CuO/HZSM-5催化溴甲烷芳构化制备芳烃

doi:10.11949/j.issn.0438-1157.20161659

化工学报 ›› 2017, Vol. 68 ›› Issue (6): 2344-2351.DOI: 10.11949/j.issn.0438-1157.20161659

• 催化、动力学与反应器 • 上一篇下一篇

CuO/HZSM-5催化溴甲烷芳构化制备芳烃

陈坦¹, 陈皓², 傅杰², 陈可泉¹, 欧阳平凯^1,2

1. 南京工业大学生物与制药工程学院, 江苏南京 211800;
2. 浙江大学生物质化工教育部重点实验室, 化学工程与生物工程学院, 浙江杭州 310027

收稿日期:2016-11-24 修回日期:2017-03-20 出版日期:2017-06-05 发布日期:2017-06-05
通讯作者: 傅杰
基金资助:
国家自然科学基金项目（21436007）；浙江省自然科学基金项目（LR17B060002）

Catalytic performance of CuO/HZSM-5 in aromatic synthesis from CH₃Br

CHEN Tan¹, CHEN Hao², FU Jie², CHEN Kequan¹, OUYANG Pingkai^1,2

1. Biotechnology and Pharmaceutical Engineering, Nanjing Tech University, Nanjing 211800, Jiangsu, China;
2. Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China

Received:2016-11-24 Revised:2017-03-20 Online:2017-06-05 Published:2017-06-05
Contact: 10.11949/j.issn.0438-1157.20161659
Supported by:
supported by the National Natural Science Foundation of China (21436007) and the Natural Science Foundation of Zhejiang Province (LR17B060002)

摘要/Abstract

摘要：

采用等体积浸渍法制备了不同负载量（1%~7%）的CuO/HZSM-5催化剂，在固定床反应器中研究了不同反应温度、溴甲烷流量以及CuO负载量对溴甲烷芳构化催化性能的影响。采用SEM、XRD、N₂吸附脱附、TEM、XPS、TG、DSC、NH₃-TPD等技术对反应前后的催化剂进行表征。XRD 结果显示活性组分CuO 在HZSM-5上具有很好的分散性，并且反应后Cu晶型不变。NH₃-TPD 结果显示3%的CuO 负载后，催化剂强酸量增加。在CuO 负载量为3%，温度为360℃，反应空速为240 ml·g^-1·h^-1 条件下得到最高的芳烃收率（22.3%）。XPS 结果显示反应后在催化剂上主要的积炭为石墨碳。催化剂稳定性测试结果表明反应40 h内催化活性没有明显下降。

关键词: CuO/HZSM-5, 溴甲烷, 催化, 固定床, 芳烃, 稳定性

Abstract:

CuO/HZSM-5 catalysts with 1%—7% CuO loading, which were prepared by incipient wetness impregnation, were used to study catalytic performance in the conversion of CH₃Br to aromatic compounds in a fixed-bed reactor by changing temperature, CH₃Br flow rate and CuO loading. Fresh and used catalysts were characterized by SEM, TEM, XRD, XPS, TG, DSC, N₂ adsorption and desorption, and NH₃-TPD. XRD results showed that CuO was highly dispersed on HZSM-5 and structure of CuO crystals did not change during reaction. NH₃-TPD results showed that 3% (mass) CuO loading increased strong acidity of catalyst. XPS results showed that coke deposition on used CuO/HZSM-5 catalyst was mainly graphite. The highest aromatic yield of 22.3% was achieved at condition of 3% (mass) CuO loading, 360℃ temperature and 240 ml·g^-1·h^-1 GHSV. The 3% (mass) CuO/HZSM-5 maintained stable catalytic activity within 40 h reaction time.

Key words: CuO/HZSM-5, CH₃Br, catalysis, fixed-bed, aromatic, stability

中图分类号:

TQ032

陈坦, 陈皓, 傅杰, 陈可泉, 欧阳平凯. CuO/HZSM-5催化溴甲烷芳构化制备芳烃[J]. 化工学报, 2017, 68(6): 2344-2351.

CHEN Tan, CHEN Hao, FU Jie, CHEN Kequan, OUYANG Pingkai. Catalytic performance of CuO/HZSM-5 in aromatic synthesis from CH₃Br[J]. CIESC Journal, 2017, 68(6): 2344-2351.

参考文献 30

[1]	张大治, 魏迎旭, 沈江汉, 等. 氯甲烷在镁修饰的ZSM-5分子筛催化剂上催化转化研究[J]. 天然气化工, 2006, 31(3): 14-17.
	ZHANG D Z, WEI Y X, SHEN J H, et al. Chloromethane conversion over Mg modified ZSM-5 zeolite catalysts[J]. Natural Gas Chemical Industry, 2006, 31(3): 14-17.
[2]	陈庆龄, 钱伯张. 天然气化工发展现状[J]. 现代化工, 2002, 22(5): 1-4.
	CHEN Q L, QIAN B Z. Current situation of nature gas chemical industry[J]. Modern Chemical Industry, 2002, 22(5): 1-4.
[3]	SOUSA-AGUIAR E F，APPEL L G，MOTA C. Natural gas chemical transformations: the path to refining in the future[J]. Catalysis Today, 2005, 101(1): 3-7.
[4]	HOLMEN A, OLSVIK O, ROKSTAD O A. Pyrolysis of nature gas: chemistry and process concepts[J]. Fuel Processing Technology, 1995, 42(2/3): 249-267.
[5]	HOLMEN A, ROKSTAD O A, SOLBAKKEN A. High-temperature pyrolysis of hydrocarbons(Ⅰ): Methane to acetylene[J]. Industrial & Engineering Chemistry Process Design & Development, 1976, 15(3): 439-444.
[6]	LIU R S, IWAMOTO M, LUNSFORD J H. Partial oxidation of methane by nitrous oxide over molybdenum oxide supported on silica[J]. Journal of the Chemical Society, Chemical Communications, 1982, 1(1): 78-79.
[7]	雍瑞生, 谭斌, 王科. 天然气化工的技术进展与发展机遇[J]. 天然气化工, 2009, 34(4): 70-75.
	YONG R S, TAN B, WANG K. Progress in the technologies for production of chemicals from natural gas and development opportunity[J]. Natural Gas Chemical Industry, 2009, 34(4): 70-75.
[8]	白尔铮. 费托合成燃料的经济性及发展前景[J]. 化工进展, 2004, 23(4): 370-374.
	BAI E Z. Economics and prospects of FT synfuels[J]. Chemical Industry and Engineering Progress, 2004, 23(4): 370-374.
[9]	陈建钢, 相宏伟, 李永旺, 等. 费托法合成液体燃料关键技术研究进展[J]. 化工学报, 2003, 54(4): 516-523.
	CHEN J G, XIANG H W, LI Y W, et al. Advance in key techniques of Fischer-Tropsch synthesis for liquid fuel production[J]. Journal of Chemical Industry and Engineering(China), 2003, 54(4): 516-523.
[10]	XIA X R, BI Y L, WU T H, et al. An infrared spectroscopic study of the mechanism of chloromethane conversion to higher hydrocarbons on HZSM-5 catalyst[J]. Catalysis Letters, 1995, 33(1): 75-90.
[11]	NORONHA L A, SOUZA-AGUIAR E F, MOTA C J A. Conversion of chloromethane to light olefins catalyzed by ZSM-5 zeolites[J]. Catalysis Today, 2005, 101(1): 9-13.
[12]	JENS K J. Methane conversion via methylchloride: condensation of methylchloride to light hydrocarbons[J]. Studies in Surface Science & Catalysis, 1988, 36: 491-495.
[13]	LERSCH P, BALLDERMANN F. Conversion of chloromethane over metal-exchanged ZSM-5 to higher hydrocarbons[J]. Applied Catalysis, 1991, 75(1): 133-152.
[14]	SUN Y, CAMPBELL S M, LUNSFORD J H, et al. The catalytic conversion of methyl chloride to ethylene and propylene over phosphorus-modified Mg-ZSM-5 zeolites[J]. Journal of Catalysis, 1993, 143(1): 32-44.
[15]	JAUMAIN D, SU B L. Direct catalytic conversion of chloromethane to higher hydrocarbons over various protonic and cationic zeolite catalysts as studied by in-situ FTIR and catalytic testing[J]. Studies in Surface Science and Catalysis, 2000, 130: 1607-1612.
[16]	JAUMAIN D, SU B L. Direct catalytic conversion of chloromethane to higher hydrocarbons over a series of ZSM-5 zeolites exchanged with alkali cations[J]. Journal of Molecular Catalysis A: Chemical, 2003, 197(1/2): 263-273.
[17]	WEI Y X, ZHANG D Z, XU L, et al. New route for light olefins production from chloromethane over HSAPO-34 molecular sieve[J]. Catalysis Today, 2005, 106(1): 84-89.
[18]	LORKOVIC I M, YILMAZ A, YILMAZ G A, et al. A novel integrated process for the functionalization of methane and ethane: bromine as mediator[J]. Catalysis Today, 2004, 98(1): 317-322.
[19]	LIU Z, HUANG L, LI W S, et al. Higher hydrocarbons from methane condensation mediated by HBr[J]. Journal of Molecular Catalysis A: Chemical, 2007, 273(1/2): 14-20.
[20]	ZHANG D Z, WEI Y X, XU L, et al. Chloromethane conversion to higher hydrocarbons over zeolites and SAPOs[J]. Catalysis Letters, 2006, 109(1): 97-101.
[21]	史风华, 宋永吉, 罗潇然, 等. 六铝酸盐负载CuO催化还原NO性能[J]. 环境化学, 2012, 31(8): 1222-1226.
	SHI F H, SONG Y J, LUO X R, et al. Catalytic reduction of NO over CuO/LaAl12O19 catalysts[J]. Environment Chemistry, 2012, 31(8): 1222-1226.
[22]	BIESINGER M C, LAU L W M, GERSON A R, et al. Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Sc, Ti, V, Cu and Zn[J]. Applied Surface Science, 2010, 257(3): 887-898.
[23]	POULSTON S, PARLETT P M, STONE P, et al. Surface oxidation and reduction of CuO and Cu2O studied using XPS and XAES[J]. Surface and Interface Analysis, 1996, 24(12): 811-820.
[24]	BENNICI S, GERVASINI A, RAVASIO N, et al. Optimization of tailoring of CuOx species of silica alumina supported catalysts for the selective catalytic reduction of NOx[J]. Journal of Physical Chemistry B, 2003, 107(22): 5168-5176.
[25]	AUROUX A, GERVASINI A, GUIMON C. Acidic character of metal-loaded amorphous and crystalline silica-aluminas determined by XPS and adsorption calorimetry[J]. Journal of Physical Chemistry B, 1999, 103(34): 7195-7205.
[26]	SONG Y, ZHU X, XIE S, et al. The effect of acidity on olefin aromatization over potassium modified ZSM-5 catalysts[J]. Catalysis Letter, 2004, 97(1): 31-36.
[27]	LOBREE L J, HWANG I C, REIMER J A, et al. Investigations of the state of Fe in H-ZSM-5[J]. Journal of Catalysis, 1999, 186(2): 242-253.
[28]	MARSCHMEYER S, PAPP H. Surface analysis of a hydrothermally treated H-ZSM-5 zeolite[J]. Surface and Interface Analysis, 1997, 25(9): 660-666.
[29]	POST J G, VAN HOOF J H C. Acidity and activity of H-ZSM-5 measured with NH3-t.p.d. and n-hexane cracking[J]. Zeolites, 1984, 4(1): 9-14.
[30]	TAJBAKHSH M, ALINEZHAD H, NASROLLAHZADEH M, et al. Preparation, characterization and application of nanosized CuO/HZSM-5 as an efficient and heterogeneous catalyst for the N-formylation of amines at room temperature[J]. Journal of Colloid and Interface Science, 2016, 471(1): 37-47.

CuO/HZSM-5催化溴甲烷芳构化制备芳烃

Catalytic performance of CuO/HZSM-5 in aromatic synthesis from CH₃Br

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

参考文献 30

相关文章 15

编辑推荐

Metrics

本文评价

[1]	江河, 袁俊飞, 王林, 邢谷雨. 均流腔结构对微细通道内相变流动特性影响的实验研究[J]. 化工学报, 2023, 74(S1): 235-244.
[2]	范孝雄, 郝丽芳, 范垂钢, 李松庚. LaMnO₃/生物炭催化剂低温NH₃-SCR催化脱硝性能研究[J]. 化工学报, 2023, 74(9): 3821-3830.
[3]	李艺彤, 郭航, 陈浩, 叶芳. 催化剂非均匀分布的质子交换膜燃料电池操作条件研究[J]. 化工学报, 2023, 74(9): 3831-3840.
[4]	杨学金, 杨金涛, 宁平, 王访, 宋晓双, 贾丽娟, 冯嘉予. 剧毒气体PH₃的干法净化技术研究进展[J]. 化工学报, 2023, 74(9): 3742-3755.
[5]	吴雷, 刘姣, 李长聪, 周军, 叶干, 刘田田, 朱瑞玉, 张秋利, 宋永辉. 低阶粉煤催化微波热解制备含碳纳米管的高附加值改性兰炭末[J]. 化工学报, 2023, 74(9): 3956-3967.
[6]	程业品, 胡达清, 徐奕莎, 刘华彦, 卢晗锋, 崔国凯. 离子液体基低共熔溶剂在转化CO₂中的应用[J]. 化工学报, 2023, 74(9): 3640-3653.
[7]	陈杰, 林永胜, 肖恺, 杨臣, 邱挺. 胆碱基碱性离子液体催化合成仲丁醇性能研究[J]. 化工学报, 2023, 74(9): 3716-3730.
[8]	盛冰纯, 于建国, 林森. 铝基锂吸附剂分离高钠型地下卤水锂资源过程研究[J]. 化工学报, 2023, 74(8): 3375-3385.
[9]	郑玉圆, 葛志伟, 韩翔宇, 王亮, 陈海生. 中高温钙基材料热化学储热的研究进展与展望[J]. 化工学报, 2023, 74(8): 3171-3192.
[10]	杨菲菲, 赵世熙, 周维, 倪中海. Sn掺杂的In₂O₃催化CO₂选择性加氢制甲醇[J]. 化工学报, 2023, 74(8): 3366-3374.
[11]	李凯旋, 谭伟, 张曼玉, 徐志豪, 王旭裕, 纪红兵. 富含零价钴活性位点的钴氮碳/活性炭设计及甲醛催化氧化应用研究[J]. 化工学报, 2023, 74(8): 3342-3352.
[12]	孟令玎, 崇汝青, 孙菲雪, 孟子晖, 刘文芳. 改性聚乙烯膜和氧化硅固定化碳酸酐酶[J]. 化工学报, 2023, 74(8): 3472-3484.
[13]	杨欣, 彭啸, 薛凯茹, 苏梦威, 吴燕. 分子印迹-TiO₂光电催化降解增溶PHE废水性能研究[J]. 化工学报, 2023, 74(8): 3564-3571.
[14]	陈雅鑫, 袁航, 刘冠章, 毛磊, 杨纯, 张瑞芳, 张光亚. 蛋白质纳米笼介导的酶自固定化研究进展[J]. 化工学报, 2023, 74(7): 2773-2782.
[15]	汤晓玲, 王嘉瑞, 朱玄烨, 郑仁朝. 基于Pickering乳液的卤醇脱卤酶催化合成手性环氧氯丙烷[J]. 化工学报, 2023, 74(7): 2926-2934.

CuO/HZSM-5催化溴甲烷芳构化制备芳烃

Catalytic performance of CuO/HZSM-5 in aromatic synthesis from CH3Br

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

参考文献 30

相关文章 15

编辑推荐

Metrics

本文评价

Catalytic performance of CuO/HZSM-5 in aromatic synthesis from CH₃Br