骨炭对地下水中氟的吸附及去除能力研究

doi:10.19741/j.issn.1673-4831.2018.0547

摘要/Abstract

摘要：

选择牛骨炭、猪骨炭、鸡骨炭和活性氧化铝为材料，开展等温吸附实验、动态吸附实验、连续进水吸附柱和小试实验，以研究不同材料对氟的吸附能力，并采用扫描电子显微镜（SEM）、比表面积分析仪（BET）、傅里叶红外光谱仪（FTIR）等对吸附材料进行表征。结果表明，4种材料对氟的吸附动力学均符合准二级动力学模型，属于化学吸附；活性氧化铝、牛骨炭、猪骨炭和鸡骨炭对氟的最大吸附量分别为2.487、5.336、7.974 和7.236 mg·g^-1；骨炭对氟的吸附能力和亲和力都远大于活性氧化铝；活性氧化铝作吸附剂处理农村低浓度含氟地下水时，出水中氟浓度未达到GB 5749-2006《生活饮用水卫生标准》；骨炭处理低氟浓度地下水时，对氟的净化效果好，处理后的水质能达到饮用水的标准。

关键词: 骨炭, 活性氧化铝, 氟, 吸附

Abstract:

Human health will be endangered by long term drinking of water containing excessive fluorine. Cow bone biochar, pig bone biochar, chicken bone biochar and activated alumina were selected as materials to study their capacity to adsorb fluorine based on isothermal adsorption experiments, dynamic adsorption experiments, continuous water column and small-scale experiments. The adsorption materials were analyzed by scanning electron microscopy (SEM), specific surface area measurement(BET) and fourier transform infrared spectrometer (FTIR). Results show that the adsorption kinetics of fluorine by the four materials accorded with quasi-second-order kinetics model, which belonged to chemical adsorption. The maximum adsorption capacity of fluorine by activated alumina, cow bone biochar, pig bone biochar and chicken bone biochar were 2.487, 5.336, 7.974 and 7.236 mg·g^-1, respectively. The adsorption capacity and affinity for fluorine was greater for bone biochar than activated alumina. Treating low-concentration fluorine groundwater in rural areas with activated alumina does not reduce the fluorine concentration sufficiently to meet the drinking water standard. However, good fluorine adsorption is found when using bone biochar resulting in the quality of treated groundwater meeting the drinking water standard.

Key words: bone biochar, activated alumina, fluorine, adsorption

中图分类号:

X523

曹俊敏, 李鑫, 徐德福. 骨炭对地下水中氟的吸附及去除能力研究[J]. 生态与农村环境学报, 2019, 35(8): 1064-1070.

CAO Jun-min, LI Xin, XU De-fu. Study on Capacity of Removal and Adsorption of Fluoride From Groundwater by Bone Biochar[J]. Journal of Ecology and Rural Environment, 2019, 35(8): 1064-1070.

参考文献 40

[1]	陈涛,杨晓瑛,朱宝余.利用自制骨炭除氟剂处理农村高氟地下水研究[J].中国农村水利水电,2011(8):100-103.[CHEN Tao,YANG Xiao-ying,ZHU Bao-yu.Research on the Disposal of Rural High-Fluorine Groundwater by Self-Made Defluorinating Agents Prepared With Bone Chars[J].China Rural Water and Hydropower,2011(8):100-103.]
[2]	赵良元,胡波,朱迟,等.沸石的载铁改性及饮用水除氟试验研究[J].环境科学研究,2008,21(1):168-173.[ZHAO Liang-yuan,HU Bo,ZHU Chi,et al.Modification of Activated Clinoptilolite With Fe3+ and the Efficiency in Fluoride Removal of Drinking Water[J].Research of Environmental Sciences,2008,21(1):168-173.]
[3]	WANG X C,KAWAHARA K,GUO X J.Fluoride Contamination of Groundwater and Its Impacts on Human Health in Inner Mongolia Area[J].Journal of Water Supply:Research and Technology - Aqua,1999,48(4):146-153.
[4]	MISRA A K,MISHRA A.Study of Quaternary Aquifers in Ganga Plain,India:Focus on Groundwater Salinity,Fluoride and Fluorosis[J].Journal of Hazardous Materials,2007,144(1/2):438-448.
[5]	WANG Y X,REARDON E J.Activation and Regeneration of a Soil Sorbent for Defluoridation of Drinking Water[J].Applied Geochemistry,2002,16(5):531-539.
[6]	BROWNE D,WHELTON H,O'MULLANE D.Fluoride Metabolism and Fluorosis[J].Journal of Dentistry,2005,33(3):177-186.
[7]	仇付国,王晓昌,王云波.活性氧化铝和骨炭除氟研究[J].西安建筑科技大学学报(自然科学版),2001,33(1):56-60.[QIU Fu-guo,WANG Xiao-chang,WANG Yun-bo.A Study on Fluoride Removal by Activated Alumina and Bone Charl[J].Journal of Xi'an University of Architecture & Technology (Natural Science Edition),2001,33(1):56-60.]
[8]	AYOOB S,GUPTA A K.Fluoride in Drinking Water:A Review on the Status and Stress Effects[J].Critical Reviews in Environmental Science and Technology,2006,36(6):433-487.
[9]	SUJANA M G,PRADHAN H K,ANAND S.Studies on Sorption of Some Geomaterials for Fluoride Removal From Aqueous Solutions[J].Journal of Hazardous Materials,2009,161(1):120-125.
[10]	SANDOVAL M A,FUENTES R,NAVA J L,et al.Fluoride Removal From Drinking Water by Electro-Coagulation in a Continuous Filter Press Reactor Coupled to a Flocculator and Clarifier[J].Separation and Purification Technology,2014,134:163-170.
[11]	LOGANATHAN P,VIGNESWARAN S,KANDASAMY J,et al.Defluoridation of Drinking Water Using Adsorption Processes[J].Journal of Hazardous Materials,2013,248/249:1-19.
[12]	SRIMURALI M,PRAGATHI A,KARTHIKEYAN J.A Study on Removal of Fluorides From Drinking Water by Adsorption Onto Low-Cost Materials[J].Environmental Pollution,1998,99(2):285-289.
[13]	BHATNAGAR A,KUMAR E,SILLANPÄÄ M.Fluoride Removal From Water by Adsorption:A Review[J].Chemical Engineering Journal,2011,171(3):811-840.
[14]	DU J Y,SABATINI D A,BUTLER E C.Synthesis,Characterization and Evaluation of Simple Aluminum-Based Adsorbents for Fluoride Removal From Drinking Water[J].Chemosphere,2014,101:21-27.
[15]	MEDELLIN-CASTILLO N A,LEYVA-RAMOS R,PADILLA-ORTEGA E,et al.Adsorption Capacity of Bone Char for Removing Fluoride From Water Solution.Role of Hydroxyapatite Content,Adsorption Mechanism and Competing Anions[J].Journal of Industrial and Engineering Chemistry,2014,20(6):4014-4021.
[16]	RAJKUMAR S,MURUGESH S,SIVASANKAR V,et al.Low-Cost Fluoride Adsorbents Prepared From a Renewable Biowaste:Syntheses,Characterization and Modeling Studies[J].Arabian Journal of Chemistry,2015.DOI:10.1016/j.arabjc.2015.06.028.
[17]	沈小娃.骨炭去除低浓度含氟废水的实验研究[D].赣州:江西理工大学,2011.
[18]	BRUNSON L R,SABATINI D A.An Evaluation of Fish Bone Char as an Appropriate Arsenic and Fluoride Removal Technology for Emerging Regions[J].Environmental Engineering Science,2009,26(12):1777-1784.
[19]	MIYAZAKI H,NAGASAWA S,MOTOYAMA A,et al.Chemical Reactions of Fluoride Removal by Chicken Bone Char[J].Journal of Japan Society of Civil Engineers,2014,70(7):527-534.
[20]	HIKARU M,SHIORI N,AYURI M,et al.Enhancement of Fluoride Removal by Acid and Alkaline Treatment on Chicken Bone Char[J].Journal of Ecotechnology Research,2014,17:137-142.
[21]	金浩.炭陶除氟吸附材料的研究[D].福州:福建农林大学,2009.[JIN Hao.Research on Carbon/Pottry Adsorption Composite for Removing Fluoride[D].Fuzhou:Fujian Agriculture and Forestry University,2009.]
[22]	BRUNSON L R,SABATINI D A.Practical Considerations,Column Studies and Natural Organic Material Competition for Fluoride Removal With Bone Char and Aluminum Amended Materials in the Main Ethiopian Rift Valley[J].Science of the Total Environment,2014,488/489:580-587.
[23]	ZÚÑIGA-MURO N M,BONILLA-PETRICIOLET A,MENDOZA-CASTILLO D I,et al.Fluoride Adsorption Properties of Cerium-Containing Bone Char[J].Journal of Fluorine Chemistry,2017,197:63-73.
[24]	LUKIKO K,MACHUNDA R L,IJUMBA J N.Regeneration of Fluoride-Saturated Bone Char by Means of Wood Ash and Heat[J].Fluoride,2016,49(4):549-559.
[25]	ROJAS-MAYORGA C K,BONILLA-PETRICIOLET A,AGUAYO-VILLARREAL I A,et al.Optimization of Pyrolysis Conditions and Adsorption Properties of Bone Char for Fluoride Removal From Water[J].Journal of Analytical and Applied Pyrolysis,2013,104:10-18.
[26]	MEDELLIN-CASTILLO N A,PADILLA-ORTEGA E,TOVAR-GARCÍA L D,et al.Removal of Fluoride From Aqueous Solution Using Acid and Thermally Treated Bone Char[J].Adsorption,2016,22(7):951-961.
[27]	CHEN Y N,CHAI L Y,SHU Y D.Study of Arsenic(Ⅴ) Adsorption on Bone Char From Aqueous Solution[J].Journal of Hazardous Materials,2008,160(1):168-172.
[28]	WEI S C,LI D T,HUANG Z,et al.High-Capacity Adsorption of Cr(Ⅵ) From Aqueous Solution Using a Hierarchical Porous Carbon Obtained From Pig Bone[J].Bioresource Technology,2013,134:407-411.
[29]	NIGRI E M,CECHINEL M A P,MAYER D A,et al.Cow Bones Char as a Green Sorbent for Fluorides Removal From Aqueous Solutions:Batch and Fixed-Bed Studies[J].Environmental Science and Pollution Research,2017,24(3):2364-2380.
[30]	李佳,詹艳慧,林建伟.镧改性沸石改良太湖底泥的磷吸附特征[J].生态与农村环境学报,2013,29(4):500-506.[LI Jia,ZHAN Yan-hui,LIN Jian-wei.Effect of La-Modified Zeolite on Phosphate Sorption of Taihu Lake Sediments[J].Journal of Ecology and Rural Environment,2013,29(4):500-506.]
[31]	李三姗,王楚楚,何晓云,等.改性水生植物生物炭对低浓度硝态氮的吸附特性[J].生态与农村环境学报,2018,34(4):356-362.[LI San-wei,WANG Chu-chu,He Xiao-yun,et al.Adsorption Characteristics of Modified Aquatic Biochar for Low Concentration Nitrate-Nitrogen Onto Modified Macrophytes Biochar[J].Journal of Ecology and Rural Environment,2018,34(4):356-362.]
[32]	NIGRI E M,BHATNAGAR A,ROCHA S D F.Thermal Regeneration Process of Bone Char Used in the Fluoride Removal From Aqueous Solution[J].Journal of Cleaner Production,2017,142:3558-3570.
[33]	林春香,詹怀宇,刘明华,等.球形纤维素吸附剂对Cu2+的吸附动力学与热力学研究[J].离子交换与吸附,2010,26(3):226-238.[LIN Chun-xiang,ZHAN Huai-yu,LIU Ming-hua,et al.Thermodynamics and Kinetics of Adsorption of Cu(Ⅱ) From Aqueous Solutions a Spherical Cellulose Adsorbent[J].Ion Exchange and Adsorption,2010,26(3):226-238.]
[34]	DURAN C,OZDES D,GUNDOGDU A,et al.Kinetics and Isotherm Analysis of Basic Dyes Adsorption Onto Almond Shell (Prunus dulcis) as a Low Cost Adsorbent[J].Journal of Chemical & Engineering Data,2011,56(5):2136-2147.
[35]	AYOOB S,GUPTA A K,BHAKAT P B,et al.Investigations on the Kinetics and Mechanisms of Sorptive Removal of Fluoride From Water Using Alumina Cement Granules[J].Chemical Engineering Journal,2008,140(1/2/3):6-14.
[36]	YADAV A K,ABBASSI R,GUPTA A,et al.Removal of Fluoride From Aqueous Solution and Groundwater by Wheat Straw,Sawdust and Activated Bagasse Carbon of Sugarcane[J].Ecological Engineering,2013,52:211-218.
[37]	赵延杰,张蒋维,迟万凯,等.纳米羟基磷灰石对氟离子的吸附[J].济南大学学报(自然科学版),2011,25(2):138-141.[ZHAO Yan-jie,ZHANG Jiang-wei,CHI Wan-kai,et al.Adsorption of Fluoride Form Aqueous Solution by Nano-Hydroxyapatite[J].Journal of University of Jinan(Science and Technology),2011,25(2):138-141.]
[38]	郝晓伟,黄益宗,崔岩山,等.赤泥和骨炭对污染土壤As化学形态及其生物可给性的影响[J].环境化学,2010,29(3):383-387.[HAO Xiao-wei,HUANG Yi-zong,CUI Yan-shan,et al.Effects of Red Mud and Bone Char Addition on Fractionation and Bio-Accessibility of Arsenic in Contaminated Soil[J].Environmental Chemistry,2010,29(3):383-387.]
[39]	EL HADDAD M,MAMOUNI R,SAFFAJ N,et al.Removal of a Cationic Dye-Basic Red 12-From Aqueous Solution by Adsorption Onto Animal Bone Meal[J].Journal of the Association of Arab Universities for Basic and Applied Sciences,2012,12(1):48-54.
[40]	王涌.饮用水骨炭除氟机理的研究[J].广州大学学报(自然科学版),2003,2(5):423-426.[WANG Yong.Research on Removing Fluoride Mechanism From Drinking Water by Using Bone Char[J].Journal of Guangzhou University(Natural Science Edition),2003,2(5):423-426.]