新型壳聚糖/锆复合球的制备及硼吸附性能

doi:10.11949/j.issn.0438-1157.20170634

摘要/Abstract

摘要：

通过氧氯化锆与壳聚糖的配位反应以及Zr （OH）4在壳聚糖内的原位沉淀，制备了一种新型壳聚糖-锆复合球（CTS-Zr）并用于硼的吸附分离。采用扫描电子显微镜（SEM）和傅里叶红外光谱（FTIR）对CTS-Zr进行了表征，系统考察了溶液pH、硼初始浓度、接触时间、温度及共存阴离子Cl^-、NO₃^-和SO₄^2-对CTS-Zr吸附性能的影响。结果表明：pH=2～7时，CTS-Zr对硼的吸附效率较高；吸附平衡行为符合Langmuir等温吸附模型；pH=7时，最大吸附量计算值为21.1 mg·g^-1；吸附动力学符合准二级动力学模型；常见的共存阴离子对硼的吸附影响很小；吸附热力学研究表明，CTS-Zr对硼的吸附过程为放热的非自发过程；使用pH=12的NaOH水溶液，对吸附剂CTS-Zr进行了洗脱，洗脱效率为96.3%，且经过3次吸附-解吸循环后，CTS-Zr的吸附效率没有明显降低。

关键词: 壳聚糖, 锆, 复合球, 硼, 吸附, 模型

Abstract:

A new type of chitosan-zirconium composite particles (CTS-Zr) has been prepared through coordination reaction between zirconium oxychloride and chitosan, and in-situ precipitation of zirconium hydroxide for the adsorption of boron from solution. The CTS-Zr composite was characterized by scanning electron microscope (SEM) and Fourier transform infrared spectroscopy (FTIR). The effects of pH, initial boron concentration, contact time, temperature and co-existing ions Cl^-, NO₃^-, and SO₄^2- on adsorption performance were also investigated systematically. The results demonstrated that prepared adsorbent could maintain high boron adsorption efficiency in a pH range from 2 to 7. The equilibrium adsorption behavior of boron on the CTS-Zr composite had a good agreement with the Langmuir isotherm model, and the maximum adsorption capacity was calculated as 21.1 mg·g^-1 with pH of 7. The uptake kinetics was fitted well with the pseudo-second order rate equation, and the common coexisting anions almost had no negative effect on the boron adsorption. The results of adsorption thermodynamics of boron on CTS-Zr indicate the exothermic and not spontaneous nature of the adsorption process. The boron adsorbed on CTS-Zr particles was regenerated with an efficiency of 96.3% using NaOH solution of pH of 12, and the adsorption efficiency was not significantly reduced after three adsorption-desorption cycles.

Key words: chitosan, zirconium, composite particles, boron, adsorption, model

中图分类号:

TQ128⁺.54

王雄, 刘明言. 新型壳聚糖/锆复合球的制备及硼吸附性能[J]. 化工学报, 2018, 69(2): 848-857.

WANG Xiong, LIU Mingyan. Characteristics of boron adsorption onto a novel chitosan/zirconium composite particles[J]. CIESC Journal, 2018, 69(2): 848-857.

参考文献

[1] GUAN Z M, LÜ J F, BAI P, et al. Boron removal from aqueous solutions by adsorption-a review[J]. Desalination, 2016, 383:29-37.
[2] Word Health Organization. Guidelines for Drinking-Water Quality[M]. Geneva:World Health Organization, 2011.
[3] LIN J Y, SHIH Y J, CHEN P Y, et al. Precipitation recovery of boron from aqueous solution by chemical oxo-precipitation at room temperature[J]. Applied Energy, 2016, 164:1052-1058.
[4] ZHANG R, XIE Y M, SONG J F, et al. Extraction of boron from salt lake brine using 2-ethylhexanol[J]. Hydrometallurgy, 2016, 160:129-136.
[5] TU K L, NGHIEM L D, CHIVAS A R. Boron removal by reverse osmosis membranes in seawater desalination applications[J]. Separation and Purification Technology, 2010, 75(2):87-101.
[6] ISA M H, EZECHI E H, AHMED Z, et al. Boron removal by electrocoagulation and recovery[J]. Water Research, 2014, 51:113-123.
[7] LIU H N, YE X S, LI Q, et al. Boron adsorption using a new boron-selective hybrid gel and the commercial resin D564[J]. Colloids and Surfaces A-Physicochemical and Engineering Aspects, 2009, 341(1/2/3):118-126.
[8] WEI Y T, ZHENG Y M, CHEN J P. Design and fabrication of an innovative and environmental friendly adsorbent for boron removal[J]. Water Research, 2011, 45(6):2297-2305.
[9] KIPCAK I, OZDEMIR M. Boron recovery from clay waste using Diaion CRB-02 resin[J]. Environmental Technology, 2010, 31(3):327-335.
[10] YAN C Y, YI W T, MA P H, et al. Removal of boron from refined brine by using selective ion exchange resins[J]. Journal of Hazardous Materials, 2008, 154(1/2/3):564-571.
[11] KAMEDA T, OBA J, YOSHIOKA T. New treatment method for boron in aqueous solutions using Mg-Al layered double hydroxide:kinetics and equilibrium studies[J]. Journal of Hazardous Materials, 2015, 293:54-63.
[12] LI P, LIU C, ZHANG L, et al. Enhanced boron adsorption onto synthesized MgO nanosheets by ultrasonic method[J]. Ultrasonics Sonochemistry, 2017, 34:938-946.
[13] GOLI E, RAHNEMAIE R, HIEMSTRA T, et al. The interaction of boron with goethite:experiments and CD-MUSIC modeling[J]. Chemosphere, 2011, 82(10):1475-1481.
[14] KIPCAK I, OZDEMIR M. Removal of boron from aqueous solution using calcined magnesite tailing[J]. Chemical Engineering Journal, 2012, 189:68-74.
[15] PEAK D, LUTHER G W, SPARKS D L. ATR-FTIR spectroscopic studies of boric acid adsorption on hydrous ferric oxide[J]. Geochimica et Cosmochimica Acta, 2003, 67(14):2551-2560.
[16] TSAI H C, LO S L. Boron recovery from high boron containing wastewater using modified sub-micron Ca(OH)2 particle[J]. International Journal of Environmental Science and Technology, 2015, 12(1):161-172.
[17] SHEN C S, CHEN H, WU S S, et al. Highly efficient detoxification of Cr(Ⅵ) by chitosan-Fe(Ⅲ) complex:process and mechanism studies[J]. Journal of Hazardous Materials, 2013, 244:689-697.
[18] SHEN C S, SHEN Y, WEN Y Z, et al. Fast and highly efficient removal of dyes under alkaline conditions using magnetic chitosan-Fe(Ⅲ) hydrogel[J]. Water Research, 2011, 45(16):5200-5210.
[19] QUIGNARD F, CHOPLIN A, DOMARD A. Chitosan:a natural polymeric support of catalysts for the synthesis of fine chemicals[J]. Langmuir, 2000, 16(24):9106-9108.
[20] SHEN C S, WU L X, CHEN Y H, et al. Efficient removal of fluoride from drinking water using well-dispersed monetite bundles inlaid in chitosan beads[J]. Chemical Engineering Journal, 2016, 303:391-400.
[21] LIU Q, HU P, WANG J, et al. Phosphate adsorption from aqueous solutions by zirconium (Ⅳ) loaded cross-linked chitosan particles[J]. Journal of the Taiwan Institute of Chemical Engineers, 2016, 59:311-319.
[22] ZHANG L F, XIA W, TENG B, et al. Zirconium cross-linked chitosan composite:preparation, characterization and application in adsorption of Cr(Ⅵ)[J]. Chemical Engineering Journal, 2013, 229:1-8.
[23] LIN J W, ZHAN Y H. Adsorption of humic acid from aqueous solution onto unmodified and surfactant-modified chitosan/zeolite composites[J]. Chemical Engineering Journal, 2012, 200:202-213.
[24] VARMA A J, DESHPANDE S V, KENNEDY J F. Metal complexation by chitosan and its derivatives:a review[J]. Carbohydrate Polymers, 2004, 55(1):77-93.
[25] SORLIER P, VITON C, DOMARD A. Relation between solution properties and degree of acetylation of chitosan:role of aging[J]. Biomacromolecules, 2002, 3(6):1336-1342.
[26] SONG J C, LIU M Y, ZHANG Y. Ion-exchange adsorption of calcium ions from water and geothermal water with modified zeolite A[J]. AIChE Journal, 2015, 61(2):640-654.
[27] MONAZAM E R, SHADLE L J, MILLER D C, et al. Equilibrium and kinetics analysis of carbon dioxide capture using immobilized amine on a mesoporous silica[J]. AIChE Journal, 2013, 59(3):923-935.
[28] DEMETRIOU A, PASHALIDIS I. Adsorption of boron on iron-oxide in aqueous solutions[J]. Desalination and Water Treatment, 2012, 37(1/2/3):315-320.
[29] ZELMANOV G, SEMIAT R. Boron removal from water and its recovery using iron (Fe³⁺) oxide/hydroxide-based nanoparticles (NanoFe) and NanoFe-impregnated granular activated carbon as adsorbent[J]. Desalination, 2014, 333(1):107-117.
[30] FERREIRA O P, MORAES S G, DURAN N, et al. Evaluation of boron removal from water by hydrotalcite-like compounds[J]. Chemosphere, 2006, 62(1):80-88.
[31] POLOWCZYK I, ULATOWSKA J, KOZLECKI T, et al. Studies on removal of boron from aqueous solution by fly ash agglomerates[J]. Desalination, 2013, 310:93-101.
[32] DEMEY H, VINCENT T, RUIZ M, et al. Development of a new chitosan/Ni(OH)2-based sorbent for boron removal[J]. Chemical Engineering Journal, 2014, 244:576-586.
[33] DEMEY H, VINCENT T, RUIZ M, et al. Boron recovery from seawater with a new low-cost adsorbent material[J]. Chemical Engineering Journal, 2014, 254:463-471.
[34] IPEK I Y, KABAY N, YUKSEL M. Modeling of fixed bed column studies for removal of boron from geothermal water by selective chelating ion exchange resins[J]. Desalination, 2013, 310:151-157.
[35] ÖZDEMIR M, KIPÇAK ?. Boron recovery from borax sludge using solid-liquid extraction followed by sorption with a boron selective resin in column[J]. Environmental Progress, 2007, 26(4):375-383.
[36] HO Y S, MCKAY G. The sorption of lead(Ⅱ) ions on peat[J]. Water Research, 1999, 33(2):578-584.
[37] HO Y S, MCKAY G. Pseudo-second order model for sorption processes[J]. Process Biochemistry, 1999, 34(5):451-465.um (IV) loaded cross-linked chitosan particles[J]. Journal of the Taiwan Institute of Chemical Engineers, 2016, 59:311-319.
[22] ZHANG L, XIA W, TENG B, et al. Zirconium cross-linked chitosan composite:Preparation, characterization and application in adsorption of Cr(VI)[J]. Chemical Engineering Journal, 2013, 229:1-8.
[23] LIN J, ZHAN Y. Adsorption of humic acid from aqueous solution onto unmodified and surfactant-modified chitosan/zeolite composites[J]. Chemical Engineering Journal, 2012, 200:202-213.
[24] VARMA A J,DESHPANDE S V,Kennedy J F. Metal complexation by chitosan and its derivatives:a review[J]. Carbohydrate Polymers, 2004, 55(1):77-93.
[25] SORLIER P, VITON C, Domard A. Relation between solution properties and degree of acetylation of chitosan:Role of aging[J]. Biomacromolecules, 2002, 3(6):1336-1342.
[26] SONG J, LIU M, ZHANG Y. Ion-exchange adsorption of calcium ions from water and geothermal water with modified zeolite A[J]. AIChE Journal, 2015, 61(2):640-654.
[27] MONAZAM E R, SHADLE L J, MILLER D C, et al. Equilibrium and kinetics analysis of carbon dioxide capture using immobilized amine on a mesoporous Silica[J]. AIChE Journal, 2013, 59(3):923-935.
[28] DEMETRIOU A, PASHALIDIS I. Adsorption of boron on iron-oxide in aqueous solutions[J]. Desalination and Water Treatment, 2012, 37(1-3):315-320.
[29] ZELMANOV G, SEMIAT R. Boron removal from water and its recovery using iron (Fe+3) oxide/hydroxidebased nanoparticles (NanoFe) and NanoFe-impregnated granular activated carbon as adsorbent[J]. Desalination, 2014, 333(1):107-117.
[30] FERREIRAO P, MORAES S G, DURAN N, et al. Evaluation of boron removal from water by hydrotalcitelike compounds[J]. Chemosphere, 2006, 62(1):80-88.
[31] POLOWCZYK I, ULATOWSKA J, KOZLECKI T, et al. Studies on removal of boron from aqueous solution by fly ash agglomerates[J]. Desalination, 2013, 310:93-101.
[32] DEMEY H, VINCENT T, RUIZ M, et al. Development of a new chitosan/Ni(OH)2-based sorbent for boron removal[J]. Chemical Engineering Journal, 2014, 244:576-586.
[33] DEMEY H, VINCENT T, RUIZ M, et al. Boron recovery from seawater with a new low-cost adsorbent material[J]. Chemical Engineering Journal, 2014, 254:463-471.
[34] IPEK I Y, KABAY N, YUKSEL M. Modeling of fixed bed column studies for removal of boron from geothermal water by selective chelating ion exchange resins[J]. Desalination, 2013, 310:151-157.
[35] OezdemIR M, KIPCAK I. Boron recovery from borax sludge using solid-liquid extraction followed by sorption with a boron selective resin in column[J]. Environmental Progress, 2007, 26(4):375-383.
[36] HO Y S, MCKAY G. The sorption of lead(Ⅱ) ions on peat[J]. Water Research, 1999, 33(2):578-584.
[37] HO Y S, MCKAY G. Pseudo-second order model for sorption processes[J]. Process Biochemistry, 1999, 34(5):451-465.