一步热解活化法制备纳米木质素基多孔炭材料

doi:10.16085/j.issn.1000-6613.2021-1219

化工进展 ›› 2022, Vol. 41 ›› Issue (5): 2582-2592.doi: 10.16085/j.issn.1000-6613.2021-1219

一步热解活化法制备纳米木质素基多孔炭材料

王鲁元¹^,²(), 金春江¹^,²^,³, 陈惠敏³, 程星星⁴, 安东海³(), 张兴宇², 孙荣峰¹^,², 耿文广¹^,²

^1.山东省科学院能源研究所，山东济南 250014
^2.齐鲁工业大学能源与动力工程学院，山东济南 250014
^3.昌吉学院，新疆昌吉 831100
^4.山东大学能源与动力工程学院，山东济南 250061

收稿日期:2021-06-10 修回日期:2021-10-07 出版日期:2022-05-05 发布日期:2022-05-24
通讯作者: 安东海 E-mail:luyuanwang1988@126.com;adhcjxy@163.com
作者简介:王鲁元（1988—），男，博士，主要研究方向为VOCs环保治理及炭材料、脱硫脱硝催化剂的制备。E-mail：luyuanwang1988@126.com。
基金资助:
国家自然科学基金(51906130);山东省自然科学基金(ZR2019BEE053);山东省科学院青年基金(2020QN009);山东省重点实验室能源碳减排技术与资源化利用实验室项目(ECRRU201804);新疆教育厅新疆维吾尔自治区高校科研计划(XJEDU2019Y025);齐鲁工业大学（山东省科学院）科教产项目（2020KJC~ZD12）

Preparation of nano-lignin-based porous carbon materials by one-step pyrolysis activation method

WANG Luyuan¹^,²(), JIN Chunjiang¹^,²^,³, CHEN Huimin³, CHENG Xingxing⁴, AN Donghai³(), ZHANG Xingyu², SUN Rongfeng¹^,², GENG Wenguang¹^,²

^1.Energy Research Institute of Shandong Academy of Sciences, Jinan 250014, Shandong, China
^2.School of Energy and Power Engineering, Qilu University of Technology, Jinan 250014, Shandong, China
^3.Changji University, Changji 831100, Xinjiang, China
^4.School of Energy and Power Engineering, Shandong University, Jinan 250061, Shandong, China

Received:2021-06-10 Revised:2021-10-07 Online:2022-05-05 Published:2022-05-24
Contact: AN Donghai E-mail:luyuanwang1988@126.com;adhcjxy@163.com

摘要/Abstract

摘要：

以木质素为原料，采用管式炉反应器通过一步热解-半活化法获得木质素基多孔炭材料（LPC）。采用氮吸附（BET）、扫描电镜（SEM）和傅里叶变换红外光谱（FTIR）对多孔炭材料的物化性质进行分析。在900℃的恒定炭化温度下，CO₂体积分数为6%、水蒸气体积分数约为20%时，LPC-C₆S₂₀表面具有良好的纳米结构，并且总孔容和比表面积分别达到0.77cm³/g和1497.51m²/g，活化气氛促进了多孔炭材料颗粒趋于均匀和微孔、中孔的形成。LPC样品含有—OH、C—H、C＝C、C—O、C＝O、CO—C、C—N、C＝N等丰富的表面官能团。随着活化剂浓度的变化，这些官能团保持相对稳定。因此，通过该方法获得的样品具有良好的纳米结构，具有较大的孔容、比表面积和表面官能团。

关键词: 木质素, 一步热解, 多孔炭, 孔结构

Abstract:

The lignin-based porous carbon material (LPC) was obtained by using lignin as raw material and tube furnace reactor through a one-step pyrolysis-activation method. Nitrogen adsorption (BET), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) were used to analyze the physical and chemical properties of porous carbon material. At a constant carbonization temperature of 900℃ with CO₂ concentration of 6% and water vapor concentration of about 20%, the surface of LPC-C₆S₂₀ had a good nanostructure, and the total pore volume and specific surface area reached 0.77cm³/g and 1497.51m²/g, respectively. The activation atmosphere promoted the uniformity of porous carbon material particles and the formation of micropores and mesopores. The LPC sample contained abundant surface functional groups such as —OH, C—H, C＝C, C—O, C＝O, CO—C, C—N and C＝N, etc. As the concentration of the activator changed, these functional groups remained relatively stable. Therefore, the sample obtained by this method had a good nanostructure with a larger pore volume, specific surface area and functional groups.

Key words: lignin, one step pyrolysis, porous carbon, pore structure

中图分类号:

王鲁元, 金春江, 陈惠敏, 程星星, 安东海, 张兴宇, 孙荣峰, 耿文广. 一步热解活化法制备纳米木质素基多孔炭材料[J]. 化工进展, 2022, 41(5): 2582-2592.

WANG Luyuan, JIN Chunjiang, CHEN Huimin, CHENG Xingxing, AN Donghai, ZHANG Xingyu, SUN Rongfeng, GENG Wenguang. Preparation of nano-lignin-based porous carbon materials by one-step pyrolysis activation method[J]. Chemical Industry and Engineering Progress, 2022, 41(5): 2582-2592.

图/表 12

表1

图1

图2

表2

图3

表3

图4

图5

图6

图7

图8

图9

参考文献 51

1	LI H Y, HE J, CHEN K Y, et al. Dynamic adsorption of sulfamethoxazole from aqueous solution by lignite activated coke[J]. Materials, 2020, 13(7): 1785.
2	BELL J G, BENHAM M J, THOMAS K M. Adsorption of carbon dioxide, water vapor, nitrogen, and sulfur dioxide on activated carbon for capture from flue gases: competitive adsorption and selectivity aspects[J]. Energy & Fuels, 2021, 35(9): 8102-8116.
3	WILSON S M W, AL-ENZI F, GABRIEL V A, et al. Effect of pore size and heterogeneous surface on the adsorption of CO₂, N₂, O₂, and Ar on carbon aerogel, RF aerogel, and activated carbons[J]. Microporous and Mesoporous Materials, 2021, 322: 111089.
4	LIANG H X, SONG B, PENG P, et al. Preparation of three-dimensional honeycomb carbon materials and their adsorption of Cr(Ⅵ)[J]. Chemical Engineering Journal, 2019, 367: 9-16.
5	CHERRAD N. Conditioning of hydrogen storage by continuous solar adsorption in activated carbon AX-21 with simultaneous production[J]. International Journal of Hydrogen Energy, 2019, 44(4): 2153-2163.
6	曾茂株, 佘煜琪, 胡玉彬, 等. 木质素多孔炭的制备及应用研究进展[J]. 化工进展, 2021, 40(8): 4573-4586.
	ZENG Maozhu, SHE Yuqi, HU Yubin, et al. Progress in preparation and application of lignin porous carbon[J]. Chemical Industry and Engineering Progress, 2021, 40(8): 4573-4586.
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	ZHUANG H F, XIE Q N, SHAN S D, et al. Performance, mechanism and stability of nitrogen-doped sewage sludge based activated carbon supported magnetite in anaerobic degradation of coal gasification wastewater[J]. Science of the Total Environment, 2020, 737: 140285.
9	LIU H, CHENG C, WU H M. Sustainable utilization of wetland biomass for activated carbon production: a review on recent advances in modification and activation methods[J]. Science of the Total Environment, 2021, 790: 148214.
10	MOCHIZUKI Y, TSUBOUCHI N. Preparation of pelletized coke by co-carbonization of caking coal and pyrolyzed char modified with tar produced during pyrolysis of woody biomass[J]. Fuel Processing Technology, 2019, 193: 328-337.
11	ALZAID M, ALSALH F, IQBAL M Z. Biomass derived activated carbon based hybrid supercapacitors[J]. Journal of Energy Storage, 2021, 40: 102751.
12	CHEN K, ZHANG H R, IBRAHIM U K, et al. The quantitative assessment of coke morphology based on the Raman spectroscopic characterization of serial petroleum cokes[J]. Fuel, 2019, 246: 60-68.
13	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.
14	姜勇, 张庆伟, 王胜, 等. 中孔煤基磁性活性炭的制备及性能表征[J]. 洁净煤技术, 2015, 21(3): 1-5, 10.
	JIANG Yong, ZHANG Qingwei, WANG Sheng, et al. Preparation and characterization of magnetic mesopores activated carbon from lignite[J]. Clean Coal Technology, 2015, 21(3): 1-5, 10.
15	俞志敏, 卫新来, 娄梅生, 等. 氯化锌活化生物质炭制备活性炭及其表征[J]. 化工进展, 2014, 33(12): 3318-3323.
	YU Zhimin, WEI Xinlai, LOU Meisheng, et al. Preparation and characterization of activated carbon from bio-char by chemical activation with ZnCl₂ [J]. Chemical Industry and Engineering Progress, 2014, 33(12): 3318-3323.
16	MALDHURE A, WAGHELA A, NAGARNAIK P, et al. Microwave treated activated carbon from industrial waste lignin for denitrification of surface water[J]. International Journal of Environmental Science and Technology, 2021: 1-10.
17	李岩松, 徐国忠, 李白冰, 等. CO₂活化兰炭粉制备粉状微孔活性炭[J]. 辽宁科技大学学报, 2018, 41(6): 462-468.
	LI Yansong, XU Guozhong, LI Baibing, et al. Preparation of micro-pore dominated active carbon powder by using semicoke powder activated with CO₂ [J]. Journal of University of Science and Technology Liaoning, 2018, 41(6): 462-468.
18	蒋绪, 兰新哲, 景兴鹏, 等. 不同介质下物理法活化制备兰炭基活性炭实验研究[J]. 煤炭转化, 2019, 42(2): 65-71.
	JIANG Xu, LAN Xinzhe, JING Xingpeng, et al. Research on experiment of blue coke-based activated carbon by physical activation with different media[J]. Coal Conversion, 2019, 42(2): 65-71.
19	李海红, 薛慧, 裴盼盼, 等. 棉纤维基活性炭制备工艺的优化及性能表征[J]. 化工进展, 2018, 37(5): 1916-1922.
	LI Haihong, XUE Hui, PEI Panpan, et al. Preparation and characterization of activated carbon from cotton fiber[J]. Chemical Industry and Engineering Progress, 2018, 37(5): 1916-1922.
20	魏庆玲, 陈志敏, 王晓峰，等. 以氯化铵为成孔助剂两步法制备玉米芯基活性炭 [J]. 新型炭材料, 2018, 33(5): 402-408.
	WEI Qingling, CHEN Zhimin, WANG Xiaofeng, et al. A two-step method for the preparation of high performance corncob-based activated carbons as supercapacitor electrodes using ammonium chloride as a pore forming additive[J]. New Carbon Materials, 2018, 33(5): 402-408.
21	左宋林. 磷酸活化法活性炭孔隙结构的调控机制[J]. 新型炭材料, 2018, 33(4): 289-302.
	ZUO Songlin. A review of the control of pore texture of phosphoric acid-activated carbons[J]. New Carbon Materials, 2018, 33(4): 289-302.
22	王晶, 韩巧宁, 雷以廷, 等. 一步法制备富氧木质素活性炭及其亚甲基蓝吸附性能[J]. 化工学报, 2021, 72(5): 2826-2836.
	WANG Jing, HAN Qiaoning, LEI Yiting, et al. One-step preparation of oxygen-enriched lignin activated carbon and its methylene blue adsorption performance[J]. CIESC Journal, 2021, 72(5): 2826-2836.
23	DONG Z, CHEN B B, ZHANG M J, et al. One-step preparation of carbon fiber-ZrO₂ hybrid and its enhancement on the wear-resistant properties of polyimide[J]. Polymer Composites, 2021, 42(5): 2598-2607.
24	JIANG Y, WANG X, YU Z Z, et al. One-step preparation of non-covalent functionalized carboxylic multi-walled carbon nanotubes/polymethyl methacrylate nanocomposites via in situ polymerization[J]. Advances in Polymer Technology, 2018, 37(4): 1008-1015.
25	姜晓威, 王会刚, 李龙之, 等. 微波辐照下炭材料升温特性试验研究[J]. 洁净煤技术, 2017, 23(5): 62-66.
	JIANG Xiaowei, WANG Huigang, LI Longzhi, et al. Heating characteristics of carbon-based materials under microwave irradiation[J]. Clean Coal Technology, 2017, 23(5): 62-66.
26	CETIN E, GUPTA R, MOGHTADERI B. Effect of pyrolysis pressure and heating rate on radiata pine char structure and apparent gasification reactivity[J]. Fuel, 2005, 84(10): 1328-1334.
27	CAI H Y, GÜELL A J, CHATZAKIS I N, et al. Combustion reactivity and morphological change in coal chars: effect of pyrolysis temperature, heating rate and pressure[J]. Fuel, 1996, 75(1): 15-24.
28	OKUMURA Y. Effect of heating rate and coal type on the yield of functional tar components[J]. Proceedings of the Combustion Institute, 2017, 36(2): 2075-2082.
29	张本镔, 刘运权, 叶跃元. 活性炭制备及其活化机理研究进展[J]. 现代化工, 2014, 34(3): 34-39.
	ZHANG Benbin, LIU Yunquan, YE Yueyuan. Progress in preparation of activated carbon and its activation mechanism[J]. Modern Chemical Industry, 2014, 34(3): 34-39.
30	田叶顺, 任文, 王国袖, 等. 微波加热CO₂活化法制备生物质活性炭及其脱硫性能研究[J]. 化工学报, 2020, 71(12): 5774-5784.
	TIAN Yeshun, REN Wen, WANG Guoxiu, et al. Study on preparation and desulfurization characteristics of biomass activated carbon by microwave heating CO₂ activation method[J].CIESC Journal, 2020, 71(12): 5774-5784.
31	RAVIKOVITCH P I, NEIMARK A V. Density functional theory model of adsorption on amorphous and microporous solids[J] . Langmuir, 2006, 22(26): 11171-11179.
32	ZHANG X Y, GAO B, CREAMER A E, et al. Adsorption of VOCs onto engineered carbon materials: a review[J]. Journal of Hazardous Materials, 2017, 338: 102-123.
33	YANG X, YI H H, TANG X L, et al. Behaviors and kinetics of toluene adsorption-desorption on activated carbons with varying pore structure[J]. Journal of Environmental Sciences, 2018, 67: 104-114.
34	ZELLAGUI S, SCHÖNNENBECK C, ZOUAOUI-MAHZOUL N, et al. Pyrolysis of coal and woody biomass under N₂ and CO₂ atmospheres using a drop tube furnace — Experimental study and kinetic modeling[J]. Fuel Processing Technology, 2016, 148: 99-109.
35	SUN Y, YANG G, ZHANG J, et al. Activated carbon preparation from lignin by H₃PO₄ activation and its application to gas separation[J]. Chemical Engineering & Technology, 2012, 35(2): 309-316.
36	黎先发. 木质素活性炭的制备及其对硝基苯的吸附[J]. 化工环保, 2014, 34(4): 305-310.
	LI Xianfa. Preparation of lignin-based activated carbons and adsorption of nitrobenzene[J]. Environmental Protection of Chemical Industry, 2014, 34(4): 305-310.
37	HO P H, LOFTY V, BASTA A, et al. Designing microporous activated carbons from biomass for carbon dioxide adsorption at ambient temperature. A comparison between bagasse and rice by-products[J]. Journal of Cleaner Production, 2021, 294: 126260.
38	WEERAWAT C, POMRNSAWAN A. Production of activated carbon from peanut hill using phosphoric acid and microwave activation[J]. KKU Engineering Journal, 2015, 42(2): 185-191.
39	LIM H K, MD ALI U F, AHMAD R, et al. Adsorption of carbon dioxide (CO₂) by activated carbon derived from waste coffee grounds[J]. IOP Conference Series: Earth and Environmental Science, 2021, 765(1): 012034.
40	PASTOR-VILLEGAS J, DURÁN-VALLE C J. Pore structure of chars and activated carbons prepared using carbon dioxide at different temperatures from extracted rockrose[J]. Journal of Analytical and Applied Pyrolysis, 2001, 57(1): 1-13.
41	许伟, 孙康, 缪存标, 等. 水蒸气活化制备竹质成型活性炭及其对二硫化碳的吸附性能[J]. 林业工程学报, 2018, 3(2): 40-46.
	XU Wei, SUN Kang, MIAO Cunbiao, et al. Preparation of bamboo molding activated carbon by steam activation and its adsorption performance on carbon disulfide[J]. Journal of Forestry Engineering, 2018, 3(2): 40-46.
42	CHEN X, GE X, ZHANG X, et al. Preparation of activated carbon from the residue of plasma pyrolysis of coal by steam activation[J]. Energy Sources A: Recovery, Utilization, and Environmental Effects, 2015, 37(4): 440-446.
43	GUPTA V K, MITTAL A, JAIN R, et al. Adsorption of Safranin-T from wastewater using waste materials—activated carbon and activated rice husks[J]. Journal of Colloid and Interface Science, 2006, 303(1): 80-86.
44	RIVERA-UTRILLA J, SÁNCHEZ-POLO M, GÓMEZ-SERRANO V, et al. Activated carbon modifications to enhance its water treatment applications. An overview[J]. Journal of Hazardous Materials, 2011, 187(1/2/3): 1-23.
45	AMIN N K. Removal of reactive dye from aqueous solutions by adsorption onto activated carbons prepared from sugarcane bagasse pith[J]. Desalination, 2008, 223(1/2/3): 152-161.
46	PIERGROSSI V, FASOLATO C, CAPITANI F, et al. Application of Raman spectroscopy in chemical investigation of impregnated activated carbon spent in hydrogen sulfide removal process[J]. International Journal of Environmental Science and Technology, 2019, 16(3): 1227-1238.
47	ALI R, ASLAM Z, SHAWABKEH R A, et al. BET, FTIR, and RAMAN characterizations of activated carbon from waste oil fly ash[J]. Turkish Journal of Chemistry, 2020, 44(2): 279-295.
48	CROCE A, RE G, BISIO C, et al. On the correlation between Raman spectra and structural properties of activated carbons derived by hyper-crosslinked polymers[J]. Research on Chemical Intermediates, 2021, 47(1): 419-431.
49	MASOUM RAMAN S N, ISMAIL N A, JAMARI S S. Preparation and characterization of impregnated commercial rice husks activated carbon with piperazine for carbon dioxide (CO₂) capture[J]. IOP Conference Series: Materials Science and Engineering, 2017, 206: 012005.
50	LAZZARINI A, PIOVANO A, PELLEGRINI R, et al. Graphitization of activated carbons: a molecular-level investigation by INS, DRIFT, XRD and Raman techniques[J]. Physics Procedia, 2016, 85: 20-26.
51	LIU Y P, LU Z W, HASI W, et al. Self-assembled activated carbon nanoparticles for reliable time-discretized quantitative surface-enhanced Raman spectroscopy[J]. Analytical Methods, 2017, 9(47): 6622-6628.

样品	总孔容/cm³·g^-1	微孔孔容/cm³·g^-1	比表面积 /m²·g^-1	微孔比表面积/m²·g^-1	平均孔径/nm
LPC-C₂S₂₀	0.50	0.43	1081.89	1004.93	1.85
LPC-C₄S₂₀	0.64	0.46	1344.80	1169.50	1.91
LPC-C₆S₂₀	0.77	0.50	1497.51	1250.21	2.06
LPC-C₈S₂₀	0.79	0.51	1294.81	1026.92	2.45

样品	总孔容/cm³·g^-1	微孔孔容/cm³·g^-1	比表面积 /m²·g^-1	微孔比表面积/m²·g^-1	平均孔径/nm
LPC-C₆S₀	0.51	0.36	992.52	856.67	2.04
LPC-C₆S₁₀	0.70	0.37	1，295.02	749.60	2.60
LPC-C₆S₂₀	0.77	0.50	1497.51	1250.21	2.06
LPC-C₆S₃₀	0.81	0.44	1409.03	1094.35	2.30

[1]	张伟, 安兴业, 刘利琴, 龙垠荧, 张昊, 程正柏, 曹海兵, 刘洪斌. 木质素纳米颗粒/天然纤维基活性碳纤维材料的制备及其电化学性能[J]. 化工进展, 2022, 41(7): 3770-3783.
[2]	张丽珠, 王欢, 李琼, 杨东杰. 木质素衍生吸附材料及其在废水处理中的应用研究进展[J]. 化工进展, 2022, 41(7): 3731-3744.
[3]	娄瑞, 刘钰, 田杰, 张亚男. 纳米木质素基多孔炭的制备及其电化学性能[J]. 化工进展, 2022, 41(6): 3170-3177.
[4]	薛李静, 费星, 刘江淋, 吴林军, 仇中杰, 许权洲, 钟晓文, 林绪亮, 秦延林. 木质素基碳材料催化剂的制备及应用研究进展[J]. 化工进展, 2022, 41(5): 2441-2450.
[5]	张雷, 王海英, 韩洪晶, 陈彦广, 王程昊. 木质素催化热解用催化剂的研究进展[J]. 化工进展, 2022, 41(5): 2429-2440.
[6]	段曼华, 程丹, 肖伟, 杨占旭. 聚丙烯腈/聚酯无纺布微孔复合锂电隔膜的制备及性能[J]. 化工进展, 2022, 41(5): 2615-2622.
[7]	申琪, 薛雨源, 杨涛伟, 张妍, 李胜任. 木质素荧光研究进展[J]. 化工进展, 2022, 41(5): 2672-2685.
[8]	简雅婷, 余强, 陈小燕, 王帆, 王忠铭, 袁振宏. 木质素制备生物液体燃料进展[J]. 化工进展, 2021, 40(S2): 109-116.
[9]	杨妍, 刘国涛, 余庆慧, 李晓娟, 张颖. 多孔炭材料改性纳米零价铁的研究进展[J]. 化工进展, 2021, 40(S2): 198-202.
[10]	李赛赛, 詹硕, 李继定, 何静, 王璐莹. 木质素磺酸钙/海藻酸钠渗透汽化膜的制备及性能调控[J]. 化工进展, 2021, 40(S1): 311-318.
[11]	葛睿, 胡旭, 董灵玉, 李丹, 郝广平. 电化学耦合阴极二氧化碳还原与阳极氧化合成[J]. 化工进展, 2021, 40(9): 5132-5144.
[12]	曾茂株, 佘煜琪, 胡玉彬, 吴林军, 袁慢景, 漆毅, 王欢, 林绪亮, 秦延林. 木质素多孔炭的制备及应用研究进展[J]. 化工进展, 2021, 40(8): 4573-4586.
[13]	郑超, 康凯, 周术元, 宋华, 白书培. 水分子在多孔炭材料上的吸附行为研究进展[J]. 化工进展, 2021, 40(7): 3803-3812.
[14]	王晶, 倪金荧, 王利群, 卿青, 严生虎, 张跃. 一株木质素降解细菌的筛选及其降解途径[J]. 化工进展, 2021, 40(7): 4021-4026.
[15]	侯璐, 胡友仁, 李文翠, 董晓玲, 陆安慧. 富氧多孔炭的合成及其在电化学储能中的作用[J]. 化工进展, 2021, 40(6): 3020-3033.

一步热解活化法制备纳米木质素基多孔炭材料

Preparation of nano-lignin-based porous carbon materials by one-step pyrolysis activation method

RichHTML

PDF (PC)

赞

可视化

摘要/Abstract

引用本文

使用本文

图/表 12

参考文献 51

相关文章 15

Metrics

本文评价

推荐阅读 0