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介孔CuO/γ-Al2O3催化剂的 制备及其在合成气制二甲醚反应中的应用

陈月仙 ,  王琰 ,  马静红 ,  李瑞丰

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引用本文: 陈月仙, 王琰, 马静红, 李瑞丰. 介孔CuO/γ-Al2O3催化剂的 制备及其在合成气制二甲醚反应中的应用[J]. 燃料化学学报, 2015, 43(1): 65-73. shu
Citation:  CHEN Yue-xian, WANG Yan, MA Jing-hong, LI Rui-feng. Preparation of mesoporous CuO/γ-Al2O3 for one-step synthesis of dimethyl ether from syngas[J]. Journal of Fuel Chemistry and Technology, 2015, 43(1): 65-73. shu

介孔CuO/γ-Al2O3催化剂的 制备及其在合成气制二甲醚反应中的应用

    通讯作者: 王琰,Tel:0351-6018384,E-mail:wangyan@tyut.edu.cn.
  • 基金项目:

    国家自然科学基金(21371129, 50772070, 51172154) (21371129, 50772070, 51172154)

    "十二五"国家科技支撑计划(SQ2011GX04E05929) (SQ2011GX04E05929)

    山西省自然科学基金(2012011005-4, 2012021006-2). (2012011005-4, 2012021006-2)

摘要: 以三嵌段共聚物F127为模板剂,以异丙醇铝、硝酸铜为原料,采用溶剂挥发自组装法制备具有介孔结构的CuO/γ-Al2O3复合催化剂.通过XRD、SEM-EDS、H2-TPR、N2-吸附脱附、TEM等技术对该催化剂的结构进行了表征.实验结果表明,通过溶剂挥发自组装法制备的催化剂CuO/γ-Al2O3具有有序的介孔结构,并且具有较大的比表面积以及均一的介孔结构,并且Cu元素均匀地分布在γ-Al2O3的表面.将该复合催化剂用于合成气直接制备二甲醚的反应,在空速1 500 h-1、温度320 ℃、压力5 MPa的条件下,CO转化率最高达到68.8%、DME选择性达到59.0%.连续反应50 h后,CO转化率从68.8%降低至59.5%,DME选择性基本保持不变,催化剂部分失活的原因是由于铜元素部分发生了聚集.

English

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    1. [1] KIM M Y, YOON S H, RYU B W, LEE C S. Combustion and emission characteristics of DME as an alternative fuel for compression ignition engines with a high pressure injection system[J]. Fuel, 2008, 87(12): 2779-2786.[1] KIM M Y, YOON S H, RYU B W, LEE C S. Combustion and emission characteristics of DME as an alternative fuel for compression ignition engines with a high pressure injection system[J]. Fuel, 2008, 87(12): 2779-2786.

    2. [2] KAJOMSAK F, TETSUYA F, RYUJI K, KOICHI E. Deactivation and regeneration behaviors of copper spinel-alumina composite catalysts in steam reforming of dimethyl ether[J]. J Catal, 2008, 256(1): 37-44.[2] KAJOMSAK F, TETSUYA F, RYUJI K, KOICHI E. Deactivation and regeneration behaviors of copper spinel-alumina composite catalysts in steam reforming of dimethyl ether[J]. J Catal, 2008, 256(1): 37-44.

    3. [3] ADACHI Y, KOMOTO M, WATANABE I, OHNO Y, FUJIMOTO K. Effective utilization of remote coal through dimethyl ether synthesis[J]. Fuel, 2000, 79(3): 229-234.[3] ADACHI Y, KOMOTO M, WATANABE I, OHNO Y, FUJIMOTO K. Effective utilization of remote coal through dimethyl ether synthesis[J]. Fuel, 2000, 79(3): 229-234.

    4. [4] 许庆利, 李庭琛, 张素平, 任铮伟, 颜涌捷. 分子筛改性对一步法合成二甲醚的影响[J]. 燃料化学学报, 2008, 36(1): 74-78.(XU Qing-li, LI Ting-chen, ZHANG Su-ping, REN Zheng-wei, YAN Yong-jie. Effect of the modified zeolite on one-step dimethyl ether synthesis[J]. J Fuel Chem Technol, 2008, 36(1): 74-78.)[4] 许庆利, 李庭琛, 张素平, 任铮伟, 颜涌捷. 分子筛改性对一步法合成二甲醚的影响[J]. 燃料化学学报, 2008, 36(1): 74-78.(XU Qing-li, LI Ting-chen, ZHANG Su-ping, REN Zheng-wei, YAN Yong-jie. Effect of the modified zeolite on one-step dimethyl ether synthesis[J]. J Fuel Chem Technol, 2008, 36(1): 74-78.)

    5. [5] MAO D S, YANG W M, XIA J C, ZHANG B, SONG Q Y, CHEN Q L. Highly effective hybrid catalyst for the direct synthesis of dimethyl ether from syngas with magnesium oxide-modified HZSM-5 as a dehydration component[J]. J Catal, 2005, 230(1): 140-149.[5] MAO D S, YANG W M, XIA J C, ZHANG B, SONG Q Y, CHEN Q L. Highly effective hybrid catalyst for the direct synthesis of dimethyl ether from syngas with magnesium oxide-modified HZSM-5 as a dehydration component[J]. J Catal, 2005, 230(1): 140-149.

    6. [6] 毛东森, 夏建超. 分子筛硅铝比及晶粒粒径对CuO-ZnO-Al2O3/HZSM-5催化剂直接合成二甲醚反应性能的影响[J]. 燃料化学学报, 2012, 40(2): 235-40.(MAO Dong-sen, XIA Jian-chao. Effects of silicon to aluminum ratio and crystal size of zeolite on catalytic properties of CuO-ZnO-Al2O3/HZSM-5 for the direct synthesis of dimethyl ether from syngas[J]. J Fuel Chem Technol, 2012, 40(2): 235-40.)[6] 毛东森, 夏建超. 分子筛硅铝比及晶粒粒径对CuO-ZnO-Al2O3/HZSM-5催化剂直接合成二甲醚反应性能的影响[J]. 燃料化学学报, 2012, 40(2): 235-40.(MAO Dong-sen, XIA Jian-chao. Effects of silicon to aluminum ratio and crystal size of zeolite on catalytic properties of CuO-ZnO-Al2O3/HZSM-5 for the direct synthesis of dimethyl ether from syngas[J]. J Fuel Chem Technol, 2012, 40(2): 235-40.)

    7. [7] WANG D S, HAN Y Z, TAN Y S, TSUBAKI N. Effect of H2O on Cu-based catalyst in one-step slurry phase dimethyl ether synthesis[J]. Fuel Process Technol, 2009, 90(3): 446-451.[7] WANG D S, HAN Y Z, TAN Y S, TSUBAKI N. Effect of H2O on Cu-based catalyst in one-step slurry phase dimethyl ether synthesis[J]. Fuel Process Technol, 2009, 90(3): 446-451.

    8. [8] 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]. J Fuel Chem Technol, 2011, 39(4): 287-292.)[8] 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]. J Fuel Chem Technol, 2011, 39(4): 287-292.)

    9. [9] RAMOS F S, DE FARIAS A M D, BORGES L E P, MONTEIRO J L, FRAGA M A, SOUSA-AGUIAR E F, APPEL L G. Role of dehydration catalyst acid properties on one-step DME synthesis over physical mixtures[J]. Catal Today, 2005, 101(1): 39-44.[9] RAMOS F S, DE FARIAS A M D, BORGES L E P, MONTEIRO J L, FRAGA M A, SOUSA-AGUIAR E F, APPEL L G. Role of dehydration catalyst acid properties on one-step DME synthesis over physical mixtures[J]. Catal Today, 2005, 101(1): 39-44.

    10. [10] QI G X, ZHENG X M, FEI J H, HOU Z Y. A novel catalyst for DME synthesis from CO hydrogenation: 1. Activity, structure and surface properties[J]. J Mol Catal A: Chem, 2001, 176(1/2): 195-203.[10] QI G X, ZHENG X M, FEI J H, HOU Z Y. A novel catalyst for DME synthesis from CO hydrogenation: 1. Activity, structure and surface properties[J]. J Mol Catal A: Chem, 2001, 176(1/2): 195-203.

    11. [11] SIERRA I, ERENA J, AGUAYO A T, ARANDES J M, BILBAO J. Regeneration of CuO-ZnO-Al2O3/γ-Al2O3 catalyst in the direct synthesis of dimethyl ether[J]. Appl Catal B: Environ, 2010, 94(1/2): 108-116.[11] SIERRA I, ERENA J, AGUAYO A T, ARANDES J M, BILBAO J. Regeneration of CuO-ZnO-Al2O3/γ-Al2O3 catalyst in the direct synthesis of dimethyl ether[J]. Appl Catal B: Environ, 2010, 94(1/2): 108-116.

    12. [12] TAKEGUCHI T, YANAGISAWA K I, INUI T, INOUE M. Effect of the property of solid acid upon syngas-to-dimethyl ether conversion on the hybrid catalysts composed of Cu-Zn-Ga and solid acids[J]. Appl Catal A: Gen, 2000, 192(2): 201-209.[12] TAKEGUCHI T, YANAGISAWA K I, INUI T, INOUE M. Effect of the property of solid acid upon syngas-to-dimethyl ether conversion on the hybrid catalysts composed of Cu-Zn-Ga and solid acids[J]. Appl Catal A: Gen, 2000, 192(2): 201-209.

    13. [13] SUN K, LU W, QIU F, XU X. Direct synthesis of DME over bifunctional catalyst: surface properties and catalytic performance[J]. Appl Catal A: Gen, 2003, 252(2): 243-249.[13] SUN K, LU W, QIU F, XU X. Direct synthesis of DME over bifunctional catalyst: surface properties and catalytic performance[J]. Appl Catal A: Gen, 2003, 252(2): 243-249.

    14. [14] GE Q, HUANG Y, QIU F, LI S. Bifunctional catalysts for conversion of synthesis gas to dimethyl ether[J]. Appl Catal A: Gen, 1998, 167: 23-30.[14] GE Q, HUANG Y, QIU F, LI S. Bifunctional catalysts for conversion of synthesis gas to dimethyl ether[J]. Appl Catal A: Gen, 1998, 167: 23-30.

    15. [15] SAI PRASAD P S, BAE J W, KANG S H, LEE Y J, JUN K W. Single-step synthesis of DME from syngas on Cu-ZnO-Al2O3/zeolite bifunctional catalysts: The superiority of ferrierite over the other zeolites[J]. Fuel Process Technol, 2008, 89(12): 1281-1286.[15] SAI PRASAD P S, BAE J W, KANG S H, LEE Y J, JUN K W. Single-step synthesis of DME from syngas on Cu-ZnO-Al2O3/zeolite bifunctional catalysts: The superiority of ferrierite over the other zeolites[J]. Fuel Process Technol, 2008, 89(12): 1281-1286.

    16. [16] WU X, ABRAHA M G, ANTHONY R G. Methanol conversion on SAPO-34: Reaction condition for fixed-bed reactor[J]. Appl Catal A: Gen, 2004, 260(1): 63-69.[16] WU X, ABRAHA M G, ANTHONY R G. Methanol conversion on SAPO-34: Reaction condition for fixed-bed reactor[J]. Appl Catal A: Gen, 2004, 260(1): 63-69.

    17. [17] FEI J H, TANG X J, HUO Z Y. Effect of copper content on Cu-Mn-Zn/zeolite-Y catalysts for the synthesis of dimethyl ether from syngas[J]. Catal Commun, 2006, 7(11): 827-831.[17] FEI J H, TANG X J, HUO Z Y. Effect of copper content on Cu-Mn-Zn/zeolite-Y catalysts for the synthesis of dimethyl ether from syngas[J]. Catal Commun, 2006, 7(11): 827-831.

    18. [18] 杨明霞, 费金华, 郑小明. 共沉淀浸渍法制备由合成气直接合成二甲醚的Cu-Mn催化剂[J]. 燃料化学学报, 2004, 32(2): 83-87.(YANG Ming-xia, FEI Jin-hua, ZHENG Xiao-ming. A novel preparetion of Cu-Mn catalysts for dimethyl ether synthesis from syngas[J]. J Fuel Chem Technol, 2004, 32(2): 83-87.)[18] 杨明霞, 费金华, 郑小明. 共沉淀浸渍法制备由合成气直接合成二甲醚的Cu-Mn催化剂[J]. 燃料化学学报, 2004, 32(2): 83-87.(YANG Ming-xia, FEI Jin-hua, ZHENG Xiao-ming. A novel preparetion of Cu-Mn catalysts for dimethyl ether synthesis from syngas[J]. J Fuel Chem Technol, 2004, 32(2): 83-87.)

    19. [19] JIANG H Q, BONGARD H, SCHMIDT W, SCHUTH F. One-pot synthesis of mesoporous Cu-γ-Al2O3 as bifunctional catalyst for direct dimethyl ether synthesis[J]. Microporous Mesoporous Mater, 2012, 164: 3-8.[19] JIANG H Q, BONGARD H, SCHMIDT W, SCHUTH F. One-pot synthesis of mesoporous Cu-γ-Al2O3 as bifunctional catalyst for direct dimethyl ether synthesis[J]. Microporous Mesoporous Mater, 2012, 164: 3-8.

    20. [20] 刘源, 钟炳, 王琴, 彭少逸. 氧化铜/氧化锆甲醇合成催化剂的性能研究[J]. 催化学报, 1995, 16(6): 442-446.(LIU Yuan, ZHONG Bing, WANG Qin, PENG Shao-yi. Study of CuO/ZrO2 catalysts for methanol synthesis from CO/H2[J]. Chin J Catal, 1995, 16(6): 442-446.)[20] 刘源, 钟炳, 王琴, 彭少逸. 氧化铜/氧化锆甲醇合成催化剂的性能研究[J]. 催化学报, 1995, 16(6): 442-446.(LIU Yuan, ZHONG Bing, WANG Qin, PENG Shao-yi. Study of CuO/ZrO2 catalysts for methanol synthesis from CO/H2[J]. Chin J Catal, 1995, 16(6): 442-446.)

    21. [21] KUNG H H. Deactivation of methanol synthesis catalysts-A review[J]. Catal Today, 1992, 11(4): 443-453.[21] KUNG H H. Deactivation of methanol synthesis catalysts-A review[J]. Catal Today, 1992, 11(4): 443-453.

    22. [22] TOPSE H. Developments in operando studies and in situ characterization of heterogeneous catalysts[J]. J Catal, 2003, 216(1/2): 155-164.[22] TOPSE H. Developments in operando studies and in situ characterization of heterogeneous catalysts[J]. J Catal, 2003, 216(1/2): 155-164.

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  • 收稿日期:  2014-07-24
  • 网络出版日期:  2014-09-19
通讯作者: 陈斌, bchen63@163.com
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