微波加热CO2活化法制备生物质活性炭及其脱硫性能研究

doi:10.11949/0438-1157.20200691

化工学报 ›› 2020, Vol. 71 ›› Issue (12): 5774-5784.DOI: 10.11949/0438-1157.20200691

微波加热CO₂活化法制备生物质活性炭及其脱硫性能研究

田叶顺(),任文,王国袖,孙爽,周萍,王文龙,宋占龙,赵希强()

山东大学能源与动力工程学院，燃煤污染物减排国家工程实验室，环境热工技术教育部工程研究中心，山东省能源碳减排技术与资源化利用重点实验室，山东济南 250061

收稿日期:2020-06-02 修回日期:2020-07-18 出版日期:2020-12-05 发布日期:2020-12-05
通讯作者: 赵希强
作者简介:田叶顺（1991—），男，博士研究生，tyshun@mail.sdu.edu.cn
基金资助:
国家重点研发计划项目(2017YFB0602903-1)

Study on preparation and desulfurization characteristics of biomass activated carbon by microwave heating CO₂ activation method

TIAN Yeshun(),REN Wen,WANG Guoxiu,SUN Shuang,ZHOU Ping,WANG Wenlong,SONG Zhanlong,ZHAO Xiqiang()

National Engineering Laboratory for Reducing Emissions from Coal Combustion, Engineering Research Center of Environmental Thermal Technology of Ministry of Education, Shandong Key Laboratory of Energy Carbon Reduction and Resource Utilization, School of Energy and Power Engineering, Shandong University, Jinan 250061, Shandong, China

Received:2020-06-02 Revised:2020-07-18 Online:2020-12-05 Published:2020-12-05
Contact: ZHAO Xiqiang

摘要/Abstract

摘要：

以富含含氮官能团的大豆秸秆为原料前体，结合微波加热的特殊优势，将微波加热技术应用于大豆秸秆热解和活化工艺。以热解固体产物为活化原料，以CO₂为活化剂进行活性炭制备研究，以期制备出高脱硫性能的生物质活性炭。首先通过正交实验设计及极差分析得出最优活化水平，再通过单因素实验法考察微波功率、CO₂流量和活化时间对活性炭产率、孔隙结构以及脱硫性能的影响。对比分析选出最佳活化条件为微波功率900 W，CO₂流量0.10 L/min，活化时间20 min。在此条件下活性炭产率为76.3%（质量），SO₂饱和吸附容量为112.56 mg/g，比表面积为466.28 m²/g。相比热解炭，活性炭的比表面积更大，孔隙更加丰富，脱硫性能显著提高。

关键词: 活性炭, 微波, 二氧化碳活化, 多孔介质, 脱硫

Abstract:

Taking soybean straw rich in nitrogen-containing functional groups as the raw material precursor, combined with the special advantages of microwave heating, microwave heating technology is applied to the pyrolysis and activation process of soybean straw. The pyrolysis solid product is used as the activation raw material, and CO₂ is used as the activator to study the preparation of activated carbon, in order to prepare the biomass activated carbon with high desulfurization performance. First, the optimal activation level was obtained by orthogonal experimental design and range analysis. Then, the effects of microwave power, CO₂ flow rate and activation time on the yield, pore structure and desulfurization performance of activated carbon were investigated by single factor experiment. The optimal activation conditions were selected by comparative analysis: microwave power 900 W, CO₂ flow rate 0.10 L/min, activation time 20 min. Under these conditions, the yield of activated carbon is 76.3%(mass), the SO₂ adsorbance quantity is 112.56 mg/g, specific surface area is 466.28 m²/g. Compared with pyrolytic carbon, activated carbon has larger specific surface area and more abundant pores and significantly improved desulfurization performance.

Key words: activated carbon, microwave, carbon dioxide activation, porous media, desulfurization

中图分类号:

TQ 028.8

田叶顺,任文,王国袖,孙爽,周萍,王文龙,宋占龙,赵希强. 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,SUN Shuang,ZHOU Ping,WANG Wenlong,SONG Zhanlong,ZHAO Xiqiang. Study on preparation and desulfurization characteristics of biomass activated carbon by microwave heating CO₂ activation method[J]. CIESC Journal, 2020, 71(12): 5774-5784.

图/表 21

表1 大豆秸秆的工业分析和元素分析

Table 1 Industrial and elemental analysis of soybean straw

工业分析/%(mass)				元素分析/%(mass)
M_ad	A_ad	V_ad	FC_ad	C	H	O	N
12.1	2.9	68.7	16.2	44.3	6.2	43.8	2.5

表2 热解炭特性

Table 2 Characteristics of pyrolytic carbon

比表面积/

(m²/g)

微孔比表面积/

(m²/g)

平均孔径/nm

SO₂饱和吸附量/

(mg/g)

图1 微波加热CO2活化实验装置1—高纯CO2气瓶; 2—减压阀; 3—流量计; 4—微波炉; 5—固定床反应器; 6—冷凝管; 7—集液瓶; 8—气体收集装置

Fig.1 Microwave heating CO2 activation experiment devices

表3 活化正交实验因素与水平设计

Table 3 Activation orthogonal experimental factors and horizontal design

水平	因素
水平	A:微波功率/W	B:活化时间/min	C:CO₂流量/(L/min)
1	300	20	0.10
2	500	30	0.15
3	700	40	0.20

图2 极差分析法示意图

Fig.2 The schematic diagram of range analysis

图3 固定床实验系统1—高压气瓶; 2—减压阀; 3—流量计; 4—水蒸气发生器; 5—恒温水浴; 6—反应器; 7—控温电炉; 8—冷凝装置; 9—过滤器; 10—FT-IR烟气分析仪; 11—数据采集

Fig.3 Fixed bed experiment system

表4 正交实验结果

Table 4 The orthogonal experimental results

序号	因素			目标函数： SO₂饱和吸附量/(mg/g)
序号	A：微波功率/W	B：活化时间/min	C： CO₂流量/ (L/min)	目标函数： SO₂饱和吸附量/(mg/g)
1	300	20	0.10	50.21
2	300	30	0.15	57.83
3	300	40	0.20	79.69
4	500	20	0.15	87.70
5	500	30	0.20	75.40
6	500	40	0.10	83
7	700	20	0.20	68.66
8	700	30	0.10	41.93
9	700	40	0.15	51.58
K₁	184.73	206.57	175.14	Σ=596.0
K₂	162.17	175.16	197.11
K₃	246.1	214.27	223.75
$K 1 ˉ$	61.58	68.86	58.38
$K 2 ˉ$	54.06	58.39	65.70
$K 3 ˉ$	82.03	71.42	74.58
优水平	A₃	B₃	C₃
R_j	27.97	13.03	16.2
因素主次	A、C、B

表4 正交实验结果

Table 4 The orthogonal experimental results

序号	因素			目标函数： SO₂饱和吸附量/(mg/g)
序号	A：微波功率/W	B：活化时间/min	C： CO₂流量/ (L/min)	目标函数： SO₂饱和吸附量/(mg/g)
1	300	20	0.10	50.21
2	300	30	0.15	57.83
3	300	40	0.20	79.69
4	500	20	0.15	87.70
5	500	30	0.20	75.40
6	500	40	0.10	83
7	700	20	0.20	68.66
8	700	30	0.10	41.93
9	700	40	0.15	51.58
K₁	184.73	206.57	175.14	Σ=596.0
K₂	162.17	175.16	197.11
K₃	246.1	214.27	223.75
$K 1 ˉ$	61.58	68.86	58.38
$K 2 ˉ$	54.06	58.39	65.70
$K 3 ˉ$	82.03	71.42	74.58
优水平	A₃	B₃	C₃
R_j	27.97	13.03	16.2
因素主次	A、C、B

图4 不同微波功率下热解炭的升温曲线

Fig.4 Temperature rise curves of pyrolytic carbon under different microwave powers

图5 不同微波功率下的活性炭产率

Fig.5 Activated carbon yield under different microwave powers

表5 不同微波功率下活性炭的孔隙结构

Table 5 Pore structure of activated carbon under different microwave powers

微波功率/W	比表面积/(m²/g)	微孔比表面积/ (m²/g)	平均孔径/nm
100	114.54	101.03	3.13
300	205.06	160.45	2.58
500	247.26	177.60	2.49
700	291.99	191.69	2.43
900	355.29	251.43	2.22

图6 不同微波功率下制得的活性炭的硫容

Fig.6 Sulfur capacity of activated carbon prepared under different microwave powers

图7 不同CO2流量下的活性炭产率

Fig.7 Activated carbon yield under different CO2 flow rates

表6 不同CO2流量下活性炭的孔隙结构

Table 6 Pore structure of activated carbon under different CO2 flow rates

CO₂流量/(L/min)	比表面积/(m²/g)	微孔比表面积/ (m²/g)	平均孔径/nm
0.05	308.48	208.41	2.24
0.10	428.51	306.34	2.03
0.15	326.68	211.26	2.23
0.20	291.99	191.69	2.43
0.25	229.13	155.32	2.48

图8 不同CO2流量下制得的活性炭的硫容

Fig.8 Sulfur capacity of activated carbon prepared under different CO2 flow rates

图9 不同活化时间下的活性炭产率

Fig.9 Activated carbon yield under different activation time

表7 不同活化时间下活性炭的孔隙结构

Table 7 Pore structure of activated carbon under different activation time

活化时间/min	比表面积/(m²/g)	微孔比表面积/ (m²/g)	平均孔径/nm
10	406.11	312.93	2.15
20	431.53	330.16	1.91
30	427.17	338.94	2.04
40	291.99	191.69	2.43
50	239.09	164.40	2.47

图10 不同活化时间下制得的活性炭的硫容

Fig.10 Sulfur capacity of activated carbon prepared under different activation time

图11 活性炭孔径分布

Fig.11 Activated carbon pore size distribution

图12 活性炭表面形貌

Fig.12 Surface morphology of activated carbon

图13 大豆秸秆、热解炭和活性炭的表面化学性质

Fig.13 Surface chemical properties of soybean straw, pyrolytic carbon and activated carbon

图14 SO2动态吸附in-situ DRIFTs谱图

Fig.14 In-situ DRIFTs spectra of dynamic adsorption of SO2

参考文献 36

1	赵雪, 程茜, 侯俊先.脱硫脱硝行业2017年发展综述[J].中国环保产业, 2018, (7): 10-24.
	Zhao X, Cheng Q, Hou J X. Development report on desulfurization and denitration industry in 2017 [J]. China Environmental Protection Industry, 2018, (7):10-24.
2	Ben B Z, Yun Q L, Yue Y Y. Progress in preparation of activated carbon and its activation mechanism [J]. Modern Chemical Industry, 2014, 34(3): 34-39.
3	Ioannidou O, Zabaniotou A. Agricultural residues as precursors for activated carbon production—a review[J]. Renewable & Sustainable Energy Reviews, 2007, 11(9): 1966-2005.
4	李艳鹰. 生物质活性炭负载零价铁纳米晶簇直接催化还原NO [J]. 化工学报, 2019, 70(3): 1111-1119.
	Li Y Y. Biomass activated carbon loaded with zero-valent iron nanocrystal clusters for direct catalytic reduction of NO [J]. CIESC Journal, 2019, 70(3): 1111-1119.
5	郭晓娜. 氮掺杂活性炭材料的制备及性能研究 [D]. 贵阳: 贵州大学, 2016.
	Guo X N. Preparation and properties of nitrogen-doped activated carbon materials [D]. Guiyang: Guizhou University, 2016.
6	王维竹, 刘勇军, 范武波, 等. 活性炭纤维改性表面官能团脱硫作用[J].化工新型材料, 2014, 42(4): 182-184.
	Wang W Z, Liu Y J, Fan W B, et al. Desulfurization of surface functional groups for modification of activated carbon fiber [J]. New Chemical Materials, 2014, 42(4): 182-184.
7	杨丽娟. 生物质活性炭的制备及应用发展研究 [J]. 黑龙江科学, 2018, 9(18): 44-45.
	Yang L J. Study on preparation and application development of biomass activated carbon [J]. Heilongjiang Science, 2018, 9(18): 44-45.
8	Zhang K, Cheung W, Valix M. Roles of physical and chemical properties of activated carbon in the adsorption of lead ions[J]. Chemosphere, 2005, 60(8): 1129-1140.
9	莫柳珍, 廖炳权, 黄向阳, 等. 甘蔗渣活性炭制备研究进展[J]. 广西糖业, 2015, (1): 31-35.
	Mo L Z, Liao B Q, Huang X Y, et al. Research progress in preparation of activated carbon from bagasse [J]. Guangxi Sugarcane & Canesugar, 2015, (1): 31-35.
10	Arenas E, Chejne F. The effect of the activating agent and temperature on the porosity development of physically activated coal chars [J]. Carbon, 2004, 42(12): 2451-2455.
11	Guo J, Lua A C. Characterization of adsorbent prepared from oil-palm shell by CO2 activation for removal of gaseous pollutants [J]. Materials Letters, 2002, 55(5): 334-339.
12	Yang K S, Yoon Y J, Lee M S, et al. Further carbonization of anisotropic and isotropic pitch-based carbons by microwave irradiation [J]. Carbon, 2002, 40(6): 897-903.
13	王超前, 王文龙, 李哲, 等. 基于微波诱导定向加热的污泥新型热解方法能耗分析 [J]. 化工学报, 2019, 70: 168-176.
	Wang C Q Wang W L, Li Z, et al. Energy consumption analysis of novel pyrolysis method of sewage sludge based on microwave-induced target-oriented heating [J]. CIESC Journal, 2019, 70: 168-176.
14	樊希安, 彭金辉, 秦文峰, 等. 微波辐射处理竹节废料制备活性炭研究 [J]. 林产化学与工业, 2003, (3): 56-60.
	Fan X A, Peng J H, Qin W F, et al. Research on preparation of activated carbon from bamboo knot by microwave radiation [J]. Chemistry and Industry of Forest Products, 2003, (3): 56-60.
15	Georgin J, Dotto G L, Mazutti M A, et al. Preparation of activated carbon from peanut shell by conventional pyrolysis and microwave irradiation-pyrolysis to remove organic dyes from aqueous solutions [J]. Journal of Environmental Chemical Engineering, 2016, 4(1): 266-275.
16	潘能婷, 苏展军, 莫家乐, 等. 新型微波适应型复合活性炭的研制及其微波再生性能 [J]. 化工学报, 2011, 62(1): 111-118.
	Pan N T, Su Z J, Mo J L, et al. Preparation of novel composite activated carbon with high applicability to microwave and its regeneration under microwave radiation [J]. CIESC Journal, 2011, 62(1): 111-118.
17	Ravikovitch P I, Neimark A V. Density functional theory model of adsorption on amorphous and microporous silica materials [J]. Langmuir the ACS Journal of Surfaces & Colloids, 2006, 22(26): 11171-11179.
18	张振. 粉状活性半焦的快速制备过程及SO2吸附特性研究 [D]. 济南: 山东大学, 2016.
	Zhang Z. Study on fast preparation of powdered active semi-coke and characteristics of SO2 adsorption [D]. Jinan: Shandong University, 2016.
19	Tsuji K, Shiraishi I. Combined desulfurization, denitrification and reduction of air toxics using activated coke(1): Activity of activated coke [J]. Fuel, 1997, 76(6): 549-553.
20	李兰廷.活性焦脱硫脱硝的机理研究——烟气组成的影响[J].煤炭学报, 2010, 35(S1): 185-189.
	Li L T. Mechanism of removal of SO2 and NO on activated coke: effect of component of flue gas on activated coke [J]. Journal of China Coal Society, 2010, 35(S1): 185-189.
21	张守玉, 朱廷玉, 杨之媛, 等. 煤制活性焦用于脱除烟道气中的SO2 [J]. 燃烧科学与技术, 2002, 8(1): 38-43.
	Zhang S Y, Zhu T Y, Yang Z Y, et al. Application of active coke derived from coal for SO2-removal from flue gas [J]. Journal of Combustion Science and Technology, 2002, 8(1): 38-43.
22	刘珂. 煤粉快速热解制备粉状活性焦及副产热解气的实验研究[D]. 济南: 山东大学, 2017.
	Liu K. Experimental study on preparation of powder activated coke and by-product pyrolysis gas by rapid pyrolysis of pulverized coal [D]. Jinan: Shandong University, 2017.
23	Chen G, Andries J, Luo Z, et al. Biomass pyrolysis/gasification for product gas production: the overall investigation of parametric effects [J]. Energy Conversion & Management, 2003, 44(11): 1875-1884.
24	Onay O, Kockar O M. Slow, fast and flash pyrolysis of rapeseed [J]. Renewable Energy, 2003, 28(15): 2417-2433.
25	Rong Y, Yang H, Chin T, et al. Influence of temperature on the distribution of gaseous products from pyrolyzing palm oil wastes [J]. Combustion & Flame, 2005, 142(1): 24-32.
26	郝博. 核桃壳废弃物流态化物理活化法制备活性炭的研究 [D]. 天津: 天津科技大学, 2014.
	Hao B. Preparation of activated carbon from walnut shell wastes by physical activation in a fluidized bed reactor [D]. Tianjin: Tianjin University of Science and Technology, 2014.
27	杨坤彬. 物理活化法制备椰壳基活性炭及其孔结构演变 [D]. 昆明: 昆明理工大学, 2010.
	Yang K B. Preparation of coconut shell-based activated carbon by physical activation and its pore structure evolution [D]. Kunming: Kunming University of Science and Technology, 2010.
28	夏洪应, 彭金辉, 张利波, 等. 微波辐射二氧化碳法制备烟秆基颗粒活性炭[J].煤炭转化, 2006, (1): 81-84.
	Xia H Y, Peng J H, Zhang L B, et al. Preparation of granular activated carbon from tobacco stems by microwave irradiation-carbon dioxide [J]. Coal Conversion, 2006, (1): 81-84.
29	Guo J, Lua A C. Preparation of activated carbons from oil-palm-stone chars by microwave-induced carbon dioxide activation [J]. Carbon, 2000, 38(14): 1985-1993.
30	张晓鸿, 詹昊, 阴秀丽, 等. 富氮生物质原料热解过程中NOx前驱物释放特性研究 [J]. 燃料化学学报, 2016, 44(12): 1464-1472.
	Zhang X H, Zhan H, Yin X L, et al. Release characteristic of NOx precursors during the pyrolysis of nitrogen-rich biomass [J]. Journal of Fuel Chemistry and Technology, 2016, 44(12): 1464-1472.
31	Ren Q, Zhao C, Chen X, et al. NOx and NO precursors (NH and HCN) from biomass pyrolysis: co-pyrolysis of amino acids and cellulose, hemicellulose and lignin [J]. Proceedings of the Combustion Institute, 2011, 33(2): 1715-1722.
32	Hansson K M, Åmand L E, Habermann A, et al. Pyrolysis of poly-L-leucine under combustion-like conditions [J]. Fuel, 2003, 82(6): 653-660.
33	唐晓帆. 基于石墨烯探究官能团对SO2吸附过程的影响 [D]. 哈尔滨: 哈尔滨工业大学, 2015.
	Tang X F. Exploring the effects of functional groups on graphene materials on the adsorptional process of SO2 [D]. Harbin: Harbin Institute of Technology, 2015.
34	张香兰, 徐德平. 活性半焦的制备: 性能与烟气脱硫机理 [M]. 北京: 化学工业出版社, 2012: 36.
	Zhang X L, Xu D P. Preparation of Activated Semi-Coke: Performance and Mechanism of Flue Gas Desulfurization [M]. Beijing: Chemical Industry Press, 2012: 36.
35	李开喜, 凌立成, 刘郎, 等. SO2在含氮沥青基活性炭纤维上的脱除 (Ⅰ): 含氮沥青基活性炭纤维的脱硫能力研究 [J]. 新型炭材料, 1998, 13(2): 37-42.
	Li K X, Ling L C, Liu L, et al. Removal of SO2 over nitrogen-containing pitch based activated carbon fiber (Ⅰ): Studies on desulfurization abilities of nitrogen-containing activated carbon fiber [J]. New Carbon Materials 1998, 13(2): 37-42.
36	Xu L, Guo J, Jin F, et al. Removal of SO2 from O2-containing flue gas by activated carbon fiber (ACF) impregnated with NH3 [J]. Chemosphere, 2006, 62(5): 823-826.

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微波加热CO₂活化法制备生物质活性炭及其脱硫性能研究

Study on preparation and desulfurization characteristics of biomass activated carbon by microwave heating CO₂ activation method

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