T, MATSUOKA H, SHISHIDO T, LI D, 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, 2006, 308: 82-90.

李吉刚, 孙杰, 张立功, 程玉龙, 邱新平, 陈立泉. 花状微球NiO/CeO₂催化剂上乙醇水蒸气重整制氢研究[J]. 燃料化学学报, 2010, 38(3): 332-336. (LI Ji-gang, SUN Jie, ZHANG Li-gong, CHENG Yu-long, QIU Xin-ping, CHEN Li-quan. Hydrogen production by steam reforming of ethanol over flower like microspheres Ni/CeO₂ catalyst[J]. Journal of Fuel Chemistry and Technology, 2010, 38(3): 332-336.)

MORPURGO S, LO JACONO M, PORTA P. Copper-zinc-cobalt-aluminum-chromium hydroxycarbonates and mixed oxides[J]. J Solid State Chem, 1996, 122(2): 324-332.

TURCO M, BAGNASCO G, COSTANTINO U, MARMOTTINI F, MONTANARI T, RAMIS G, BUSCA G. Production of hydrogen from oxidative steam reforming of methanol: II Catalytic activity and reaction mechanism on Cu/ZnO/Al₂O₃ hydrotalcite-derived catalysts[J]. J Catal, 2004, 228(1): 56-65.

MELIAN C I, GRANADOS M L, FIERRO J L G. Thermal decomposition of a hydrotalcite-containing Cu-Zn-Al precursor: Thermal methods combined with an in situ DRIFT study[J]. Phys Chem Chem Phys, 2002, 4(13): 3122-3127.

KANNAN S, RIVES V, KNOZINGER H. High-temperature transformations of Cu-rich hydrotalcites[J]. J Solid State Chem, 2004, 177(1): 319-331.

SHEN G-C, FUJITA S-I, MATSUMOTO S, TAKEZAWA N. Steam reforming of methanol on binary Cu/ZnO catalysts: Effects of preparation condition upon precursors, surface structure and catalytic activity[J]. J Mol Catal A, 1997, 124(2/3): 123-136.

FUJITANI T, NAKAMURA J. The effect of ZnO in methanol synthesis catalysts on Cu dispersion and the specific activity[J]. Catal Lett, 1998, 56(2/3): 119-124.

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