双活化法制备山竹壳多孔炭材料及其对刚果红的吸附性能研究

doi:10.13304/j.nykjdb.2023.0917

摘要/Abstract

摘要：

采用新型绿色的复合活化剂酒石酸钾与氯化锌一步碳化法制备山竹壳多孔炭材料，优化制备条件并探究其吸附性能。以碘吸附值为评价指标，测定山竹壳多孔炭在不同条件下的吸附能力，结果表明，在山竹壳粉与复合活化剂浸渍比1∶1.5、酒石酸钾∶氯化锌质量比为1.5∶1、活化温度700 ℃、活化时间1 h条件下，山竹壳多孔炭材料（SSZAC3-700）吸附量最大，为1 068 mg·g^-1。通过场发射扫描电子显微镜、比表面积及孔隙分析仪、红外光谱对材料进行形貌特征、孔隙结构以及表面官能团进行表征发现，SSZAC3-700材料比表面积为1 294.69 m²·g^-1，总孔容为0.651 0 cm³·g^-1，材料孔隙结构以微孔为主，存在大量的含氧官能团。对刚果红的吸附试验表明，SSZAC3-700的吸附动力学符合准二级动力学模型，以化学吸附为主。等温吸附过程符合Langmuir吸附等温吸附模型，为单分子层吸附。热力学结果?H>0，吸附过程为吸热过程。SSZAC3-700材料对刚果红吸附再生次数为3次，去除率远高于市售活性炭。该制备方法实现了对农业废弃物山竹壳的重复再利用，为山竹壳的综合循环再利用提供了一种新思路，为环境中去除染料残留提供了一种简单快速的方法。

关键词: 山竹壳, 多孔炭, 吸附性能, 刚果红, 酒石酸钾

Abstract:

The porous carbon material-based mangosteen shells had been successfully prepared by a one-step carbonization method of potassium tartrate and zinc chloride， a new green compound activator. The preparation conditions were optimized and the adsorption properties were investigated. Taking the iodine adsorption value as the evaluation index， the adsorption capacity of porous carbon in mangosteen shell was determined under different conditions， the results showed that under the conditions of impregnation ratio between mangosteen shell powder and composite activator was 1∶1.5， the mass ratio of potassium tartrate to zinc chloride was 1.5∶1，activation temperature 700 ℃ and activation time 1 h， the adsorption capacity of porous carbon material based mangosteen shell （SSZAC3-700） was the highest， reaching 1 068 mg·g^-1. The morphology， pore structure and surface functional groups of the materials were characterized by field emission scanning electron microscopy， specific surface area and pore analyzer， and infrared spectroscopy， respectively. The results showed that the specific surface area of SSZAC3-700 was 1 294.69 m²·g^-1， and the total pore volume was 0.651 0 cm³·g^-1. The pore structure was dominated by micropores， and there were a large number of oxygen-containing functional groups. The adsorption experiments of Congo red showed that the adsorption kinetics of SSZAC3-700 conformed to the quasi-second-order kinetic model， which was mainly chemisorption. The isothermal adsorption process was the Langmuir adsorption isothermal adsorption model with monolayer adsorption. The thermodynamic results （ΔH>0） indicated that the adsorption process was an endothermic process. The adsorption and regeneration times of SSZAC3-700 for Congo red were 3 times， and the removal rate was much higher than that of the commercially available activated carbon. The preparation method facilitated the utilization of agricultural waste mangosteen shells， offering a novel approach for the comprehensive recycling of such shells and presenting a straightforward and expeditious solution for eliminating dye residues in the environment.

Key words: mangosteen shell, porous carbon, adsorption performance, Congo red, potassium tartrate

中图分类号:

S216.2

王宏利, 牛琳, 赵晓丹, 陈雷, 刘冰. 双活化法制备山竹壳多孔炭材料及其对刚果红的吸附性能研究[J]. 中国农业科技导报, 2025, 27(5): 239-249.

Hongli WANG, Lin NIU, Xiaodan ZHAO, Lei CHEN, Bing LIU. Preparation of Porous Carbon Material from Mangosteen Shell by Double Activation Method and Its Adsorption Properties for Congo Red[J]. Journal of Agricultural Science and Technology, 2025, 27(5): 239-249.

图/表 10

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样品 Sample	元素 Element
样品 Sample	碳 Carbon	氮 Nitrogen	氧 Oxygen	硫 Sulfur
SZK	74.26	1.58	22.89	1.18
SZAC	86.32	1.13	12.15	0.74
SZAC2-700	93.48	1.05	8.36	1.23
SSZAC3-700	94.62	1.12	7.05	0.68

样品 Sample	元素 Element
样品 Sample	碳 Carbon	氮 Nitrogen	氧 Oxygen	硫 Sulfur
SZK	74.26	1.58	22.89	1.18
SZAC	86.32	1.13	12.15	0.74
SZAC2-700	93.48	1.05	8.36	1.23
SSZAC3-700	94.62	1.12	7.05	0.68

模型 Sample	参数 Argument	温度 Temperature/℃			刚果红质量浓度 Congo red mass concentration/（mg·L^-1）
模型 Sample	参数 Argument	25	35	45	150	200	250
准一级动力学模型 Quasi-first-order kinetic model	平衡吸附量q_e/（mg·g^-1）	95.357 9	101.762 7	105.728 8	86.627 8	95.357 9	102.093 8
	准一级动力学常数K₁/（·min^-1）	0.237 6	0.224 2	0.228 9	0.174 6	0.237 6	0.254 2
	相关系数R²	0.993 6	0.980 0	0.990 7	0.944 1	0.993 6	0.966 2
准二级动力学模型 Quasi-second-order kinetic model	平衡吸附量q_e/（mg·g^-1）	97.519 2	104.627 4	108.383 7	90.234 4	97.519 2	106.868 5
	准二级动力学常数K₂/（g·mg^-1·min^-1）	0.004 5	0.003 5	0.003 7	0.002 7	0.004 5	0.004 0
	相关系数R²	0.998 7	0.995 2	0.999 4	0.980 9	0.998 7	0.987 8
颗粒内扩散模型 Intra particle diffusion model	平衡吸附量q_e/（mg·g^-1）	50.866 7	50.992 1	54.765 3	40.195 5	50.866 6	52.010 8
	颗粒内扩散常数K_pi/（g·mg^-1·min^-1）	2.977 0	3.454 5	3.435 4	3.164 1	2.977 0	3.428 4
	相关系数R²	0.423 6	0.508 7	0.463 8	0.563 3	0.423 6	0.498 0

模型 Sample	参数 Argument	温度 Temperature/℃			刚果红质量浓度 Congo red mass concentration/（mg·L^-1）
模型 Sample	参数 Argument	25	35	45	150	200	250
准一级动力学模型 Quasi-first-order kinetic model	平衡吸附量q_e/（mg·g^-1）	95.357 9	101.762 7	105.728 8	86.627 8	95.357 9	102.093 8
	准一级动力学常数K₁/（·min^-1）	0.237 6	0.224 2	0.228 9	0.174 6	0.237 6	0.254 2
	相关系数R²	0.993 6	0.980 0	0.990 7	0.944 1	0.993 6	0.966 2
准二级动力学模型 Quasi-second-order kinetic model	平衡吸附量q_e/（mg·g^-1）	97.519 2	104.627 4	108.383 7	90.234 4	97.519 2	106.868 5
	准二级动力学常数K₂/（g·mg^-1·min^-1）	0.004 5	0.003 5	0.003 7	0.002 7	0.004 5	0.004 0
	相关系数R²	0.998 7	0.995 2	0.999 4	0.980 9	0.998 7	0.987 8
颗粒内扩散模型 Intra particle diffusion model	平衡吸附量q_e/（mg·g^-1）	50.866 7	50.992 1	54.765 3	40.195 5	50.866 6	52.010 8
	颗粒内扩散常数K_pi/（g·mg^-1·min^-1）	2.977 0	3.454 5	3.435 4	3.164 1	2.977 0	3.428 4
	相关系数R²	0.423 6	0.508 7	0.463 8	0.563 3	0.423 6	0.498 0

模型 Model	参数 Parameter	温度 Temperature/℃
模型 Model	参数 Parameter	25	35	45
Langmuir模型 Langmuir model	吸附常数K_L/（L·mg^-1）	0.268 3	0.274 9	0.286 3
	最大饱和吸附量q_m/（mg·g^-1）	167.870 3	171.313 2	174.432 3
	决定系数R²	0.997 6	0.994 4	0.996 1
Freundlich模型 Freundlich model	吸附常数K_F/（mg·g^-1·（1/mg）^1/n）	84.673 8	87.751 8	91.178 2
	常数n	7.370 4	7.547 6	7.780 3
	决定系数R²	0.904 7	0.885 6	0.877 6
Temkin模型 Temkin model	模型常数A/（L·mg^-1）	44.238 2	51.309 5	63.979 4
	吸收热常数B	14.821 8	16.785 3	17.791 1
	决定系数R²	0.941 8	0.925 8	0.918 1