利用含有模板剂的SAPO-34分子筛制备高效铜基催化剂

doi:10.15541/jim20170612

无机材料学报 ›› 2018, Vol. 33 ›› Issue (9): 956-962.DOI: 10.15541/jim20170612 CSTR: 32189.14.10.15541/jim20170612

所属专题：环境材料优选论文

利用含有模板剂的SAPO-34分子筛制备高效铜基催化剂

孔祥力¹, 邱鸣慧¹, 杨璐¹, 王安然¹, 范益群¹, 孔德双², 谷昌军², 宦秀桦², 孔令仁²

1. 南京工业大学化工学院材料化学工程国家重点实验室, 南京 210009;
2. 江苏高淳陶瓷股份有限公司, 南京 211300

收稿日期:2017-12-28 修回日期:2018-02-06 出版日期:2018-09-20 网络出版日期:2018-08-14
作者简介:孔祥力(1993-), 男, 博士研究生. E-mail: ginolax@njtech.edu.cn
基金资助:
国家重点研发计划项目(2016YFC0205700);国家自然科学基金项目(91534108, 21506093);国家高技术研究发展计划项目(2012AA03A606);江苏省基础研究计划(自然科学基金)青年基金(BK20150947);江苏高校优势学科建设工程(PAPD);江苏省“六大人才高峰”项目(2012JNHB016)

Preparation of High-performance Cu-SAPO-34 Catalysts without Removal of Templating Agents

KONG Xiang-Li¹, QIU Ming-Hui¹, YANG Lu¹, WANG An-Ran¹, FAN Yi-Qun¹, KONG De-Shuang², GU Chang-Jun², HUAN Xiu-Hua², KONG Ling-Ren²

1. State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing 210009, China;
2. Jiangsu Gaochun Ceramics Co., Ltd, Nanjing 211300, China

Received:2017-12-28 Revised:2018-02-06 Published:2018-09-20 Online:2018-08-14
About author:KONG Xiang-Li. E-mail: ginolax@njtech.edu.cn
Supported by:
National Key R&D Plan (2016YFC0205700);National Natural Science Foundation of China (91534108, 21506093);National High Technical Research Program of China (2012AA03A606);Natural Science Foundation of Jiangsu Province (BK20150947);Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD);"Peak Specialists in Six Industries" High-level Specialist Fund of Jiangsu Province (2012JNHB016)

摘要/Abstract

摘要：

氮氧化物污染已经成为一个严重的环境问题。利用分子筛催化剂进行选择性催化还原(SCR)处理氮氧化物是最有效的方法之一。为了降低现有催化剂的制备成本, 本工作直接利用含有模板剂的分子筛浆料为原料, 通过预处理、离子交换及一次焙烧的方法制备Cu-SAPO-34催化剂。采用XRD、BET、TG、ICP、XPS、SEM、TPR、TPD及NH₃-SCR等对制备的Cu-SAPO-34样品进行表征, 并对离子交换过程中的pH条件进行了优化。研究结果表明: 利用含模板剂的分子筛浆料制备得到催化剂含有2.43% Cu、立方晶型完整、酸性较强以及催化还原性能优秀。在200~450℃下, NO转化率超过80%, 并且在300℃时转化率达到最高97.8%。与使用商品化SAPO-34制备的催化剂相比, 两者具有相似的微观结构和SCR性能。SAPO-34分子筛中少量模板剂的存在对最终制备得到的Cu-SAPO-34催化剂的性能影响很小。因此采用含有模板剂的分子筛浆料制备高效Cu-SAPO-34催化剂是可行的。

关键词: 离子交换, 催化剂, 分子筛, 模板剂

Abstract:

The pollution of nitrogen oxides has become a serious environmental problem. Selective catalytic reduction (SCR) with zeolites is one of the most effective ways to remove nitrogen oxides. To reduce the cost of the catalysts’ preparation, a facile fabrication method of high-performance Cu-SAPO-34 catalysts without removal of templating agents was proposed. Zeolite slurry containing templating agents was directly applied as a raw material to prepare the Cu-SAPO-34 catalyst followed by pretreatment, ion exchange and one-time calcination. As prepared catalysts were systematically investigated by XRD, BET, TG, ICP, XPS, SEM, TPR, TPD, and NH₃-SCR. In the ion exchange process, different pH conditions were studied and optimized. The optimized catalyst with Cu content of 2.43% performed a cubic crystal, high acidity and catalytic activity. The NO conversion rate was more than 80% in the range of 200~450℃, and the highest value was 97.8% obtained at 300℃. Compared with the catalyst prepared from commercial SAPO-34, the as-prepared Cu-SAPO-34 catalysts without removal of templating agents exhibited similar microstructure and catalytic performance. These results indicate that the presence of a small amount of templating agent in the SAPO-34 zeolites makes no difference to fabricate high-performance Cu-SAPO-34 catalysts. It is a feasible method to prepare high-performance Cu-SAPO-34 catalysts without removal of templating agents.

Key words: ion exchange, catalyst, zeolite, template agent

中图分类号:

TQ174

孔祥力, 邱鸣慧, 杨璐, 王安然, 范益群, 孔德双, 谷昌军, 宦秀桦, 孔令仁. 利用含有模板剂的SAPO-34分子筛制备高效铜基催化剂[J]. 无机材料学报, 2018, 33(9): 956-962.

KONG Xiang-Li, QIU Ming-Hui, YANG Lu, WANG An-Ran, FAN Yi-Qun, KONG De-Shuang, GU Chang-Jun, HUAN Xiu-Hua, KONG Ling-Ren. Preparation of High-performance Cu-SAPO-34 Catalysts without Removal of Templating Agents[J]. Journal of Inorganic Materials, 2018, 33(9): 956-962.

图/表 11

图1 传统方法与本研究所采用方法制备Cu-SAPO-34催化剂的流程图

Fig. 1 Traditional and present preparation flow chart for Cu-SAPO-34

表1 预处理前后SAPO-34和商业SAPO-34的BET结果

Table 1 BET results of raw, pretreated and commercial SAPO-34

	Specific surface area/(m²•g^-1)	Pore volume/ (m³•g^-1)	Pore size/nm
Raw SAPO-34	~119.0	~0.123	~5.9
Pretreated SAPO-34	375.8	0.248	10.5
Pretreated SAPO-34 after calcination	489.1	0.265	12.7
Commercial SAPO-34	512.4	0.271	13.3

图2 预处理前后SAPO-34和商业SAPO-34XRD曲线

Fig. 2 XRD patterns of raw, pretreated and commercial SAPO-34

图3 预处理SAPO-34和商业SAPO-34热重曲线

Fig. 3 Thermogravimetric curves of pretreated SAPO-34 and commercial SAPO-34

图4 不同pH条件下制备的催化剂XRD(a)及XPS(b)图谱

Fig. 4 XRD patterns (a) and XPS spectra (b) of catalysts prepared with different pH

表2 不同pH条件下制备的催化剂ICP和BET结果

Table 2 ICP and BET of catalysts prepared with different pH

pH	Cu content/wt%	Specific surface area/(m²•g^-1)	Pore volume/ (m³•g^-1)
4.8	0.82	204.9	0.170
5.0	2.03	184.3	0.165
5.2	2.43	176.4	0.157
5.4	5.15	143.2	0.123
5.6	6.57	139.6	0.118
5.2 (Commercial)	2.50	208.4	0.165

图5 不同pH条件下制备的催化剂N2吸附-脱附等温线

Fig. 5 N2 adsorption-desorption isotherms of catalysts prepared with different pH

图6 不同pH条件下制备的催化剂SEM照片

Fig. 6 SEM images of catalysts prepared with different pH

图7 不同pH条件下制备的催化剂TPR曲线

Fig. 7 TPR curves of catalysts prepared with different pH

图8 预处理Cu-SAPO-34和商业Cu-SAPO-34的TPD曲线

Fig. 8 TPD curves of pretreated and commercial Cu-SAPO-34

图9 预处理Cu-SAPO-34和商业Cu-SAPO-34的SCR测试结果

Fig. 9 SCR tests of pretreated and commercial Cu-SAPO-34

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利用含有模板剂的SAPO-34分子筛制备高效铜基催化剂

Preparation of High-performance Cu-SAPO-34 Catalysts without Removal of Templating Agents

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