龙凤檀磷酸法活性炭的孔径分布与吸附性能的构效关系

doi:10.3969/j.issn.0253-2417.2023.01.006

林产化学与工业 ›› 2023, Vol. 43 ›› Issue (1): 51-56.doi: 10.3969/j.issn.0253-2417.2023.01.006

龙凤檀磷酸法活性炭的孔径分布与吸附性能的构效关系

马名哲¹^,²(), 孙昊¹^,²^,*(), 孙康¹^,², 范孟孟², 张燕萍¹^,², 蒋剑春¹^,²

1. 中国林业科学研究院林产化学工业研究所；江苏省生物质能源与材料重点实验室；国家林业和草原局林产化学工程重点实验室；林木生物质低碳高效利用国家工程研究中心，江苏南京 210042
2. 南京林业大学江苏省林业资源高效加工利用协同创新中心，江苏南京 210037

收稿日期:2021-12-05 出版日期:2023-02-28 发布日期:2023-02-28
通讯作者: 孙昊 E-mail:398779536@qq.com;15850534739@163.com
作者简介:孙昊, 副研究员, 主要从事生物质基炭材料和炭基催化剂的研究工作; E-mail: 15850534739@163.com
马名哲(1997—), 男, 黑龙江黑河人, 研究实习员, 本科, 主要从事生物质炭材料研究; E-mail: 398779536@qq.com
基金资助:
江苏省自然科学基金资助项目(BK20201127);国家自然科学基金资助项目(32101474)

The Relationship Between Pore Size Distribution and Adsorption Properties of Cumaru Activated Carbon Prepared by Phosphoric Acid Method

Mingzhe MA¹^,²(), Hao SUN¹^,²^,*(), Kang SUN¹^,², Mengmeng FAN², Yanping ZHANG¹^,², Jianchun JIANG¹^,²

1. Institute of Chemical Industry of Forest Products, CAF; Key Lab. of Biomass Energy and Material, Jiangsu Province; Key Lab. of Chemical Engineering of Forest Products, National Forestry and Grassland Administration; National Engineering Research Center of Low-Carbon Processing and Utilization of Forest Biomass, Nanjing 210042, China
2. Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Najing Forestry University, Najing 210037, China

Received:2021-12-05 Online:2023-02-28 Published:2023-02-28
Contact: Hao SUN E-mail:398779536@qq.com;15850534739@163.com

摘要/Abstract

摘要：

以硬杂木龙凤檀的加工剩余物为原料，研究了磷酸活化法的活化温度、磷酸质量分数和浸渍比对龙凤檀活性炭吸附性能的影响，通过N₂吸附-脱附等温线对活性炭的结构进行分析，并根据吸附理论和DFT孔径分布图，拟合计算出活性炭有效孔道所占的孔容积与液相吸附性能(碘吸附值、亚甲基蓝吸附值和焦糖脱色率)的构效关系。研究结果表明：在磷酸质量分数60%、磷酸溶液与龙凤檀浸渍比3∶1(mL∶g)、活化温度500 ℃、活化时间120 min的条件下，磷酸活化法制备的龙凤檀活性炭具有最佳的吸附性能和优异的孔隙结构，碘吸附值为841 mg/g，亚甲基蓝吸附值为270 mg/g，焦糖脱色率为120%，比表面积为1 516 m²/g，总孔容为1.145 cm³/g，均优于软杂木杉木制备得到的活性炭。应用密度泛函理论(DFT)，计算出龙凤檀活性炭不同孔径区间对应的孔容积，经过理论分析和拟合计算，发现碘吸附值与孔径在1.0~2.7 nm之间的孔容积、亚甲基蓝吸附值与孔径在1.7~5.0 nm之间的孔容积、焦糖脱色率与孔径在2.7~6.3 nm之间的孔容积有着很好的线性关系(R²>0.95)，表明活性炭的孔隙结构分布与其液相特征吸附性能之间具有很好的关联度。

关键词: 龙凤檀, 磷酸法活性炭, 孔径分布, 液相吸附, 线性拟合

Abstract:

The influences of phosphoric acid method activation temperature, phosphoric acid concentration and impregnation ratio on adsorption performance of cumaru activated carbon were investigated by using the processing the residue of hardwood cumaru as a raw material. Structural analysis of activated carbon was analyzed by N₂ adsorption-desorption isotherm, and the structure-activity relationship between the effective pore volume and the liquid phase adsorption results(iodine adsorption value, methylene blue adsorption value and caramel decolorization rate) were calculated according to the adsorption theory and DFT pore size distribution map. The results showed that the synthesized activated carbon exhibited excellent adsorption properties and pore structure under the conditions of 60% phosphoric acid solution, the impregnation ratio of phosphoric acid to cumaru 3∶1(mL∶g), the activation temperature of 500 ℃ and the activation time of 120 min. Its iodine value, methylene blue value, caramel decolorization, specific surface area, and total pore volume were 841 mg/g, 270 mg/g, 120%, 1 516 m²/g and 1.145 cm³/g, respectively. These properties were comprehensively superior to those of the activated carbon prepared from the residues of soft wood fir. The corresponding pore volume of different pore size distributions was calculated for cumaru activated carbon using the Density Functional Theory(DFT). After theoretical analysis and fitting calculation, it was found that there was a good linear relationship between iodine adsorption value and pore volume with pore diameter of 1.0-2.7 nm, between methylene blue adsorption value and pore volume with pore diameter of 1.7-5.0 nm, and between caramel decolorization rate and pore volume with pore diameter of 2.7-6.3 nm. These results indicated a good degree of association(R²>0.95) between the pore structure distribution of activated carbon and its liquid phase adsorbing performance.

Key words: cumaru, phosphoric acid activated carbon, pore size distribution, liquid phase adsorption, linear fitting

中图分类号:

TQ35
TQ424.1

马名哲, 孙昊, 孙康, 范孟孟, 张燕萍, 蒋剑春. 龙凤檀磷酸法活性炭的孔径分布与吸附性能的构效关系[J]. 林产化学与工业, 2023, 43(1): 51-56.

Mingzhe MA, Hao SUN, Kang SUN, Mengmeng FAN, Yanping ZHANG, Jianchun JIANG. The Relationship Between Pore Size Distribution and Adsorption Properties of Cumaru Activated Carbon Prepared by Phosphoric Acid Method[J]. Chemistry and Industry of Forest Products, 2023, 43(1): 51-56.

图/表 4

表1

表2

图1

表3

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样品 sample	元素分析element analysis¹⁾/%				工业分析proximate analysis²⁾/%
样品 sample	C	H	N	O^*	水分 moisture	灰分 ash	挥发分 volatile	固定碳 fixed carbon
龙凤檀cumaru	50.92	6.35	—	42.73	0.78	0.48	81.21	17.53
杉木fir	50.63	6.49	—	42.88	1.31	0.76	81.35	16.58

条件condition		碘吸附值/ (mg·g^-1) iodine value	亚甲基蓝吸附值/ (mg·g^-1) methylene blue value	焦糖脱色率/% caramel decolorization rate
活化温度 activation temperature	400 ℃	829	225	50
	450 ℃	845	240	105
	500 ℃	850	262.5	110
	550 ℃	750	270	80
	600 ℃	734	255	75
浸渍比 impregnation ratio	2∶1	683	240	40
	3∶1	850	262.5	110
	4∶1	879	262.5	112
	5∶1	813	270	115
磷酸质量分数 phosphoric acid mass fraction	40%	806	225	80
	50%	850	262.5	110
	60%	841	270	120
	70%	835	277.5	115

磷酸质量分数/% phosphoric acid mass fraction	碘吸附值/(mg·g^-1) iodine value	V_1.0-2.7/ (cm³·g^-1)	亚甲基蓝吸附值/(mg·g^-1) methylene blue value	V_1.7-5.0/ (cm³·g^-1)	焦糖脱色率/% caramel decolorization rate	V_2.7-6.3/ (cm³·g^-1)
40	806	0.311 4	225	0.309 5	80	0.211 8
48	814	0.328 2	240	0.348 4	90	0.246 0
50	850	0.410 5	262.5	0.421 4	110	0.293 5
60	841	0.396 3	270	0.471 4	120	0.362 1
70	835	0.394 9	277.5	0.462 5	115	0.328 4

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[2]	陈继锡, 左宋林, 王永芳, 郝婧. 磷酸法活性炭的三聚氰胺表面改性及其电化学性能研究[J]. 林产化学与工业, 2016, 36(2): 37-44.
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龙凤檀磷酸法活性炭的孔径分布与吸附性能的构效关系

The Relationship Between Pore Size Distribution and Adsorption Properties of Cumaru Activated Carbon Prepared by Phosphoric Acid Method

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