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

doi:10.11949/0438-1157.20200691

Abstract

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

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

CLC Number:

TQ 028.8

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.

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.

Figures/Tables 21

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

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)

Fig.1 Microwave heating CO2 activation experiment devices

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

Fig.2 The schematic diagram of range analysis

Fig.3 Fixed bed experiment system

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

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

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

Fig.5 Activated carbon yield under different microwave powers

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

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

Fig.7 Activated carbon yield under different CO2 flow rates

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

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

Fig.9 Activated carbon yield under different activation time

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

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

Fig.11 Activated carbon pore size distribution

Fig.12 Surface morphology of activated carbon

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

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

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

微波加热CO₂活化法制备生物质活性炭及其脱硫性能研究

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