Activation mechanisms on potassium hydroxide enhanced microstructures development of coke powder

doi:10.1016/j.cjche.2019.07.023

Chinese Journal of Chemical Engineering ›› 2020, Vol. 28 ›› Issue (1): 299-306.DOI: 10.1016/j.cjche.2019.07.023

• Energy, Resources and Environmental Technology • Previous Articles Next Articles

Activation mechanisms on potassium hydroxide enhanced microstructures development of coke powder

Xiaojing Chen¹, Huirong Zhang¹, Yanxia Guo¹, Yan Cao², Fangqin Cheng¹

1 State Environmental Protection Key Laboratory on Efficient Resource-utilization Techniques of Coal Waste, Institute of Resources and Environmental Engineering, Shanxi Collaborative Innovation Center of High Value-added Utilization of Coal-related Wastes, Shanxi University, Taiyuan 030006, China;
2 Institute for Combustion Science and Environmental Technology(ICSET), Western Kentucky University(WKU), Bowling Green, KY 42101, United States

Received:2018-10-14 Revised:2019-07-15 Online:2020-03-31 Published:2020-01-28
Contact: Huirong Zhang, Yanxia Guo, Yan Cao, Fangqin Cheng
Supported by:
Supported by the National Key R&D Plan (2016YFE0131100, 2017YFB0603101) and the Program for Sanjin Scholars of Shanxi Province and the Talent Training Program of Shanxi Joint Postgraduate Training Base (2016JD07).

Activation mechanisms on potassium hydroxide enhanced microstructures development of coke powder

Xiaojing Chen¹, Huirong Zhang¹, Yanxia Guo¹, Yan Cao², Fangqin Cheng¹

1 State Environmental Protection Key Laboratory on Efficient Resource-utilization Techniques of Coal Waste, Institute of Resources and Environmental Engineering, Shanxi Collaborative Innovation Center of High Value-added Utilization of Coal-related Wastes, Shanxi University, Taiyuan 030006, China;
2 Institute for Combustion Science and Environmental Technology(ICSET), Western Kentucky University(WKU), Bowling Green, KY 42101, United States

通讯作者: Huirong Zhang, Yanxia Guo, Yan Cao, Fangqin Cheng
基金资助:
Supported by the National Key R&D Plan (2016YFE0131100, 2017YFB0603101) and the Program for Sanjin Scholars of Shanxi Province and the Talent Training Program of Shanxi Joint Postgraduate Training Base (2016JD07).

Abstract

Abstract: Coke powder is expected to be an excellent raw material to produce activated carbon because of its high carbon content. Potassium hydroxide (KOH), as an effective activation agent, was reported to be effective in activating coke powder. However, the microstructures development in the coke powder and its mechanisms when KOH was applied were still unclear. In this study, effects of KOH on the microstructure activation of coke powder were investigated using the surface area and pore structure analyzer, scanning electron microscope (SEM) and thermogravimetry-differential scanning calorimetry-mass spectrometry (TG-DSC-MS), etc. Results revealed that the addition KOH at its lower ratio (mass ratios of KOH and coke powder in a range of 0.5 and 1) decreased the specific surface area and average lateral sizes, but sharply increased of the specific surface area to 132 m²·g^-1 and 355 m²·g^-1 and decreased of the space size of aromatic crystallites upon the further increase of the KOH addition amounts (ratios of KOH and coke powder in a range of 3 and 7), generating a number of new micropores and mesopores. The mechanisms study implied surface reactions between KOH and aliphatic hydrocarbon side chain and other carbon functional groups of the coke powder to destruct aromatic crystallites in one dimension and broaden pores at lower KOH addition. In the activation process, KOH was decomposed to be more active components, which can be rapidly destruct the aromatic layers in spatial scope to form developed porous carbon structures within coke powder at higher KOH addition.

Key words: Activated carbon, Coke powder, Activation, Structure, Potassium hydroxide

摘要： Coke powder is expected to be an excellent raw material to produce activated carbon because of its high carbon content. Potassium hydroxide (KOH), as an effective activation agent, was reported to be effective in activating coke powder. However, the microstructures development in the coke powder and its mechanisms when KOH was applied were still unclear. In this study, effects of KOH on the microstructure activation of coke powder were investigated using the surface area and pore structure analyzer, scanning electron microscope (SEM) and thermogravimetry-differential scanning calorimetry-mass spectrometry (TG-DSC-MS), etc. Results revealed that the addition KOH at its lower ratio (mass ratios of KOH and coke powder in a range of 0.5 and 1) decreased the specific surface area and average lateral sizes, but sharply increased of the specific surface area to 132 m²·g^-1 and 355 m²·g^-1 and decreased of the space size of aromatic crystallites upon the further increase of the KOH addition amounts (ratios of KOH and coke powder in a range of 3 and 7), generating a number of new micropores and mesopores. The mechanisms study implied surface reactions between KOH and aliphatic hydrocarbon side chain and other carbon functional groups of the coke powder to destruct aromatic crystallites in one dimension and broaden pores at lower KOH addition. In the activation process, KOH was decomposed to be more active components, which can be rapidly destruct the aromatic layers in spatial scope to form developed porous carbon structures within coke powder at higher KOH addition.

关键词: Activated carbon, Coke powder, Activation, Structure, Potassium hydroxide

Xiaojing Chen, Huirong Zhang, Yanxia Guo, Yan Cao, Fangqin Cheng. Activation mechanisms on potassium hydroxide enhanced microstructures development of coke powder[J]. Chinese Journal of Chemical Engineering, 2020, 28(1): 299-306.

Xiaojing Chen, Huirong Zhang, Yanxia Guo, Yan Cao, Fangqin Cheng. Activation mechanisms on potassium hydroxide enhanced microstructures development of coke powder[J]. 中国化学工程学报, 2020, 28(1): 299-306.

References

[1] H. Luo, P. Yang, F. Zhang, Preparation and electrochemical properties of coke powder activated carbon based electrode materials, J. Mater. Sci. Mater. Electron. 24(2013) 586-593.
[2] J. Feng, P. Chen, Z. Shi, T. Li, S. Shen, CO₂-COG reforming over ni/coke powder catalyst, Nat. Gas Chem. Ind. 42(2017) 52-57.
[3] M. Zheng, S. Yan, X. He, High value-added-value utilization of coke fine, Fuel Chem. Processes 38(2007) 21-23.
[4] Y. Tian, X. Lan, H. Ma, X. Zhao, Research progress in preparation of activated carbon from coke powder and its application, Coal Technol. 29(2010) 163-165.
[5] C. Liu, H. Luo, G. Gou, The shaping technology of powdered coke, Techniques Equipment Enviro. Poll. Cont. 3(2002) 73-75.
[6] X. Py, V. Goetz, G. Plantard, Activated carbons textural optimization for gas storage processes, Chem. Eng. Process. 47(2008) 308-315.
[7] G. Tzvetkov, S. Mihaylova, K. Stoitchkova, P. Tzvetkov, T. Spassov, Mechanochemical and chemical activation of lignocellulosic material to prepare powdered activated carbons for adsorption applications, Powder Technol. 299(2016) 41-50.
[8] H. Sayğılı, F. Güzel, Novel and sustainable precursor for high-quality activated carbon preparation by conventional pyrolysis:optimization of produce conditions and feasibility in adsorption studies, Adv. Powder Technol. 29(2018) 726-736.
[9] L. Liu, Z. Liu, J. Yang, Z. Huang, Z. Liu, Effect of preparation conditions on the properties of a coal-derived activated carbon honeycomb monolith, Carbon 45(2007) 2836-2842.
[10] S. Wong, Y. Lee, N. Ngadi, I.M. Inuwa, N.B. Mohamed, Synthesis of activated carbon from spent tea leaves for aspirin removal, Chin. J. Chem. Eng. 26(2018) 1003-1011.
[11] Y. Li, Y. Li, L. Li, X. Shi, Z. Wang, Preparation and analysis of activated carbon from sewage sludge and corn stalk, Adv. Powder Technol. 27(2016) 684-691.
[12] F. Shen, S. Gupta, Y. Liu, Q. Meng, D. French, V. Sahajwalla, Effect of reaction conditions on coke tumbling strength, carbon structure and mineralogy, Fuel 111(2013) 223-228.
[13] R. Gupta, Advanced coal characterization:a review, Energy Fuel 21(2007) 451-460.
[14] S. Pusz, M. Krzesińska, Ł. Smędowski, J. Majewska, B. Pilawa, B. Kwiecińska, Changes in a coke structure due to reaction with carbon dioxide, Int. J. Coal Geol. 81(2010) 287-292.
[15] C. Zhang, W. Song, Q. Ma, L. Xie, X. Zhang, H. Guo, Enhancement of CO₂ capture on biomass-based carbon from black locust by KOH activation and ammonia modification, Energy Fuel 30(2016) 4181-4190.
[16] P. Nowicki, J. Kazmierczak, R. Pietrzak, Comparison of physicochemical and sorption properties of activated carbons prepared by physical and chemical activation of cherry stones, Powder Technol. 269(2015) 312-319.
[17] N.A. Rashidi, S. Yusup, A review on recent technological advancement in the activated carbon production from oil palm wastes, Chem. Eng. J. 314(2017) 277-290.
[18] S. Li, K. Han, J. Li, M. Li, C. Lu, Preparation and characterization of super activated carbon produced from gulfweed by KOH activation, Microporous Mesoporous Mater. 243(2017) 291-300.
[19] S.Y. Sawant, K. Munusamy, R.S. Somani, M. John, B.L. Newalkar, H.C. Bajaj, Precursor suitability and pilot scale production of super activated carbon for greenhouse gas adsorption and fuel gas storage, Chem. Eng. J. 315(2017) 415-425.
[20] X. Zhang, Z. Zou, Study on the preparation of activated carbon by coke powder, Wuhan Iron Steel Corp. Technol. (1998) 1-8.
[21] H. Luo, H. Feng, Y. Wang, D. Zhang, Z. Xia, Preparation of activated carbon from coke powder and its application, Environ. Prot. Chem. Ind. 27(2007) 481-483.
[22] B. Sakintuna, Y. Yürüm, S. Çetinkaya, Evolution of carbon microstructures during the pyrolysis of Turkish Elbistan lignite in the temperature range 700-1000℃, Energy Fuel 18(2004) 883-888.
[23] Z. Wan, W. Wu, W. Chen, H. Yang, D. Zhang, Direct synthesis of hierarchical ZSM-5 zeolite and its performance in catalyzing methanol to gasoline conversion, Ind. Eng. Chem. Res. 53(2014) 19471-19478.
[24] M. Zhang, J. Fan, K. Chi, A. Duan, Z. Zhao, X. Meng, H. Zhang, Synthesis, characterization, and catalytic performance of NiMo catalysts supported on different crystal alumina materials in the hydrodesulfurization of diesel, Fuel Process. Technol. 156(2017) 446-453.
[25] M.A. Lillo-Ródenas, J. Juan-Juan, D. Cazorla-Amorós, A. Linares-Solano, About reactions occurring during chemical activation with hydroxides, Carbon 42(2004) 1371-1375.
[26] C. Lu, S. Xu, Y. Gan, S. Liu, C. Liu, Effect of pre-carbonization of petroleum cokes on chemical activation process with KOH, Carbon 43(2005) 2295-2301.
[27] M. Yu, J. Li, L. Wang, KOH-activated carbon aerogels derived from sodium carboxymethyl cellulose for high-performance supercapacitors and dye adsorption, Chem. Eng. J. 310(2017) 300-306.
[28] N. Yoshizawa, K. Maruyama, Y. Yamada, E. Ishikawa, M. Kobayashi, Y. Toda, M. Shiraishi, XRD evaluation of KOH activation process and influence of coal rank, Fuel 81(2002) 1717-1722.
[29] Y. Zhang, X. Kang, J. Tan, R.L. Frost, Influence of calcination and acidification on structural characterization of Anyang anthracites, Energy Fuel 27(2013) 7191-7197.
[30] D. Liu, J. Gao, S. Wu, Y. Qin, Effect of char structures caused by varying the amount of FeCl₃ on the pore development during activation, RSC Adv. 6(2016) 87478-87485.
[31] W.A. Khanday, F. Marrakchi, M. Asif, B.H. Hameed, Mesoporous zeolite-activated carbon composite from oil palm ash as an effective adsorbent for methylene blue, J. Taiwan Inst. Chem. Eng. 70(2017) 32-41.
[32] T.A. Saleh, A. Sarı, M. Tuzen, Effective adsorption of antimony(III) from aqueous solutions by polyamide-graphene composite as a novel adsorbent, Chem. Eng. J. 307(2017) 230-238.
[33] D. Özçimen, A. Ersoy-Meriçboyu, Characterization of biochar and bio-oil samples obtained from carbonization of various biomass materials, Renew. Energy 35(2010) 1319-1324.
[34] W. Li, Y. Zhu, Structural characteristics of coal vitrinite during pyrolysis, Energy Fuel 28(2014) 3645-3654.
[35] C. Lu, S. Xu, C. Liu, The role of K₂CO₃ during the chemical activation of petroleum coke with KOH, J. Anal. Appl. Pyrolysis 87(2010) 282-287.
[36] B. Xing, L. Chen, C. Zhang, G. Huang, H. Guo, B. Xu, M. Ma, Activation mechanism of lignite-based activated carbon prepared by KOH activation, J. China Univ. Min. Technol. 43(2014) 1038-1045.
[37] J. DíAz-Terán, D.M. Nevskaia, J.L.G. Fierro, A.J. López-Peinado, A. Jerez, Study of chemical activation process of a lignocellulosic material with KOH by XPS and XRD, Microporous Mesoporous Mater. 60(2003) 173-181.
[38] X. Dai, X. Liu, L. Qian, Z. Yan, J. Zhang, A novel method to synthesize super-activated carbon for natural gas adsorptive storage, J. Porous. Mater. 13(2006) 399-405.
[39] S. Chun, J.F. Whitacre, Formation of micro/mesopores during chemical activation in tailor-made nongraphitic carbons, Microporous Mesoporous Mater. 251(2017) 34-41.

Activation mechanisms on potassium hydroxide enhanced microstructures development of coke powder

Activation mechanisms on potassium hydroxide enhanced microstructures development of coke powder

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Yifan Jiang, Bingqi Xie, Jisong Zhang. Highly reactive and reusable heterogeneous activated carbons-based palladium catalysts for Suzuki-Miyaura reaction [J]. Chinese Journal of Chemical Engineering, 2023, 60(8): 165-172.
[2]	Lijuan Zhao, Zhe Tan, Xiaoguang Zhang, Qijun Zhang, Wei Wang, Qiang Deng, Jie Ma, De'an Pan. Research on process modeling and simulation of spent lead paste desulfurization enhanced reactor [J]. Chinese Journal of Chemical Engineering, 2023, 60(8): 293-303.
[3]	Haixiang Liu, Jun Zhang, Chunlei Dong, Gang Zhu, Guanben Du, Shuduan Deng. Synthesis, performance and structure characterization of glyoxal-monomethylolurea-melamine (G-MMU-M) co-condensed resin [J]. Chinese Journal of Chemical Engineering, 2023, 59(7): 92-104.
[4]	Minjie Shi, Nianting Chen, Yue Zhao, Cheng Yang, Chao Yan. Facile wet-chemical fabrication of bi-functional coordination polymer nanosheets for high-performance energy storage and anti-corrosion engineering [J]. Chinese Journal of Chemical Engineering, 2023, 59(7): 118-127.
[5]	Chen Chen, Qiong Tang, Hong Xu, Mingxing Tang, Xuekuan Li, Lei Liu, Jinxiang Dong. Alkyl-tetralin base oils synthesized from coal-based chemicals and evaluation of their lubricating properties [J]. Chinese Journal of Chemical Engineering, 2023, 58(6): 20-28.
[6]	Kai Xue, Yanchun Xue, Jing Wang, Shuya Zhang, Xingmei Guo, Xiangjun Zheng, Fu Cao, Qinghong Kong, Junhao Zhang, Zhong Jin. KOH-assisted aqueous synthesis of ZIF-67 with high-yield and its derived cobalt selenide/carbon composites for high-performance Li-ion batteries [J]. Chinese Journal of Chemical Engineering, 2023, 57(5): 214-223.
[7]	Shiyong Xing, Yan Cui, Tiefeng Wang, Jinwei He, Minghan Han. Elucidating the effect of oxides on the zeolite catalyzed alkylation of benzene with 1-dodecene [J]. Chinese Journal of Chemical Engineering, 2023, 56(4): 126-135.
[8]	Lianlian Zhao, Fufu Di, Xiaonan Wang, Sumbal Farid, Suzhen Ren. Constructing a hollow core-shell structure of RuO₂ wrapped by hierarchical porous carbon shell with Ru NPs loading for supercapacitor [J]. Chinese Journal of Chemical Engineering, 2023, 55(3): 93-100.
[9]	Zhihao Zhu, Ying Sun, Haijun Yu, Meng Li, Xingming Jie, Guodong Kang, Yiming Cao. Effect of polytetrafluoroethylene hollow fiber microstructure on formaldehyde carbonylation performance in membrane contactor [J]. Chinese Journal of Chemical Engineering, 2023, 55(3): 148-155.
[10]	Da Ke, Minjia Wang, Jiancheng Ruan, Xinzhi Chen, Shaodong Zhou. Efficient, continuous oxidation of durene to pyromellitic dianhydride mediated by a V-Ti-P ternary catalyst: The remarkable doping effect [J]. Chinese Journal of Chemical Engineering, 2023, 55(3): 156-164.
[11]	Zhenzhou Ma, Xu Hou, Bochong Chen, Liu Zhao, Enxian Yuan, Tingting Cui. Experiment and modeling of coke formation and catalyst deactivation in n-heptane catalytic cracking over HZSM-5 zeolites [J]. Chinese Journal of Chemical Engineering, 2023, 55(3): 165-172.
[12]	Qiongna Xiao, Yuyan Jiang, Weiqiang Yuan, Jingjing Chen, Haohong Li, Huidong Zheng. Styrene epoxidation catalyzed by polyoxometalate/quaternary ammonium phase transfer catalysts: The effect of cation size and catalyst deactivation mechanism [J]. Chinese Journal of Chemical Engineering, 2023, 55(3): 192-201.
[13]	Yu Wang, Qunfeng Zhang, Xinlei Liu, Junqi Weng, Guanghua Ye, Xinggui Zhou. Probing deactivation by coking in catalyst pellets for dry reforming of methane using a pore network model [J]. Chinese Journal of Chemical Engineering, 2023, 55(3): 293-303.
[14]	Jianhui Zhou, Guohao Du, Jianfeng Hu, Xin Lai, Shan Liu, Zhengguo Zhang. The establishment of Boron nitride@sodium alginate foam/polyethyleneglycol composite phase change materials with high thermal conductivity, shape stability, and reusability [J]. Chinese Journal of Chemical Engineering, 2023, 54(2): 11-21.
[15]	Mengge Shang, Jing Zhang, Jinqiang Sun, Shimo Yu, Feng Hua, Xiaoxu Xuan, Xun Sun, Serguei Filatov, Xibin Yi. Amine-functionalized mesoporous UiO-66 aerogel for CO₂ adsorption [J]. Chinese Journal of Chemical Engineering, 2023, 54(2): 36-43.