Pore forming mechanism and ethyl acetate adsorption performance of coal-biomass based activated carbon

doi:10.16085/j.issn.1000-6613.2021-0557

Abstract

Abstract:

Activated carbon was prepared from the mixture of Heishan coal powder and biomass by one step rapid pyrolysis activation method with CO₂ as activation atmosphere. The effects of different mass ratio, activation temperature and CO₂ concentration on the specific surface area of activated carbon were discussed. The properties of activated carbon were characterized by N₂ adsorption (BET), scanning electron microscopy (SEM), Raman spectroscopy (Raman) and infrared spectroscopy (FTIR). The optimum conditions for preparation of activated carbon were determined as follows: when the activation temperature was 900℃, the mass ratio was 1, the concentration of CO₂ was 30%, and the activation time was 120min, the specific surface area and pore volume of activated carbon were the largest, which were 910m²/g and 0.39cm³/g, respectively. The adsorption capacity of activated carbon was verified by the adsorption capacity of ethyl acetate, and the maximum cumulative adsorption capacity was 766.51mg/g.

Key words: coal, biomass, activation, activated carbon, adsorption

摘要：

以CO₂为活化气氛，通过一步快速热解活化法从黑山煤粉与生物质混合物中制取活性炭。讨论了不同质量比率、活化温度和CO₂浓度对活性炭比表面积的影响。通过N₂吸附（BET）、扫描电镜（SEM）、拉曼光谱（Raman）和红外光谱（FTIR）对活性炭的性能进行了表征。确定了制备活性炭的最佳条件为活化温度900℃、质量比1、CO₂体积分数30%、活化时间120min时，活性炭的比表面积和孔容最大，分别为901m²/g和0.39cm³/g。最后，用乙酸乙酯吸附量验证了其吸附性能，最大累积吸附量为766.51mg/g。

关键词: 煤, 生物质, 活化, 活性炭, 吸附

CLC Number:

JIN Chunjiang, WANG Luyuan, CHEN Huimin, CHENG Xingxing, ZHANG Xingyu, SUN Rongfeng, GENG Wenguang, QIU Hongbo. Pore forming mechanism and ethyl acetate adsorption performance of coal-biomass based activated carbon[J]. Chemical Industry and Engineering Progress, 2021, 40(S2): 162-175.

金春江, 王鲁元, 陈惠敏, 程星星, 张兴宇, 孙荣峰, 耿文广, 仇洪波. 煤-生物质基活性炭成孔机制及其吸附乙酸乙酯的性能[J]. 化工进展, 2021, 40(S2): 162-175.

Figures/Tables 21

References 50

1	CHINGOMBE P, SAHA B, WAKEMAN R J. Surface modification and characterisation of a coal-based activated carbon[J]. Carbon, 2005, 43(15): 3132-3143.
2	LI L, QUINLIVAN P A, KNAPPE D R U. Effects of activated carbon surface chemistry and pore structure on the adsorption of organic contaminants from aqueous solution[J]. Carbon, 2002, 40(12): 2085-2100.
3	LI L, LIU S Q, LIU J X. Surface modification of coconut shell based activated carbon for the improvement of hydrophobic VOC removal[J]. Journal of Hazardous Materials, 2011, 192(2): 683-690.
4	ANIA C O, PARRA J B, PIS J J. Effect of texture and surface chemistry on adsorptive capacities of activated carbons for phenolic compounds removal[J]. Fuel Processing Technology, 2002, 77/78: 337-343.
5	AN D H, SUN X F, CHENG X X, et al. Investigation on mercury removal and recovery based on enhanced adsorption by activated coke[J]. Journal of Hazardous Materials, 2020, 384: 121354.
6	PUREVSUREN B, LIOU Y H, DAVAAJAV Y, et al. Investigation of adsorption of methylene blue from aqueous phase onto coal-based activated carbons[J]. Journal of the Chinese Institute of Engineers, 2017, 40(4): 355-360.
7	PREMARATHNA K S D, RAJAPAKSHA A U, SARKAR B, et al. Biochar-based engineered composites for sorptive decontamination of water: a review[J]. Chemical Engineering Journal, 2019, 372: 536-550.
8	PENA J, VILLOT A, GERENTE C. Pyrolysis chars and physically activated carbons prepared from buckwheat husks for catalytic purification of syngas[J]. Biomass and Bioenergy, 2020, 132: 105435.
9	张振, 王涛, 马春元, 等. 低氧快速热解过程中氧气体积分数对活性焦孔隙结构的影响[J]. 煤炭学报, 2014, 39(10): 2107-2113.
	ZHANG Zhen, WANG Tao, MA Chunyuan, et al. Effect of oxygen concentration on activated char pore structure during low oxygen fast pyrolysis[J]. Journal of China Coal Society, 2014, 39(10): 2107-2113.
10	史蕊, 李依丽, 尹晶, 等. 玉米秸秆活性炭的制备及其吸附动力学研究[J]. 环境工程学报, 2014, 8(8): 3428-3432.
	SHI Rui, LI Yili, YIN Jing, et al. Preparation of activated carbon from corn straw and research of adsorption kinetics[J]. Chinese Journal of Environmental Engineering, 2014, 8(8): 3428-3432.
11	LI Z, LIANG Q, YANG C, et al. Convenient preparation of nitrogen-doped activated carbon from Macadamia nutshell and its application in supercapacitor[J]. Journal of Materials Science: Materials in Electronics, 2017, 28(18): 13880-13887.
12	FU J P, ZHOU B X, ZHANG Z, et al. One-step rapid pyrolysis activation method to prepare nanostructured activated coke powder[J]. Fuel, 2020, 262: 116514.
13	WANG L J, SUN F, GAO J H, et al. Adjusting the porosity of coal-based activated carbons based on a catalytic physical activation process for gas and liquid adsorption[J]. Energy & Fuels, 2018, 32(2): 1255-1264.
14	MENG F R, XIAO K M, LI X C, et al. Characteristics of chars prepared by low-temperature co-pyrolysis of lignite and biomass[J]. Combustion Science and Technology, 2020, 192(3): 513-530.
15	陈璐, 张秀惠, 李向尧, 等. 二氧化碳活化制备杏壳活性炭及对其孔径影响[J]. 广州化工, 2019, 47(20): 87-89, 102.
	CHEN Lu, ZHANG Xiuhui, LI Xiangyao, et al. Preparation of apricot shell activated carbon by carbon dioxide activation and effect on its pore size[J]. Guangzhou Chemical Industry, 2019, 47(20): 87-89, 102.
16	李大伟, 田原宇, 郝俊辉, 等. 炭活化一步法制备豆渣基极微孔活性炭[J]. 农业工程学报, 2015, 31(19): 309-314.
	LI Dawei, TIAN Yuanyu, HAO Junhui, et al. Preparation of N-doped ultramicropore-containing active carbons from waste soybean dreg by one-step carbonization/activation[J]. Transactions of the Chinese Society of Agricultural Engineering, 2015, 31(19): 309-314.
17	FU J P, JIN C J, ZHANG J R, et al. Pore structure and VOCs adsorption characteristics of activated coke powders derived via one-step rapid pyrolysis activation method[J]. Asia-Pacific Journal of Chemical Engineering, 2020, 15(5): e2503.
18	张东东, 易川, 金哲, 等. 活性炭吸附乙酸乙酯的动态吸附和动力学研究[J]. 环境科学与技术, 2018, 41(4): 17-21, 115.
	ZHANG Dongdong, YI Chuan, JIN Zhe, et al. Dynamic adsorption and kinetics of activated carbon adsorbing ethyl acetate[J]. Environmental Science & Technology, 2018, 41(4): 17-21, 115.
19	解强, 姚鑫, 杨川, 等. 压块工艺条件下煤种对活性炭孔结构发育的影响[J]. 煤炭学报, 2015, 40(1): 196-202.
	XIE Qiang, YAO Xin, YANG Chuan, et al. Effect of coal type on pore structure development of activated carbon under briquetting process[J]. Journal of China Coal Society, 2015, 40(1): 196-202.
20	MAO Y B, DONG L, DONG Y P, et al. Fast co-pyrolysis of biomass and lignite in a micro fluidized bed reactor analyzer[J]. Bioresource Technology, 2015, 181: 155-162.
21	程松, 张利波, 夏洪应, 等. 响应曲面法优化CO₂活化制备夏威夷坚果壳基活性炭[J]. 环境工程学报, 2015, 9(9): 4495-4502.
	CHENG Song, ZHANG Libo, XIA Hongying, et al. Preparation of activated carbon from Hawaii nut shell via CO₂ activation using response surface methodology[J]. Chinese Journal of Environmental Engineering, 2015, 9(9): 4495-4502.
22	LI S D, CHEN X L, WANG L, et al. Co-pyrolysis behaviors of saw dust and Shenfu coal in drop tube furnace and fixed bed reactor[J]. Bioresource Technology, 2013, 148: 24-29.
23	TOPTAS A, YILDIRIM Y, DE DUMAN G, et al. Combustion behavior of different kinds of torrefied biomass and their blends with lignite[J]. Bioresource Technology, 2015, 177: 328-336.
24	WU Z Q, LI Y W, XU D H, et al. Co-pyrolysis of lignocellulosic biomass with low-quality coal: optimal design and synergistic effect from gaseous products distribution[J]. Fuel, 2019, 236: 43-54.
25	曲健林, 韩敏, 张秀丽, 等. 棉杆活性炭负载Co-B催化剂催化硼氢化钠水解制氢的性能[J]. 化工学报, 2015, 66(1): 105-113.
	QU Jianlin, HAN Min, ZHANG Xiuli, et al. Hydrogen generation by sodium borohydride hydrolysis on Co-B catalysts supported on cotton stalk-based activated carbon[J]. CIESC Journal, 2015, 66(1): 105-113.
26	王成勇, 石开仪, 邓红江, 等. 煤岩显微组分对活性炭表面性质的协同效应机理[J]. 煤炭转化, 2020, 43(5): 82-87.
	WANG Chengyong, SHI Kaiyi, DENG Hongjiang, et al. Synergistic mechanism of coal macerals on the surface properties of activated carbon[J]. Coal Conversion, 2020, 43(5): 82-87.
27	刘冬冬, 高继慧, 吴少华, 等. FeCl₃和空气预氧化对煤焦结构及活化过程中孔隙生成的影响[J]. 煤炭学报, 2017, 42(4): 1034-1042.
	LIU Dongdong, GAO Jihui, WU Shaohua, et al. Effects of FeCl₃ and air pre-oxidation on char structure and pore development during activation[J]. Journal of China Coal Society, 2017, 42(4): 1034-1042.
28	YOON I H, MENG X G, WANG C, et al. Perchlorate adsorption and desorption on activated carbon and anion exchange resin[J]. Journal of Hazardous Materials, 2009, 164(1): 87-94.
29	LI X J, HAYASHI J I, LI C Z. FT-Raman spectroscopic study of the evolution of char structure during the pyrolysis of a Victorian brown coal[J]. Fuel, 2006, 85(12/13): 1700-1707.
30	刘冬冬, 高继慧, 吴少华, 等. 闪热解对烟煤焦结构及活化过程孔隙生成的影响[J]. 煤炭学报, 2016, 41(11): 2867-2875.
	LIU Dongdong, GAO Jihui, WU Shaohua, et al. Effect of flash pyrolysis on bituminous char structure and pore development during activation[J]. Journal of China Coal Society, 2016, 41(11): 2867-2875.
31	廖希凯, 满小媛, 宁寻安, 等. 炭化温度对废旧布袋制备活性炭性能的影响及其表征[J]. 环境科学学报, 2015, 35(11): 3775-3780.
	LIAO Xikai, MAN Xiaoyuan, NING Xun’an, et al. Effects of carbonization temperature on characteristics of activated carbon from waste filter bag[J]. Acta Scientiae Circumstantiae, 2015, 35(11): 3775-3780.
32	蔡政汉, 林咏梅, 陈翠霞, 等. 椰壳碎炭制备高强度柱状颗粒活性炭试验[J]. 林业工程学报, 2016, 1(4): 74-79.
	CAI Zhenghan, LIN Yongmei, CHEN Cuixia, et al. Preparation of high strength granular activated carbon with powder coconut shell charcoal[J]. Journal of Forestry Engineering, 2016, 1(4): 74-79.
33	SHANG T X, REN R Q, ZHU Y M, et al. Oxygen- and nitrogen-co-doped activated carbon from waste particleboard for potential application in high-performance capacitance[J]. Electrochimica Acta, 2015, 163: 32-40.
34	郭秉霖, 侯彩霞, 樊丽华, 等. 萃取温度对无灰煤结构及煤基活性炭电化学性能的影响[J]. 无机化学学报, 2018, 34(9): 1615-1624.
	GUO Binglin, HOU Caixia, FAN Lihua, et al. Effect of extraction temperature on hyper-coal structure and electrochemistry of coal-based activated carbon[J]. Chinese Journal of Inorganic Chemistry, 2018, 34(9): 1615-1624.
35	刘伟, 李立清, 姚小龙, 等. 活性炭孔隙结构在其丙酮吸附中的作用[J]. 中南大学学报(自然科学版), 2012, 43(4): 1574-1583.
	LIU Wei, LI Liqing, YAO Xiaolong, et al. Role of pore structure of activated carbon in adsorption for acetone[J]. Journal of Central South University (Science and Technology), 2012, 43(4): 1574-1583.
36	LIEVENS C, MOURANT D, HE M, et al. An FT-IR spectroscopic study of carbonyl functionalities in bio-oils[J]. Fuel, 2011, 90(11): 3417-3423.
37	姜可茂, 吴琪琳. 高比表面积生物质活性炭的制备及其电化学性能研究[J]. 功能材料, 2017, 48(11): 11153-11156, 11160.
	JIANG Kemao, WU Qilin. Preparation and electrochemical performance of activated carbon with high specific surface area[J]. Journal of Functional Materials, 2017, 48(11): 11153-11156, 11160.
38	YANG J, QIU K Q. Preparation of activated carbons from walnut shells via vacuum chemical activation and their application for methylene blue removal[J]. Chemical Engineering Journal, 2010, 165(1): 209-217.
39	LAINE J, CALAFAT A, LABADY M. Preparation and characterization of activated carbons from coconut shell impregnated with phosphoric acid[J]. Carbon, 1989, 27(2): 191-195.
40	李大伟, 朱锡锋. CO₂活化-碱液沸煮制备高介孔率的稻壳活性炭[J]. 新型炭材料, 2013, 28(5): 363-368.
	LI Dawei, ZHU Xifeng. Rice husk-based activated carbons with high mesoporosity prepared by a combination of CO₂ activation and boiling in an alkaline solution[J]. New Carbon Materials, 2013, 28(5): 363-368.
41	KIM Y, OH J I, VITHANAGE M, et al. Modification of biochar properties using CO₂[J]. Chemical Engineering Journal, 2019, 372: 383-389.
42	CHEN X J, GUO Y X, CUI J L, et al. Activated carbon preparation with the addition of coke-making by-product—coke powder: texture evolution and mechanism[J]. Journal of Cleaner Production, 2019, 237: 117812.
43	邢宝林, 黄光许, 谌伦建, 等. 高品质低阶煤基活性炭的制备与表征[J]. 煤炭学报, 2013, 38(S1): 217-222.
	XING Baolin, HUANG Guangxu, CHEN Lunjian, et al. Preparation and characterization of high quality low-rank coal based activated carbon[J]. Journal of China Coal Society, 2013, 38(S1): 217-222.
44	张小兵, 郇璇, 张航, 等. 不同煤体结构煤基活性炭微观结构与甲烷吸附性能[J]. 中国矿业大学学报, 2017, 46(1): 155-161.
	ZHANG Xiaobing, HUAN Xuan, ZHANG Hang, et al. Microstructure and methane adsorption of coal-based activated carbons with different coal body structures[J]. Journal of China University of Mining & Technology, 2017, 46(1): 155-161.
45	CASTRO-MUÑIZ A, SUÁREZ-GARCÍA F, MARTÍNEZ-ALONSO A, et al. Activated carbon fibers with a high content of surface functional groups by phosphoric acid activation of PPTA[J]. Journal of Colloid and Interface Science, 2011, 361(1): 307-315.
46	杨坤彬, 彭金辉, 夏洪应, 等. CO₂活化制备椰壳基活性炭[J]. 炭素技术, 2010, 29(1): 20-23.
	YANG Kunbin, PENG Jinhui, XIA Hongying, et al. Preparation of coconut shells-based activated carbons with CO₂ activation[J]. Carbon Techniques, 2010, 29(1): 20-23.
47	YI S, HE X M, LIN H T, et al. Synergistic effect in low temperature co-pyrolysis of sugarcane bagasse and lignite[J]. Korean Journal of Chemical Engineering, 2016, 33(10): 2923-2929.
48	KILDUFF J E, KARANFIL T, WEBER W J. Competitive interactions among components of humic acids in granular activated carbon adsorption systems: effects of solution chemistry[J]. Environmental Science & Technology, 1996, 30(4): 1344-1351.
49	李立清, 宋剑飞, 孙政, 等. 三种VOCs物性对其在活性炭上吸附行为的影响[J]. 化工学报, 2011, 62(10): 2784-2790.
	LI Liqing, SONG Jianfei, SUN Zheng, et al. Effects of properties of three VOCs on activated carbon adsorption[J]. CIESC Journal, 2011, 62(10): 2784-2790.
50	RODRÍGUEZ-REINOSO F, MOLINA-SABIO M, GONZÁLEZ M T. The use of steam and CO₂ as activating carbons[J]. Carbon, 1995, 33(1):15-23.

原料	工业分析/%				元素分析/%
原料	水分	灰分	挥发分	固定碳	碳	氢	氮	硫	氧	水分
黑山煤	3.68	35.32	38.83	5.36	83.46	54.10	4.84	30.7	0.53	0.79
野生桃核	6.84	71.43	80.32	4.23	17.5	44.7	5.08	37.74	0.88	0.53

原料	工业分析/%				元素分析/%
原料	水分	灰分	挥发分	固定碳	碳	氢	氮	硫	氧	水分
黑山煤	3.68	35.32	38.83	5.36	83.46	54.10	4.84	30.7	0.53	0.79
野生桃核	6.84	71.43	80.32	4.23	17.5	44.7	5.08	37.74	0.88	0.53

可变条件	取值
煤与生物质质量比	0.2	0.5	1	1.5
温度/℃	600	700	800	900
CO₂含量/%	10	20	30

可变条件	取值
煤与生物质质量比	0.2	0.5	1	1.5
温度/℃	600	700	800	900
CO₂含量/%	10	20	30

[1]	CUI Shoucheng, XU Hongbo, PENG Nan. Simulation analysis of two MOFs materials for O₂/He adsorption separation [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 382-390.
[2]	CHEN Chongming, CHEN Qiu, GONG Yunqian, CHE Kai, YU Jinxing, SUN Nannan. Research progresses on zeolite-based CO₂ adsorbents [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 411-419.
[3]	XU Chunshu, YAO Qingda, LIANG Yongxian, ZHOU Hualong. Research progress on functionalization strategies of covalent organic frame materials and its adsorption properties for Hg(Ⅱ) and Cr(Ⅵ) [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 461-478.
[4]	GU Yongzheng, ZHANG Yongsheng. Dynamic behavior and kinetic model of Hg⁰ adsorption by HBr-modified fly ash [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 498-509.
[5]	GUO Qiang, ZHAO Wenkai, XIAO Yonghou. Numerical simulation of enhancing fluid perturbation to improve separation of dimethyl sulfide/nitrogen via pressure swing adsorption [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 64-72.
[6]	WANG Shengyan, DENG Shuai, ZHAO Ruikai. Research progress on carbon dioxide capture technology based on electric swing adsorption [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 233-245.
[7]	LUO Cheng, FAN Xiaoyong, ZHU Yonghong, TIAN Feng, CUI Louwei, DU Chongpeng, WANG Feili, LI Dong, ZHENG Hua’an. CFD simulation of liquid distribution in different distributors in medium-low temperature coal tar hydrogenation reactor [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4538-4549.
[8]	LAI Shini, JIANG Lixia, LI Jun, HUANG Hongyu, KOBAYASHI Noriyuki. Research progress of ammonia blended fossil fuel [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4603-4615.
[9]	CHENG Tao, CUI Ruili, SONG Junnan, ZHANG Tianqi, ZHANG Yunhe, LIANG Shijie, PU Shi. Analysis of impurity deposition and pressure drop increase mechanisms in residue hydrotreating unit [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4616-4627.
[10]	ZHU Jie, JIN Jing, DING Zhenghao, YANG Huipan, HOU Fengxiao. Modification of CaSO₄ oxygen carrier by Zhundong coal ash in chemical looping gasification and its mechanism [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4628-4635.
[11]	WANG Jingang, ZHANG Jianbo, TANG Xuejiao, LIU Jinpeng, JU Meiting. Research progress on modification of Cu-SSZ-13 catalyst for denitration of automobile exhaust gas [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4636-4648.
[12]	GE Yafen, SUN Yu, XIAO Peng, LIU Qi, LIU Bo, SUN Chengying, GONG Yanjun. Research progress of zeolite for VOCs removal [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4716-4730.
[13]	YANG Ying, HOU Haojie, HUANG Rui, CUI Yu, WANG Bing, LIU Jian, BAO Weiren, CHANG Liping, WANG Jiancheng, HAN Lina. Coal tar phenol-based carbon nanosphere prepared by Stöber method for adsorption of CO₂ [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 5011-5018.
[14]	ZHANG Lihong, JIN Yaoru, CHENG Fangqin. Resource utilization of coal gasification slag [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4447-4457.
[15]	WANG Shuaiqing, YANG Siwen, LI Na, SUN Zhanying, AN Haoran. Research progress on element doped biomass carbon materials for electrochemical energy storage [J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4296-4306.