Process monitoring of the Au-S bond conversion in acetylene hydrochlorination

doi:10.1016/j.cjche.2021.04.026

中国化学工程学报 ›› 2022, Vol. 45 ›› Issue (5): 32-40.DOI: 10.1016/j.cjche.2021.04.026

Process monitoring of the Au-S bond conversion in acetylene hydrochlorination

Lutai Song¹, Li Liu¹, Mingyuan Zhu^1,2, Bin Dai^1,2

1 School of Chemistry and Chemical Engineering, Shihezi University, Shihezi 832000, China;
2 Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan, Shihezi 832000, China

收稿日期:2021-01-30 修回日期:2021-03-30 出版日期:2022-05-28 发布日期:2022-06-22
通讯作者: Mingyuan Zhu,E-mail:zhuminyuan@shzu.edu.cn;Bin Dai,E-mail:db_tea@shzu.edu.cn
基金资助:
This work was supported by the National Natural Science Foundation of China (21666033), the State Key Research and Development Project of China (2016YFB0301603), the International Corporation of S&T Project in Xinjiang Bingtuan (2018BC003), and the International Corporation of S&T Project in Shihezi University (GJHZ201701).

Process monitoring of the Au-S bond conversion in acetylene hydrochlorination

Lutai Song¹, Li Liu¹, Mingyuan Zhu^1,2, Bin Dai^1,2

1 School of Chemistry and Chemical Engineering, Shihezi University, Shihezi 832000, China;
2 Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan, Shihezi 832000, China

Received:2021-01-30 Revised:2021-03-30 Online:2022-05-28 Published:2022-06-22
Contact: Mingyuan Zhu,E-mail:zhuminyuan@shzu.edu.cn;Bin Dai,E-mail:db_tea@shzu.edu.cn
Supported by:
This work was supported by the National Natural Science Foundation of China (21666033), the State Key Research and Development Project of China (2016YFB0301603), the International Corporation of S&T Project in Xinjiang Bingtuan (2018BC003), and the International Corporation of S&T Project in Shihezi University (GJHZ201701).

摘要/Abstract

摘要： The continuous expansion of vinyl chloride production increases environmental pollution caused by mercury catalysts, which is an issue that urgently needs to be solved. Green and stable catalysts should be researched to alleviate this issue. In this research, Thiolactic acid acts as a ligand where sulfhydryl groups form a stable complex with Au on the surface of a spherical activated carbon (SAC). An Au-thiolactic acid/SAC catalyst was designed with a Au theoretical loading of 0.5% (mass) to overcome the disadvantages of traditional Au-based catalysts, such as a low conversion rate and poor life cycle. The ratio of Au to ligand was screened, and the activity was best when Au/S = 1:8. The formation of the Au-S bond was proven by FT-IR and UV–vis. The longevity test of the Au1S8 /SAC catalyst was carried out at 1200 h^-1 for 50 h. Samples with reaction times of 0 h, 5 h, 10 h, 20 h, and 50 h were taken to monitor the catalyst status. The XPS and TPR tests proved that the Au-S bond broke as the acetylene hydrochlorination reaction proceeded. The DFT calculation proved that the Au-S bond is the active site, and the sulfur atom promotes the adsorption of C₂H₂ by the catalyst.

关键词: Acetylene hydrochlorination, Au-S bond, Process monitoring, Valence shift

Abstract: The continuous expansion of vinyl chloride production increases environmental pollution caused by mercury catalysts, which is an issue that urgently needs to be solved. Green and stable catalysts should be researched to alleviate this issue. In this research, Thiolactic acid acts as a ligand where sulfhydryl groups form a stable complex with Au on the surface of a spherical activated carbon (SAC). An Au-thiolactic acid/SAC catalyst was designed with a Au theoretical loading of 0.5% (mass) to overcome the disadvantages of traditional Au-based catalysts, such as a low conversion rate and poor life cycle. The ratio of Au to ligand was screened, and the activity was best when Au/S = 1:8. The formation of the Au-S bond was proven by FT-IR and UV–vis. The longevity test of the Au1S8 /SAC catalyst was carried out at 1200 h^-1 for 50 h. Samples with reaction times of 0 h, 5 h, 10 h, 20 h, and 50 h were taken to monitor the catalyst status. The XPS and TPR tests proved that the Au-S bond broke as the acetylene hydrochlorination reaction proceeded. The DFT calculation proved that the Au-S bond is the active site, and the sulfur atom promotes the adsorption of C₂H₂ by the catalyst.

Key words: Acetylene hydrochlorination, Au-S bond, Process monitoring, Valence shift

Lutai Song, Li Liu, Mingyuan Zhu, Bin Dai. Process monitoring of the Au-S bond conversion in acetylene hydrochlorination[J]. 中国化学工程学报, 2022, 45(5): 32-40.

Lutai Song, Li Liu, Mingyuan Zhu, Bin Dai. Process monitoring of the Au-S bond conversion in acetylene hydrochlorination[J]. Chinese Journal of Chemical Engineering, 2022, 45(5): 32-40.

参考文献

[1] M. Cont, A.F. Carley, C. Heirene, D.J. Willock, P. Johnston, A.A. Herzing, C.J. Kiely, G.J. Hutchings, Hydrochlorination of acetylene using a supported gold catalyst:A study of the reaction mechanism, J. Catal., 250 (2007) 231-239
[2] M.Y. Zhu, Q.Q. Wang, K. Chen, Y. W, C.F. Huang, H. Dai, F. Yu, L.H. Kang, B. Dai, Development of a heterogeneous non-mercury catalyst for acetylene hydrochlorination, ACS Catal., 5 (2015) 5306-5316
[3] J.W. Zhong, Y.P. Xu, Z.M. Liu, Heterogeneous non-mercury catalysts for acetylene hydrochlorination:progress, challenges, and opportunities, Green Chem., 20 (2018) 2412-2427
[4] K. Zhou, J.C. Jia, C.H. Li, H. Xu, J. Zhou, G.H. Luo, F. Wei, A low content Au-based catalyst for hydrochlorination of C₂H₂ and its industrial scale-up for future PVC processes, Green Chem., 17 (2015) 356-364
[5] H.Y. Zhang, B. Dai, W. Li, X. Wang, J.L. Zhang, M.Y. Zhu, J.J. Gu, Non-mercury catalytic acetylene hydrochlorination over spherical activated-carbon-supported Au-Co(III)-Cu(II) catalysts, J. Catal., 316 (2014) 141-148
[6] L. Wang, B.X. Shen, J.G. Zhao, X.T. Bi, Trimetallic Au-Cu-K/AC for acetylene hydrochlorination, Can. J. Chem. Eng., 95 (2017) 1069-1075
[7] Y. Jia, R.S. Hu, Q.H. Zhou, H.Y. Wang, X. Gao, J. Zhang, Boron-modified activated carbon supporting low-content Au-based catalysts for acetylene hydrochlorination, J. Catal., 348 (2017) 223-232
[8] G.J. Lan, Q.F. Ye, Y.H. Zhu, H.D. Tang, W.F. Han, Y. Li, Single-Site Au/Carbon Catalysts with Single-Atom and Au Nanoparticles for Acetylene Hydrochlorination, ACS Appl. Nano Mater., 3 (2020) 3004-3010
[9] X.B. Dong, S.L. Chao, F.F. Wan, Q.X. Guan, G.C. Wang, W. Li, Sulfur and nitrogen co-doped mesoporous carbon with enhanced performance for acetylene hydrochlorination, J. Catal., 359 (2018) 161-170
[10] S.K. Kaiser, E. Fako, G. Manzocchi, F. Krumeich, R. Hauert, A.H. Clark, O.V. Safonova, N. Lopez, J. Perez-Ramirez, Nanostructuring unlocks high performance of platinum single-atom catalysts for stable vinyl chloride production, Nat. Catal., 3 (2020) 376-385
[11] B.L. Wang, J. Zhao, Y.X. Yue, G.F. Sheng, H.X. Lai, J.Y. Rui, H.H. He, Z.T. Hu, F. Feng, Q.F. Zhang, L.L. Guo, X.N. Li, Carbon with Surface-Enriched Nitrogen and Sulfur Supported Au Catalysts for Acetylene Hydrochlorination, ChemCatChem, 11 (2018) 1002-1009
[12] X.P. Duan, L.C. Ning, Y. Yin, Y.T. Huang, J. Gao, H.Q. Lin, K. Tan, H.F. Fang, L.M. Ye, X. Lu, Y.Z. Yuan, Sulfur Moiety as a Double-Edged Sword for Realizing Ultrafine Supported Metal Nanoclusters with a Cationic Nature, ACS Appl. Mater. Inter., 11 (2019) 11317-11326
[13] M. Cai, H.Y. Zhang, B.C. Man, J. Li, L.F. Li, Y.Q. Li, D.Y. Xie, R.P. Deng, J.L. Zhang, Synthesis of a vinyl chloride monomer via acetylene hydrochlorination with a ruthenium-based N-heterocyclic carbene complex catalyst, Catal. Sci. Technol., 10 (2020) 3552-3560
[14] C.F. Huang, M.Y. Zhu, L.H. Kang, B. Dai, A novel high-stability Au(III)/Schiff-based catalyst for acetylene hydrochlorination reaction, Catal. Commun., 54 (2014) 61-65
[15] Y.Z. Dong, W. Li, Z. Yan, J.L. Zhang, Hydrochlorination of acetylene catalyzed by an activated carbon supported chlorotriphenylphosphine gold complex, Catal. Sci. Technol., 6 (2016) 7946-7955
[16] P. Johnston, N. Carthey, G.J. Hutchings, Discovery, Development, and Commercialization of Gold Catalysts for Acetylene Hydrochlorination, J. Am. Chem. Soc., 137 (2015) 14548-14557
[17] Y. Deng, Z. Zhang, P.Y. Du, X.M. Ning, Y. Wang, D.X. Zhang, J. Liu, S.T. Zhang, X.Q. Lu, Embedding Ultrasmall Au Clusters into the Pores of a Covalent Organic Framework for Enhanced Photostability and Photocatalytic Performance, Angew. Chem. Int. Ed., 59 (2020) 6082-6089
[18] Y. Li, X. Wang, L. Gao, P. Hu, L. Jiang, T. Ren, R. Fu, D. Yang, X. Jiang, Aptamer-conjugated gold nanostars for targeted cancer photothermal therapy, J. Mater. Sci., 53 (2018) 14138-14148
[19] V.M. Karpan, G. Giovannetti, P.A. Khomyakov, M. Talanana, A.A. Starikov, M. Zwierzycki, J. van den Brink, G. Brocks, P.J. Kelly, Graphite and graphene as perfect spin filters, Phys. Rev. Lett., 99 (2007) 176602
[20] B.P. Pritchard, D. Altarawy, B. Didier, T.D. Gibson, T.L. Windus, New Basis Set Exchange:An Open, Up-to-Date Resource for the Molecular Sciences Community, J. Chem. Inf. Model., 59 (2019) 4814-4820
[21] T. Lu, F. Chen, Multiwfn:a multifunctional wavefunction analyzer, J. Comput. Chem., 33 (2012) 580-592
[22] E. Andris, P.C. Andrikopoulos, J. Schulz, J. Turek, A. Růžička, J. Roithová, L. Rulíšek, Aurophilic Interactions in[(L)AuCl]..[(L')AuCl] Dimers:Calibration by Experiment and Theory, J. Am. Chem. Soc., 140 (2018) 2316-2325
[23] X.Y. Qi, W. Li, J.J. Gu, C.L. Guo, J.L. Zhang, Gold-glutathione complex catalysts with carbon support for non-mercury catalytic acetylene hydrochlorination, RSC Adv., 6 (2016) 105110-105118
[24] Y.X. Yue, B.L. Wang, S.S. Wang, C.X. Jin, J.Y. Lu, Z. Fang, S.J. Shao, Z.Y. Pan, J. Ni, J. Zhao, X.N. Li, Boron-doped carbon nanodots dispersed on graphitic carbon as high-performance catalysts for acetylene hydrochlorination, Chem. Commun., 56 (2020) 5174-5177
[25] G.B. Li, W. Li, J.L. Zhang, Non-mercury catalytic acetylene hydrochlorination over activated carbon-supported Au catalysts promoted by CeO₂, Catal. Sci. Technol., 6 (2016) 1821-1828
[26] X. Yin, C.F. Huang, L.H. Kang, M.Y. Zhu, B. Dai, Novel AuCl₃-thiourea catalyst with a low Au content and an excellent catalytic performance for acetylene hydrochlorination, Catal. Sci. Technol., 6 (2016) 4254-4259

Process monitoring of the Au-S bond conversion in acetylene hydrochlorination

Process monitoring of the Au-S bond conversion in acetylene hydrochlorination

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	Fei Li, Xuemei Wang, Pengze Zhang, Qinqin Wang, Mingyuan Zhu, Bin Dai. Nitrogen and phosphorus co-doped activated carbon induces high density Cu⁺ active center for acetylene hydrochlorination[J]. 中国化学工程学报, 2023, 59(7): 193-199.
[2]	Xiongzhuo Zhu, Dali Gao, Chong Yang, Chunjie Yang. A blast furnace fault monitoring algorithm with low false alarm rate: Ensemble of greedy dynamic principal component analysis-Gaussian mixture model[J]. 中国化学工程学报, 2023, 57(5): 151-161.
[3]	Fangyuan Ma, Cheng Ji, Jingde Wang, Wei Sun. Early identification of process deviation based on convolutional neural network[J]. 中国化学工程学报, 2023, 56(4): 104-118.
[4]	Weipeng Lu, Xuefeng Yan. Balanced multiple weighted linear discriminant analysis and its application to visual process monitoring[J]. 中国化学工程学报, 2021, 36(8): 128-137.
[5]	Yuan Li, Dongsheng Yang. Local component based principal component analysis model for multimode process monitoring[J]. 中国化学工程学报, 2021, 34(6): 116-124.
[6]	Fangjie Lu, Dong Xu, Yusheng Lu, Bin Dai, Mingyuan Zhu. High nitrogen carbon material with rich defects as a highly efficient metal-free catalyst for excellent catalytic performance of acetylene hydrochlorination[J]. 中国化学工程学报, 2021, 29(1): 196-203.
[7]	Muhammad Nawaz, Abdulhalim Shah Maulud, Haslinda Zabiri, Syed Ali Ammar Taqvi, Alamin Idris. Improved process monitoring using the CUSUM and EWMA-based multiscale PCA fault detection framework[J]. 中国化学工程学报, 2021, 29(1): 253-265.
[8]	Shutian Chen, Qingchao Jiang, Xuefeng Yan. Multimodal process monitoring based on transition-constrained Gaussian mixture model[J]. 中国化学工程学报, 2020, 28(12): 3070-3078.
[9]	Chao Liu, Chenhui Liu, Jinhui Peng, Libo Zhang, Shixing Wang, Aiyuan Ma. Surface chemical characterization of deactivated low-level mercury catalysts for acetylene hydrochlorination[J]. Chinese Journal of Chemical Engineering, 2018, 26(2): 364-372.
[10]	Xiaolong Xu, Haihua He, Jia Zhao, Bailin Wang, Shanchuan Gu, Xiaonian Li. The ligand coordination approach for improving the stability of low-mercury catalyst in the hydrochlorination of acetylene[J]. , 2017, 25(9): 1217-1221.
[11]	Guozhu Wang, Jianchang Liu, Yuan Li, Cheng Zhang. Fault diagnosis of chemical processes based on partitioning PCA and variable reasoning strategy[J]. , 2016, 24(7): 869-880.
[12]	Zhengshun Fei, Kangling Liu. Online process monitoring for complex systems with dynamic weighted principal component analysis[J]. Chinese Journal of Chemical Engineering, 2016, 24(6): 775-786.
[13]	Tongtong Zhang, Jia Zhao, Jiangtao Xu, Jinhui Xu, Xiaoxia Di, Xiaonian Li. Oxygen and nitrogen-doped metal-free carbon catalysts for hydrochlorination of acetylene[J]. Chinese Journal of Chemical Engineering, 2016, 24(4): 484-490.
[14]	Yawei Yang, Yuxin Ma, Bing Song, Hongbo Shi. An aligned mixture probabilistic principal component analysis for fault detection of multimode chemical processes[J]. Chinese Journal of Chemical Engineering, 2015, 23(8): 1357-1363.
[15]	Shijin Ren, Zhihuan Song, Maoyun Yang, Jianguo Ren . A novel multimode processmonitoring method integrating LCGMMwith modified LFDA[J]. Chinese Journal of Chemical Engineering, 2015, 23(12): 1970-1980.