生物炭吸附重金属离子的研究进展

doi:10.16085/j.issn.1000-6613.2018-0993

化工进展 ›› 2019, Vol. 38 ›› Issue (01): 692-706.DOI: 10.16085/j.issn.1000-6613.2018-0993

生物炭吸附重金属离子的研究进展

王重庆¹(),王晖²,江小燕¹,黄荣¹,曹亦俊¹()

1. 郑州大学化工与能源学院，河南郑州 450001
2. 中南大学化学化工学院，湖南长沙 410083

收稿日期:2018-05-14 修回日期:2018-07-05 出版日期:2019-01-05 发布日期:2019-01-05
通讯作者: 曹亦俊
作者简介:王重庆（1990—），男，博士，讲师，研究方向为固体废弃物资源化和废水处理。E-mail：<email>zilangwang@126.com</email>。|曹亦俊，博士，教授，博士生导师，研究方向为微细粒浮选理论及工艺。E-mail：<email>yijuncao@126.com</email>。
基金资助:
中国博士后科学基金项目(2018M630838);河南省高等学校重点科研项目(19B530002);中国博士后科学基金项目（2018M630838）；河南省高等学校重点科研项目（19B530002）。

Research advances on adsorption of heavy metals by biochar

Chongqing WANG¹(),Hui WANG²,Xiaoyan JIANG¹,Rong HUANG¹,Yijun CAO¹()

1. School of Chemical Engineering and Energy, Zhengzhou University, Zhengzhou 450001, Henan, China
2. School of Chemistry and Chemical Engineering, Central South University, Changsha 410083, Hunan, China

Received:2018-05-14 Revised:2018-07-05 Online:2019-01-05 Published:2019-01-05
Contact: Yijun CAO

摘要/Abstract

摘要：

生物炭在过去的十几年里受到了广泛关注，由于其低成本、环境友好、可再生等优点，在环境管理方面具有良好的应用前景。本文介绍了生物炭的概念、应用和性质，重点综述了生物炭吸附重金属离子的研究进展，并探讨了目前面临的挑战和应用前景。生物炭是在缺氧或无氧条件下热化学转化生物质得到多孔富碳材料，主要用于土壤改良，可以提高作物产量、实现碳封存以及减少温室气体排放，并且在催化、能源和水处理等方面具有潜在的应用。生物炭制备方法包括热解、气化、水热炭化等，生物炭的性质受生物质原料、制备工艺和技术参数影响。重点介绍了生物炭吸附重金属离子的相关研究，包括生物炭吸附重金属离子的影响因素、吸附机理和改性生物炭的制备。通过吸附动力学、吸附等温线、吸附热力学和表征技术可以揭示表面络合、静电引力、表面沉淀和离子交换等吸附机理。生物炭吸附重金属离子的最新研究主要致力于通过改性提高生物炭的吸附性能，改性方法主要包括物理化学活化以及复合金属氧化物或化合物、功能有机物、纳米粒子等。生物炭吸附重金属离子面临一些问题和挑战，距离实际废水处理应用还有一定差距。

关键词: 吸附, 解吸, 生物炭, 表面改性, 重金属, 废水

Abstract:

In the past decades, biochar has received considerable attention due to potential environmental applications and advantages of low cost, environmental friendliness and renewability. In this paper, the concept, applications and properties of biochar were summarized, as well as research advances on adsorption of heavy metals. Biochar is the porous carbonaceous materials produced by thermochemical conversion of biomass in zero or limited oxygen atmosphere and it is suitable for soil amendment. Biochar can improve crop yields, realize carbon sequestration and mitigate climate change, and also has potential applications in catalysis, energy production and wastewater treatment. Biochar can be prepared by pyrolysis, gasification and hydrothermal carbonization, and its properties depend on biomass feeds, thermochemical process and technical parameters. Adsorption of heavy metals onto biochar was surveyed, including affecting parameters, adsorption mechanism and modifications of biochar. Adsorption mechanism can be revealed by adsorption kinetics, isotherms, thermodynamics and advanced characterizations. Recent advances focus on improving adsorption performance of biochar by surface modifications, which are achieved via physicochemical activations or impregnating metal oxides, functional organics or nano particles. There exist some challenges and wide gap for treatment of real wastewater by biochar.

Key words: adsorption, desorption, biochar, surface modification, heavy metals, waste water

中图分类号:

王重庆, 王晖, 江小燕, 黄荣, 曹亦俊. 生物炭吸附重金属离子的研究进展[J]. 化工进展, 2019, 38(01): 692-706.

Chongqing WANG, Hui WANG, Xiaoyan JIANG, Rong HUANG, Yijun CAO. Research advances on adsorption of heavy metals by biochar[J]. Chemical Industry and Engineering Progress, 2019, 38(01): 692-706.

图/表 10

图2 2008—2017年生物炭相关论文数量和引用量以及研究方向分布（Web of Science ? 2018 Clarivate Analytics）

图2 减缓全球气候变化的可持续性生物炭理念

图3 生物炭的的生命周期评估

表1 生物炭不同用途及优缺点[9]

用途	作用	优点	缺点
土壤修复	碳封存、土壤改良	廉价、可持续性资源、保留水分和养分、降低肥料消费、减少温室气体释放	重金属和多环芳烃污染风险
吸附剂	吸附土壤和水体中的重金属和有机污染物	廉价、丰富的可持续资源、表面基团有利于吸附	吸附性能随前体的不同变化较大、对有机/无机污染物修复效率不稳定
生物质废弃物管理	碳封存、减少废弃物排放	实现废弃生物质资源化、减少温室气体释放	存在污染的潜在风险
燃料电池	燃料电池燃料	可再生能源	高灰分、电压和能量输出较低
储存材料	二氧化碳封存、氢气储存	廉价、丰富的可持续资源	需要表面处理
催化剂	负载活性组分、催化作用	共催化、廉价、易于回收负载的金属	效率低、耐磨性差

表2 生物炭制备工艺[19]

工艺	温度 /℃	加热速率 /℃·min^-1	停留时间	目标产物	生物炭产率/%
快速热解	400～600	约60000	数秒	生物油	10～20
慢速热解	350～800	<10	数分到数小时	生物炭	20～40
气化	700～1500	＞100	数秒到数分	合成气	约10
水热炭化	175～250	＜10	数小时	水热炭	30～60
烘焙	200～300	＜10	数分到数小时	坚硬生物炭	67～84

图4 生物质热解的动态分子演变机制

图5 不同生物炭氢碳比和氧碳比对温度的响应关系

表3 吸附动力学模型[40,41,42]

动力学模型	线性方程	线性拟合	特征参数
准一级动力学	$l n Q e - Q t = l n Q e - k 1 t$	ln(Q _e-Q_t )对t	Q _e，k ₁
准二级动力学	$t Q t = 1 k 2 Q e 2 + t Q e$	t/Q_t 对t	Q _e，k ₂
内扩散动力学	$Q t = k t + C$	Q_t 对t ^0.5	k
液膜扩散动力学	$l n 1 - Q t Q e = - k t + B$	ln(1-Q_t /Q _e)对t	k
Elovich动力学	$Q t = l n t β + l n α β β$	Q_t 对lnt	α，β

表3 吸附动力学模型[40,41,42]

动力学模型	线性方程	线性拟合	特征参数
准一级动力学	$l n Q e - Q t = l n Q e - k 1 t$	ln(Q _e-Q_t )对t	Q _e，k ₁
准二级动力学	$t Q t = 1 k 2 Q e 2 + t Q e$	t/Q_t 对t	Q _e，k ₂
内扩散动力学	$Q t = k t + C$	Q_t 对t ^0.5	k
液膜扩散动力学	$l n 1 - Q t Q e = - k t + B$	ln(1-Q_t /Q _e)对t	k
Elovich动力学	$Q t = l n t β + l n α β β$	Q_t 对lnt	α，β

表4 吸附等温线模型

模型	非线性方程	线性方程	线性拟合	特征参数
Langmuir	$Q e = Q m b C e 1 + b C e$	$C e Q e = 1 b Q e + C e Q m$	C _e/Q _e对C _e	Q _m，b，R _L
Freundlich	$Q e = K F C e 1 / n$	$l g Q e = l g K F + 1 n l g C e$	lgQ _e对lgC _e	n，K _F
Dubinin-Radushkevich	$Q e = Q m e x p - β ε 2$ $E = 1 / 2 β$	$l n Q e = l n Q m - β ε 2$	lnQ _e对ε²	Β，ε，E
Temkin	$Q e = R T b l n A C e$	$Q e = R T b l n A + R T b l n C e$	Q _e对lnC _e	b，A
Flory–Huggins	$θ C 0 = K 1 - θ n$	$l g θ C 0 = l g K + n l g 1 - θ$	lg $θ C 0$ 对lg(1-θ)	θ，K
Hill	$Q e = Q m C e n K + C e n$	$l g Q e Q m - Q e = n l g C e - l g K$	lg $Q e Q m - Q e$ 对lgC _e	K _， n
Sips	$Q e = K C e β 1 + a C e β$	$l n K Q e = l n a - β l n C e$	ln $K Q e$ 对lnC _e	K，a，β
Toth	$Q e = K C e a + C e 1 / n$	$l n Q e K = l n C e - 1 n l n a + C e$	ln $Q e K$ 对lnC _e	K，a_. ，n

表4 吸附等温线模型

模型	非线性方程	线性方程	线性拟合	特征参数
Langmuir	$Q e = Q m b C e 1 + b C e$	$C e Q e = 1 b Q e + C e Q m$	C _e/Q _e对C _e	Q _m，b，R _L
Freundlich	$Q e = K F C e 1 / n$	$l g Q e = l g K F + 1 n l g C e$	lgQ _e对lgC _e	n，K _F
Dubinin-Radushkevich	$Q e = Q m e x p - β ε 2$ $E = 1 / 2 β$	$l n Q e = l n Q m - β ε 2$	lnQ _e对ε²	Β，ε，E
Temkin	$Q e = R T b l n A C e$	$Q e = R T b l n A + R T b l n C e$	Q _e对lnC _e	b，A
Flory–Huggins	$θ C 0 = K 1 - θ n$	$l g θ C 0 = l g K + n l g 1 - θ$	lg $θ C 0$ 对lg(1-θ)	θ，K
Hill	$Q e = Q m C e n K + C e n$	$l g Q e Q m - Q e = n l g C e - l g K$	lg $Q e Q m - Q e$ 对lgC _e	K _， n
Sips	$Q e = K C e β 1 + a C e β$	$l n K Q e = l n a - β l n C e$	ln $K Q e$ 对lnC _e	K，a，β
Toth	$Q e = K C e a + C e 1 / n$	$l n Q e K = l n C e - 1 n l n a + C e$	ln $Q e K$ 对lnC _e	K，a_. ，n

图6 生物炭对重金属离子吸附机理

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生物炭吸附重金属离子的研究进展

Research advances on adsorption of heavy metals by biochar

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