摘要
本试验将原钙基膨润土钠化、酸化,通过原位插层聚合法制备膨润土负载壳聚糖复合吸附剂。研究最优制备条件,并采用红外光谱分析、X衍射和扫描电镜等表征手段分析其表面性质、结构性能以及复合机理。为改善壳聚糖的水溶性,制备羧甲基壳聚糖以及膨润土负载羧甲基壳聚糖复合吸附剂。通过对染料碱性品红和靛蓝的吸附评价不同复合吸附剂的吸附性能,拟合NaBent-CTS和HBent-CTS对碱性品红和靛蓝的等温吸附行为,研究其吸附机理。
结果表明：制备NaBent-CTS的最优制备条件为壳聚糖浓度20g/L、温度45℃、搅拌时间4h; HBent-CTS为壳聚糖浓度20g/L、温度65℃、搅拌时间2h。壳聚糖通过与钠基膨润土间静电引力吸附作用进入其层间,扩大其层间距,得到壳聚糖插层钠基膨润土复合吸附剂；壳聚糖负载在酸性膨润土上,酸性膨润土层片间范德华作用力增强,改变其无序松散状态。制备的羧甲基壳聚糖较壳聚糖水溶性增强,并没有进入膨润土层间,仅在其表面附着堆积,吸附性能并没有明显提高。不同复合吸附剂中NaBent-CTS和HBent-CTS处理染料的效果最好,对碱性品红的脱色率分别为99.31%、99.10%；靛蓝60.06%、87.11%。研究等温吸附行为发现,Langmuir模型的拟合程度均优于Freundlich模型,对碱性品红和靛蓝的吸附为氢键作用、静电引力和物理吸附。
A bentonite composite absorbent was prepared by in-situ intercalation polymerization of chitosan directly intercalating into modified-bentonit, taking the Ca-bentonite from Linan as raw material, get the sodium modification and acidified bentonite. investigated its best preparation condition by the determination of interlayer spacing and loading amount of chitosan. The structure and composite mechanism of obtained composite adsorbent was studied by using small angle X-ray diffraction(XRD), scanning electronic microscopy(SEM), infrared spectroscopy (FIRT). Carboxymethyl chitosan(CMC) was prepared for improving the water solubility of chitosan.
The adsorption performance of all obtained composite adsorbent and modified bentonite to basic fuchsin and indigo was studied, compared their adsorption capacity, and fitted the experimental date which had highest adsorption capacity by utilizing typical adsorption isotherm models.
The results showed that the optimal condition for prepared Nabent-CTS was that chitosan concentration at 20g/L,4h stirring time and 45℃; the Hbent-CTS was 20g/L,2h and 65℃.Na-bentonite compound chitosan, chitosan had been inserted into the sodium bentonite's layer successfully by electrostatic attraction. As for HBent-CTS, the disorder state between interlayers was changed by enhanced van der waals force. Carboxymethyl chitosan had been successfully prepared, and the experimental results revealed that its water solubility was improved, but the adsorption capacity of bentonite compound Carboxymethyl chitosan was not increased significantly, Carboxymethyl chitosan had not been inserted into the modified bentonite's layer, just adhered to the surface of bentonite. Compared the adsorption capacity of both obtained adsorbent showed that the NaBent-CTS and HBent-CTS were best. Fitting the experimental data of NaBent-CTS and HBent-CTS by utilizing typical adsorption isotherm models, show Langmuir's adsorption process well relevance to the Freundlich, and the adsorption mechanism of basic fuchsin and indigo were hydrogen bonding, electrostatic force and physical adsorption.
引文
[1]阮文楼,李明路.膨润土的开发应用[M].北京：地质出版社,1998.
[2]吴东印.膨润土的提纯与开发应用[J].矿产保护与应用,2000,3:14-16.
[3]A.S Allen,J.Oliver and I.J.Black.Clay compositions and their use in paper making[J].WO 97/33041
[4]M. Vlasova,I. Leon,Y. Enriquez Mendez,G. Dominguez-Patin,M. Kakazey,M. Dominguez-Patin, M.V. Nikolic, M.M. Ristic. Monitoring of transformations in bentonite after NaOH-TMA treatment[J].2006,2295:1-8.
[5]Evans W C.Linear Systems,Compartmental Modeling,and Estimability Issues in IAQ studies Characterizing Sources of Indoor Air Pollution and Related Sink Effects[J].American Society for Testing and Materials,1996,239-262.
[6]赵丽红,刘温霞.膨润土的特点及其在造纸工业中的应用[J].中国造纸,2004,23(10):49-53.
[7]刘阳,汪永清,陈虎,等.膨润土的改性及其应用[J].中国陶瓷工业,2001,8(2):39-42.
[8]曹明礼,张凌燕,荣葵一.膨润土制备高效活性白土的研究[J].化工矿物工,2000,2:5-8.
[9]陈美,敖宁建,周慧莲等.超声技术制备蒙脱土/天然橡胶纳米复合材料[J],电子显微学报,2002,21(2)：199-202
[10]李济吾,朱利中,蔡伟建.微波合成有机膨润土及其吸附水中有机物的性能[J].中国环境科学2004,24(6)：665-669.
[11]于瑞莲,胡恭任,蔡德钰.膨润土小球的制备及其对废水中镍(Ⅱ)的吸附作用研究[J].中国矿业,2009,18(2)：105-108.
[12]Oyanedel-Craver V A, FullerM and Smith J A. Simultaneous sorption of benzene and heavy metals onto two organoclays[J].Journal of Colloid and Interface Science,2007,309(2):485-492.
[13]BentouamiM S.Cadmium removal from aqueous solutions by hy-droxy-8 quinoline in tercalated bentonite [J]. Journal of Cooloid and Interface Science,2006,29(2):270-277.
[14]孙洪良,朱利中.十六烷基三甲基季铵盐-乙硫醇铵盐复合改性膨润土吸附性能研究[J].环境科学学报,2010,30(5)：1037-1042
[15]于瑞莲,胡恭任,蔡德钰.膨润土小球的制备及其对废水中镍(Ⅱ)的吸附作用研究[J].中国矿业,2008,18(2)：105-108.
[16]潘嘉芬,卢杰.天然及改性膨润土吸附废水中Pb2+、Ni2+、Cd2+的试验研究[J].金属矿山,2008,9:130-133.
[17]R.Naseem. Removal of Pb2+ from acidic solution by using bentonite as an adsorbent[J]. Wat.Res,2001,35(16):3982-3986.
[18]沈学优.不同粘土处理水中重金属的性能研究[J].环境污染与防治,1998,20(3):15-18.
[19]孙家寿,刘羽,鲍世聪,等.交联粘土矿物的吸附特性研究(Ⅵ)-铝锆交联膨润土对废水中有机物的吸附[J].武汉化工学院学报,2000,22(2):33-35.
[20]David Christian Rodriguez.Adsorption of sodium dodecylbenzene suffonate on organphilic bentonite[J]. Applied Clay Science,2001,18(6):173-181.
[21]Chen,B.;Zhu,L.Partition of Polycyclic aromatic hydrocarbons on ogranobentonites from wate. [J]. Environ. Sci.,2001.13(2):129-36.
[22]朱利中,陈宝梁,罗瑜.有机膨润土吸附水中多环芳烃的性能及机理研究[J].环境科学学报,2000,20(1)：21-26.
[23]朱利中,陈宝梁.多环芳烃在水/膨润十间的分配行为[J].中国环境科学,2000,20(2):119-123.
[24]Naoji K, Nobuhide T, Takayuki S, etc. A simple preparation of half N-acetylated chitosan highly soluble in water and aqueous organic solvents[J].Carbohydrate Research,2000,324:268-274.
[25]蒋挺大.甲壳素[M].北京：化学工业出版社,2003.
[26]肖振宇,原续波,盛京.甲壳素、壳聚糖的改性[J].广州化学,2002,27(2):60-64.
[27]Wan Ngah W.S.,Endud C.S.,Mayanar R. Removal of copper(Ⅱ) ions from aqueous solution onto chitosan and cross-linked chitosan beads[J].Reactive & Functional Polymers,2001,50:181-190.
[28]陈培榕,吴耀国,刘保超.壳聚糖吸附处理低浓度重金属废水[J].工业水处理,2009,29(9):6-10.
[29]Hasan S,Ghosh T,Viswanath D,et al. Dispersion of chitosan on perlite for enhancement of copper(Ⅱ) adsorption capacity[J] Journal of Hazardous Materials,2008,152(2):826-837.
[30]Wu Zhongbiao, Ni Weimin, Guan Baohong. Application of chitosan as flocculant for coprecipitation of Mn(II) and suspended solids from dual-alkali FGD regenerating process [J] Journal of Hazardous Materials,2008,152(2):757-764.
[31]贝利平,单宝田,唐洪杰,等.壳聚糖的改性及其在重金属吸附方面的应用[J].海洋科学,2010,34(6)：100-103.
[32]邬建敏,王莹.以硅胶为基质的交联壳聚糖对Ni2+的吸附研究[J].环境污染与防治,2001,23(6):276-269.
[33]Choong J, Wolfgang H. Chemical modification of chitosan and equilibrium study for mercury ion remova[J].WaterRes,2003,37(19):4770-4780.
[34]孙新枝,苏中兴.改性壳聚糖的制备及其对金属离子的吸附性能[J].化学研究,2005,16(1):29-31.
[35]Chiou M S.Equilibrium and Kinetic modeling of adsorption of reactive dye on cross-linked chitosan beads[J].Journal of Hazardous Material,2002,93(2):233-248.
[36]Jung R S. Use of chemically modified chitosan beads for sorption and enzyme immobilization[J]. Advances in Environmental Research.2002,6(2):171-177.
[37]蒋明,娄金生,谢水波,等.壳聚糖絮凝剂处理水源水中有机物的实验研究[J].水处理技术,2005,31(5)：14-18.
[38]施国键,乔俊莲,王国强,等.活化粉煤灰改性壳聚糖絮凝除藻的研究[J].环境污染与防治,2009,31(9):45-48.
[39]胡慧玲,苏敏刚,徐江萍.改性壳聚糖的制备及对Cu2+ Pb2+的吸附研究[J].离子交换吸附,2007,23(3)：274-281.
[40]刘振儒,田重威.壳聚糖复合粘土矿凝聚铜绿微囊藻的研究[J].环境工程,2004,22(3):80-82.
[41]Tania Chatterjee, Sudipta Chatterjee, Seung HanWoo.Enhanced coagulation of bentonite particles in water by a modified chitosan biopolymer[J]. Chemical Enginee ring Journal,2009,148:414-419.
[42]马娟娟,刘霖,王新龙,等.壳聚糖-蒙脱土复合材料对活性艳橙X-GN吸附行为的研究[J].化学研究与应用,2009,21(4):562-565.
[43]万清黎,王琼生,黄群增,等.膨润土-壳聚糖复合吸附剂处理水中Cr(Ⅵ)的研究[J].工业用水与废水,2006,37(1):44-47.
[44]张安超,孙路石,向军,等.膨润土-壳聚糖及其改性吸附剂脱除燃烧烟气中Hg0的性能研究[J].燃料化学学报,2009,37(4):489-495.
[45]杨莹琴,陈慧娟.壳聚糖插层膨润土的制备及其对Zn2+的吸附[J].信阳师范学院学报,2007,20(3)：338-340.
[46]马勇,王恩德,邵红.膨润土负载壳聚糖对Cu2+的吸附作用[J].安全与环境学报,2005,5(1):41-43.
[47]刘维俊,刘兰侠,刘志芳,等.壳聚糖改性膨润土吸附剂的研制及其吸附性能研究[J].化学世界,2005,7：385-388.
[48]祝春水,黄丽燕,陈文宾,等.膨润土负载壳聚糖吸附镍离子研究[J].淮海工学院学报,2006,15(2):37-40.
[49]Eric Guibal. Interactions of metal ions with chitosan-based sorbents:a review[J]. Separation and Purification Technology,2004,38(1):43-74.
[50]李增新,王彤,黄海兰,等.壳聚糖改性膨润土修复土壤镉污染的研究[J].土壤通报,2009,40(1):176-179.
[51]李增新,王彤,张道来,等.膨润土负载壳聚糖修复土壤镉污染的效果[J].生态环境2008,17(1):241-244.
[52]余宙,仵彦卿,刘预.新型交联壳聚糖材料对地下水重金属Zn2+的吸附性能[J].生态环境学报2009,18(6)：2102-2107.
[53]杨莹琴,陈慧娟.羧甲基壳聚糖插层膨润土的研制及其对Cu2+的吸附[J].非金属矿,2009,32(1):81-83.
[54]Yoshinari Baba Hiroshi Noma,et al. Preparation of chitosan dfrvatives cotaining methyhiocarbamoyl and phenythioccarbamoyl groups and their selective adsorption[J].Analytical Sciences March,2002,18(6):359-361.
[55]邵红,程慧,李佳琳.负载壳聚糖膨润土的制备及其吸附性能的影响[J].环境工程学报,2009,3(9)：1597-1501.
[56]张春,任建敏,王媛媛,等.壳聚糖改性膨润土对罗丹明吸附特性研究[J].广州化工,2009,37(3):122-124.
[57]Tao Xia,Su Jingmei,Wang Lingxuan,et al. A new heterogeneous catalytic system for wastewater treatment:Fe-immobilized polyelec-trolyte microshells for accumulation and visible light-assisted photooxidative degradation of dye pollutants. Journal of Molecular Catalysis A[J].Chemistry,2008,280(1/2):186-193.
[58]杨莹琴,王建旭,陈慧娟.N,O-羧甲基壳聚糖插层膨润土纳米复合材料的结构和性能[J].非金属矿,2009,32(5):39-41.
[59]Yang Yingqin,WANG Jianxu. Preparation and Characterisation of Carboxymethyl Chitosan Intercalated Bentonites and Its Decolorisation Performance of Organic Dyes[J]. Natural Science dition,2010,23(4):575-578.
[60]杨莹琴,陈慧娟,武瑞.分光光度法研究插层膨润土对有机染料的脱色性能[J].光谱实验室,2010,27(6)：2318-2321.
[61]陈慧娟,赵瑜藏,刘小玉,等.插层膨润土复合材料对酸性蓝吸附性能研究[J].信阳师范学院学报,2009,22(3):445-447.
[62]陈天明,王世和,许琦,等.膨润土负载壳聚糖吸附剂对苯酚的吸附性能研究[J].化工时刊,2006,20(7)：1-3.
[63]孙建华,孙伶.壳聚糖改性膨润土处理实验室废水的研究[J].辽宁化工,2007,36(2):107-109.
[64]马勇,王恩德,邵红.膨润土负载壳聚糖制备吸附剂[J].应用化学,2004,21(6):587-600.
[65]周继伟,陆荣杰,杨岳平,等.印染废水达标处理与回用技术研究[J].浙江大学学报,2010,37(3):306-309.
[66]郑广宏,夏邦天,许璨.光化学氧化技术处理印染废水研究进展[J].水处理技术,2008,34(2):5-7.
[67]丁绍兰,李郑坤,王睿.染料废水处理技术综述[J].水资源保护,2010,26(3):73-78.
[68]姜桂兰,张培萍.膨润土加工与应用[M].北京：化学工业出版社,2005.
[69]崔学奇,吕宪俊,周国华.膨润土的性能及其应用[J].中国非金属矿工业导刊,2000,2:6-9.
[70]HEBEISH A,HIGAZY A,EI-SHAFEI A.Newsizing agents and floccu-lants derived from chitosan[J]. Starch,2006,58(8):401-410.
[71]胡巧开.改性壳聚糖的制备及其对印染废水的脱色处理研究[J].印染助剂,2008.25(3):17-19.
[72]陈树培.改性膨润土的制备及其对室内污染气体甲醛吸附的研究[D].南京林业大学硕士研究生学位论文,2008,6:16-17.
[73]岩矿石分析(第三版)第一分册[M],北京：地质出版社,1991.
[74]吴国杰,禹慧明,黎碧娜.羧甲基壳聚糖的研制[J].江西农业大学学报,2002,24(1):63-65.
[75]刘长霞,陈国华,晋治涛,等.N,O-羧甲基壳聚糖羧化度计算式的修正[J].北京化工大学学报,2004,31(2)：14-17.
[76]黄强,郑建仙.N,O-羧甲基壳聚糖的制备及其理化特性研究[J].食品与发酵工业,2009,35(7):63-69.
[77]Rong Huei Chen, Min Larng Tsaih. Urea-induced Conformational Changes of Chitosan Molecules and the Shift of BreakPoint of Mark-Houwink Eguation by Increasing Urea Concentration[J], J Appl Polym Sci, 2000,75:452-457.
[78]朱华明.仪器分析[M].北京：高等教育出版社,2003:4-50.
[79]杨建红,杜予民,覃彩芹.红外光谱与核磁共振波谱在甲壳素结构研究中的应用[J].分析科学学报,2003,19(3)：282-287.
[80]朱利中,陈宝梁.有机膨润土及其在污染控制中的应用[M].北京：科学出版社,2006:51-58.
[81]姜桂兰,张培萍.膨润土加工与应用[M].北京：化学工业出版社,2005:25-26.
[82]付桂珍,龚文琪,曹敏.蒙脱石有机插层复合物的制备及表征[J].武汉理工大学学报,2006,28(8):50-53.
[83]蒋挺大.壳聚糖[M].北京：化学工业出版社,2006:121-125.
[84]Keisuke Kurita, Junji Amemiya,Tomonori Mori, et al. Comb-shaped Chitosan Derivatives having Oligo (ethylene glycol) side chains[J].Polymer Bulletin,1999,42:387-393.
[85]刘万顺,陈西广.羧甲基壳多糖毒理学研究[J].中国海洋药物,1997,16(3):17-19.
[86]吴刚,沈玉华,谢安建,等,N,O-羧甲基壳聚糖的合成和性质研究[J].化学物理学报,2003,16(6):499-503.
[87]Farrell J, Reinhard M. Desorption of halogentanted organics from model solids,sediments,soil under unsaturated condition[J].Environ Sci Technol,1994,28(1):53-62.
[88]戴树桂.环境化学[M].北京：高等教育出版社,2002.
[89]Malik P K. Dye removal from waste water using activated carbon developed from sawdust:adsorption equilibrium and kinetics[J].Hazard Mater B,2004,113:81-88.
[90]朱仙弟,梁华定,闫华,等.竹炭对碱性品红的吸附性能研究[J].应用化工,2008,37(10):1134-1137.
[91]蒋月秀,张雪徐,慧娟,等.改性膨润土对酸性靛蓝的吸附性能研究[J].非金属矿,2007,30(5):63-65.
[92]Blackbmu,R.S. Natural Polysaccharides and their interactions with dye molecules:applications in effluent treatment[J].Environ. Sci&Technol,2004,38:4905-4909.
[93]黄中华,孙秀云,李燕,等.壳聚糖的吸附行为及其FTIR光谱研究[J].光谱学与光谱分析,2005,25(5)：698-700.