Effect of forming conditions on the performance of catalytic decomposition of N2O over Co/ZSM-5 catalyst

doi:10.16085/j.issn.1000-6613.2018-0943

Chemical Industry and Engineering Progress ›› 2019, Vol. 38 ›› Issue (04): 1746-1752.DOI: 10.16085/j.issn.1000-6613.2018-0943

• Industrial catalysis • Previous Articles Next Articles

Effect of forming conditions on the performance of catalytic decomposition of N₂O over Co/ZSM-5 catalyst

Sixuan LI^1,²(),Lei XIA¹,Jingyu LI¹,Xiaogang LIU¹,Jinru SUN^1,³,Yaoling CHI¹,Hong WANG¹(),Cuiqing LI¹,Yongji SONG¹

1. Beijing Key Laboratory of Fuels Cleaning and Advanced Catalytic Emission Reduction Technology, College of Chemical Engineering, Beijing Institute of Petrochemical Technology, Beijing Institute of Petrochemical Technology, Beijing 102617, China
2. College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, China
3. College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124, China

Received:2018-05-08 Revised:2018-09-12 Online:2019-04-05 Published:2019-04-05
Contact: Hong WANG

成型条件对Co/ZSM-5催化剂催化分解N₂O性能影响

李思漩^1,²(),夏蕾¹,李靖宇¹,刘晓刚¹,孙巾茹^1,³,迟姚玲¹,王虹¹(),李翠清¹,宋永吉¹

1. 北京石油化工学院化学工程学院，燃料清洁化及高效催化减排技术北京市重点实验室，北京 102617
2. 北京化工大学化学工程学院，北京 100029
3. 北京工业大学环境与能源工程学院，北京 100124

通讯作者: 王虹
作者简介:<named-content content-type="corresp-name">李思漩</named-content>（1989—），女，硕士研究生，研究方向为工业催化。E-mail：<email>1302680058@qq.com</email>。|王虹，教授，硕士生导师，研究方向为工业催化。E-mail：<email>wanghong@bipt.edu.cn</email>。
基金资助:
国家自然科学基金(21343009，U1662103，21673290);燃料清洁化及高效催化减排技术北京市重点实验室项目(BZ041420180007);北京市大学生创新创业训练计划(2018J00035)

Abstract

Abstract:

The Co/ZSM-5 catalysts were prepared by extruding strip forming method and were characterized by XRD, BET, H₂-TPR, NH₃-TPD and particle radial crushing (side pressure) strength tests. The activity stability tests of the catalysts for catalytic decomposition of N₂O were carried out in a fixed-bed micro reactor. It was found that the cobalt spices in the catalysts were Co₃O₄and the type of peptizers obviously influenced the mechanical strength of catalysts. The amount of adhesive also influenced the mechanical strength, the amount of acid centers, redox properties and the activities of the catalysts. Co/ZSM-5(N-50) catalyst was prepared with nitric acid as peptizer and SB powder (mass fraction of 30% and 50%) as adhesive. It has strong mechanical strength (208N/cm and 230N/cm, respectively) and the T ₉₅ for N₂O decomposition were 485℃ and 500℃, respectively. Under the simulated industrial tail gas (φ $N 2 O$ =11%, φ $O 2$ =16% and N₂ as balance gas) condition, when the reaction temperature was 446℃ and space velocity was 6000h^-1 in the fixed-bed micro reactor, the Co/ZSM-5(N-50) catalyst showed prominent stability, and the N₂O decomposition conversion was above 98% in a 1000h test.

Key words: catalysts, cobalt, the conditions of molding, mechanical properties, catalytic decomposition of N₂O

摘要：

采用挤条成型法制备Co/ZSM-5催化剂，通过X射线衍射、BET比表面积、氢气程序升温还原（H₂-TPR）、氨气程序升温脱附法（NH₃-TPD）和颗粒径向抗压碎（侧压）强度测试对催化剂进行表征，在固定床微型反应器中评价催化剂催化分解N₂O活性，对Co/ZSM-5(N-50)催化剂进行稳定性测试。结果表明，钴物种以Co₃O₄尖晶石氧化物形式存在于Co/ZSM-5催化剂中，胶溶剂种类显著影响催化剂抗压碎强度；黏合剂用量影响催化剂抗压碎强度、酸量、氧化还原性和催化剂催化分解N₂O活性；以硝酸为胶溶剂，黏合剂（SB粉）用量为30%和50%制备的催化剂，抗压碎强度大，分别为208N/cm和230N/cm，催化分解N₂O温度T ₉₅分别为485℃和500℃。在固定床微型反应器中，模拟工业尾气组成（ $φ N 2 O$ =11%、 $φ O 2$ =16%、N₂为平衡气），反应温度446℃、空速6000h^-1条件下，Co/ZSM-5(N-50)催化剂在1000h稳定性测试中表现出良好的催化活性和稳定性，N₂O转化率高于98%。

关键词: 催化剂, 钴, 成型条件, 力学性能, N₂O分解

CLC Number:

TQ426.68

Sixuan LI, Lei XIA, Jingyu LI, Xiaogang LIU, Jinru SUN, Yaoling CHI, Hong WANG, Cuiqing LI, Yongji SONG. Effect of forming conditions on the performance of catalytic decomposition of N₂O over Co/ZSM-5 catalyst[J]. Chemical Industry and Engineering Progress, 2019, 38(04): 1746-1752.

李思漩, 夏蕾, 李靖宇, 刘晓刚, 孙巾茹, 迟姚玲, 王虹, 李翠清, 宋永吉. 成型条件对Co/ZSM-5催化剂催化分解N₂O性能影响[J]. 化工进展, 2019, 38(04): 1746-1752.

Figures/Tables 10

References 19

1	YU H B ， WANG X P , WU X X , et al ．Promotion of Ag for Co₃O₄ catalyzing N₂O decomposition under simulated real reaction conditions[J]. Chemical Engineering Journal, 2018, 334: 800-806.
2	CHEN H , LU Q H , YI C H , et al . Bimetallic Rh-Fe catalysts for N₂O decomposition: effects of surface structures on catalytic activity[J]. Physical Chemistry Chemical Physics, 2018, 20(7): 5103-5111.
3	丁林, 曹雨来, 宋永吉, 等 . Co-Cu-M(M=Fe, Mn, Ni, Zn, Ce)催化剂催化分解N₂O性能[J]. 化工进展, 2016, 35(11): 3519-3523.
	DING Lin , CAO Yulai , SONG Yongji , et al . The study of catalytic decomposition of N₂O over Cu-Co-M(M=Fe, Mn, Ni, Zn, Ce)[J]. Chemical Industry and Engineering Progress, 2016, 35(11): 3519-3523.
4	WANG A Y , WANG Y L , WALTER ERIC D , et al . Catalytic N₂O decomposition and reduction by NH₃ over Fe/Beta and Fe/SSZ-13 catalysts[J]. Journal of Catalysis, 2018, 358: 199-210.
5	SHEN Q , WU M F , WANG H , et al . The influence of desilication on high-silica MFI and its catalytic performance for N₂O decomposition[J]. Applied Surface Science, 2018, 441: 474-481.
6	李宁 . N₂O分解催化剂的制备[J]. 化工进展, 2007, 26(11): 1659-1661.
	LI Ning . Research on catalyst of nitrous oxide decomposition[J]. Chemical Industry and Engineering Progress, 2007, 26(11): 1659-1661.
7	王虹, 王军利, 李翠清, 等 . ACo₂O₄/HZSM-5催化剂上N₂O 的直接分解[J]. 物理化学学报, 2010, 26(10): 2739-2744.
	WANG Hong , WANG Junli , LI Cuiqing , et al . Decomposition of N₂O on ACo₂O₄/HZSM-5 catalysts[J]. Acta Physico-Chimica Sinica, 2010, 26(10): 2739-2744.
8	李孟丽, 杨晓龙, 唐立平, 等 . N₂O的催化分解研究[J]. 化学进展, 2012, 24(9): 1801-1817.
	LI Mengli , YANG Xiaolong , TANG Liping , et al . Catalysts for catalytic decomposition of nitrous oxide[J]. Progress in Chemistry, 2012, 24(9): 1801-1817.
9	赵晓旭, 程党国, 陈丰秋, 等 . N₂O直接分解催化剂的研究进展[J]. 化工进展, 2009, 28(9): 1562-1567.
	ZHAO Xiaoxu , CHENG Dangguo , CHEN Fengqiu , et al . Review of catalysts for catalytic decomposition of N₂O[J]. Chemical Industry and Engineering Progress, 2009, 28(9): 1562-1567.
10	徐向阳, 谷成, 王虹, 等 . Co/Hβ催化剂上N₂O的分解性能研究[J]. 燃料化学学报, 2014, 42(7): 877-883.
	XU Xiangyang , GU Cheng , WANG Hong , et al . Catalytic performance of Co/Hβ in N₂O decomposition[J]. Journal of Fuel Chemistry and Technology, 2014, 42(7): 877-883.
11	仇媛, 王长真, 李海涛, 等 . 单分散Co₃O₄@SiO₂核壳催化剂的制备及N₂O催化分解性能[J]. 化工学报, 2018, 69(4): 1493-1499.
	QIU Yuan , WANG Changzhen , LI Haitao , et al . Preparation of monodispersed core-shell Co₃O₄@SiO₂ catalyst and its application in N₂O catalytic decomposition[J]. CIESC Journal, 2018, 69(4): 1493-1499.
12	程火生 . 辽阳石化己二酸生产中N₂O减排技术应用研究[D]. 北京: 清华大学, 2010.
	CHENG Huosheng . Applied abatement technology of N₂O in adipic acid production in Liaoyang petrochemical company[D]. Beijing: Tsinghua University, 2010.
13	于长凤, 朱小平, 戴静 . 拟薄水铝石为粘结剂成型氧化铝陶瓷的研究[J]. 中国陶瓷, 2008, 44(1): 35-37.
	YU Changfeng , ZHU Xiaoping , DAI Jing . Alumina ceramic was formed after gelling and soliding using boehmite[J]. China Ceramics, 2008, 44(1): 35-37.
14	王继元, 顾越峰, 陈韶辉, 等 . 胶溶剂对TiO₂成型载体性能的影响[J]. 石油化工高等学校学报, 2009, 22(1): 26-30.
	WANG Jiyuan , GU Yuefeng , CHEN Shaohui , et al . Effect of peptizers on properties of formed TiO₂ supports[J]. Journal of Petrochemcal Universities, 2009, 22(1): 26-30.
15	王维华, 袁华, 吴元欣, 等 . 成型条件对CuO-Ce_0.5Mn_0.5O₂成型载体性能的影响[J]. 精细化工, 2011, 28(3): 247-252.
	WANG Weihua , YUAN Hua , WU Yuanxin , et al . Effect of forming conditionson properties of formed CuO-Ce_0.5Mn_0.5O₂ supports[J]. Fine Chemicals, 2011, 28(3): 247-252.
16	余海清, 李建伟, 孙晓岩, 等 . 胶溶剂对MCM-22分子筛催化剂性能的影响[J]. 石油化工高等学校学报, 2009, 22(1): 1-4.
	YU Haiqing , LI Jianwei , SUN Xiaoyan , et al . Effect of peptizator on performance of MCM-22 zeolite catalyst[J]. Journal of Petrochemical Universities, 2009, 22(1): 1-4.
17	JIRATOVA K , JANACEK L . Effect of peptizing on the physical and chemical properties of extruded alumina[J]. International Chemical Engineering, 1983, 23(1): 167-174.
18	邱正璞 . N₂O氧化苯制苯酚Fe-ZSM-5催化剂成型及宏观性能研究[D]. 北京: 北京化工大学, 2016.
	QIU Zhengpu . Research on extrusion conditions and macro performance of the Fe-ZSM-5 catalyst for N₂O benzene to phenol[D]. Beijing: Beijing University of Chemical Technology, 2016.
19	任冬梅, 王祥生, 李钢, 等 . 不同载体成型的Mo/ZSM-5催化剂上甲烷无氧芳构化反应[J]. 催化学报, 2010, 31(3): 348-352.
	REN Dongmei , WANG Xiangsheng , LI Gang , et al . Methane dehydroaromatization in the absence of oxygen over Mo/ZSM-5 extruded with different oxides[J]. Chinese Journal of Catalysis, 2010, 31(3): 348-352.

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