焙烧程序对一步合成Cu-SSZ-13催化剂NH3-SCR性能的影响

doi:10.16085/j.issn.1000-6613.2016.08.24

化工进展 ›› 2016, Vol. 35 ›› Issue (08): 2464-2468.DOI: 10.16085/j.issn.1000-6613.2016.08.24

焙烧程序对一步合成Cu-SSZ-13催化剂NH₃-SCR性能的影响

谢利娟^1,2, 刘福东², 石晓燕², 贺泓²

1. 江南大学环境与土木工程学院, 江苏无锡 214122;
2. 中国科学院生态环境研究中心, 北京 100085

收稿日期:2015-10-29 修回日期:2016-01-15 出版日期:2016-08-05 发布日期:2016-08-05
通讯作者: 谢利娟(1985—),女,博士,讲师,从事机动车尾气催化净化方面的研究。E-mail:ljxie@jiangnan.edu.cn。
作者简介:谢利娟(1985—),女,博士,讲师,从事机动车尾气催化净化方面的研究。E-mail:ljxie@jiangnan.edu.cn。
基金资助:
国家自然科学基金项目（51278486，51508231）。

Influence of calcination procedure on the one-pot synthesized Cu-SSZ-13 catalysts and their performance in NH₃-SCR

XIE Lijuan^1,2, LIU Fudong², SHI Xiaoyan², HE Hong²

1. School of Environment and Civil Engineering, Jiangnan University, Wuxi 214122, Jiangsu, China;
2. Research Center for Eco-environmental Science, Chinese Academy of Sciences, Beijing 100085, China

Received:2015-10-29 Revised:2016-01-15 Online:2016-08-05 Published:2016-08-05

摘要/Abstract

摘要： 焙烧程序影响一步合成法制备Cu-SSZ-13催化剂中Cu物种的种类及分布，是影响催化剂在NH₃选择性催化还原（NH₃-SCR）氮氧化物反应中催化性能的重要因素。为研究焙烧程序对该方法制备Cu-SSZ-13催化剂性能的影响，采用不同的焙烧温度及升温速率制备Cu-SSZ-13催化剂，并考察各催化剂的催化活性、水热稳定性及活性物种形态。结果表明焙烧温度不改变催化剂的晶型结构，但影响催化剂的活性物种形态及稳定性。当焙烧温度为600℃时，催化剂中Cu物种全部为孤立的Cu²⁺，并具有极高的稳定性，催化剂具有最佳的活性及水热稳定性。固定焙烧温度为600℃，随升温速率的提高，催化剂活性及水热稳定性表现出下降趋势，考虑经济成本，最佳的升温速率应为1℃/min。因此，以1℃/min的升温速率升至600℃焙烧6h是一步合成法制备Cu-SSZ-13催化剂的最佳焙烧程序，所得催化剂具备优异的NH₃-SCR活性和水热稳定性。

关键词: 选择催化还原, 分子筛, 催化, Cu-SSZ-13, 焙烧程序

Abstract: The calcination procedures affected the state and the distribution of Cu species in the one-pot synthesized Cu-SSZ-13,which then influenced their catalytic performance greatly. In order to investigate the effect of calcination procedure on the Cu-SSZ-13 in the selective catalytic reduction of NO_x by ammonia(NH₃-SCR),we prepared the catalysts with different temperatures and ramp rates. The catalytic activity and hydrothermal stability and state of active species of the catalysts were tested. The calcination temperature did not change the structure of the catalyst,but affected the state and the stability of the active species. When the temperature was set at 600℃,all Cu species in the catalyst were isolated Cu²⁺ with excellent stability,and the catalyst showed the best catalytic performance and hydrothermal stability. When the temperature was fixed at 600℃,the activity and hydrothermal stability of the catalysts decreased with the increase of ramp rate. Considering the cost,we had better set the ramp rate as 1℃/min. Thus,the optimal procedure was to calcine sample at 600℃ for 6h with a ramp rate of 1℃/min,and the catalyst showed the best NH₃-SCR activity and the highest hydrothermal stability.

Key words: selective catalytic reduction (SCR), molecular sieves, catalysis, Cu-SSZ-13, calcination procedures

中图分类号:

TB34

谢利娟, 刘福东, 石晓燕, 贺泓. 焙烧程序对一步合成Cu-SSZ-13催化剂NH₃-SCR性能的影响[J]. 化工进展, 2016, 35(08): 2464-2468.

XIE Lijuan, LIU Fudong, SHI Xiaoyan, HE Hong. Influence of calcination procedure on the one-pot synthesized Cu-SSZ-13 catalysts and their performance in NH₃-SCR[J]. Chemical Industry and Engineering Progree, 2016, 35(08): 2464-2468.

参考文献

[1] 顾卫荣,周明吉,马薇,等. 选择性催化还原脱硝催化剂的研究进展[J]. 化工进展,2012,31(7):1493-1500.
[2] 姜建清,潘华,孙国金,等. 过渡金属/分子筛催化剂上选择性催化还原氮氧化物的研究进展[J]. 化工进展,2012,31(1):98- 106.
[3] 杨博,郭翠梨,程景耀. SSZ-13分子筛的合成及应用进展[J]. 化工进展,2014,33(2):368-373.
[4] SCHMIEG S J,OH S H,KIM C H,et al. Thermal durability of Cu-CHA NH₃-SCR catalysts for diesel NO_x reduction[J]. Catalysis Today,2012,184:252-261.
[5] PARK J,PARK H,BAIK J,et al. Hydrothermal stability of CuZSM5 catalyst in reducing NO by NH₃ for the urea selective catalytic reduction process[J]. Journal of Catalysis,2006,240:47-57.
[6] KWAK J H,TONKYN R G,KIM D H,et al. Excellent activity and selectivity of Cu-SSZ-13 in the selective catalytic reduction of NO_x with NH₃[J]. Journal of Catalysis,2010,275:187-190.
[7] KWAK J H,TRAN D,BURTON S D,et al. Effects of hydrothermal aging on NH₃-SCR reaction over Cu/zeolites[J]. Journal of Catalysis,2012,287:203-209.
[8] KWAK J H,TRAN D,SZANYI J,et al. The effect of copper loading on the selective catalytic reduction of nitric oxide by ammonia over Cu-SSZ-13[J]. Catalysis Letters,2012,142:295-301.
[9] YE Q,WANG L,YANG R T. Activity,propene poisoning resistance and hydrothermal stability of copper exchanged chabazite-like zeolite catalysts for SCR of NO with ammonia in comparison to Cu/ZSM-5[J]. Applied Catalysis A:General,2012,427/428:24-34.
[10] FICKEL D W,ELIZABETH D A,LAUTERBACH J A,et al. The ammonia selective catalytic reduction activity of copper-exchanged small-pore zeolites[J]. Applied Catalysis B:Environmental,2011,102:441-448.
[11] ZONES S I. Conversion of faujasites to high-silica chabazite SSZ-13 in the presence of N,N,N-trimethyl-1-adamantammonium iodide[J]. Journal of the Chemical Society,Faraday Transactions,1991,87:3709-3716.
[12] WANG D,GAO F,PEDEN C H F,et al. Selective catalytic reduction of NO_xwith NH₃over a Cu-SSZ-13 catalyst prepared by a solid-state ion-exchange method [J]. ChemCatChem,2014,6:1579-1583.
[13] MARTíNEZ-FRANCO R,MOLINER M,THOGERSEN J R,et al. Efficient one-pot preparation of Cu-SSZ-13 materials using cooperative OSDAs for their catalytic application in the SCR of NO_x [J]. ChemCatChem,2013,5:3316-3323.
[14] REN L M,ZHU L F,YANG C G,et al. Designed copper-amine complex as an efficient template for one-pot synthesis of Cu-SSZ-13 zeolite with excellent activity for selective catalytic reduction of NO_x by NH₃[J]. Chemical Communication(Camb),2011,47:9789-9791.
[15] DEKA U,LEZCANO-GONZALEZ I,WARRENDER S J,et al. Changing active sites in Cu-CHA catalysts:deNO_x selectivity as a function of the preparation method[J]. Microporous and Mesoporous Materials,2013,166:144-152.
[16] XIE L J,LIU F D,REN L M,et al. Excellent performance of one-pot synthesized Cu-SSZ-13 catalyst for the selective catalytic reduction of NO with NH₃[J]. Environmental Science & Technology,2014,48:566-572.
[17] XIE L J,LIU F D,LIU K,et al. Inhibitory effect of NO₂ on the selective catalytic reduction of NO_x with NH₃ over one-pot-synthesized Cu-SSZ-13 catalyst[J]. Catalysis Science & Technology,2014,4:1104-1110.
[18] 任利敏,张一波,曾尚景,等. 由新型铜胺络合物模板剂设计合成活性优异的Cu-SSZ-13分子筛[J]. 催化学报 2012,33(1):92-105.
[19] GAO F,WALTER E D,KARP E M,et al. Structure-activity relationships in NH₃-SCR over Cu-SSZ-13 as probed by reaction kinetics and EPR studies[J]. Journal of Catalysis,2013,300:20-29.
[20] KWAK J H,ZHU H,LEE J H,et al. Two different cationic positions in Cu-SSZ-13?[J]. Chemical Communication(Camb),2012,48:4758-4760.
[21] KWAK J H,VARGA T,PEDEN C H F,et al. Following the movement of Cu ions in a SSZ-13 zeolite during dehydration,reduction and adsorption:a combined in situ TP-XRD,XANES/DRIFTS study[J]. Journal of Catalysis,2014,314:83-93.
[22] DEKA U,JUHIN A,EILERTSEN E A,et al. Confirmation of isolated Cu²⁺ ions in SSZ-13 zeolite as active sites in NH₃ selective catalytic reduction[J]. The Journal of Physical Chemistry C,2012,116:4809-4818.
[23] KEFIROV R,PENKOVA A,HADJIIVANOV K,et al. Stabilization of Cu⁺ ions in BEA zeolite:study by FTIR spectroscopy of adsorbed CO and TPR[J]. Microporous and Mesoporous Materials,2008,116:180-187.
[24] RICHTER M,FAIT M,ECKELT R,et al. Gas-phase carbonylation of methanol to dimethyl carbonate on chloride-free Cu-precipitated zeolite Y at normal pressure[J]. Journal of Catalysis,2007,245:11-24.
[25] XIE L J,LIU F D,SHI X Y,et al. Effects of post-treatment method and Na co-cation on the hydrothermal stability of Cu-SSZ-13 catalyst for the selective catalytic reduction of NO_x with NH₃[J]. Applied Catalysis B:Environmental,2015,179:206-212.

焙烧程序对一步合成Cu-SSZ-13催化剂NH₃-SCR性能的影响

Influence of calcination procedure on the one-pot synthesized Cu-SSZ-13 catalysts and their performance in NH₃-SCR

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