毛豆壳生物炭的活化及其对甲萘威的吸附性能

doi:10.3969/j.issn.1004-1524.20220998

浙江农业学报 ›› 2023, Vol. 35 ›› Issue (9): 2202-2211.DOI: 10.3969/j.issn.1004-1524.20220998

毛豆壳生物炭的活化及其对甲萘威的吸附性能

韩静(), 朱依婷, 郑驰, 马莉红, 张亚男, 曾秋艳, 刘书亮, 陈姝娟()

四川农业大学食品学院,四川雅安 625014

收稿日期:2022-07-05 出版日期:2023-09-25 发布日期:2023-10-09
作者简介:韩静(1998—),女,四川眉山人,硕士研究生,研究方向为食品安全快速检测。E-mail:813376771@qq.com
通讯作者: 陈姝娟,E-mail:chenshujuan1@163.com
基金资助:
国家重点研发计划(2019YFC1605302)

Activation of soybean shell biochar and its adsorption performance for carbaryl

HAN Jing(), ZHU Yiting, ZHENG Chi, MA Lihong, ZHANG Yanan, ZENG Qiuyan, LIU Shuliang, CHEN Shujuan()

College of Food Science, Sichuan Agricultural University, Ya’an 625014, Sichuan, China

Received:2022-07-05 Online:2023-09-25 Published:2023-10-09

摘要/Abstract

摘要：

以KOH为活化剂,优化毛豆壳活化生物炭(A-SBC)的制备条件,研究不同体系对A-SBC吸附甲萘威的影响,分析A-SBC对甲萘威的吸附动力学、热力学特性,以期为实现毛豆壳的资源化利用和控制甲萘威农药的环境污染提供理论依据和技术支撑。结果表明:将毛豆壳在700 ℃、1 h预碳化后,与KOH按1∶2.0的质量比混合,在750 ℃、1.5 h的条件下活化,获得的A-SBC对甲萘威的吸附性能最佳,吸附率达89.63%,吸附容量为113.28 mg·g^-1。与未经活化的毛豆壳生物炭相比,A-SBC的表面凹陷,孔隙密集,有机官能团减少。当体系pH为2.0~6.5时,A-SBC对甲萘威的吸附良好,并在pH值为5.5时吸附容量最大;A-SBC对甲萘威的吸附随温度升高而增多,在离子强度(NaCl)为0.01 mol·L^-1时吸附容量最大。A-SBC对甲萘威的吸附更符合准二级动力学模型,等温吸附曲线更适于用朗缪尔(Langmuir)方程拟合,说明其以化学吸附为主。吸附热力学结果表明,A-SBC对甲萘威的吸附由疏水作用主导,是自发的吸热反应。A-SBC对甲萘威的吸附性能优良,可为去除水体环境中的甲萘威污染提供新途径与新材料。

关键词: 生物炭, 碱活化, 甲萘威, 吸附

Abstract:

In order to provide theoretical basis and technical support for the utilization of soybean shell and the control of environmental pollution of carbaryl, KOH was used as activator to optimize the preparation conditions of soybean shell activated biochar (A-SBC). The effects of different systems on the adsorption capacity of A-SBC for carbaryl were studied. The adsorption kinetics and adsorption thermodynamics of carbaryl by A-SBC were analyzed. The results showed that the A-SBC obtained by pre-carbonizing the soybean shell at 700 ℃ for 1 h, mixed with KOH at a mass ratio of 1∶2.0, and activation at 750 ℃ for 1.5 h exhibited the best adsorption performance for carbaryl. The adsorption rate and adsorption capacity were 89.63% and 113.28 mg·g^-1, respectively. After activation, the surface of A-SBC was concave, the pores were dense, and the organic functional groups wre reduced. When the pH of the system was 2.0-6.5, the adsorption performance of A-SBC was good, and the maximum adsorption capacity was recorded at the pH value of 5.5. The adsorption capaticy increased with the elevated temperature. The maximium adsorption capacity was found when the ionic strength (NaCl) was 0.01 mol·L^-1. The adsorption of carbaryl by A-SBC was more consistent with the quasi second-order dynamic model. The isothermal adsorption curve was more suitable to be fitted by Langmuir equation, which indicated that this process was mainly chemical adsorption. Thermodynamics test results showed that the adsorption of carbaryl by A-SBC was dominated by hydrophobic interaction and was a spontaneous endothermic reaction. The adsorption performance of A-SBC for carbaryl was excellent, which could provide new ways and new materials for removing carbaryl in water environment.

Key words: biochar, alkali activation, carbaryl, adsorption

中图分类号:

S609.9
X592

韩静, 朱依婷, 郑驰, 马莉红, 张亚男, 曾秋艳, 刘书亮, 陈姝娟. 毛豆壳生物炭的活化及其对甲萘威的吸附性能[J]. 浙江农业学报, 2023, 35(9): 2202-2211.

HAN Jing, ZHU Yiting, ZHENG Chi, MA Lihong, ZHANG Yanan, ZENG Qiuyan, LIU Shuliang, CHEN Shujuan. Activation of soybean shell biochar and its adsorption performance for carbaryl[J]. Acta Agriculturae Zhejiangensis, 2023, 35(9): 2202-2211.

图/表 10

图1 不同生物炭对甲萘威吸附的影响 S-500、S-600、S-700分别为在500、600、700 ℃制备的毛豆壳生物炭。A-SBC为S-700活化后的产物,即毛豆壳活化生物炭。柱上无相同字母的表示差异显著(P<0.05)。下同。

Fig.1 Effect of biochars on carbary adsorption S-500, S-600, S-700 represent soybean shell biochars produced at 500, 600, 700 ℃, respectively. A-SBC represents the activated biochar from S-700, namely, the activated soybeam shell biochar. Bars marked without the same letters indicate significant difference at P<0.05. The same as below.

图2 不同活化条件对毛豆壳活化生物炭(A-SBC)吸附甲萘威的影响

Fig.2 Effect of activation conditions on carbary adsorption by activated soybean shell biochar (A-SBC)

图3 毛豆壳生物炭活化前(a、b)和活化后(c、d)的扫描电镜图

Fig.3 Scanning electron microscope (SEM) images of soybean shell biochar before activation (a, b) and after activation (c, d)

图4 毛豆壳生物炭活化前后的红外谱图 A-SBC*为最佳活化条件下制备的毛豆壳活化生物炭。

Fig.4 Infrared spectra of soybean shell biochar before and after activation A-SBC* represents the activated soybeam shell biochar produced under the optimized activation conditions.

图5 不同体系条件下A-SBC对甲萘威的吸附容量(Q)和吸附率(R) 吸附容量柱(点)上无相同字母的表示差异显著(P<0.05)。

Fig.5 Adsorption capacity (Q) and adsorption rate (R) of carbaryl by A-SBC under different system conditions Absorption capacity columns (dots) marked without the same letter indicate significant difference at P<0.05.

图6 A-SBC对甲萘威的动力吸附曲线

Fig.6 Dynamic adsorption curves of carbaryl by A-SBC

表1 A-SBC吸附甲萘威的动力学模型参数

Table 1 Adsorption kinetics parameters of carbaryl by A-SBC

吸附剂 Adsorbent	准一级动力学模型Quasi first-order dynamic model			准二级动力学模型Quasi second-order dynamic model
吸附剂 Adsorbent	K₁/min^-1	q_e/(mg·g^-1)	R²	K₂/(g·mg^-1·min^-1)	q_e/(mg·g^-1)	R²
A-SBC	0.123 5	115.10	0.904	2.5×10^-3	118.18	0.974

图7 A-SBC对甲萘威的等温吸附曲线

Fig.7 Isothermal adsorption curves of carbaryl by A-SBC

表2 A-SBC对甲萘威的等温吸附平衡参数

Table 2 Adsorption equilibrium isothermal parameters of carbaryl by A-SBC

θ/℃	朗缪尔方程Langmuir equation			弗罗因德利希方程Freundlich equation
θ/℃	q_m/(mg·g^-1)	K_L/(L·mg^-1)	R²	K_F/[mg·g^-1·(L·mg^-1)^1/ⁿ]	1/n	R²
25	246.61	0.563	0.951	83.61	0.524	0.947
35	255.86	0.701	0.968	96.65	0.520	0.952
45	279.16	1.028	0.940	128.84	0.475	0.834

表3 A-SBC对甲萘威的吸附热力学参数

Table 3 Thermodynamic parameters of adsorption of carbaryl by A-SBC

θ/℃	ΔG⁰/(kJ· mol^-1)	ΔH⁰/(kJ· mol^-1)	ΔS⁰/(J· mol^-1·K^-1)
25	-23.671	27.471	172.695
35	-25.386	27.471	172.695
45	-27.445	27.471	172.695

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毛豆壳生物炭的活化及其对甲萘威的吸附性能

Activation of soybean shell biochar and its adsorption performance for carbaryl

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