Synergistic effect between nitrogen-doped sites and metal chloride for carbon supported extra-low mercury catalysts in acetylene hydrochlorination

doi:10.1016/j.cjche.2024.11.007

中国化学工程学报 ›› 2025, Vol. 79 ›› Issue (3): 145-154.DOI: 10.1016/j.cjche.2024.11.007

Synergistic effect between nitrogen-doped sites and metal chloride for carbon supported extra-low mercury catalysts in acetylene hydrochlorination

Yiyang Qiu¹, Chong Liu², Xueting Meng¹, Yuesen Liu¹, Jiangtao Fan¹, Guojun Lan¹, Ying Li¹

1. Institute of Industry Catalysis, Zhejiang University of Technology, Hangzhou 310014, China;
2. Fujian Institute of Research on Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China

收稿日期:2024-10-10 修回日期:2024-11-17 接受日期:2024-11-18 出版日期:2025-03-28 发布日期:2025-01-09
通讯作者: Chong Liu,E-mail:chongliu@fjirsm.ac.cn;Ying Li,E-mail:liying@zjut.edu.cn
基金资助:
This work is supported by the National Key Research and Development Program of China (2024YFC3907904).

Synergistic effect between nitrogen-doped sites and metal chloride for carbon supported extra-low mercury catalysts in acetylene hydrochlorination

Yiyang Qiu¹, Chong Liu², Xueting Meng¹, Yuesen Liu¹, Jiangtao Fan¹, Guojun Lan¹, Ying Li¹

1. Institute of Industry Catalysis, Zhejiang University of Technology, Hangzhou 310014, China;
2. Fujian Institute of Research on Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China

Received:2024-10-10 Revised:2024-11-17 Accepted:2024-11-18 Online:2025-03-28 Published:2025-01-09
Supported by:
This work is supported by the National Key Research and Development Program of China (2024YFC3907904).

摘要/Abstract

摘要： Carbon-supported mercury catalysts are extensively employed in calcium carbide-based polyvinyl chloride (PVC) industries, but the usage of mercury-based catalysts can pose an environmental threat due to the release of mercury into the surrounding area during the operation period. In this study, a highly active and stable mercury-based catalyst was developed, utilizing the nitrogen atom of the support as the anchor site to enhance the interaction between active sites (HgCl₂) and the carbon support (N-AC). Thermal loss rate testing and thermogravimetric analysis results demonstrate that, compared to commercial activated carbon, N-doped carbon can effectively increase the heat stability of HgCl₂. The obtained mercury-based catalysts (HgCl₂/N-AC) exhibit significant catalytic performance, achieving 2.5 times the C₂H₂ conversion of conventional HgCl₂/AC catalysts. Experimental analysis combined with theoretical calculations reveals that, contrary to the Eley-Rideal (ER) mechanism of HgCl₂/AC, the HgCl₂/N-AC catalyst follows the Langmuir-Hinshelwood (LH) adsorption mechanism. The nitrogen sites and HgCl₂ on the catalyst enhance the adsorption capabilities of the HCl and C₂H₂, thereby improving the catalytic performance. Based on the modification of the active center by these solid ligands, the loading amount of HgCl₂ on the catalyst can be further reduced from the current 6.5% to 3%. Considering the absence of successful industrial applications for mercury-free catalysts, and based on the current annual consumption of commercial mercury chloride catalysts in the PVC industry, the widespread adoption of this technology could annually reduce the usage of chlorine mercury by 500 tons, making a notable contribution to mercury compliance, reduction, and emissions control in China. It also serves as a bridge between mercury-free and low-mercury catalysts. Moreover, this solid ligand technology can assist in the application research of mercury-free catalysts.

关键词: Acetylene hydrochlorination, Activated carbon, Catalyst support, Mercury catalyst, DFT calculation, Kinetics

Abstract: Carbon-supported mercury catalysts are extensively employed in calcium carbide-based polyvinyl chloride (PVC) industries, but the usage of mercury-based catalysts can pose an environmental threat due to the release of mercury into the surrounding area during the operation period. In this study, a highly active and stable mercury-based catalyst was developed, utilizing the nitrogen atom of the support as the anchor site to enhance the interaction between active sites (HgCl₂) and the carbon support (N-AC). Thermal loss rate testing and thermogravimetric analysis results demonstrate that, compared to commercial activated carbon, N-doped carbon can effectively increase the heat stability of HgCl₂. The obtained mercury-based catalysts (HgCl₂/N-AC) exhibit significant catalytic performance, achieving 2.5 times the C₂H₂ conversion of conventional HgCl₂/AC catalysts. Experimental analysis combined with theoretical calculations reveals that, contrary to the Eley-Rideal (ER) mechanism of HgCl₂/AC, the HgCl₂/N-AC catalyst follows the Langmuir-Hinshelwood (LH) adsorption mechanism. The nitrogen sites and HgCl₂ on the catalyst enhance the adsorption capabilities of the HCl and C₂H₂, thereby improving the catalytic performance. Based on the modification of the active center by these solid ligands, the loading amount of HgCl₂ on the catalyst can be further reduced from the current 6.5% to 3%. Considering the absence of successful industrial applications for mercury-free catalysts, and based on the current annual consumption of commercial mercury chloride catalysts in the PVC industry, the widespread adoption of this technology could annually reduce the usage of chlorine mercury by 500 tons, making a notable contribution to mercury compliance, reduction, and emissions control in China. It also serves as a bridge between mercury-free and low-mercury catalysts. Moreover, this solid ligand technology can assist in the application research of mercury-free catalysts.

Key words: Acetylene hydrochlorination, Activated carbon, Catalyst support, Mercury catalyst, DFT calculation, Kinetics

Yiyang Qiu, Chong Liu, Xueting Meng, Yuesen Liu, Jiangtao Fan, Guojun Lan, Ying Li. Synergistic effect between nitrogen-doped sites and metal chloride for carbon supported extra-low mercury catalysts in acetylene hydrochlorination[J]. 中国化学工程学报, 2025, 79(3): 145-154.

参考文献

[1] Y.X. Liu, L. Zhao, Y.G. Zhang, L.T. Zhang, X.J. Zan, Progress and challenges of mercury-free catalysis for acetylene hydrochlorination, Catalysts 10 (10) (2020) 1218.
[2] X.X. Wang, W.Q. Chen, X.J. Lei, C. Lei, N.W. Zhu, B.B. Huang, Progress of p-block element-regulated catalysts for acetylene hydrochlorination, Coord. Chem. Rev. 500 (2024) 215541.
[3] Z.B. Chen, S.S. Wang, J. Zhao, R.H. Lin, Advances in single-atom-catalyzed acetylene hydrochlorination, ACS Catal. 14 (2) (2024) 965-980.
[4] S.Y. Sun, H.M. Xu, Y.R. Fan, Z.S. Liu, Q.Y. Hong, W.J. Huang, Z. Qu, N.Q. Yan, Construction of a thermally stable low-HgCl₂ catalyst via chalcogen bonding and its enhanced activity in acetylene hydrochlorination, Ind. Eng. Chem. Res. 61 (46) (2022) 17057-17064.
[5] 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.J. Kiely, G.J. Hutchings, Identification of single-site gold catalysis in acetylene hydrochlorination, Science 355 (6332) (2017) 1399-1403.
[6] 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 (4) (2020) 376-385.
[7] B.L. Wang, Y.X. Yue, C.X. Jin, J.Y. Lu, S.S. Wang, L. Yu, L.L. Guo, R.R. Li, Z.T. Hu, Z.Y. Pan, J. Zhao, X.N. Li, Hydrochlorination of acetylene on single-atom Pd/N-doped carbon catalysts: importance of pyridinic-N synergism, Appl. Catal. B Environ. 272 (2020) 118944.
[8] X.L. Wang, G.J. Lan, Z.Z. Cheng, W.F. Han, H.D. Tang, H.Z. Liu, Y. Li, Carbon-supported ruthenium catalysts prepared by a coordination strategy for acetylene hydrochlorination, Chin. J. Catal. 41 (11) (2020) 1683-1691.
[9] Y.X. Yue, S.S. Wang, Q. Zhou, B.L. Wang, C.X. Jin, R.Q. Chang, L.Q. Wan, Z.Y. Pan, Y.H. Zhu, J. Zhao, X.N. Li, Tailoring asymmetric Cu-O-P coupling site by carbothermal shock method for efficient vinyl chloride synthesis over carbon supported Cu catalysts, ACS Catal. 13 (14) (2023) 9777-9791.
[10] Y.L. Zhang, S. Li, X.L. Qiao, Q.X. Guan, W. Li, Efficient and stable N-heterocyclic ketone-Cu complex catalysts for acetylene hydrochlorination: the promotion effect of ligands revealed from DFT calculations, Phys. Chem. Chem. Phys. 25 (37) (2023) 25581-25593.
[11] X.Y. Qiao, Z.H. Zhao, J. Zhang, Progress in mercury-free catalysts for acetylene hydrochlorination, Catal. Sci. Technol. 14 (14) (2024) 3838-3852.
[12] X.L. Xu, J. Zhao, C.S. Lu, T.T. Zhang, X.X. Di, S.C. Gu, X.N. Li, Improvement of the stability of Hg/AC catalysts by CsCl for the high-temperature hydrochlorination of acetylene, Chin. Chem. Lett. 27 (6) (2016) 822-826.
[13] X.L. Xu, H.H. He, J. Zhao, B.L. Wang, S.C. Gu, X.N. Li, The ligand coordination approach for improving the stability of low-mercury catalyst in the hydrochlorination of acetylene, Chin. J. Chem. Eng. 25 (9) (2017) 1217-1221.
[14] J. Li, J.T. Fan, S. Ali, G.J. Lan, H.D. Tang, W.F. Han, H.Z. Liu, B. Li, Y. 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, Chin. J. Catal. 40 (2) (2019) 141-146.
[15] S. Ahmad, L.N. Liu, S.C. Zhang, J.C. Tang, Nitrogen-doped biochar (N-doped BC) and iron/nitrogen Co-doped biochar (Fe/N Co-doped BC) for removal of refractory organic pollutants, J. Hazard. Mater. 446 (2023) 130727.
[16] S.Y. Liang, L. Huang, Y.S. Gao, Q. Wang, B. Liu, Electrochemical reduction of CO₂ to CO over transition metal/N-doped carbon catalysts: the active sites and reaction mechanism, Adv. Sci. 8 (24) (2021) e2102886.
[17] D.B. basha, S. Ahmed, A. Ahmed, M. Gondal, Recent advances on nitrogen doped porous carbon micro-supercapacitors: new directions for wearable electronics, J. Energy. Storage. 60 (2023) 106581-106600.
[18] J. Li, H.Y. Zhang, H.X. Liang, L.S. Yao, C.C. Li, J.L. Zhang, Construction of Ru single-atom catalyst with abundant Ru-N active domains for highly efficient acetylene hydrochlorination, Mol. Catal. 543 (2023) 113158.
[19] 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, Wheat flour-derived N-doped mesoporous carbon extrudate as superior metal-free catalysts for acetylene hydrochlorination, Chem. Commun. 54 (6) (2018) 623-626.
[20] G.J. Lan, J.L. Zhou, Q.F. Ye, D. Lin, Y.Y. Qiu, Z.Z. Cheng, X.C. Sun, Y. Li, A hierarchically porous carbon stabilized atomically dispersed Au catalyst for acetylene hydrochlorination, Inorg. Chem. Front. 11 (17) (2024) 5657-5665.
[21] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. Montgomery, J. A, J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, N. J. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, D. J. Fox, Gaussian 09, Revision B.01, Gaussian, Inc., Wallingford CT, 2009.
[22] J.D. Chai, M. Head-Gordon, Long-range corrected hybrid density functionals with damped atom-atom dispersion corrections, Phys. Chem. Chem. Phys. 10 (44) (2008) 6615-6620.
[23] P.C. Hariharan, J.A. Pople, The influence of polarization functions on molecular orbital hydrogenation energies, Theor. Chim. Acta 28 (3) (1973) 213-222.
[24] M.J. Frisch, J.A. Pople, J.S. Binkley, Self-consistent molecular orbital methods 25. Supplementary functions for Gaussian basis sets, 80 (7) (1984) 3265-3269.
[25] P.J. Hay, W.R. Wadt, Ab initio effective core potentials for molecular calculations. Potentials for the transition metal atoms Sc to Hg, J. Chem. Phys. 82 (1) (1985) 270-283.
[26] Y.Y. Qiu, D. Fan, G.J. Lan, S.H. Wei, X.J. Hu, Y. Li, Generalized reactivity descriptor of defective carbon catalysts for acetylene hydrochlorination: the ratio of sp²: sp³ hybridization, Chem. Commun. 56 (94) (2020) 14877-14880.
[27] S. Aswathappa, L.D. Dai, S.A.T. Redfern, S. Sahaya Jude Dhas, X.L. Feng, E. Palaniyasan, R.S. Kumar, Acoustic shock wave-induced sp²-to-sp³-type phase transition: a case study of a graphite single crystal, J. Mater. Chem. C 12 (36) (2024) 14581-14589.
[28] L.L. Ma, W.J. Liu, X. Hu, P.K.S. Lam, J.R. Zeng, H.Q. Yu, Ionothermal carbonization of biomass to construct sp²/sp³ carbon interface in N-doped biochar as efficient oxygen reduction electrocatalysts, Chem. Eng. J. 400 (2020) 125969.
[29] A. Kovtun, D. Jones, S. Dell’Elce, E. Treossi, A. Liscio, V. Palermo, Accurate chemical analysis of oxygenated graphene-based materials using X-ray photoelectron spectroscopy, Carbon 143 (2019) 268-275.
[30] X.D. Liang, N. Tian, Z.Y. Zhou, S.G. Sun, N, P dual-doped porous carbon nanosheets for high-efficiency CO₂ electroreduction, ACS Sustainable Chem. Eng. 10 (5) (2022) 1880-1887.
[31] S.H. Wei, Y.Y. Qiu, X.C. Sun, X.L. Wang, H.T. Li, G.J. Lan, J. Liu, Y. Li, Sustainable Nanoporous Carbon Catalysts Derived from Melamine Assisted Cross-Linking of Poly(vinyl chloride) Waste for Acetylene Hydrochlorination, ACS Sustainable Chem. Eng. 10 (2022) 10476–10485.
[32] Y. Xie, Q. Xu, Y. Tang, C. Bai, C. Dai, Scanning tunneling microscopy investigation of a spontaneous monolayer dispersion system: HgCl₂ on highly oriented pyrolitic graphite surface, J. Vac. Sci. Technol. A Vac. Surf. Films 8 (1) (1990) 610-613.
[33] C.M. Wang, B.Y. Zhao, Y.C. Xie, Advances in the studies of spontaneous monolayer dispersion of oxides and salts on supports, Chin. J. Catal. 24 (6) (2003) 475-482.
[34] L. He, Y.Y. Qiu, C. Yao, G.J. Lan, N. Li, H.C. Zhou, Q.S. Liu, X.C. Sun, Z.Z. Cheng, Y. Li, Role of intrinsic defects on carbon adsorbent for enhanced removal of Hg²⁺ in aqueous solution, Chin. J. Chem. Eng. 61 (2023) 129-139.
[35] Y. Zhang, X.X. Zhang, K. Sang, W.Y. Chen, G. Qian, J. Zhang, X.Z. Duan, X.G. Zhou, W.K. Yuan, Kinetics insights into size effects of carbon nanotubes’ growth and their supported platinum catalysts for 4, 6-dinitroresorcinol hydrogenation, Chin. J. Chem. Eng. 72 (2024) 133-140.
[36] C.T. Toh, H. Zhang, J. Lin, A.S. Mayorov, Y.P. Wang, C.M. Orofeo, D.B. Ferry, H. Andersen, N. Kakenov, Z. Guo, I.H. Abidi, H. Sims, K. Suenaga, S.T. Pantelides, B. Ozyilmaz, Synthesis and properties of free-standing monolayer amorphous carbon, Nature 577 (7789) (2020) 199-203.
[37] Y. Qiu, S. Ali, G. Lan, H. Tong, J. Fan, H. Liu, B. Li, W. Han, H. Tang, H. Liu, Y. Li, Defect-rich activated carbons as active and stable metal-free catalyst for acetylene hydrochlorination, Carbon 146 (2019) 406–412.
[38] X.Y. Luo, H. Zheng, W.D. Lai, P. Yuan, S.W. Li, D. Li, Y. Chen, Defect engineering of carbons for energy conversion and storage applications, Energy Environ. Mater. 6 (3) (2023) 12402.
[39] P. Behra, P. Bonnissel-Gissinger, M. Alnot, R. Revel, J.J. Ehrhardt, XPS and XAS study of the sorption of Hg(II) onto pyrite, Langmuir 17 (13) (2001) 3970-3979.
[40] P.J. Lv, S. Chang, Q.Q. Hong, J. Mei, S.J. Yang, Outstanding performance of reproducible sulfureted Fe-Ti spinel for the centralized control of Hg (both gaseous Hg0 and aqueous Hg²⁺) emitted from coal-fired power plants with seawater flue gas desulfurization, Chem. Eng. J. 483 (2024) 148955.

编辑推荐 0

Metrics

阅读次数

全文

HTML			PDF

最新录用	在线预览	正式出版	最新录用	在线预览	正式出版
0	0	0	0	0	18

来源	本网站	其他网站

次数	4	14
比例	22%	78%

摘要

最新录用	在线预览	正式出版

0	0	20

来源	本网站	其他网站

次数	3	17
比例	15%	85%

Synergistic effect between nitrogen-doped sites and metal chloride for carbon supported extra-low mercury catalysts in acetylene hydrochlorination

Synergistic effect between nitrogen-doped sites and metal chloride for carbon supported extra-low mercury catalysts 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 0

Metrics

本文评价

[1]	Aleksey K. Sagidullin, Sergey S. Skiba, Tatyana P. Adamova, Andrey Y. Manakov. Investigation of the formation processes of CO₂ hydrate films on the interface of liquid carbon dioxide with humic acids solutions[J]. 中国化学工程学报, 2025, 79(3): 53-61.
[2]	Feng Gao, Sixiao Zhu, Liping Chang, Weiren Bao, Jinghong Ma, Junjie Liao. Kinetics of hydrogen sulfide removal from coke oven gas over faujasite zeolite: Experimental and modeling studies[J]. 中国化学工程学报, 2025, 78(2): 232-244.
[3]	Yilin Wang, Shijie Li, Jianhui Qi, Hui Li, Kuihua Han, Jianli Zhao. Preparation and characterization of high performance super activated carbon based on coupled coal/sargassum precursors[J]. 中国化学工程学报, 2025, 77(1): 81-92.
[4]	Lejun Wu, Jingbo Gao, Jing Li, Haibo Liu, Qiang Sun. The investigation of Gemini surfactant effects on CH₄ and CO₂ hydrates[J]. 中国化学工程学报, 2025, 77(1): 167-174.
[5]	Zhongxiang Ding, Wei Song, Tong Zhou, Weihua Cui, Changsong Wang. Thiourea crystal growth kinetics, mechanism and process optimization during cooling crystallization[J]. 中国化学工程学报, 2024, 73(9): 62-69.
[6]	Jinrong Zhong, Yu Tian, Yifei Sun, Li Wan, Yan Xie, Yujie Zhu, Changyu Sun, Guangjin Chen, Yuefei Zhang. The dual action of N₂ on morphology regulation and mass-transfer acceleration of CO₂ hydrate film[J]. 中国化学工程学报, 2024, 73(9): 120-129.
[7]	Bingying Han, Neng Shi, Mengjie Dong, Ye Liu, Runping Ye, Lixia Ling, Riguang Zhang, Baojun Wang. Theoretically predicted innovative palladium stripe dopingcobalt (1 1 1) surface with excellent catalytic performance for carbon monoxide oxidative coupling to dimethyl oxalate[J]. 中国化学工程学报, 2024, 73(9): 235-243.
[8]	Kai Ji, Zhencheng Ye, Feng Qian. Reaction network design and hybrid modeling of S Zorb[J]. 中国化学工程学报, 2024, 73(9): 301-310.
[9]	Maoqiao Xiang, Wenjun Ding, Qinghua Dong, Qingshan Zhu. Synthesis methods and powder quality of titanium monocarbide[J]. 中国化学工程学报, 2024, 72(8): 10-18.
[10]	Pengcheng Lu, Yaoyao Li, Jianjun Zhang, Yuchao Zhao, Qingqiang Wang, Ying Chen, Nan Jin, Xiugang Yu. Continuous synthesis of N, N-dicyanoethylaniline in microreactors: Reaction kinetics and process intensification[J]. 中国化学工程学报, 2024, 72(8): 95-105.
[11]	Yan Zhang, Xiangxue Zhang, Keng Sang, Wenyao Chen, Gang Qian, Jing Zhang, Xuezhi Duan, Xinggui Zhou, Weikang Yuan. Kinetics insights into size effects of carbon nanotubes’ growth and their supported platinum catalysts for 4,6-dinitroresorcinol hydrogenation[J]. 中国化学工程学报, 2024, 72(8): 133-140.
[12]	Tianxiao Huang, Binhang Yan. Evaluation and application of kinetic models for Cu-catalyzed acetylene hydrochlorination[J]. 中国化学工程学报, 2024, 72(8): 209-219.
[13]	Songshan Zhou, Yunhui Han, Rong Huang, Yin Huang, Qingyuan Dong, Haiyin Gang, Jinchuan Qin, Xi Yu, Xiangfei Zeng, Wenxing Cao, Jiqin Wang, Shaoqin Chen, Rong Wang, Mengjun Chen. Making waste profitable: Efficient recovery of metallic iron from jarosite residues[J]. 中国化学工程学报, 2024, 71(7): 66-76.
[14]	Mohammed Benjelloun, Youssef Miyah, Salma Ssouni, Soulaiman Iaich, Mohamed El-habacha, Salek Lagdali, Khadija Saka, El Mustafa Iboustaten, Abdelaziz Ait Addi, Sanae Lairini, Rabia Bouslamti. Capparis spinosa L waste activated carbon as an efficient adsorbent for crystal violet toxic dye removal: Modeling, optimization by experimental design, and ecological analysis[J]. 中国化学工程学报, 2024, 71(7): 283-302.
[15]	Yanli Qu, Peng Dong, Li Yang, Yuanyuan Yue, Haoliang Wang, Jingcai Cheng, Chao Yang. Synthesis of NaY zeolite from a submolten depolymerized perlite: Alkalinity effect and crystallization kinetics[J]. 中国化学工程学报, 2024, 70(6): 130-138.