改性生物炭对土壤重金属污染修复研究进展

doi:10.16085/j.issn.1000-6613.2020-0263

摘要/Abstract

摘要：

土壤中金属污染导致食用林产品、农产品中重金属高富集，严重威胁人类健康。生物炭作为简单易得，来源广泛的吸附材料，可用于土壤重金属污染物修复。本文主要综述了生物炭的制备、改性剂的选择与功能、改性方法及改性生物炭的特性。介绍了改性生物炭的表征手段如傅里叶变换红外光谱、扫描电子显微镜、X射线光电子能谱和比表面积和孔径分析仪在生物炭改性过程中的作用及分析方法。客观分析了改性生物炭的制备方式及对土壤重金属污染修复的机制及效果，并讨论生物炭及改性生物炭对重金属常见的吸附机理以及表面吸附、静电作用、离子交换和共沉淀的特征和条件。大量的研究结果表明，生物炭对降低土壤中重金属的有效态含量具有显著效果，且经过酸碱、氧化还原、吸附剂复合等方式改性后吸附性能更加高效和稳定。生物炭改性是为了提高生物炭的安全性、高效性、重复使用性和环境友好性，同时加强生物炭的重金属修复性能。因此，功能型生物炭的研制及拓展改性生物炭的应用是生物炭改性的进一步深入研究方向。

关键词: 土壤, 改性生物炭, 重金属污染, 表征技术, 修复机理

Abstract:

The high concentration of heavy metals in edible forest products and agricultural products, which results from metal pollution in soil is seriously dangerous to human health. Biochar, as a kind of easily and widely sourced adsorption material, can be available in soil remediation of heavy metal pollutants. The article reviews the preparation of biochar, selections and functions of modifier, modification methods, and the characteristics of modified biochar. Analysis methods and applications of Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), X-ray photoelectron spectroscopy(XPS) and specific surface area and pore size analyzers are introduced. The preparation method, repair mechanism and effect of modified biochar are analyzed, and the adsorption mechanism of biochar and modified biochar on heavy metals including surface adsorption, electrostatic interaction, ion exchange and coprecipitation are discussed. A large number of research results show that biochar has a significant effect on reducing the available content of heavy metals in soil, and is more efficient and stable after modification by acid/base, redox and adsorbent compound. Therefore, the goal of biochar modification is to improve the safety, efficiency, reusability, environmental friendliness, and to strengthen the capacity of heavy metal pollution remediation. Developing functional biochar and expanding the application of modified biochar are further research direction of modified biochar.

Key words: soil, modified biochar, heavy metal contamination, characterization technique, repair mechanism

中图分类号:

S156.2

黄安香, 杨定云, 杨守禄, 周显勇, 王忠伟, 刘竹, 张彦雄, 许杰. 改性生物炭对土壤重金属污染修复研究进展[J]. 化工进展, 2020, 39(12): 5266-5274.

Anxiang HUANG, Dingyun YANG, Shoulu YANG, Xianyong ZHOU, Zhongwei WANG, Zhu LIU, Yanxiong ZHANG, Jie XU. Advance in remediation of heavy metal pollution in soil by modified biochar[J]. Chemical Industry and Engineering Progress, 2020, 39(12): 5266-5274.

参考文献

1	DIELS L, VAND L N, BASTIACENS L H. New developments in treatment of heavy metal contaminated soils[J]. Reviews in Environmental Science and Biotechnology, 2002, 1(1): 75-82.
2	梁明昌.农田土壤重金属含量对农产品安全的影响研究[D]. 兰州: 兰州大学, 2016.
2	LIANG Mingchang. Effects of heavy metals in soil of farmland on the safety of agricultural products[D]. Lanzhou: Lanzhou University, 2016.
3	UCHIMIYA M, BANNON D I, WARTELLE L H. Retention of heavy metals by carboxyl functional groups of biochars in small arms range soil[J]. Journal of Agricultural and Food Chemistry, 2012, 60(7): 1798-1809.
4	唐行灿. 生物炭修复重金属污染土壤的研究[D]. 泰安: 山东农业大学, 2013.
4	TANG Xingcan. Amelioration effect of biochar on heavy metal contaminated soil[D]. Tai’an: Shandong Agricultural University, 2013.
5	计海洋, 汪玉瑛, 刘玉学, 等. 生物炭及改性生物炭的制备与应用研究进展[J]. 核农学报, 2018, 32(11): 207-213.
5	JI Haiyang, WANG Yuying, LIU Yuxue, et al. Advance in preparation and application of biochar and modified biochar research[J]. Journal of Nuclear Agricultural Science, 2018, 32(11): 207-213.
6	郭文娟, 梁学峰, 林大松, 等. 土壤重金属钝化修复剂生物炭对镉的吸附特性研究[J]. 环境科学, 2013, 34(9): 3716-3721.
6	GUO Wenjuan, LIANG Xuefeng, LIN Dasong, et al. Adsorption of Cd²⁺ on biochar from aqueous solutions[J]. Environmental Science, 2013, 34(9): 3716-3721.
7	高瑞丽, 朱俊, 汤帆, 等. 水稻秸秆生物炭对镉、铅复合污染土壤中重金属形态转化的短期影响[J]. 环境科学学报, 2016, 36(1): 251-256.
7	GAO Ruili, ZHU Jun, TANG Fan, et al. Fractions transformation of Cd, Pb in contaminated soil after short-term application of rice straw biochar[J]. Acta Scientiae Circumstantiae, 2016, 36(1): 251-256.
8	YANG Xing, LIU Jingjing, MCGROUTHER Kim, et al. Effect of biochar on the extractability of heavy metals (Cd, Cu, Pb, and Zn) and enzyme activity in soil[J]. Environmental Science and Pollution Research, 2016, 23: 974-984.
9	KOMKIENE J, BALTRENAITE E. Biochar as adsorbent for removal of heavy metal ions cadmium??, Copper??, Lead??, Zinc??] from aqueous phase[J]. International Journal of Environmental Science and Technology, 2016, 13(2): 471-482.
10	甘超. 改性生物炭的表征特性及其对Cr(Ⅵ)的吸附性能研究[D]. 长沙: 湖南大学, 2016.
10	GAN Chao. The characterizations of the modified biochar and its adsorption capacity for chromium()[D]. Changsha: Hunan University, 2016.
11	KO Y H, RAMANA D K V, YU J S. Electrochemical synthesis of ZnO branched submicrorods on carbon fibers and their feasibility for environmental applications[J]. Nanoscale Research Letters, 2013, 8(1): 1-7.
12	ALAM M A, SHAIKH W A, ALAM M O, et al. Adsorption of As (Ⅲ) and As () from aqueous solution by modified cassia fistula (golden shower) biochar[J]. Applied Water Science, 2018, 8(7): 198-212.
13	ZOU Q，AN W，WU C，et al. Red mud-modified biochar reduces soil arsenic availability and changes bacterial composition[J]. Environmental Chemistry Letters, 2018, 16(2): 615-622.
14	张越, 林珈羽, 刘沅, 等. 改性生物炭对镉离子吸附性能研究[J]. 武汉科技大学学报, 2015, 39(1): 48-52.
14	ZHANG Yue, LIN Jiayu, LIU Yuan, et al. Adsorption of cadmiumions by chemically modified biochar[J]. Journal of Wuhan University of Science and Technology, 2015, 39(1): 48-52.
15	董双快, 徐万里, 吴福飞, 等. 铁改性生物炭促进土壤砷形态转化抑制植物砷吸收[J]. 农业工程学报, 2016, 32(15): 204-212.
15	DONG Shuangkuai, XU Wanli, WU Fufei, et al. Fe-modified biochar improving transformation of arsenic form in soil and inhibiting its absorption of plant[J]. Transactions of the Chinese Society of Agricultural Engineering, 2016, 32(15): 204-212.
16	BRIDGWATER A V. Review of fast pyrolysis of biomass and product upgrading[J]. Biomass and Bioenergy, 2012, 38(2): 68-94.
17	LIU Z G, ZHANG F S, WU J. Characterization and application of chars produced from pinewood pyrolysis and hydrothermal treatment[J]. Fuel, 2010, 89(2): 510-514.
18	毛俏婷, 胡俊豪, 姚丁丁, 等. 生物炭催化生物质热化学转化利用的研究进展[J]. 化工进展, 2020, 39(4): 1302-1307.
18	MAO Xiaoting, HU Junhao, YAO Dingding, et al. Biochar for thermo-chemical conversion of biomass: a review[J]. Chemical Industry and Engineering Progress, 2020, 39(4): 1302-1307.
19	AKIYA N，SAVAGE P E．Roles of water for chemical reactions in high temperature water[J]. Chemical Reviews, 2002, 102(8): 2725-2750.
20	王秀芳. 高比表面积活性炭的制备、表征及应用[D]. 广州: 华南理工大学, 2006.
20	WANG Xiufang. Preparation, characterization and application of high specific surface area activated carbon[D]. Guangzhou: South China University of Technology, 2006.
21	赵明静. 改性生物炭的制备及其对Pb⁽²⁺⁾的吸附作用[D]. 石家庄: 河北师范大学, 2017.
21	ZHAO Mingjing. Synthesis and adsorption properties of modified biochars for Pb²⁺ removal[D]. Shijiazhuang: Hebei Normal University, 2017.
22	夏靖靖, 刘沅, 童仕唐, 等. 改性生物炭对Ni²⁺和Cu²⁺的吸附[J]. 化工环保, 2016, 36(4): 428-433.
22	XIA Jingjing, LIU Yuan, TONG Shitang, et al. Adsorption of Ni²⁺ and Cu²⁺ on modified biochar[J]. Environmental Protection of Chemical Industry, 2016, 36(4): 428-433.
23	郭大勇, 商东耀, 王旭刚, 等. 改性生物炭对玉米生长发育、养分吸收和土壤理化性状的影响[J]. 河南农业科学, 2017, 46(2): 22-27.
23	GUO Dayong, SHANG Dongyao, WANG Xugang, et al. Effects of modified biochar on growth，nutrients uptake of maize and soil physicochemical properties[J]. Journal of Henan Agricultural Sciences, 2017, 46(2): 22-27.
24	DING Zhuhong， HU Xin， WAN Yongshan, et al. Removal of lead, copper, cadmium, zinc, and nickel from aqueous solutions by alkali-modified biochar: batch and column tests[J]. Journal of Industrial & Engineering Chemistry, 2015, 33:239-245.
25	KOLODY?SKA D, B?K J, KOZIOL M, et al. Investigations of heavy metal ion sorption using nanocomposites of iron-modified biochar[J]. Nanoscale Research Letters, 2017, 12(1): 433-446.
26	张明明. 生物炭改性材料的制备及其对水体中六价铬的吸附机理研究[D]. 长沙: 湖南大学, 2016.
26	ZHANG Mingming. Research on the preparation of the modified materials of biological carbon and the adsorption mechanism of six chromium in water[D]. Changsha: Hunan University, 2016.
27	FRI?TáK V, RICHVEISOVá B M, VIGLA?OVá E, et al. Sorption separation of Eu and As from single-component systems by Fe-modified biochar: kinetic and equilibrium study[J]. Journal of the Iranian Chemical Society, 2017, 14(3): 521-530.
28	MONSER L, ADHOUM N. Modified activated carbon for the removal of copper, zinc, chromium and cyanide from wastewater[J]. Separation and Purification Technology, 2002, 26(2): 137-146.
29	杨兰, 李冰, 王昌全, 等. 改性生物炭材料对稻田原状和外源镉污染土钝化效应[J]. 环境科学, 2016, 37(9): 3562-3574.
29	YANG Lan, LI Bing, WANG Changquan, et al. Effect of modified biochars on soil cadmium stabilization in paddy soil suffered from original or exogenous contamination[J]. Environmental Science, 2016, 37(9): 3562-3574.
30	于长江. 生物炭复合材料的制备及其对重金属离子的吸附行为和机制研究[D]. 昆明: 昆明理工大学, 2018.
30	YU Changjiang. Preparation and characterization of biochar composites and its adsorption behavior and mechanism investigation of heavy metal ions[D]. Kunming: Kunming University of Science and Technology, 2018.
31	YAMASHITA T, HAYES P. Analysis of XPS spectra of Fe²⁺ and Fe³⁺ ions in oxide materials[J]. Applied Surface Science, 2008, 254(8): 2441-2449.
32	LIU Fenglin, ZUO Jiane, CHI Tong, et al. Removing phosphorus from aqueous solutions by using iron-modified corn straw biochar[J]. Frontiers of Environmental Science and Engineering, 2015, 9(6): 1066-1075.
33	孟繁健, 朱宇恩, 李华, 等. 改性生物炭负载nZVI对土壤Cr(Ⅵ)的修复差异研究[J]. 环境科学学报, 2017, 37(12): 270-278.
33	MENG FanJian, ZHU Yuen, LI Hua, et al．Effects of the remediation of Cr() in soil by nanoscale zero-valent iron (nZVI) with modified biochar[J]. Acta Scientiae Circumstantiae, 2017, 37(12): 4715-4723.
34	肖正辉, 李学良, 邢高瞻, 等．酸处理对秸秆基活性炭电化学性能的影响[J]. 硅酸盐学报, 2011, 39(4): 596-600.
34	XIAO Zhenghui, LI Xueliang, XING Gaozhan, et al. Effects of acidic solution treatmen on electrochemical performance of straw based activated carbon[J]. Journal of the Chinese Ceramic Society, 2011, 39(4): 596-600.
35	O'CONNOR D, PENG T Y, LI G H, et al. Sulfur-modified rice husk biochar: a green method for the remediation of mercury contaminated soil[J]. Science of the Total Environment, 2017, 621: 819-826.
36	袁志辉. 改性牛粪生物炭对重金属的吸附及稳定化研究[D]. 江门: 五邑大学, 2016.
36	YUAN Zhihui. Study on the adsorption and stabilization of heavy metals by modified cow manure biochar[D]. Jiangmen: Wuyi University, 2016.
37	PATRA J M, PANDA S S, DHAL N K. Biochar as a low-cost adsorbent for heavy metal removal: a review[J]. Int. J. Res. Biosci., 2017, 6: 1-7.
38	朱永琪, 董天宇, 宋江辉, 等. 生物炭影响土壤重金属生物有效性的研究进展[J]. 江苏农业科学, 2018, 46(16): 9-14.
38	ZHU Yongqi, DONG Tianyu, SONG Jianghui, et al. Research progress of effect of biochar on heavy metal bioavailability in soils[J]. Jiangsu Agricultural Sciences, 2018, 46(16): 9-14.
39	WANG H, GAO B, WANG S, et al. Removal of Pb(), Cu(), and Cd() from aqueous solutions by biochar derived from KMnO₄ treated hickory wood[J]. Bioresour. Technol., 2015, 197: 356-362.
40	AHMAD M, RAJAPAKSHA A U, LIM J E, et al. Biochar as a sorbent for contaminant management in soil and water: a review[J]. Chemosphere, 2014, 99(3): 19-33.
41	MUKHERJE A, ZIMMERMAN A R, HARRIS W. Surface chemistry variations among a series of laboratory-produced biochars[J]. Geoderma, 2011, 163: 247-255.
42	QIAN L B, CHEN M F, CHEN B L. Competitive adsorption of cadmium and aluminum onto fresh and oxidized biochars during aging processes[J]. J. Soil. Sedim., 2015, 15: 1130-1138.
43	李力, 陆宇超, 刘娅, 等. 玉米秸秆生物炭对Cd(Ⅱ)的吸附机理研究[J]. 农业环境科学学报, 2012(11): 2277-2283.
43	LI Li, LU Yuchao, LIU Ya, et al. Adsorption mechanisms of cadmium() on biochars derived from corn straw[J]. Journal of Agro-Environment Science, 2012, 31(11): 2277-2283.
44	DONG X L, MA L Q, ZHU Y J, et al. Mechanistic investigation of mercury sorption by Brazilian pepper biochars of different pyrolytic temperatures based on X-ray photoelectron spectroscopy and flow calorimetry[J]. Environ. Sci. Technol., 2013, 47: 12156-12164.
45	SHAFEY E I. Removal of Zn(Ⅱ) and Hg(Ⅱ) from aqueous solution on a carbonaceous sorbent chemically prepared from rice husk[J]. J. Hazard Mater., 2010, 175: 319-327.
46	CAO Xinde, MA Lena, GAO Bin, et al. Dairy-manure derived biochar effectively sorbs lead and atrazine[J]. Environmental Science & Technology, 2009, 43(9): 3285-3291.
47	MELO L C A, PUGA A P, COSCIONE A R, et al. Sorption and desorption of cadmium and zinc in two tropical soils amended with sugarcane-straw-derived biochar[J]. Journal of Soils and Sediments, 2016, 16(1): 226-234.
48	QIAN Linbo, ZHANG Wenying, YAN Jingchun, et al. Effective removal of heavy metal by biochar colloids under different pyrolysis temperatures[J]. Bioresource Technology, 2016, 206: 217-224.
49	UCHIMIYA M, WARTELLE L H, KLASSON K T, et al. Influence of pyrolysis temperature on biochar property and function as a heavy metal sorbent in soil[J]. Journal of Agricultural & Food Chemistry, 2011, 59(6): 2501-2510.
50	HUAN Liang, LU Weihua, ZHANG Yuxi, et al. Relative distribution of Pb²⁺ sorption mechanisms by sludge-derived biochar[J]. Water Research, 2012, 46(3): 854-862.
51	UCHIMIYA M, BANNON D I, WARTELLE L H, et al. Lead retention by broiler litter biochars in small arms range soil: impact of pyrolysis temperature[J]. Journal of Agricultural and Food Chemistry, 2012, 60(20): 5035-5044.
52	UCHIMIYA M. KLASSON K T, WARTELLE L H,et al. Influence of soil properties on heavy etal sequestration by biochar amendment: 1. Copper sorption isotherms and the release of cations[J]. Chemosphere, 2011, 82(10): 1431-1437.

[1]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[2]	刘柏成, 李法云, 赵琦慧, 吝美霞. 禾本科植物修复多环芳烃污染土壤研究进展[J]. 化工进展, 2023, 42(7): 3736-3748.
[3]	吴中杰, 谢连科, 王晶辉, 黄仁亮. 多级结构羟基硝酸铜纳米酶的制备及其对酚类污染物的降解[J]. 化工进展, 2023, 42(1): 497-505.
[4]	颜子涵, 陈群云, 李卓, 付融冰, 李彦伟, 吴志根. 改进型土壤破碎混拌结构的性能数值分析与优化[J]. 化工进展, 2022, 41(S1): 72-80.
[5]	郑瑾, 韩瑞瑞, 李丹丹, 王馨妤, 高春阳, 杜显元, 张晓飞, 邹德勋. 过氧化尿素与微生物联合修复石油污染土壤[J]. 化工进展, 2022, 41(9): 5085-5093.
[6]	吕莹, 胡学武, 陈素素, 刘兴宇, 陈勃伟, 张明江. 多环芳烃污染土壤的微生物修复技术研究进展[J]. 化工进展, 2022, 41(6): 3249-3262.
[7]	汪林, 蒲思淇, 王明新, 薛金娟, 韩莹. 过碳酸钠修复石油污染土壤及其环境效应[J]. 化工进展, 2022, 41(4): 2171-2179.
[8]	竹涛, 韩一伟, 刘帅, 谢蔚, 苑博, 宋慧平, 程芳琴. 单原子位点催化剂及其电催化应用研究进展[J]. 化工进展, 2022, 41(2): 666-681.
[9]	唐垂云, 钟娟, 吕莹, 张明江, 孙娟, 刘兴宇. 土壤中铀污染修复技术研究进展[J]. 化工进展, 2021, 40(8): 4587-4599.
[10]	潘云飞, 唐正, 彭欣怡, 高品. 石油烃污染土壤微生物修复技术研究现状及进展[J]. 化工进展, 2021, 40(8): 4562-4572.
[11]	李薇, 王信粉, 时利香, 宋瑶, 张杰, 杜显元. 表面活性剂复配体系修复芘污染土壤实验[J]. 化工进展, 2021, 40(6): 3526-3535.
[12]	李松旌, 樊向阳, 崔二苹, 胡超, 崔丙健, 刘源, 李中阳, 景若瑶, 李胜曙. PPCPs在土壤-作物系统行为特征及环境风险的研究进展[J]. 化工进展, 2021, 40(5): 2827-2838.
[13]	幸艳, 张雪凯, 周康根, 彭长宏. CaCl₂回收液赤泥碱性调控[J]. 化工进展, 2021, 40(5): 2909-2916.
[14]	刘贤力, 侯昭胤. 重金属污染土壤回转窑协同处置和资源化利用[J]. 化工进展, 2020, 39(S1): 287-291.
[15]	王龙, 刘会娥, 于云飞, 王娩, 刘宇童, 陈爽, 王彬. 槐糖脂用于含油砂质土壤处理及石油资源回收[J]. 化工进展, 2020, 39(5): 1930-1937.