1.School of Chemical and Environmental Engineering, China University of Mining & Technology (Beijing)), Beijing 100083, China
2.The Coal Chemical Engineering Collaborative Innovation Center of Guizhou Province, Guizhou University of Engineering Science, Bijie 551700, Guizhou, China
收稿:2019-04-01,
修回:2019-07-24,
纸质出版:2019-11-05
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邓锋, 解强, 刘德钱, 万超然, 黄小晴, 顾雪梅. 2~5 nm孔集中分布泥炭基中孔活性炭的制备[J]. 化工学报, 2019, 70(11): 4457-4468
DENG Feng, XIE Qiang, LIU Deqian, WAN Chaoran, HUANG Xiaoqing, GU Xuemei. Preparation of mesoporous peat-based activated carbon with peak distribution of 2—5 nm pores[J]. CIESC Journal, 2019, 70(11): 4457-4468
邓锋, 解强, 刘德钱, 万超然, 黄小晴, 顾雪梅. 2~5 nm孔集中分布泥炭基中孔活性炭的制备[J]. 化工学报, 2019, 70(11): 4457-4468 DOI: 10.11949/0438-1157.20190331.
DENG Feng, XIE Qiang, LIU Deqian, WAN Chaoran, HUANG Xiaoqing, GU Xuemei. Preparation of mesoporous peat-based activated carbon with peak distribution of 2—5 nm pores[J]. CIESC Journal, 2019, 70(11): 4457-4468 DOI: 10.11949/0438-1157.20190331.
将泥炭破碎、粉磨、浸渍磷酸后,压块成型、再破碎,置于管式炉经不同活化温度、活化时间制得活性炭。对浸渍磷酸后的泥炭样品在氮气下进行热重分析;测定活性炭样品的碘吸附值、亚甲蓝吸附值和焦糖脱色率,利用气体吸附仪、激光拉曼光谱、傅里叶变换红外光谱和扫描电子显微镜分别表征其孔结构、碳结构、表面化学和微观形貌。结果表明:泥炭在磷酸活化过程中发生了交联反应,炭化/活化最大失重温度从300℃附近降低至200℃附近;随着磷酸浸渍比和活化温度的升高,活性炭中的无规则石墨层增多、羟基含量减少;磷酸浸渍比增加时,孔隙逐渐发达、吸附性能增强、2~5 nm孔段孔容增大;活化温度升高时,孔隙先收缩(400~550℃)后发生破坏(600℃)、吸附性能下降、2~5 nm孔段孔容减小;随着活化时间延长,活性炭的羟基含量先大幅减小(120~150 min)后无规律变化,孔隙先扩大(120~180 min)后收缩(
>
180 min),吸附性能
>
180 min后迅速下降,碳结构和2~5 nm孔段孔容无显著变化。在磷酸浸渍比1.5、活化温度500℃、活化时间180 min条件下,制得活性炭的比表面积为678.52
m
2
·g
-1
,2~5 nm孔段的孔容达0.1475 cm
3
·g
-1
、占总孔容比率为31.04%、占中孔容比率为70.24%。
Peat was sampled
crushed
ground
impregnated with H
3
PO
4
briquetted and re-crushed
then a series of activated carbon samples were prepared by activation in tube furnace at different temperature and time. Thermogravimetric analysis of H
3
PO
4
impregnated peat samples were performed in a nitrogen environment. The adsorption capacity indexes including iodine value
methylene blue value and caramel decolorization rate were determined
and pore structure
carbonaceous structure
surface chemistry and micro morphology of activated carbon samples were characterized by gas adsorption instrument
Raman spectroscopy
infrared spectrum and scanning electron microscope
respectively. The results show that peat is cross-linked during phosphoric acid activation
and the maximum mass-loss temperature of carbonization/activation drops from around 300℃ to
ca.
200℃. With the increase of H
3
PO
4
impregnation ratio and activation temperature
content of irregular graphitic layers in activated carbon increases
and hydroxyls groups on surface of activated carbon decreases. The increase of H
3
PO
4
impregnation ratio results in gradual increase of pore development
absorption performance and volume of 2—5 nm pores. And the increase of activation temperature results in shrink firstly (at 400—550℃) and then destroy ( at 600℃) of pore structure
decrease of absorption performance and volume of 2—5 nm pores. With the increase of activation time
the content of hydroxyl groups on surface of activated carbon firstly reduces greatly (during 120—150 min) and then undergoes irregular changes
meanwhile
the pores firstly expand (during 120—180 min) and then shrink (
>
180 min)
and the absorption performance reduce rapidly after 180 min
at the same time the carbon structure and the volume of 2—5 nm pore section don t show significant change. An activated carbon with a specific surface area of 678.52
m
2
·g
-1
volume of 2—5 nm pores of 0.1475 cm
3
·g
-1
accounting for 31.04% of the total pore volume and 70.24% of the mesopore volume
can be derived under the conditions of H
3
PO
4
impregnation ratio 1.5
activation temperature 500℃
and activation time 180 min.
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