留言板

尊敬的读者、作者、审稿人, 关于本刊的投稿、审稿、编辑和出版的任何问题, 您可以本页添加留言。我们将尽快给您答复。谢谢您的支持!

姓名
邮箱
手机号码
标题
留言内容
验证码

不同分子筛负载锰铈催化剂的低温NH3-SCR脱硝性能

黄增斌 李翠清 王振 徐胜美 冯凌波 王虹 宋永吉 张伟

黄增斌, 李翠清, 王振, 徐胜美, 冯凌波, 王虹, 宋永吉, 张伟. 不同分子筛负载锰铈催化剂的低温NH3-SCR脱硝性能[J]. 燃料化学学报, 2016, 44(11): 1388-1393.
引用本文: 黄增斌, 李翠清, 王振, 徐胜美, 冯凌波, 王虹, 宋永吉, 张伟. 不同分子筛负载锰铈催化剂的低温NH3-SCR脱硝性能[J]. 燃料化学学报, 2016, 44(11): 1388-1393.
HUANG Zeng-bin, LI Cui-qing, WANG Zhen, XU Sheng-mei, FENG Ling-bo, WANG Hong, SONG Yong-ji, ZHANG Wei. Performance of Mn-Ce catalysts supported on different zeolites in the NH3-SCR of NOx[J]. Journal of Fuel Chemistry and Technology, 2016, 44(11): 1388-1393.
Citation: HUANG Zeng-bin, LI Cui-qing, WANG Zhen, XU Sheng-mei, FENG Ling-bo, WANG Hong, SONG Yong-ji, ZHANG Wei. Performance of Mn-Ce catalysts supported on different zeolites in the NH3-SCR of NOx[J]. Journal of Fuel Chemistry and Technology, 2016, 44(11): 1388-1393.

不同分子筛负载锰铈催化剂的低温NH3-SCR脱硝性能

基金项目: 

国家自然科学基金 21343009

详细信息
    通讯作者:

    李翠清, Tel:010-81292124, E-mail:licuiqing@bipt.edu.cn

  • 中图分类号: O643

Performance of Mn-Ce catalysts supported on different zeolites in the NH3-SCR of NOx

Funds: 

the National Natural Science Foundation of China 21343009

  • 摘要: 分别以β、ZSM-5和USY分子筛为载体,采用浸渍法制备了锰铈催化剂,对其低温NH3-SCR反应性能进行了评价,并采用XRD、BET、NH3-TPD、H2-TPR以及XPS对催化剂进行了表征。结果表明,三种分子筛负载的锰铈催化剂均具有较好的低温NH3-SCR反应活性,其中,Mn-Ce/USY的催化性能最好,在107℃时NOx转化率可达到90%。负载锰铈后催化剂的比表面积和孔体积均有所下降;活性组分MnOx主要以无定型态分布于催化剂表面,且在ZSM-5上检测到聚集的CeO2。催化剂表面弱酸对低温NH3-SCR反应起主要作用,催化剂表面上活性组分的表面浓度和氧化态明显不同,较高的Mn4+/Mn3+原子比和吸附氧表面浓度对提高催化剂的低温NH3-SCR反应活性有利。
  • 图  1  不同载体负载的Mn-Ce催化剂的XRD谱图

    Figure  1  XRD patterns of the Mn-Ce catalysts supported on different zeolites

    图  2  不同载体负载的Mn-Ce催化剂的H2-TPR谱图

    Figure  2  H2-TPR profiles of Mn-Ce catalysts supported on different zeolites

    图  3  不同载体负载的Mn-Ce催化剂的NH3-TPD谱图

    Figure  3  NH3-TPD profiles of the Mn-Ce catalysts supported on different zeolites

    图  4  不同载体负载的Mn-Ce催化剂的XPS谱图

    Figure  4  XPS spectra of the Mn-Ce catalysts supported on different zeolites

    图  5  不同载体负载的Mn-Ce催化剂的NOx转化率

    Figure  5  NOx conversion for NH3-SCR over the Mn-Ce catalysts supported on different zeolites

    表  1  不同载体负载的Mn-Ce催化剂的BET及孔径

    Table  1  BET surface area and pore size distribution of the Mn-Ce catalysts supported on different zeolites

    Catalyst Pore size d/nm Pore volume v/(cm3·g-1) ABET/(m2·g-1)
    β 45.51 0.95 492.08
    Mn-Ce/β 45.76 0.87 306.74
    USY 43.22 0.86 520.35
    Mn-Ce/USY 44.06 0.79 362.27
    ZSM-5 41.44 0.73 302.25
    Mn-Ce/ZSM-5 42.99 0.69 199.38
    下载: 导出CSV

    表  2  不同载体负载的Mn-Ce催化剂的H2-TPR表征

    Table  2  H2-TPR results of the Mn-Ce catalysts supported on different zeolites

    Catalyst Temperature for the low temperature reduction peak t/℃ Area for the low temperature reduction peak
    Mn-Ce/ZSM-5 345 24.6
    Mn-Ce/USY 350 29.7
    Mn-Ce/β 340 22.9
    下载: 导出CSV

    表  3  不同载体负载的Mn-Ce催化剂的NH3-TPD表征

    Table  3  NH3-TPD results of the Mn-Ce catalysts supported on different zeolites

    Catalyst Low temperature of desorption peaks t/℃ Peak area of low temperature desorption peak
    Mn-Ce/ZSM-5 160 30.3
    Mn-Ce/USY 155 31.1
    Mn-Ce/β 157 30.6
    下载: 导出CSV

    表  4  催化剂Mn 2p3/2 XPS表征

    Table  4  Results of curve-fittings on the Mn 2p3/2 peak in XPS patterns of the Mn-Ce catalysts

    Catalyst Mn4+watom/% Mn4+EB/eV Mn3+watom/% Mn3+EB/eV Mn4+/Mn3+(atomic ratio)
    Mn-Ce/ZSM-5 59.6 642.7 40.4 641.2 1.48
    Mn-Ce/USY 92.7 642.7 7.3 641.2 12.70
    Mn-Ce/β 62.1 642.7 37.9 641.2 1.64
    下载: 导出CSV

    表  5  催化剂O 1s XPS表征

    Table  5  Results of curve-fittings on the O 1s speak in XPS patterns of the Mn-Ce catalysts

    Catalyst Chemisorbed oxygen watom/% Chemisorbed oxygen EB/eV Lattice oxygen watom/% Lattice oxygen EB/eV
    Mn-Ce/ZSM-5 73.9 532.2 26.1 529.5
    Mn-Ce/USY 95.5 532.2 4.5 529.5
    Mn-Ce/β 91.7 532.2 8.3 529.5
    下载: 导出CSV
  • [1] SHEN B X, LIU T. Deactivation of MnOx-CeOx/ACF catalysts for lower-temperature NH3-SCR in the presence of SO2[J]. Acta Phys Chim Sin, 2010, 26(11):3009-3016.
    [2] 沈伯雄, 郭宾彬, 史展亮, 吴春飞, 梁材. CeO2/ACF的低温SCR烟气脱硝性能研究[J].燃料化学学报, 2007, 35(1):125-128. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract17102.shtml

    SHEN Bo-xiong, GUO Bin-bin, SHI Zhan-liang, WU Chun-fei, LIANG Cai. Low temperature SCR of NO in flue gas on CeO2/ACF[J]. J Fuel Chem Technol, 2007, 35(1):125-128. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract17102.shtml
    [3] 胡艳妮, 胡将军, 刘静, 马倩. USY负载MnOx催化剂NH3选择还原NOx性能的研究[J].环境科学与技术, 2011, 34(8):54-56+108. http://www.cnki.com.cn/Article/CJFDTotal-FJKS201108011.htm

    HU Yan-ni, HU Jiang-jun, LIU Jing, MA Qian. Selective catalytic reduction of NOx by NH3 using USY-supported MnOx catalyst[J]. Environ Sci Technol, 2011, 34(8):54-56+108. http://www.cnki.com.cn/Article/CJFDTotal-FJKS201108011.htm
    [4] 张惠, 方和良, 李伟, 谭天恩, 郑小明. H-USY负载MnOx催化剂上CH4选择催化还原NOx性能的研究[J].高校化学工程学报, 2006, 20(5):820-824. http://www.cnki.com.cn/Article/CJFDTotal-GXHX200605026.htm

    ZHANG Hui, FANG He-liang, LI Wei, TAN Tian-en, ZHENG Xiao-ming. Selective catalytic reduction of NOx by CH4 over H-USY supported MnOxcatalysts[J]. J Chem Eng Chin Univ, 2006, 20(5):820-824. http://www.cnki.com.cn/Article/CJFDTotal-GXHX200605026.htm
    [5] 柯琰, 范志取, 陈仟, 王虹, 徐向阳, 李翠清, 宋永吉. M (0.1) Mn (15)/H β催化剂的低温NH3选择还原NO性能[J].工业催化, 2014, 22(3):221-224. http://www.cnki.com.cn/Article/CJFDTotal-GYCH201403015.htm

    KE Yan, FAN Zhi-qu, CHEN Qian, WANG Hong, XU Xiang-qian, LI Cui-qing, SONG Yong-ji. Performance of M (0.1) Mn (15)/H β catalysts for the selective catalytic reduction of NO with NH3 at low temperature[J]. Ind Catal, 2014, 22(3):221-224. http://www.cnki.com.cn/Article/CJFDTotal-GYCH201403015.htm
    [6] 吕刚, 吴虎, 宋崇林, 宾峰. Mn/ZSM-5催化剂及其SCR催化性能研究[J].工程热物理学报, 2011, 32(9):1597-1600. http://www.cnki.com.cn/Article/CJFDTOTAL-GCRB201109043.htm

    LV Gang, WU Hu, SONG Chong-lin, BIN Feng.Mn/ZSM-5 catalysts and the properties of selective catalytic reduction[J]. J Eng Thermophys, 2011, 32(9):1597-1600. http://www.cnki.com.cn/Article/CJFDTOTAL-GCRB201109043.htm
    [7] 贺丽芳, 刘建东, 黄伟, 李哲.制备方法对Mn-Ce/ZSM-5催化剂低温选择性催化还原NO性能的影响[J].高等学校化学学报, 2012, 33(11):2532-2536. http://www.cnki.com.cn/Article/CJFDTOTAL-GDXH201211028.htm

    HE Li-fang, LIU Jian-dong, HUANG Wei, LI Zhe. Effect of preparation method on performance of Mn-Ce/ZSM-5 catalyst for low-temperature selective catalytic reduction of NO[J]. Chem Res Chin Univ, 2012, 33(11):2532-2536. http://www.cnki.com.cn/Article/CJFDTOTAL-GDXH201211028.htm
    [8] 刘鹏飞, 娄晓荣, 何凯, 李哲, 黎俊, 杨成武.表面活性剂对Fe-Mn/ZSM-5/CC整体式催化剂结构及NOx催化还原性能的影响[J].分子催化, 2014, 28(3):227-233. http://www.cnki.com.cn/Article/CJFDTotal-FZCH201403006.htm

    LIU Peng-fei, LOU Xiao-rong, HE Kai, LI Zhe, LI Jun, YANG Chen-wu. Effect of surfactants on the structure and catalytic performance of Fe-Mn/ZSM-5/CC monolithic honeycomb catalyst[J]. J Mol Catal (China), 2014, 28(3):227-233. http://www.cnki.com.cn/Article/CJFDTotal-FZCH201403006.htm
    [9] 张治安, 杨邦朝, 邓梅根, 胡永达, 汪斌华.超级电容器纳米氧化锰电极材料的合成与表征[J].化学学报, 2004, 62(17):1617-1620. http://www.cnki.com.cn/Article/CJFDTOTAL-HXXB200417007.htm

    ZHANG Zhi-an, YANG Bang-chao, DENG Mei-gen, HU Yong-da, WANG Bin-hua. Synthesis and characterization of nanostructured MnO2 for supercapacitor[J]. Acta Chim Sin, 2004, 62(17):1617-1620. http://www.cnki.com.cn/Article/CJFDTOTAL-HXXB200417007.htm
    [10] 杨颖欣, 马杰文, 喻成龙, 孙梦婷, 黄碧纯, 吴友明.不同SAPO分子筛负载MnOx催化剂的低温NH3-SCR性能研究[J].环境科学学报, 2016, 36(9):3400-3408. http://www.cnki.com.cn/Article/CJFDTotal-HJXX201609037.htm

    YANG Yin-xin, MA Jie-wen, YU chen-long, SUN Meng-ting, HUANG Bi-chun, WU You-ming. Lower-temperature NH3-SCR activity of manganese oxides supported on different SAPO molecular sieves catalysts[J]. J Environ Sci China, 2016, 36(9):3400-3408. http://www.cnki.com.cn/Article/CJFDTotal-HJXX201609037.htm
    [11] 万义玲, 张传辉, 郭杨龙, 郭耘, 卢冠忠. CeO2-MnOx催化剂上氯乙烯有机废气的催化燃烧[J].催化学报, 2012, 33(3):557-562. http://www.cqvip.com/QK/93027X/201203/41460049.html

    WAN Yi-ling, ZHANG Chuan-hui, GUO Yang-long, GUO Yun, LU Guan-zhong. Catalytic combustion of vinyl chloride emission over CeO2-MnOxcatalyst[J]. Chin J Catal, 2012, 33(3):557-562. http://www.cqvip.com/QK/93027X/201203/41460049.html
    [12] 安忠义, 禚玉群, 陈昌和.煅烧温度对Mn/TiO2催化剂催化NO氧化活性的影响[J].燃料化学学报, 2014, 42(3):370-376. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18381.shtml

    AN Zhong-yi, ZHUO Yu-qun, CHEN Chang-he. Influence of calcinations temperature on the catalytic activity of Mn/TiO2 for NO oxidation[J]. J Fuel Chem Technol, 2014, 42(3):370-376. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18381.shtml
    [13] 曹锐, 费兆阳, 陈献, 汤吉海, 崔咪芬, 乔旭. CuO和CeO2在氯化氢氧化反应中的协同作用[J].化学反应工程与工艺, 2013, 29(4):295-300. http://d.wanfangdata.com.cn/Periodical/hxfygcygy201304002

    CAO Rui, FEI Zhao-yang, CHEN Xian, TANG Ji-mei, CUI Mi-fen, QIAO Xu. Synergetic effects of CuO and CeO2 on hydrogen chloride catalytic oxidation[J]. Chem React Eng Technol, 2013, 29(4):295-300. http://d.wanfangdata.com.cn/Periodical/hxfygcygy201304002
    [14] 李云涛, 钟秦.低温NH3-SCR反应机理及动力学研究进展[J].化学进展, 2009, 21(6):1094-1100. http://www.cnki.com.cn/Article/CJFDTotal-HXJZ200906003.htm

    LI Yun-tao, ZHONG Qin. Recent advances in mechanisms and kinetics of low-temperature selective catalytic reduction of NOx with NH3[J]. Prog Chem, 2009, 21(6):1094-1100. http://www.cnki.com.cn/Article/CJFDTotal-HXJZ200906003.htm
    [15] LIU F D, HE H, ZHANG C B, SHAN W P, SHI X Y. Mechanism of the selective catalytic reduction of NOx with NH3 over environment-friendly iron titanate catalyst[J]. Catal Today, 2011, 175:18-25. doi: 10.1016/j.cattod.2011.02.049
    [16] DONOVA A P, BALU S U, ETTIREDDY P R, PANAGIOTIS G S. Identification of surface on titania-supported manganese, chromium, and copper oxide low-temperature SCR catalysts[J]. J Phys Chem B, 2004, 108(28):9927-9936. doi: 10.1021/jp0313122
    [17] 宾峰.改性分子筛材料用于选择催化还原柴油机氮氧化物的研究[D].天津:天津大学, 2011.

    BING Feng. Study on modified molecular sieve materials for the selective catalytic reduction of NOx from diesel engines[D]. Tianjin:Tianjin University, 2011.
    [18] 杨睿, 黄海凤, 陈一杰, 张细雄, 卢晗锋. Cr改性钒基催化剂对NH3低温选择性催化还原NOx的影响[J]. 2015, 36(8):1256-1262.

    YANG Rui, HUANG Hai-feng, CHEN Yi-jie, ZHANG Xi-xiong, LU Han-feng. Performance of Cr-doped vanadia/titania catalysts for low-temperature selective catalytic reduction of NOx with NH3[J]. Chin J Catal, 2015, 36(8):1256-1262.
    [19] WU Z B, JIN R B, WANG H Q, LIU Y. Effect of ceria doping on SO2 resistance of Mn/TiO2 for selective catalytic reduction of NO with NH3 at low temperature[J]. Catal Commun, 2009, 10(6):935-939. doi: 10.1016/j.catcom.2008.12.032
    [20] ZHANG Q L, QIU C T, XU H D, LIN T, LIN Z E, GONG M C, CHEN Y Q. Low-temperature selective catalytic reduction of NO with NH3 over monolith catalyst of MnOx/CeO2-ZrO2-Al2O3[J]. Catal Today, 2011, 175(1):171-176. doi: 10.1016/j.cattod.2011.05.009
    [21] 楚英豪, 王天泽, 遥远, 宋鹏, 尹华强, 郭家秀. Mn-Ce/AC催化剂低温NH3选择性催化还原NO的性能[J].四川大学学报(工程科学版), 2013, 45(3):127-132. http://www.cnki.com.cn/Article/CJFDTotal-SCLH201303019.htm

    CHU Ying-hao, WANG Tian-ze, YAN Yuan, SONG Peng, YIN Hua-qiang, GUO Jia-xiu. Performance of Mn-Ce/AC catalyst for low temperature selective catalytic reduction of NO with NH3[J]. J Sichuan Univ (Eng Sci Ed), 2013, 45(3):127-132. http://www.cnki.com.cn/Article/CJFDTotal-SCLH201303019.htm
    [22] 谭月, 杨柳, 盛重义, 周爱奕, 单云霞, 胡宇峰. Mn-Ce改性活性焦催化剂低温SCR性能[J].环境工程学报, 2015, 9(11):5515-5520. http://www.cnki.com.cn/Article/CJFDTOTAL-HJJZ201511062.htm

    TAN Yue, YANG Liu, SHENG Chong-yi, ZHOU Ai-yi, SHAN Yun-xia, HU Yu-feng. Mn-Ce modified activated coke (AC) catalyst for desulfurization and denitration at low-temperature[J]. Chin J Environ Eng, 2015, 9(11):5515-5520. http://www.cnki.com.cn/Article/CJFDTOTAL-HJJZ201511062.htm
    [23] LIU F D, HE H. Selective catalytic reduction of NO with NH3 over manganese substituted iron titanate catalyst:Reaction mechanism and H2O/SO2 inhibition mechanism study[J]. Catal Today, 2010, 153(3/4):70-76. https://www.researchgate.net/publication/228421602_Selective_catalytic_reduction_of_NO_with_NH3_over_iron_titanate_catalyst_Catalytic_performance_and_characterization?_sg=OC6Rw6vN_iRFVK3rZQA_Xf_sicFyEuL6tH7kDMuyOEMtH1KLNgCrb51eTtGoC-bWJmHIlbYIWAnyMG5_Qc7E2A
    [24] TANG X F, LI Y G, HUANG X M, XU Y D, ZHU H Q, WANG J G, SHEN W J. MnOx-CeO2 mixed oxide catalysts for complete oxidation of formaldehyde:Effect of preparation method and calcinations temperature[J]. Appl Catal B:Environ, 2006, 62(3/4):265-273.
  • 加载中
图(5) / 表(5)
计量
  • 文章访问数:  94
  • HTML全文浏览量:  59
  • PDF下载量:  4
  • 被引次数: 0
出版历程
  • 收稿日期:  2016-04-15
  • 修回日期:  2016-07-19
  • 网络出版日期:  2021-01-23
  • 刊出日期:  2016-11-10

目录

    /

    返回文章
    返回