1,2-二氯乙烷在CoxTi1-x氧化物上的催化降解性能

doi:10.16085/j.issn.1000-6613.2020-1967

摘要/Abstract

摘要：

随着工业和经济的快速发展，含氯挥发性有机化合物（CVOCs）排放量日益增多，对人体健康以及环境造成严重危害。催化燃烧法是治理CVOCs最有效和经济的方法之一。本文采用溶胶-凝胶法制备出了不同Ti掺杂量的Co_xTi_1-_x复合氧化物，并对其物理化学性质进行了表征。研究了Co_xTi_1-_x催化剂对1,2-二氯乙烷（1,2-DCE）的催化氧化性能。结果表明，当Ti掺杂量低于0.6时，Co_xTi_1-_x复合氧化物呈现非晶相结构，形成无定形结构的Co-O-Ti固溶体。Ti元素的掺杂增加了Co_xTi_1-_x复合氧化物的表面酸位点及吸附态氧含量。其中，Co_0.8Ti_0.2催化剂具有较大的比表面积、良好的氧化还原性能、丰富的表面吸附态氧及中强酸位点，对1,2-DCE表现出较高的催化氧化能力；在气时空速为20000mL/(g·h)、1,2-DCE浓度为4060mg/m³的条件下，其对1,2-DCE的转化率达90%时所需温度为318℃。此外，在380℃长时间运行时，Co_0.8Ti_0.2也显示出较好的稳定性。

关键词: 催化剂, 复合材料, 二元混合物, 二氯乙烷, 钴氧化物

Abstract:

With the rapid development of industry and economy, the increasing emission of chlorine-containing volatile organic compounds (CVOCs) have caused serious harm to human health and environment. Catalytic combustion is one of the most effective and economical methods to treat CVOCs. Co_xTi_1-_x composite oxides with different Ti loading were prepared by sol-gel method, their physical and chemical properties were characterized and the catalytic performance for 1,2-dichloroethane (1,2-DCE) degradation was investigated. The results showed that the Co_xTi_1-_xcomposite oxides formed amorphous Co-O-Ti solid solution when Ti loading was less than 0.6. The addition of Ti increased the surface acid sites and the adsorbed oxygen content for the prepared Co_xTi₁_-xcatalysts. Among them, Co_0.8Ti_0.2 had large specific surface area, good redox performance, abundant surface adsorbed oxygen and medium-strong acid sites, and hence showed high catalytic oxidation ability for 1,2-DCE. When the gas space-time velocity was 20000mL/(g·h) and the concentration of 1,2-DCE was 4060mg/m³, the temperature required for 90% conversion of 1,2-DCE was 318℃. Besides, Co_0.8Ti_0.2 also exhibited good stability at 380℃ in long-time runs.

Key words: catalyst, composites, binary mixture, dichloroethane, cobalt oxide

中图分类号:

TB331

石怀启, 朱鹏飞, 吴帅妮, 李娜, 胡朝霞, 陈守文. 1,2-二氯乙烷在Co_xTi_1-_x氧化物上的催化降解性能[J]. 化工进展, 2021, 40(8): 4253-4258.

SHI Huaiqi, ZHU Pengfei, WU Shuaini, LI Na, HU Zhaoxia, CHEN Shouwen. Catalytic degradation of 1,2-dichloroethane on Co_xTi_1-_xcomposite oxides[J]. Chemical Industry and Engineering Progress, 2021, 40(8): 4253-4258.

图/表 9

图1 CoxTi1-x系列催化剂的XRD谱图

图2 CoxTi1-x系列催化剂的拉曼光谱图

图3 CoxTi1-x系列催化剂的SEM及EDS图像(a)~(f)—TiO2、Co0.2Ti0.8、Co0.4Ti0.6、Co0.6Ti0.4、Co0.8Ti0.2、Co3O4的SEM图；(g)—Co0.8Ti0.2的EDS分布图

图4 CoxTi1-x系列催化剂的H2-TPR及NH3-TPD曲线

图5 CoxTi1-x系列催化剂的XPS曲线

表1 CoxTi1-x系列催化剂的XPS分析及催化性能

样品	Co³⁺/Co^{2+ ①}	O_ads/O_lat^①	T₅₀^②/℃	T₉₀^②/℃
Co₃O₄	0.707	0.448	320	378
Co_0.8Ti_0.2	0.997	0.500	268	318
Co_0.6Ti_0.4	0.737	0.401	262	358
Co_0.4Ti_0.6	0.584	0.383	294	>420
Co_0.2Ti_0.8	0.500	0.314	306	>420
TiO₂	—	0.167	315	400

图6 1,2-DCE转化率随温度的变化曲线

图7 1,2-DCE转化率随时间的变化曲线

图8 Co0.8Ti0.2在380℃下长时间运行结果

参考文献 16

1	楚英豪, 宋欣橙, 冯欣怡, 等. 制备方法对CeO₂及CoO_x/CeO₂催化燃烧甲苯的影响[J]. 工程科学与技术, 2020, 52(3): 186-193.
	CHU Yinghao, SONG Xincheng, FENG Xinyi, et al. Effect of preparation methods of CeO₂ and CoO_x/CeO₂ on catalytic combustion toluene[J]. Advanced Engineering Sciences, 2020, 52(3): 186-193.
2	高寒, 董艳春, 周术元. 贵金属催化剂催化燃烧挥发性有机物(VOCs)的研究进展[J]. 环境工程, 2019, 37(3): 136-141.
	GAO Han, DONG Yanchun, ZHOU Shuyuan. Catalytic combustion of volatile organic compounds by noble metals catalysts[J]. Environmental Engineering, 2019, 37(3): 136-141.
3	ZHAO Haijun, HAN Weiliang, TANG Zhicheng. Tailored design of high-stability CoMn_1.5O_x@TiO₂ double-wall nanocages derived from Prussian blue analogue for catalytic combustion of o-dichlorobenzene[J]. Applied Catalysis B: Environmental, 2020, 276: 119133.
4	LI Jingwei, ZHAO Pei, LIU Shantang. SnO_x-MnO_x-TiO₂ catalysts with high resistance to chlorine poisoning for low-temperature chlorobenzene oxidation[J]. Applied Catalysis A: General, 2014, 482: 363-369.
5	FEI Xiaoqi, CAO Shuang, OUYANG Weilong, et al. A convenient synthesis of core-shell Co₃O₄@ZSM-5 catalysts for the total oxidation of dichloromethane (CH₂Cl₂)[J]. Chemical Engineering Journal, 2020, 387: 123411.
6	张悦, 刘志英, 李溪, 等. 添加铈对Cu-Co-O催化剂催化燃烧VOCs性能影响[J]. 中国环境科学, 2017, 37(6): 2087-2091.
	ZHANG Yue, LIU Zhiying, LI Xi, et al. Effect of Ce on the activity of Cu-Co-O catalyst in catalytic combustion of VOCs[J]. China Environmental Science, 2017, 37(6): 2087-2091.
7	YANG Peng, YANG Shanshan, SHI Zhinan, et al. Deep oxidation of chlorinated VOCs over CeO₂-based transition metal mixed oxide catalysts[J]. Applied Catalysis B: Environmental, 2015, 162: 227-235.
8	LAO Yijie, ZHU Naxin, JIANG Xingxing, et al. Effect of Ru on the activity of Co₃O₄ catalysts for chlorinated aromatics oxidation[J]. Catalysis Science & Technology, 2018, 8(18): 4797-4811.
9	CAI Ting, HUANG Hao, DENG Wei, et al. Catalytic combustion of 1,2-dichlorobenzene at low temperature over Mn-modified Co₃O₄ catalysts[J]. Applied Catalysis B: Environmental, 2015, 166/167: 393-405.
10	DENG Wei, DAI Qiguang, LAO Yijie, et al. Low temperature catalytic combustion of 1,2-dichlorobenzene over CeO₂-TiO₂ mixed oxide catalysts[J]. Applied Catalysis B: Environmental, 2016, 181: 848-861.
11	CHEN Lin, HU Fengchun, DUAN Hengli, et al. Intrinsic ferromagnetic coupling in Co₃O₄ quantum dots activatedby graphene hybridization[J]. Applied Physics Letters, 2016, 108(25): 252402.
12	SHARMA Yogesh Kumar, KHARKWAL Mamta, UMA S, et al. Synthesis and characterization of titanates of the formula MTiO₃ (M=Mn, Fe, Co, Ni and Cd) by co-precipitation of mixed metal oxalates[J]. Polyhedron, 2009, 28(3): 579-585.
13	戴启广, 王幸宜. 含氯挥发性有机物废气在CeO₂基催化剂上的低温催化燃烧净化: 从高活性到高稳定性再到高选择性[J]. 工业催化, 2020, 28(4): 1-15.
	DAI Qiguang, WANG Xingyi. Low-temperature catalytic combustion of chlorinated volatile organic compounds over CeO₂-based catalysts: from high activity to high stability and high selectivity[J]. Industrial Catalysis, 2020, 28(4): 1-15.
14	SUN Wei, GONG Binwei, PAN Jun, et al. Catalytic combustion of CVOCs over Cr_xTi_1-_x oxide catalysts[J]. Journal of Catalysis, 2020, 391: 132-144.
15	刘照, 程丽军, 胡鑫, 等. Mg改性对Co/γ-Al₂O₃-TiO₂催化燃烧丙烷性能影响[J]. 燃料化学学报, 2020, 48(7): 867-874.
	LIU Zhao, CHENG Lijun, HU Xin, et al. Effect of Mg modification on the catalytic performance of Co/γ-Al₂O₃-TiO₂ in the combustion of propane[J]. Journal of Fuel Chemistry and Technology, 2020, 48(7): 867-874.
16	HE Chi, CHENG Jie, ZHANG Xin, et al. Recent advances in the catalytic oxidation of volatile organic compounds: a review based on pollutant sorts and sources[J]. Chemical Reviews, 2019, 119(7): 4471-4568.

[1]	张明焱, 刘燕, 张雪婷, 刘亚科, 李从举, 张秀玲. 非贵金属双功能催化剂在锌空气电池研究进展[J]. 化工进展, 2023, 42(S1): 276-286.
[2]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[3]	谢璐垚, 陈崧哲, 王来军, 张平. 用于SO₂去极化电解制氢的铂基催化剂[J]. 化工进展, 2023, 42(S1): 299-309.
[4]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[5]	胡喜, 王明珊, 李恩智, 黄思鸣, 陈俊臣, 郭秉淑, 于博, 马志远, 李星. 二硫化钨复合材料制备与储钠性能研究进展[J]. 化工进展, 2023, 42(S1): 344-355.
[6]	王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.
[7]	邓丽萍, 时好雨, 刘霄龙, 陈瑶姬, 严晶颖. 非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs[J]. 化工进展, 2023, 42(S1): 542-548.
[8]	程涛, 崔瑞利, 宋俊男, 张天琪, 张耘赫, 梁世杰, 朴实. 渣油加氢装置杂质沉积规律与压降升高机理分析[J]. 化工进展, 2023, 42(9): 4616-4627.
[9]	王鹏, 史会兵, 赵德明, 冯保林, 陈倩, 杨妲. 过渡金属催化氯代物的羰基化反应研究进展[J]. 化工进展, 2023, 42(9): 4649-4666.
[10]	张启, 赵红, 荣峻峰. 质子交换膜燃料电池中氧还原反应抗毒性电催化剂研究进展[J]. 化工进展, 2023, 42(9): 4677-4691.
[11]	王伟涛, 鲍婷玉, 姜旭禄, 何珍红, 王宽, 杨阳, 刘昭铁. 醛酮树脂基非金属催化剂催化氧气氧化苯制备苯酚[J]. 化工进展, 2023, 42(9): 4706-4715.
[12]	葛亚粉, 孙宇, 肖鹏, 刘琦, 刘波, 孙成蓥, 巩雁军. 分子筛去除VOCs的研究进展[J]. 化工进展, 2023, 42(9): 4716-4730.
[13]	林晓鹏, 肖友华, 管奕琛, 鲁晓东, 宗文杰, 傅深渊. 离子聚合物-金属复合材料（IPMC）柔性电极的研究进展[J]. 化工进展, 2023, 42(9): 4770-4782.
[14]	吴海波, 王希仑, 方岩雄, 纪红兵. 3D打印催化材料开发与应用进展[J]. 化工进展, 2023, 42(8): 3956-3964.
[15]	向阳, 黄寻, 魏子栋. 电催化有机合成反应的活性和选择性调控研究进展[J]. 化工进展, 2023, 42(8): 4005-4014.