Research progress of microplastic removal from water environment by biochar

doi:10.16085/j.issn.1000-6613.2022-2168

Abstract

Abstract:

A brand-new pollutant in the aquatic environment is microplastics. Microplastic removal by conventional water treatment techniques was more constrained. The advantages of economic and environmental protection and high removal efficiency are demonstrated by the effective adsorption of microplastics with a low spontaneous desorption rate on the diversified microporous structure, high hydrophobicity and high carbon content of biochar. However, there are still some issues, such as the inability to eliminate and breakdown microplastics and the low application of biochar in multiple environments. In this review, the current state of microplastic water pollution and conventional water treatment techniques for removing them were overviewed. Firstly, the research progress of microplastic removal by adsorption on biochar was introduced, focusing on the characteristics, action mechanism and affecting factors of biochar. Secondly, the effects of physicochemical characteristics of biochar (raw materials, preparation conditions and modification methods) and microplastics (species, grain size and structural traits), and environmental factors (pH, coexisting ion and dissolved organic matter) on adsorption behavior were summarized. The current state of biochar and microplastic coexistence in soils was described. Finally, in order to provide theoretical support for the biochar removal of common microplastics from various water bodies, some recommendations were proposed for future research, including uniform microplastic classification for targeted development of biochar materials, improved experimental conditions to more accurately simulate the real world, exploration of the mechanisms of synergistic effects of biochar and microplastics, and a focus on biochar recycling.

Key words: biochar, microplastics, adsorption, aquatic environment, influencing factors

摘要：

微塑料已成为水体环境中的一种新污染物。常规水处理方法去除微塑料局限较多，生物炭的多样微孔结构、高疏水性和高碳含量能够有效吸附微塑料且自发解吸率较低，表现出经济环保、去除效率高的优势，但仍存在无法降解除去微塑料以及生物炭多环境应用性低的问题。本文概述了微塑料的水污染现状和常规水处理去除方法，重点从生物炭特性、作用机理和影响因素等方面综述了生物炭吸附去除微塑料的研究进展，分析了生物炭（原料成分、制备条件、改性方式等）和微塑料（种类、粒径、结构特征等）自身的理化性质以及环境因素（pH、共存离子、有机干扰物质等）对吸附行为的影响，并介绍了土壤中生物炭与微塑料的共存现状。最后对未来工作提出进一步统一归类微塑料以针对性开发生物炭材料、改进实验条件以真实性模拟实际环境、探索生物炭与微塑料的协同效应机制及重视生物炭循环再生等建议，以期为生物炭针对性去除不同水体中常见微塑料提供理论支持。

关键词: 生物炭, 微塑料, 吸附作用, 水体环境, 影响因素

CLC Number:

SU Jingzhen, ZHAN Jian. Research progress of microplastic removal from water environment by biochar[J]. Chemical Industry and Engineering Progress, 2023, 42(10): 5445-5458.

苏景振, 詹健. 生物炭对水环境中微塑料的去除研究进展[J]. 化工进展, 2023, 42(10): 5445-5458.

Figures/Tables 8

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主要形状分布	主要（微）塑料种类	化学式	密度/g·cm^-3	结晶度/%	主要产生途径	参考文献
碎片、薄膜类	聚乙烯（PE）	[C₂H₄] _n	0.91~0.97	55~95^[20]	工程包装材料、薄膜制品等领域	[25-26]
	聚丙烯（PP）	[C₃H₆] _n	0.90~0.91	38.4^[20]	食品包装器具、服装、管道和车辆零部件等领域
	聚酰胺（PA）	[NH-R-CO] _x	1.04~1.14	30~40^[21]	工业涂料、树脂、纺织业等领域
纤维类	聚对苯二甲酸乙二醇酯（PET）	[C₁₀H₁₂O₆] _n	1.37~1.38	0.5^[22]	电子元件、机械工业等领域
	聚氯乙烯（PVC）	[C₂H₃Cl] _n	1.35~1.45	5~10^[23]	管、线材料等领域
泡沫颗粒类	聚苯乙烯（PS）	[C₈H₈] _n	1.04~1.07	3.7^[24]	化妆品、泡沫塑料制品等领域

主要形状分布	主要（微）塑料种类	化学式	密度/g·cm^-3	结晶度/%	主要产生途径	参考文献
碎片、薄膜类	聚乙烯（PE）	[C₂H₄] _n	0.91~0.97	55~95^[20]	工程包装材料、薄膜制品等领域	[25-26]
	聚丙烯（PP）	[C₃H₆] _n	0.90~0.91	38.4^[20]	食品包装器具、服装、管道和车辆零部件等领域
	聚酰胺（PA）	[NH-R-CO] _x	1.04~1.14	30~40^[21]	工业涂料、树脂、纺织业等领域
纤维类	聚对苯二甲酸乙二醇酯（PET）	[C₁₀H₁₂O₆] _n	1.37~1.38	0.5^[22]	电子元件、机械工业等领域
	聚氯乙烯（PVC）	[C₂H₃Cl] _n	1.35~1.45	5~10^[23]	管、线材料等领域
泡沫颗粒类	聚苯乙烯（PS）	[C₈H₈] _n	1.04~1.07	3.7^[24]	化妆品、泡沫塑料制品等领域

水环境介质	采样地点（位置）和年份	主要微塑料成分（粒径分布）	主要形状	平均丰度水平（采集网/膜）	参考文献
海洋	大西洋（表层海水），2015	PET、PA（0.25~0.5mm）	纤维（94%）	(1.15±1.45)颗粒/m³（曼塔拖网，333μm）	[30]
	美国南加州太平洋（表层海水），2001	—（0.35~4.7mm）	碎片（92.7%以上）	7.25颗粒/m³（曼塔拖网，333μm）	[31]
	中国东海，2014	—（0.5~5mm，91.2%）	纤维（83.2%）	(0.167±0.138)颗粒/m³（Neuston网，333μm）	[32]
	韩国东南海，2012	PE、PP、PS、PET（2~5mm）	纤维（17.48%~35.52%）、薄膜（20.47%~39.78%）	1.92~5.51颗粒/m³；2.3~38.77颗粒/m³（曼塔拖网，330μm）	[33]
	印度洋南非东南部（海滩沉积物、冲浪带水域），2014	PS等（0.065~5mm）	纤维（90%）、碎片	(688.9±348.2)~(3308±1449)颗粒/m³； (257.9±53.36)~(1215±276.7)颗粒/m³ （WP-2 type网，80μm）	[34]
河湖	英国塔马尔河（河口地表水），2012	PE、PP、PS（>270μm）	碎片	0.028颗粒/m³（曼塔拖网，300μm）	[35]
	中国太湖，2014	PET、PP、PE （100~1000μm）	纤维	3400~25800颗粒/m³（尼龙浮游生物网，333μm）	[36]
	汉江、长江部分河段，2016	PET、PP（<2mm，80%）	纤维	(1660.0±639.1)~(8925±1591)颗粒/m³（不锈钢筛网，50μm）	[37]
	中国洞庭湖、洪湖（表层水），2014	PE、PP（<2mm，80%）	纤维	1250~4650颗粒/m³（不锈钢筛网，50μm）	[38]
	德国莱茵河（表层水），2015	PS、PE（300~1000μm）	碎片、球状	693颗粒/m³（—）	[39]
饮用水	德国饮用水处理厂（地下30m水井），2014	PE、PA、PET、PVC、EP （50~150μm）	纤维、碎片	0~7颗粒/m³（不锈钢筒式过滤器，3μm）	[40]
	中国部分地区自来水，2020	PE、PP（<50μm）	碎片（53.85%~100%）、纤维（1.13%~30.77%）、球体（2.27%~36.36%）	(0.440±0.275)颗粒/m³[黑色聚碳酸酯（PC）膜，0.2μm]	[41]
	捷克共和国饮用水处理厂，2018	PET、PP、PE （<10μm，95%）	碎片、纤维	(0.338±0.076)~(0.628±0.028)颗粒/m³[聚四氟乙烯（PTFE）膜，0.2μm]	[42]
	中国塑料/玻璃瓶（饮料/啤酒），2022	PS、PP（300~1000μm）	碎片、准球形	10颗粒/mL、20~80颗粒/mL（—）	[43]

水环境介质	采样地点（位置）和年份	主要微塑料成分（粒径分布）	主要形状	平均丰度水平（采集网/膜）	参考文献
海洋	大西洋（表层海水），2015	PET、PA（0.25~0.5mm）	纤维（94%）	(1.15±1.45)颗粒/m³（曼塔拖网，333μm）	[30]
	美国南加州太平洋（表层海水），2001	—（0.35~4.7mm）	碎片（92.7%以上）	7.25颗粒/m³（曼塔拖网，333μm）	[31]
	中国东海，2014	—（0.5~5mm，91.2%）	纤维（83.2%）	(0.167±0.138)颗粒/m³（Neuston网，333μm）	[32]
	韩国东南海，2012	PE、PP、PS、PET（2~5mm）	纤维（17.48%~35.52%）、薄膜（20.47%~39.78%）	1.92~5.51颗粒/m³；2.3~38.77颗粒/m³（曼塔拖网，330μm）	[33]
	印度洋南非东南部（海滩沉积物、冲浪带水域），2014	PS等（0.065~5mm）	纤维（90%）、碎片	(688.9±348.2)~(3308±1449)颗粒/m³； (257.9±53.36)~(1215±276.7)颗粒/m³ （WP-2 type网，80μm）	[34]
河湖	英国塔马尔河（河口地表水），2012	PE、PP、PS（>270μm）	碎片	0.028颗粒/m³（曼塔拖网，300μm）	[35]
	中国太湖，2014	PET、PP、PE （100~1000μm）	纤维	3400~25800颗粒/m³（尼龙浮游生物网，333μm）	[36]
	汉江、长江部分河段，2016	PET、PP（<2mm，80%）	纤维	(1660.0±639.1)~(8925±1591)颗粒/m³（不锈钢筛网，50μm）	[37]
	中国洞庭湖、洪湖（表层水），2014	PE、PP（<2mm，80%）	纤维	1250~4650颗粒/m³（不锈钢筛网，50μm）	[38]
	德国莱茵河（表层水），2015	PS、PE（300~1000μm）	碎片、球状	693颗粒/m³（—）	[39]
饮用水	德国饮用水处理厂（地下30m水井），2014	PE、PA、PET、PVC、EP （50~150μm）	纤维、碎片	0~7颗粒/m³（不锈钢筒式过滤器，3μm）	[40]
	中国部分地区自来水，2020	PE、PP（<50μm）	碎片（53.85%~100%）、纤维（1.13%~30.77%）、球体（2.27%~36.36%）	(0.440±0.275)颗粒/m³[黑色聚碳酸酯（PC）膜，0.2μm]	[41]
	捷克共和国饮用水处理厂，2018	PET、PP、PE （<10μm，95%）	碎片、纤维	(0.338±0.076)~(0.628±0.028)颗粒/m³[聚四氟乙烯（PTFE）膜，0.2μm]	[42]
	中国塑料/玻璃瓶（饮料/啤酒），2022	PS、PP（300~1000μm）	碎片、准球形	10颗粒/mL、20~80颗粒/mL（—）	[43]

生物炭类型	制备方法	表面参数			目标微塑料（粒径，初始浓度）	吸附动力学模型（R²）	吸附等温线模型（R²）	吸附平衡时间	最大吸附容量（Q_m） /mg·g^-1	主要吸附机理	参考文献
生物炭类型	制备方法	比表面积 /m²·g^-1	总孔隙体积 /cm³·g^-1	平均孔径 /nm	目标微塑料（粒径，初始浓度）	吸附动力学模型（R²）	吸附等温线模型（R²）	吸附平衡时间	最大吸附容量（Q_m） /mg·g^-1	主要吸附机理	参考文献
污泥	650℃热解	—	—	—	PET（6.5μm，0.5g/L）	拟一级0.832 拟二级0.832	—	6h	0.008	物理吸附	[67]
秸秆						拟一级0.709 拟二级0.679		6h	0.004
梧桐皮						拟一级0.845 拟二级0.689		4h	0.008
苏格兰松	475℃慢热解3h（原始），800℃ 蒸汽活化3.5h	454~615	0.165~0.2	<2	PE（10μm，4g/L）	—	—	—	200	物理截留/粒子内扩散	[68]
云杉树皮	475℃慢热解3h（原始），800℃ 蒸汽活化3.5h	185~369	0.071~0.132	<2	PE（10μm，4g/L）	—	—	—	200	物理截留/粒子内扩散	[68]
玉米芯	500℃热解/酸氧化改性	17.8/36.9	0.04/0.09	7.31/7.07	PS（50nm，1g/L）	拟一级0.86 拟二级0.96	Langmuir 0.97 Freundlich 0.88	4h内/8h内	16/18	疏水作用、静电相互作用、孔隙填充、氢键	[69]
	700℃热解/酸氧化改性	34.5/48.2	0.06/0.11	9.12/8.82		拟一级0.93 拟二级0.98	Langmuir 0.98 Freundlich 0.94
	900℃热解/酸氧化改性	36.3/40.8	0.06/0.13	9.79/9.09		拟一级0.97 拟二级0.98	Langmuir 0.98 Freundlich 0.92
松木锯末	475℃慢热解2h（原始）	405.76	0.19	1.86	PS（1μm，0.1g/L）	拟一级0.9996	Langmuir 0.929 Freundlich 0.919	5h内	374.57	静电相互作用、表面络合作用	[70]
	475℃慢热解2h，金属Mg改性	265.47	0.41	3.83		拟一级0.9991	Langmuir 0.897 Freundlich 0.877		334.03
	475℃慢热解2h，金属Zn改性	329.87	0.34	3.83		拟一级0.9991	Langmuir 0.939 Freundlich 0.915		355.72
生物质材料	500℃、热解2h，金属Fe改性	164.6	0.12	5.2	PS（1μm，0.01g/L）	拟一级>0.95 拟二级>0.99	Langmuir>0.95 Freundlich>0.88	<10min	290.2	静电相互作用、表面络合作用	[71]
生物质材料	850℃热解2h，金属Fe改性	302.9	0.18	3.4	PS（1μm，0.01g/L）	拟一级>0.98 拟二级>0.98	Langmuir>0.93 Freundlich>0.85	<10min	290.2	静电相互作用、表面络合作用	[71]
甘蔗渣	350℃热解	1.44	—	—	PS（<500nm，0.5g/L）	拟一级0.99 拟二级0.96	Langmuir 0.939 Freundlich 0.915	<5min	44.9	静电相互作用/粒子内扩散	[72]
	550℃热解	88.18					Langmuir 0.939 Freundlich 0.915		32.6
	750℃热解	540.36					Langmuir 0.939 Freundlich 0.915		26.7
玉米芯	预处理6h，650℃热解	216.01	0.22	4.58	PS（100nm，0.02g/L）	拟一级0.99 拟二级0.98	Langmuir 0.91 Freundlich 0.90	12h	56.02	静电相互作用、氢键、疏水相互作用	[73]