改性豆饼生物质炭对铅的吸附特性

doi:10.11934/j.issn.1673-4831.2018.07.010

摘要/Abstract

摘要：

以豆饼为前驱体制备生物炭，并对其进行KOH刻蚀改性，利用场发射扫描电子显微镜（SEM）、比表面积及孔径分析仪（BET）、X-ray能谱仪（EDS）、多晶X射线衍射仪（XRD）和傅里叶变换红外光谱仪（FTIR）等对豆饼生物炭（SYB）和改性豆饼生物炭（SYBK）进行表征，比较SYB和SYBK对Pb²⁺的吸附性能，并研究时间、Pb²⁺溶液初始浓度和pH对吸附效果的影响规律。结果表明，SYBK含有更丰富的官能团，且比表面积大大增加，SYB和SYBK对Pb²⁺的等温吸附曲线均符合Langmuir吸附模型，SYBK对Pb²⁺的实际最大吸附量达711.0 mg·g^-1，明显高于SYB（293.0 mg·g^-1）。对比SYB和SYBK的XRD谱图可知，吸附过程中SYB和SYBK表面形成了碱式碳酸铅沉淀，且吸附后溶液中含有大量矿物阳离子Ca²⁺、Mg²⁺等。上述结果可为高效吸附环境中Pb的生物炭的修饰或改性方法的研究提供参考。

关键词: 豆饼, 生物炭, 改性, 铅

Abstract:

In this study, bean cake derived biochar (SYB) was modified by potassium hydroxide (KOH) (SYBK) to improve sorptive removal of Pb²⁺ from aqueous solutions. Batch sorption experiments were carried out with different sorption time, initial sorbate concentrations and pH values. The pristine and Pb²⁺ spent sorbents were characterized with the field emission scanning electron microscopy (SEM), specific surface area and pore size analyzer (BET), X-ray spectrometer (EDS), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). Results show that the SYBK has more abundant surface functional groups and higher specific surface area. Pb²⁺ adsorption data by SYB and SYBK were well fitted with the Langmuir adsorption model and the predicted maximum adsorption capacities were 711.0 and 293.0 mg·g^-1 for SYBK and SYB, respectively. The XRD spectra of both spent sorbents revealed that Pb₃(CO₃)₂(OH)₂ precipitate was formed after sorption reaction. Besides, large quantities of alkaline cations (e. g., Ca²⁺ and Mg²⁺) was released into solution after sorption. The results above can provide reference for preparation of biochar-based sorbents for Pb²⁺ removal from aqueous solutions.

Key words: bean cake, biochar, modification, Pb²⁺

中图分类号:

X52
X712

孟莉蓉, 俞浩丹, 杨婷婷, 尹微琴, 侯建华, 王圣森, 王小治. 改性豆饼生物质炭对铅的吸附特性[J]. 生态与农村环境学报, 2018, 34(7): 643-650.

MENG Li-rong, YU Hao-dan, YANG Ting-ting, YIN Wei-qin, HOU Jian-hua, WANG Sheng-sen, WANG Xiao-zhi. Adsorption of Pb in Solution By Modified Bean Cake Biochar[J]. Journal of Ecology and Rural Environment, 2018, 34(7): 643-650.

参考文献

[1] LEHMANN J,SKJEMSTAD J,SOHI S,et al.Australian Climate-Carbon Cycle Feedback Reduced by Soil Black Carbon[J].Nature Geoscience,2008,1(12):832-835.
[2] 张千丰,王光华.生物炭理化性质及对土壤改良效果的研究进展[J].土壤与作物,2012,1(4):219-226.[ZHANG Qian-feng,WANG Guang-hua.Research Progress of Physiochemical Properties of Biochar and Its Effects as Soil Amendments[J].Soil and Crop,2012,1(4):219-226.]
[3] 吴萍萍,李录久,王家嘉,等.秸秆生物炭对矿区污染土壤重金属形态转化的影响[J].生态与农村环境学报,2017,33(5):453-459.[WU Ping-ping,LI Lu-jiu,WANG Jia-jia,et al.Effect of Application of Straw-Biochar on Forms of Heavy Metals in Mining Contaminated Soil[J].Journal of Ecology and Rural Environment,2017,33(5):453-459.]
[4] 肖承坤.我国铅污染现状分析[J].环境与可持续发展,2017,42(5):91-92.[XIAO Cheng-kun.Analysis of Present Situation About Lead Pollution in China[J].Environmental and Sustainable Development,2017,42(5):91-92.]
[5] 林宁,张晗,贾珍珍,等.不同生物质来源生物炭对Pb(Ⅱ)的吸附特性[J].农业环境科学学报,2016,35(5):992-998.[LIN Ning,ZHANG Han,JIA Zhen-zhen,et al.Adsorption of Pb(Ⅱ) by Biochar Derived From Three Types of Biomass[J].Journal of Agro-Environment Science,2016,35(5):992-998.]
[6] 安增莉,侯艳伟,蔡超,等.水稻秸秆生物炭对Pb(Ⅱ)的吸附特性[J].环境化学,2011,30(11):1851-1857.[AN Zeng-li,HOU Yan-wei,CAI Chao,et al.Lead (Ⅱ) Adsorption Characteristics on Different Biochars Derived Form Rice Straw[J].Environmental Chemistry,2011,30(11):1851-1857.]
[7] 王瑞峰,周亚男,孟海波,等.不同改性生物炭对溶液中Cd的吸附研究[J].中国农业科技导报,2016,18(6):103-111.[WANG Rui-feng,ZHOU Ya-nan,MENG Hai-bo,et al.Adsorption of Cd in Solution by Different Modified Biochar[J].Journal of Agricultural Science and Technology,2016,18(6):103-111.]
[8] 李蕊宁,王兆炜,郭家磊,等.酸碱改性生物炭对水中磺胺噻唑的吸附性能研究[J].环境科学学报,2017,37(11):4119-4128.[LI Rui-ning,WANG Zhao-wei,GUO Jia-lei,et al.Adsorption of Characteristics of Sulfathiazole in Aqueous Solution by Acid/Alkali Modified Biochars[J].Acta Scientiae Circumstantiae,2017,37(11):4119-4128.]
[9] 吕美芳.豆饼肥料发酵方法[J].河北农业,2016(4):34.
[10] 刘国成.生物炭对水体和土壤环境中重金属铅的固持[D].青岛:中国海洋大学,2014.[LIU Guo-cheng.Immobilization of Pb²⁺ in Contaminated Waters and Soils by Biochars[D].Qingdao:Ocean University of China,2014.]
[11] CHEN D H,HUANG F Z,CHENG Y B,et al.Mesoporous Anatase TiO₂ Beads With High Surface Areas and Controllable Pore Sizes:A Superior Candidate for High-Performance Dye-Sensitized Solar Cells[J].Advanced Materials,2009,21(21):2206-2210.
[12] 张小勇,刘锐,胡浩权,等.KOH活化法制备气体分离用炭分子筛膜[J].新型炭材料,2012,27(1):61-66.[ZHANG Xiao-yong,LIU Rui,HU Hao-quan,et al.Preparation of Carbon Molecular Sieve Membranes by KOH Activation for Gas Separation[J].New Carbon Materials,2012,27(1):61-66.]
[13] 夏广洁,宋萍,邱宇平.牛粪源和木源生物炭对Pb(Ⅱ)和Cd(Ⅱ)的吸附机理研究[J].农业环境科学学报,2014,33(3):569-575.[XIA Guang-jie,SONG Ping,QIU Yu-ping.Sorption of Pb(Ⅱ) and Cd(Ⅱ) by Manure-and Wood-Derived Biochars[J].Journal of Agro-Environment Science,2014,33(3):569-575.]
[14] SALEMA A A,AFZAL M T,MOTASEMI F.Is There Synergy Between Carbonaceous Material and Biomass During Conventional Pyrolysis?A TG-FTIR Approach[J].Journal of Analytical and Applied Pyrolysis,2014,105:217-226.
[15] 杜文慧,朱维琴,潘晓慧,等.牛粪源蚓粪及其生物炭对Pb²⁺、Cd²⁺的吸附特性[J].环境科学,2017,38(5):2172-2181.[DU Wen-hui,ZHU Wei-qin,PAN Xiao-hui,et al.Adsorption of Pb²⁺ and Cd²⁺From Aqueous Solution Using Vermicompost Derived Form Cow Manure and Its Biochar[J].Environmental Science,2017,38(5):2172-2181.]
[16] QIU Y P,CHENG H Y,XU C,et al.Surface Characteristics of Crop-Residue-Derived Black Carbon and Lead(Ⅱ) Adsorption[J].Water Research,2008,42(3):567-574.
[17] 徐楠楠,林大松,徐应明,等.玉米秸秆生物炭对Cd²⁺的吸附特性及影响因素[J].农业环境科学学报,2014,33(5):958-964.[XU Nan-nan,LIN Da-song,XU Ying-ming,et al.Adsorption of Aquatic Cd²⁺ by Biochar Obtained Form Corn Stover[J].Journal of Agro-Environment Science,2014,33(5):958-964.]
[18] LIANG B,LEHMANN J,SOLOMON D,et al.Black Carbon Increases Cation Exchange Capacity in Soils[J].Soil Science Society of America,2006,70(5):1719-1730.
[19] 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.[LI Li,LU Yu-chao,LIU Ya,et al.Adsorption Mechanisms of Cadmium (Ⅱ) on Biochars Derived From Corn Straw[J].Journal of Agro-Environment Science,2012,31(11):2277-2283.]
[20] 木冠南,李琳,杨立英.氧化活性炭吸附Cd(Ⅱ)离子及表面活性剂对其吸附量的影响[J].云南大学学报(自然科学版),1999,21(4):329-331.[MU Guan-nan,LI Lin,YANG Li-ying.Adsorption of Cd(Ⅱ) Ion by Activated Charcoal Oxidized and Effect of Surfactant on the Adsorption Amount[J].Journal of Yunnan University (Natural Sciences),1999,21(4):329-331.]
[21] 戈明亮,杜明艺,王雁武.介孔材料麦羟硅钠石吸附Pb²⁺的行为及机理[J].硅酸盐学报,2017,45(1):37-45.[GE Ming-liang,DU Ming-yi,WANG Yan-wu.Adsorption Performance and Mechanism of Pb²⁺ on Mesoporous Material Magadiite[J].Journal of the Chinese Ceramic Society,2017,45(1):37-45.]
[22] CAO X D,HARRIS W.Properties of Dairy-Manure-Derived Biochar Pertinent to Its Potential Use in Remediation[J].Bioresource Technology,2010,101(14):5222-5228.
[23] INYANG M,GAO B,PULLAMMANAPPALLIL P,et al.Biochar From Anaerobically Digested Sugarcane Bagasse[J].Bioresource Technology,2010,101(22):8868-8872.
[24] KAUDAL B B,CHEN D,MADHAVAN D B,et al.An Examination of Physical and Chemical Properties of Urban Biochar for Use as Growing Media Substrate[J].Biomass and Bioenergy,2016,84:49-58.
[25] 陈再明,方远,徐义亮,等.水稻秸秆生物碳对重金属Pb²⁺的吸附作用及影响因素[J].环境科学学报,2012,32(4):769-776.[CHEN Zai-ming,FANG Yuan,XU Yi-liang,et al.Absorption of Pb²⁺ by Rice Straw Derived-Biochar and Its Influential Factors[J].Acta Scientiae Circumstantiae,2012,32(4):769-776.]
[26] 潘萌娇,孙姣,贺强,等.热解终温和加热速率对棉秆热解生物炭的影响研究[J].河北工业大学学报,2014,43(5):60-66.[PAN Meng-jiao,SUN Jiao,HE Qiang,et al.The Effect of Pyrolysis Temperature and Heating Rate on Biochar Obtained From Pyrolysis of Cotton Stalk[J].Journal of Hebei University of Technology,2014,43(5):60-66.]
[27] CHEN B L,ZHOU D D,ZHU L Z.Transitional Adsorption and Partition of Nonpolar and Polar Aromatic Contaminants by Biochars of Pine Needles With Different Pyrolytic Temperatures[J].Environmental Science & Technology,2008,42(14):5137-5143.
[28] 郝蓉,彭少麟,宋艳暾,等.不同温度对黑碳表面官能团的影响[J].生态环境学报,2010,19(3):528-531.[HAO Rong,PENG Shao-lin,SONG Yan-tun,et al.Effects of Different Temperatures on Surface Functional Groups of Black Carbon[J].Ecology and Environmental Sciences,2010,19(3):528-531.]
[29] 王向前,胡学玉,陈窈君,等.生物炭及改性生物炭对水环境中重金属的吸附固定作用[J].环境工程,2016,34(12):32-37.[WANG Xiang-qian,HU Xue-yu,CHEN Yao-jun,et al.Effect of Biochar and Modified Biochar on the Adsorption and Immobilization of Heavy Metals in Water Environment[J].Environmental Engineering,2016,34(12):32-37.]
[30] 王震宇,刘国成,XING Monica,等.不同热解温度生物炭对Cd(Ⅱ)的吸附特性[J].环境科学,2014,35(12):4735-4744.[WANG Zhen-yu,LIU Guo-cheng,XING Monica,et al.Adsorption of Cd(Ⅱ) Varies With Biochars Derived at Different Pyrolysis Temperatures[J].Environmental Science,2014,35(12):4735-4744.]
[31] 董传山,李加智,孙中溪.碳酸铅及碱式碳酸铅的合成与转化[J].济南大学学报(自然科学版),2012,26(1):73-77.[DONG Chuan-shan,LI Jia-zhi,SUN Zhong-xi.Synthesis and Transformation of Cerussite and Hydrocerussite[J].Journal of University of Jinan(Science and Technology),2012,26(1):73-77.]
[32] 李瑞月,陈德,李恋卿,等.不同作物秸秆生物炭对溶液中Pb²⁺、Cd²⁺的吸附[J].农业环境科学学报,2015,34(5):1001-1008.[LI Rui-yue,CHEN De,LI Lian-qing,et al.Adsorption of Pb²⁺ and Cd²⁺ in Aqueous Solution by Biochars Dervied From Different Crop Residues[J].Journal of Agro-Environment Science,2015,34(5):1001-1008.]
[33] CAO X D,MA L N,GAO B,et al.Dairy-Manure Derived Biochar Effectively Sorbs Lead and Atrazine[J].Environmental Science & Technology,2009,43(9):3285-3291.
[34] 赵巍.水钠锰矿吸附Pb²⁺微观机理的研究[D].武汉:华中农业大学,2009.[ZHAO Wei.Study on Mechanism of Pb²⁺ Adsorption on Birnessite[D].Wuhan:Huazhong Agricultural University,2009.]