超稳低汞催化剂的稳定机理:炭表面含氧基团及缺陷协同作用实验及理论研究

引用本文: 李健, 范江涛, Sajjad Ali, 蓝国钧, 唐浩东, 韩文锋, 刘化章, 李波, 李瑛. 超稳低汞催化剂的稳定机理:炭表面含氧基团及缺陷协同作用实验及理论研究[J]. 催化学报, 2019, 40(2): 141-146. doi: S1872-2067(19)63271-7 shu

Citation: Jian Li, Jiangtao Fan, Sajjad Ali, Guojun Lan, Haodong Tang, Wenfeng Han, Huazhang Liu, Bo Li, Ying Li. The origin of the extraordinary stability of mercury catalysts on the carbon support: the synergy effects between oxygen groups and defects revealed from a combined experimental and DFT study[J]. Chinese Journal of Catalysis, 2019, 40(2): 141-146. doi: S1872-2067(19)63271-7 shu

超稳低汞催化剂的稳定机理:炭表面含氧基团及缺陷协同作用实验及理论研究

李健 ^a, ,
范江涛 ^a, ,
Sajjad Ali ^b, ,
蓝国钧 ^a, ,
唐浩东 ^a, ,
韩文锋 ^a, ,
刘化章 ^a, ,
李波 ^b, ,
李瑛 ^a,

a 浙江工业大学工业催化研究所, 浙江杭州 310014;
b 中国科学院金属研究所, 辽宁沈阳 110016
基金项目:
This work was supported by Qihe Investigation Company.

摘要: 聚氯乙烯（PVC）作为五大工程塑料之首在材料领域应用广泛.2017年，中国PVC产能逾2600万吨，占世界总产量的70%以上，PVC产业是我国重要支柱产业之一.基于中国富煤少气缺油的能源格局，PVC产量的90%以上都是基于煤化工的乙炔法生产的，而氯化汞催化剂是目前乙炔法氯乙烯工业上唯一实现产业化应用的催化剂.但是由于氯化汞属于金属氯化物中唯一的共价化合物，其热稳定极差，涉汞催化剂的汞污染问题一直是氯乙烯行业的世界级难题.中国电石法聚氯乙烯产业每年催化剂消耗量高达2.0万吨，年耗汞近1000吨，可回收不足40%，占世界汞消耗量的70%.而无汞催化剂由于成本高、使用寿命短等原因，短期内实现工业化应用及推广仍有困难.中国政府早在2014年开始限汞行动，提出了氯乙烯产业汞催化剂减量化直至无汞化的战略目标.根据2015年拟定的氯乙烯用低汞触媒的国标要求，氯化汞负载量最高不得超过6.5%，而高汞催化剂的氯化汞负载量在10%-12%之间，在氯化汞负载量降低一半的情况下保持催化剂的高性能及高热稳定性对催化剂的制备技术提出了很大的挑战.催化剂是参与化学反应而自身不会消耗的物质，其在工业使用过程中理论上并不会消耗，解决了催化剂的热稳定性问题，不但可以延长催化剂使用寿命，而且还可以缓解涉汞催化剂的资源消耗及环境污染问题.
活性炭具有较高的比表面积、可调控的表面化学性质和耐酸碱腐蚀性，在工业中应用广泛.氯乙烯单体合成的原料为氯化氢和乙炔，由于氯化氢的腐蚀性，活性炭基催化剂在工业化应用方面具有明显的优势.而活性炭载体的表面性质调控及对负载型金属催化剂的相互作用研究一直是近年来多相催化领域的一个热点.本文通过热处理的方法调控了活性炭的表面含氧基团，研究了活性炭的表面结构的区别，通过浸渍法制备了三种活性炭负载的低汞催化剂，对比了三种不同的活性炭载体的乙炔氢氯化性能及稳定性，发现表面基团的调控对低汞催化剂的稳定性具有较大的影响.热重实验表明，HgCl₂/AC-C催化剂中氯化汞的最大失重温度提高到了380℃以上.该催化剂在反应温度140℃，乙炔空速30h^-1条件下稳定运行10000h，乙炔转化率只下降了8%.DFT理论计算发现，碳氧双键旁边的缺陷位和氯化汞可以形成强的化学吸附，其吸附能可达120-130kJ/mol，而氯化汞在含氧基团的表面吸附能只有3-35kJ/mol.本文通过对活性炭表面结构的调控，使氯化汞和炭表面活性位形成化学吸附，可大大提高催化剂的耐热稳定性，从理论上给出了低汞催化剂的热稳定性解决方案，目前该催化剂已经成功实现了产业化应用，在工业转化器上使用寿命超过12000h，性能表现卓越.超稳低汞催化剂的工业化应用不仅能够降低氯乙烯单体生产过程中的单耗，节约PVC生产成本，还能够有效减少汞触媒使用过程中造成的重金属污染，为我国电石法氯碱行业的节能减排及限汞公约履约提供了很好的技术支撑和保障.

关键词:

English

The origin of the extraordinary stability of mercury catalysts on the carbon support: the synergy effects between oxygen groups and defects revealed from a combined experimental and DFT study

a Institute of Industry Catalysis, Zhejiang University of Technology, Hangzhou 310014, Zhejiang, China;
b Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, Liaoning, China
Received Date: 30 November 2018
Revised Date: 04 December 2018
Fund Project:
This work was supported by Qihe Investigation Company.

Abstract: Thermal stability of HgCl₂ has a pivotal importance for the hydrochlorination reaction as the loss of mercuric compounds is toxic and detrimental to environment. Here we report a low-mercury catalyst which has durability over 10000 h for acetylene hydrochlorination under the industrial condition. The stability of the catalyst is carefully analyzed from a combined experimental and density functional theory study. The analysis shows that the extraordinary stability of mercury catalyst is resulted from the synergy effects between surface oxygen groups and defective edge sites. The binding energy of HgCl₂ is increased to be higher than 130 kJ/mol when adsorption is at the edge site with a nearby oxygen group. Therefore, the present study revealed that the thermal stability problem of mercury-based catalyst can be solved by simply adjusting the surface chemistry of activated carbon. Furthermore, the reported catalyst has already been successfully applied in the commercialized production of vinyl chloride.

Key words:

1. [1] H. Schobert, Chem. Rev., 2014, 114, 1743-1760.
2. [2] J. Liu, G. J. Lan, Y. Y. Qiu, X. L. Wang, Y. Li, Chin. J. Catal., 2018, 39, 1664-1671.
3. [3] T. Degnan, Focus on Catalysts, 2016, 3, 1-2.
4. [4] Y. Lin, S. X. Wang, Q. R. Wu, T. Larssen, Environ. Sci. Technol., 2016, 50, 2337-2344.
5. [5] P. Johnston, N. Carthey, G. J. Hutchings, J. Am. Chem. Soc., 2016, 137, 14548-14557.
6. [6] G. Malta, S. A. Kondrat, S. J. Freakley, C. J. Davies, L. Lu, S. Dawson, A. Thetford, E. K. Gibson, D. J. Morgan, W. Jones, P. P. Wells, P. Johnston, C. R. A. Catlow, C. J. Kiely, G. J. Hutchings, Science, 2017, 355, 1399-1403.
7. [7] X. Y. Li, X. L. Pan, L. Yu, P. J. Ren, X. Wu, L. T. Sun, F. Jiao, X. H. Bao, Nat. Commun., 2014, 5, 3688.
8. [8] G. J. Lan, Y. Wang, Y. Y. Qiu, X. L. Wang, J. Liang, W. F. Han, H. D. Tang, H. Z. Liu, J. Liu, Y. Li, Chem. Commun., 2018, 54, 623-626.
9. [9] Y. Yang, G. J. Lan, X. L. Wang, Y. Li, Chin. J. Catal., 2016, 37, 1242-1248.
10. [10] C. Liu, C. H. Liu, J. H. Peng, L. B. Zhang, S. X. Wang, A. Y. Ma, Chin. J. Chem. Eng., 2018, 26, 364-372.
11. [11] Y. C. Xie, Y. Q. Tang, Adv. Catal., 1990, 37, 1-43.
12. [12] G. J. Hutchings, D. T. Grady, Appl. Catal., 1985, 16, 411-415.
13. [13] G. J. Hutchings, J. Catal., 1985, 96, 292-295.
14. [14] X. L. Xu, J. Zhao, C. S. Lu, T. T. Zhang, X. X. Di, S. C. Gu, X. N. Li, Chin. Chem. Lett., 2016, 27, 822-826.
15. [15] X. B. Wei, H. B. Shi, W. Z. Qian, G. H. Luo, Y. Jin, F. Wei, Ind. Eng. Chem. Res., 2009, 48, 128-133.
16. [16] L. L. Xu, X. G. Wang, H. Y. Zhang, B. Dai, Z. Y. Liu, Q. F. Zhang, Chem. Ind. End. Prog., 2011, 30, 536-541.
17. [17] Y. Li, G. J. Lan, G. Q. Feng, J. Wei, W. F. Han, H. D. Tang, H. Z. Liu, ChemCatChem, 2014, 6, 572-579.
18. [18] X. M. Wang, N. Li, J. A. Webb, L. D. Pfefferle, G. L. Haller, Appl. Catal. B, 2010, 101, 21-30.
19. [19] J. H. Xu, J. Zhao, J. Xu, T. T. Zhang, X. N. Li, X. X. Di, J. Ni, J. G. Wang, C. Jie, Ind. Eng. Chem. Res., 2014, 53, 14272-14281.
20. [20] M. R. Axet, O. Dechy-Cabaret, J. Durand, M. Gouygou, P. Serp, Coord. Chem. Rev., 2016, 308, 236-345.
21. [21] H. Yan, H. Cheng, H. Yi, Y. Lin, T. Yao, C. L. Wang, J. J. Li, S. Q. Wei, J. L. Lu, J. Am. Chem. Soc., 2015, 137, 10484-10487.
22. [22] W. Y. Chen, J. Ji, S. Z. Duan, G. Qian, P. Li, X. G. Zhou, D, Chen, W. K. Yuan, Chem. Commun., 2014, 50, 2142-2144.
23. [23] W. Y. Chen, X. Z. Duan, G. Qian, D. Chen, X. G. Zhou, ChemSusChem, 2015, 8, 2927-2931.
24. [24] P. Behra, P. Bonnissel-Gissinger, M. Alnot, R. Revel, J. J. Ehrhardt, Langmuir, 2001, 17, 3970-3979.
25. [25] R. S. Vieira, M. L. M. Oliveira, E. Guibal, E. Rodríguez-Castellón, M. M. Beppu, Colloids Surf. A, 2011, 374, 108-114.
26. [26] Y. V. Fedoseeva, A. S. Orekhov, G. N. Chekhova, V. O. Koroteev, M. A. Kanygin, B. V. Senkovskiy, A. Chuvilin, D. Pontiroli, M. Ricco, L. G. Bulusheva, A. V. Okotrub, ACS Nano, 2017, 11, 8643-8649.
27. [27] E. Sasmaz, A. Kirchofer, A. D. Jew, A. Saha, D. Abram, T. F. Jaramillo, J. Wilcox, Fuel, 2012, 99, 188-196.
28. [28] X. Y. Sun, B. Li, D. S. Su, Chem. Asian J., 2016, 11, 1668-1671.
29. [29] W. Ren, L. Duan, Z. W. Zhu, W. Du, Z. Y. An, L. J. Xu, C. Zhang, Y. Q. Zhuo, C. H. Chen, Environ. Sci. Technol., 2014, 48, 2321-2327.
30. [30] M. Y. Zhu, Q. Q. Wang, K. Chen, Y. Wang, C. F. Huang, H. Dai, F. Yu, L. H. kang, B. Dai, ACS Catal., 2015, 5, 5306-5316.

扫一扫看文章

计量

PDF下载量: 9
文章访问数: 1098
HTML全文浏览量: 155

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

超稳低汞催化剂的稳定机理:炭表面含氧基团及缺陷协同作用实验及理论研究

English

The origin of the extraordinary stability of mercury catalysts on the carbon support: the synergy effects between oxygen groups and defects revealed from a combined experimental and DFT study

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

超稳低汞催化剂的稳定机理:炭表面含氧基团及缺陷协同作用实验及理论研究

English

The origin of the extraordinary stability of mercury catalysts on the carbon support: the synergy effects between oxygen groups and defects revealed from a combined experimental and DFT study

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs