壳聚糖改性沸石对刚果红、亮绿和酸性铬蓝K的吸附研究
|
摘要
沸石比表面积大,离子交换性强,再生容易,广泛应用于水处理中,但对阴离子染料的吸附性能较差；壳聚糖资源丰富、生物相容性好、具有优良的吸附性能且可以降解,广泛应用于环境工程、生命科学等领域,但由于价格昂贵应用受到一定限制。为改善沸石吸附性能,提高壳聚糖的利用率,本文将壳聚糖负载于天然沸石表面,制备了壳聚糖改性沸石吸附剂(CCZ),并研究了其对刚果红、亮绿和酸性铬蓝K的静态吸附行为,以及刚果红和亮绿混合体系中两者的竞争吸附行为。
静态吸附试验研究了吸附时间、吸附剂用量、溶液pH值、盐浓度、染料浓度、溶液温度等条件对CCZ吸附水溶液中阴离子染料(刚果红、亮绿、酸性铬蓝K)的影响。研究结果表明：当pH值为4时,CCZ对三者的吸附量最佳；其中,对刚果红的吸附在pH为4-10范围内变化不大。溶液初始浓度和温度对吸附速率均有不同程度的影响,平衡吸附量都随溶液初始浓度的增加而增大,平衡吸附行为可以用Langmuir方程来描述,室温下CCZ对刚果红、亮绿和酸性铬蓝K的饱和吸附量qm分别为10.0、40.7、29.8 mg·g-1。与沸石相比,CCZ对三种染料的最大吸附量均有所提高。CCZ对三种染料的吸附过程可分为快速和慢速两个阶段；其中,刚果红和酸性铬蓝K的吸附动力学过程用Elovich动力学方程描述较好,亮绿的吸附则用准二级动力学方程描述较好。CCZ对三种染料的吸附包含多种机理,但主要靠静电引力进行。CCZ对刚果红、亮绿和酸性铬蓝K的表观吸附活化能分别为：66.0、37.3和57.4kJ·mol-1,ΔG均为负值,表明吸附过程是自发的。CCZ对刚果红和亮绿的双组份吸附实验表明,在混合体系中存在着竞争吸附,且两者是同时被吸附的。此外,CCZ吸附刚果红和酸性铬蓝K后,可采用0.01 mol·L-1的NaOH溶液处理的方法再生,一次再生率分别为98.7%和40.9%；CCZ吸附亮绿后可用微波在320 W下辐照10 min的方法再生,一次再生率可达98.7%。
Zeolite has a relatively large surface area, and good adsorption properties, which has been widely used in water treatment, but it has a low capacity on the adsorption of anionic dyes. Chitosan is a renewable and abundant natural macromolecule compound, which is nontoxic, biocompatible and biodegradarable, and it has been widely used in environmental engineering, life sciences and other fields, but it is expensive. To improve the adsorption properties of zeolite and the utilization of chitosan, the research designed an adsorbent, chitosan coated zeolite (CCZ), which was prepared by coating chitosan onto the surface of zeolite, for removal of congo red (CR), light green (LG) and acid chrome blue K (AK) from synthetic solutions.
In the batch adsorption, the effect of various experimental conditions, such as contact time, adsorbents dose, pH values, coexisting ions, initial concentration of the adsorbate and temperature were carried out. The experimental results showed that the appropriate initial pH for the three dyes adsorption on CCZ was 4. During the pH value 4～10, the adsorption quantity of CCZ binding CR was approximately constant. Adsorbate concentration and temperature had varying degrees on the adsorption rates. The adsorption quantities of dyes increased with the increase of the adsorbate concentration, and all the isothermal data followed the Langmuir model. The maximum adsorption capacity (qm) of CR, LG and AK from Langmuir model was 10.0,40.7 and 29.8 mg·g-1, respectively. Compared with zeolite, adsorption quantities of CCZ for three dyes were all improved. The kinetics process of adsorption consisted of two phases:an initial rapid phase and a slower second phase. The Elocich model showed good correlation for the adsorption of CR and AK on CCZ, while for LG adsorption, it was the pseudo-second-order model fitted best. Electrostatic attraction may be the main mechanism of the three dyes adsorption. The activation energy (Ea) of CCZ binding CR, LG and AK was determined as 66.0, 37.3 and 57.4 kJ·mol-1, respectively. The negative values of AG indicated that the adsorption processes were spontaneous. In the binary system, CR and LG were simultaneously adsorbed, and there was competitive adsorption between them. In addition, the used CCZ, which was used to remove CR and AK, could be regenerated by NaOH solution (0.01 mol·L-1) and the regeneration rate could reach 98.7% and 40.9%, respectively. But the LG-loaded CCZ was regenerated by microwave irradiation with 320 W for 10 min, and the regeneration rate was 98.7%.
静态吸附试验研究了吸附时间、吸附剂用量、溶液pH值、盐浓度、染料浓度、溶液温度等条件对CCZ吸附水溶液中阴离子染料(刚果红、亮绿、酸性铬蓝K)的影响。研究结果表明：当pH值为4时,CCZ对三者的吸附量最佳；其中,对刚果红的吸附在pH为4-10范围内变化不大。溶液初始浓度和温度对吸附速率均有不同程度的影响,平衡吸附量都随溶液初始浓度的增加而增大,平衡吸附行为可以用Langmuir方程来描述,室温下CCZ对刚果红、亮绿和酸性铬蓝K的饱和吸附量qm分别为10.0、40.7、29.8 mg·g-1。与沸石相比,CCZ对三种染料的最大吸附量均有所提高。CCZ对三种染料的吸附过程可分为快速和慢速两个阶段；其中,刚果红和酸性铬蓝K的吸附动力学过程用Elovich动力学方程描述较好,亮绿的吸附则用准二级动力学方程描述较好。CCZ对三种染料的吸附包含多种机理,但主要靠静电引力进行。CCZ对刚果红、亮绿和酸性铬蓝K的表观吸附活化能分别为：66.0、37.3和57.4kJ·mol-1,ΔG均为负值,表明吸附过程是自发的。CCZ对刚果红和亮绿的双组份吸附实验表明,在混合体系中存在着竞争吸附,且两者是同时被吸附的。此外,CCZ吸附刚果红和酸性铬蓝K后,可采用0.01 mol·L-1的NaOH溶液处理的方法再生,一次再生率分别为98.7%和40.9%；CCZ吸附亮绿后可用微波在320 W下辐照10 min的方法再生,一次再生率可达98.7%。
Zeolite has a relatively large surface area, and good adsorption properties, which has been widely used in water treatment, but it has a low capacity on the adsorption of anionic dyes. Chitosan is a renewable and abundant natural macromolecule compound, which is nontoxic, biocompatible and biodegradarable, and it has been widely used in environmental engineering, life sciences and other fields, but it is expensive. To improve the adsorption properties of zeolite and the utilization of chitosan, the research designed an adsorbent, chitosan coated zeolite (CCZ), which was prepared by coating chitosan onto the surface of zeolite, for removal of congo red (CR), light green (LG) and acid chrome blue K (AK) from synthetic solutions.
In the batch adsorption, the effect of various experimental conditions, such as contact time, adsorbents dose, pH values, coexisting ions, initial concentration of the adsorbate and temperature were carried out. The experimental results showed that the appropriate initial pH for the three dyes adsorption on CCZ was 4. During the pH value 4～10, the adsorption quantity of CCZ binding CR was approximately constant. Adsorbate concentration and temperature had varying degrees on the adsorption rates. The adsorption quantities of dyes increased with the increase of the adsorbate concentration, and all the isothermal data followed the Langmuir model. The maximum adsorption capacity (qm) of CR, LG and AK from Langmuir model was 10.0,40.7 and 29.8 mg·g-1, respectively. Compared with zeolite, adsorption quantities of CCZ for three dyes were all improved. The kinetics process of adsorption consisted of two phases:an initial rapid phase and a slower second phase. The Elocich model showed good correlation for the adsorption of CR and AK on CCZ, while for LG adsorption, it was the pseudo-second-order model fitted best. Electrostatic attraction may be the main mechanism of the three dyes adsorption. The activation energy (Ea) of CCZ binding CR, LG and AK was determined as 66.0, 37.3 and 57.4 kJ·mol-1, respectively. The negative values of AG indicated that the adsorption processes were spontaneous. In the binary system, CR and LG were simultaneously adsorbed, and there was competitive adsorption between them. In addition, the used CCZ, which was used to remove CR and AK, could be regenerated by NaOH solution (0.01 mol·L-1) and the regeneration rate could reach 98.7% and 40.9%, respectively. But the LG-loaded CCZ was regenerated by microwave irradiation with 320 W for 10 min, and the regeneration rate was 98.7%.
引文
[1]张林生.印染废水处理技术及典型工程[M].北京,化学工业出版社,2005.44-171.
[2]Crini G. Non-conventional low-cost adsorbents for dye removal:A review[J]. Bioresource Technology,2005,97(2006):1061-1085.
[3]明欲晓,曹敬华.压力生物氧化法处理印染废水试验研究[J].中国给水排水,1996,12(4)：6-9.
[4]刘文琦.一种新型壳聚糖絮凝剂的合成及其对印染废水的脱色研究[D].[硕士学位论文].南昌：南昌大学,2006.
[5]徐肖邢,曾小君,陆雪良.采用高效脱色剂处理染料废水的研究[J].工业用水与废水,2003,34(1)：39-42.
[6]胡俊生,任雪冬,马广韬等.臭氧高级氧化技术处理酸性红B染料废水[J].沈阳建筑大学学报(自然科学版),2009,25(2)：320-324.
[7]张乃东,林秀,郑威.UV-vis/H2O2/草酸铁络合物法光解焦化含酚废水的研究[J].黑龙江大学自然科学学报,2002,19(1)：103-105.
[8]陈季华.纺织染整废水处理技术及工程实例[M].北京,化学工业出版社,2008.14-15.
[9]汤义武,舒余德,蒋汉濒.活性炭处理冶炼厂废水的基础研究[J].湘潭矿业学院学报,1997,2(4)：69-73.
[10]Kuma K V, Ramamurthi V, Sivanesan S. Modeling the mechanism involved during the sorption of methylene blue onto fly ash[J]. Journal of Colloid Interface Science,2005, 284:14-21.
[11]Janos P, Buchtova H, Ryznarov M. Sorption of dyes from aqueoussolutions onto fly ash[J]. Water Research,2003,37:4938-4944.
[12]山本良一.环境材料[M].北京：化学工业出版社,1997.
[13]王泽民.利用硅藻土复合净水剂处理造纸废水的研究[J].非金属矿,1993,(3)：33-35.
[14]曾清华,王栋知,王淀佐.粘土-无机层间化合物的制备、表征和应用[J].非金属矿,1998,123(3)：8-28.
[15]Aksu Z. Application of biosorption for the removal of organic pollutants:a review[J]. Process Biochemistry.2005,40(3-4):997-1026.
[16]李亚峰,佟玉衡,陈立杰.实用废水处理技术[M].第二版,北京,化学工业出版社,2007.112-115.
[17]王爱琴.甲壳素化学[M].北京,科学出版社,2008,1-443.
[18]Shigemasa Y, Ishida A, Sashiwa H, et al. Synthesis of a new chitin derivative, (1-carboxyethy) chitosan[J]. Chemistry Letters,1995,24(8):623-624
[19]许晨,卢灿辉.壳聚糖季铵化衍生物的吸湿与保湿性[J].应用化学,1996,13(5)：94-95.
[20]俞继华,冯才旺,唐有根.甲壳素和壳聚糖的化学改性及其应用[J].广西化工,1997,26(3)：28-32.
[21]张亚静,朱瑞芬,童兴龙.壳聚糖季铵盐对味精废水絮凝作用[J].水处理技术,2001,27(5)：281-283.
[22]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,2005,46(7)：385-388
[23]卜洪忠,于文涛.壳聚糖与凹凸棒土对金属离子吸附作用研究[J].化学世界,2005,46(8)：468-470.
[24]Knorr D. Dye binding properties of chitin and chitosan[J]. Journal of Food Science,1983, 48(1):36-37.
[25]McKay G, Blair H S, J Gardner. The adsoprtion of dyes in chitin. Equilibrium studies[J]. Journal of Applied Polymer Science,1982,27:3043-3057.
[26]徐景华,鲁越青,李益民等.壳聚糖对重金属离子吸附作用的研究[J].水处理技术,1998,24(6)：359-362.
[27]杨洪.壳聚糖对重金属离子的吸附行为[J].烟台大学学报(自然科学与工程版),1999,12(4)：309-312.
[28]李静,高玉杰,任继春.天然高分子絮凝剂壳聚糖[J].天津造纸,2003,25(1)：33-34.
[29]周能,蒋先明,黎庆涛等.壳聚糖净化味精废水的研究[J].广西化工,1999,28(3)：57-60.
[30]邢锋,丁浩,冯乃谦.活化处理提高天然沸石吸附能力的研究[J].矿产保护与利用,2000,(2)：17-21.
[31]周明达,张晖,邵凯等.改性沸石处理含磷废水的实验研究[J].环境污染与防治,2005,27(2)：137-138.
[32]程晓维,汪靖,张枚等.CXN天然沸石的研究Ⅶ骨架高硅超稳化改性[J].化学学报,2006,64(1)：1-8.
[33]曹建劲.沸石改性及其吸附性能研究[J].化工矿物与加工,2002,(12)：10-11.
[34]谢晓凤.改性沸石应用于废水处理的研究[D].[硕士学位论文].北京：北京化工大学,2003.
[35]潘嘉芬.天然斜发沸石吸附高浓度氨氮废水实验研究[J].中国矿业,2008,17(2)：87-89.
[36]蔡青青.改性沸石吸附废水中磷污染物的研究[J].环境科学与管理,2008,33(7)：92-94
[37]罗道成,易平贵,陈安国.改性沸石对电镀废水中的Pb、Zn、Ni的吸附[J].材料保护,2002,35(7)：20-22.
[38]李曼尼,刘晓飞,江雅新等.改性斜发沸石在水处理中的应用[J].环境化学,2007,26(1)：21-26.
[39]程明,袁凤英.改性沸石在废水处理中的应用[J].工业水处理,2004,24(12)：6-8.
[40]葛学贵,太玉明,李大好等.沸石在环境治理工程中的应用[J].环境科学与技术,2001,24(6)：21-24.
[41]李增新,梁强,段春生等.天然沸石负载壳聚糖去除废水中铜离子的研究[J].非金属 矿,2007,30(1)：57-59.
[42]李增新,李俊,王国明等.天然沸石负载壳聚糖去除水中砷的研究[J].现代化工,2007,27(增2)：196-197.
[43]李增新,段春生,王彤等.天然沸石负载壳聚糖去除水中Cr6+的研究[J].非金属矿,2006,29(4)：46-49.
[44]王擎.壳聚糖包覆粉煤灰对模拟染料废水的脱色实验研究[D].[硕士学位论文].成都：西南交通大学,2006.
[45]卢晓岩,朱琨,梁莹等.改性沸石对水中铬酸盐的吸附和解吸性能研究[J].兰州交通大学学报(自然科学版),2005,24(4)：72-74.
[1]郑光洪,冯西宁.染料化学[M].北京：中国纺织出版社,2001.
[2]王擎.壳聚糖包覆粉煤灰对模拟染料废水的脱色实验研究[D].[硕士学位论文].成都：西南交通大学,2006.
[3]Han R P, Zhang J J, Han P, et al. Study of equilibrium, kinetic and thermodynamic parameters about methylene blue adsorption onto natural zeolite[J]. Chemical Engineering Journal,2009,145(3):496-504.
[4]何永祥.天然沸石对水体中甲基橙和亚甲基蓝的吸附研究[D].[硕士学位论文].郑州：郑州大学,2007.
[5]Han R P, Zou L N, Zhao X, et al. Characterization and properties of iron oxide-coated zeolite as adsorbent for removal of copper (Ⅱ) from solution in fixed bed column[J]. Chemical Engineering Journal,2009,149(1-3):123-131.
[6]Farmer V C.矿物的红外光谱(应育浦等译)[M].北京：科学出版社,1982,289.
[7]邹卫华.锰氧化物改性过滤材料对铜和铅离子的吸附研究[D].[博士学位论文].长沙：湖南大学,2006.
[1]Faria P, Orfao J, Pereira M. Adsorption of anionic and cationic dyes on activated carbons with different surface chemistries[J]. Water Research,2004,38(8):2043-2052.
[2]Al-Degs Y, Khraisheh M, Allen S, et al. Effect of carbon surface chemistry on the removal of reactive dyes from textile effluents[J]. Water Research,2000,34(3):927-935.
[3]王丽，王爱琴.壳聚糖/蒙脱土纳米复合材料的制备及对染料的吸附性能[J].高分子材料科学与工程.2007,23(5)：104-107.
[4]Alberghina G, Bianchini R, Fichera M, et al. Dimerization of Cibacron Blue F3GA and other dyes:influence of salts and temperature[J]. Dyes and Pigments,2000,46(3):129-137.
[5]Crini G. Non-conventional low-cost adsorbents for dye removal:A review[J]. Bioresource Technology,2005,97(2006):1061-1085.
[6]Strawn D G, Scheidegger A M, Sparks D L. Kinetics and mechanisms of Pb(Ⅱ) sorption and desorption at the aluminum oxide-water interface[J]. Environmental Science and Technology, 1998,32(17):2596-2601.
[7]Han R P, Zhu L, Zou W H, et al. Removal of copper(Ⅱ) and lead(Ⅱ) from aqueous solution by manganese oxide coated sand-II. Equilibrium study and competitive adsorption[J]. Journal of Hazardous materials,2006,137(1):480-488.
[8]卢丽霞,雷彤,林群龙等.壳聚糖复合微球的制备及其对F-的吸附[J].化工时刊,2004,18(2)：45-46.
[9]洪爱真,魏燕芳,陈盛.磁性壳聚糖微球对酸性偶氮染料废水的脱色研究[J].福建轻纺,2003,(2)：1-5.
[10]Al-Degs Y S, El-Barghouthi M I, El-Sheikh A H, et al. Effect of solution pH, ionic strength, and temperature on adsorption behavior of reactive dyes on activated carbon[J]. Dyes and pigments,2007,77(2008):16-23.
[11]Majeti N V, Kumar R. A review of chitin and chitosan applications[J]. Reactive and Functional Polymers,2000,46(1):1-27.
[12]Harry S. The theory of coloration of textiles. In:Johnson A, editor. Thermodynamics of dye adsorption.2nd ed. West Yorkshire, UK:Society of Dyers and Colorists; 1989.255.
[13]Rathinam A, Jonnalagadda R R, Balachandran U N. Removal of basic yellow dye from aqueous solution by sorption on green alga Caulerpa scalpelliformis[J]. Reactive and Functional Polymers,2007,142(1-2):68-76.
[14]邹宗柏,傅大放,张璐.用微波辐照消除磺基水杨酸污染物[J].环境污染与防治,1999,21(1)：22-24.
[15]Chiou M S, Li H Y. Adsorption behavior of reactive dye in aqueous solution on chemical cross-linked chitosan beads[J]. Chemosphere,2003,50(8):1095-1105.
[16]朱启忠,赵亮云,赵宏等.壳聚糖处理印染废水的研究[J].四川环境,2006,25(1)：17-19.
[17]高晓荣,任广军.糠醛渣对刚果红的吸附性能研究[J].当代化工,2008,37(6)：575-578.
[18]蔡冬鸣,任南琪.酸改性δ-MnO2去除水中染料的特性和机理[J].环境化学,2007,26(2)：171-174.
[19]李乐勇,王毅力,廖柏寒.官厅水库底泥对染料的吸附特征研究[J].安全与环境学报,2006,6(1)：91-95.
[20]詹予忠,杨向东,李玉博.刚果红和结晶紫在锯末上的吸附性能研究[J].离子交换与吸附,2006,22(2)：134-139.
[21]马淞江,李方文,磁性磺化煤吸附水溶性有机染料的研究[J].湖南科技大学学报,2006,21(3)：90-92.
[22]许卉,申景强,杨昕.石莼吸附脱色处理水溶性染料[J].化学研究与应用,2002,14(4)：394-396.
[23]郭黎平.钙基膨润土的改性以及对刚果红染料的吸附研究[D].[硕士学位论文].哈尔滨：东北师范大学,2008.
[24]王元凤.谷壳和梧桐树叶对水体中亚甲基蓝和刚果红的吸附研究[D].[硕士学位论文].郑州：郑州大学,2007.
[25]孙影芝,龚仁敏,张小平等.苤蓝皮生物吸附去除水体中的阴离子染料[J].安徽师范 大学学报(自然科学版),2005,28(1)：80-83.
[26]马延军,王修林,范典高.水溶液中有机染料分子在甲基(苯乙基)键合硅胶上的吸附[J].海洋湖沼通报,1994,(4)：24-29.
[27]孙迎芝.稻壳吸附剂去除水体中的离子型染料及其吸附机理研究[D].[硕士学位论文].芜湖：安徽师范大学硕士学位论文,2005.
[28]申震,唐先进,刘超等.焙烧态镁铝水滑石处理阴离子染料废水研究[J].环境科学与技术,2006,29(3)：89-91.
[1]Langmuir I. The constitution and fundamental properties of solids and liquids[J]. Journal of the Franklin Institute,1917,183(1):102-105.
[2]Freundlich H M F. Uber die adsorption in lasungen[J]. Physical Chemistry,1906,57: 385-470.
[3]Guibal E, Saucedo I, Roussy J. Uptake of uranyl ions by new sorbing polymers:discussion of adsorption isotherms and pH effect[J]. Reactive Polymers,1994,23(2-3):147-156.
[4]Redlich O, Peterson D L. A useful adsorption isotherm[J]. Physical Chemistry,1959,63(6): 1024.
[5]Jossens L, Prausnitz J M, Fritz W, et al. Thermodynamics of multi-solute adsorption from dilute aqueous solutions[J]. Chemical Engineering Science,1978,33(8):1097-1106.
[6]Unlu N, Ersoz M. Adsorption characteristics of heavy metal ions onto a low cost biopolymeric sorbent from aqueous solutions[J]. Journal of Hazardous Materials,2006,136(2):272-280.
[7]Butler J A V, Ockrent C. Studies in electrocapillarity:Part Ⅲ[J]. Physical Chemistry,1930, 34(12):2841-2859.
[8]Fritz W, Schuender E U. Simultaneous adsorption equilibria of organic solution in dilute aqueous solution on activated carbon[J]. Chemical Engineer Science,1974,29(5): 1279-1288.
[9]Sheidrof C, Rebhum M, Sheintuch M. Organic pollutants adsorption from multicomponent systems modeled by Freundlich type isotherm[J]. Water Research,1982,16(3):357-362.
[10]Murali V, Aylmore A G. Competitive adsorption during solute transport in soils:1. Mathematical models[J]. Soil Science,1983,135(3),143-150.
[11]Fritz W, Schuender E U. Simultaneous adsorption equilibria of organic solution in dilute aqueous solution on activated carbon[J]. Chemical Engineer Science,1974,29(5): 1279-1288.
[12]Aksu Z, Akpinar D. Competitive biosorption of phenol and chromium(Ⅵ) from binary mixtures onto dried anaerobic activated sludge[J]. Biochemical Engineering Journal,2001, 7(3):183-193.
[13]Cavazzini A, Felinger A, Guiochon G. Study of the adsorption equilibria of the enantiomers of 1-phenyl-1-propanol on cellulose tribenzoate using a microbore column[J]. Journal of chromatography,2002,953(1-2):55-66.
[14]Critenden J C, Luft P, Hand D W. Prediction of multicomponent adsorption equilibria using Ideal Adsorbed Solution theory[J]. Environmental Science and Technology,1985,19(11): 1037-1043.
[15]Aksu Z. Determination of the equilibrium, kinetic and thermodynamic parameters of the batch biosorption of lead(Ⅱ) ions onto Chlorella vulgaris[J]. Process Biochemistry,2002, 38(1):89-99.
[16]Han R P, Wang Y, Zou W H, et al. Comparison of linear and nonlinear analysis in estimating the Thomas model parameters for methylene blue adsorption onto natural zeolite in fixed-bed column[J]. Journal of Hazardous Materials,2007,145:331-335.
[17]Ho Y S, Porter J F, McKay G. Equilibrium isotherm studies for the sorption of divalent metal ions onto peat:copper, nickel and lead single component systems[J]. Water, Air, and Soil Pollution,2002,141:1-33.
[18]Kundu S, Gupta A K. Arsenic adsorption onto iron oxide-coated cement (IOCC):regression analysis of equilibrium data with several isotherm models and their optimization[J]. Chemical Engineering Journal,2006,122:93-106.
[19]王爱琴.甲壳素化学[M].北京,科学出版社,2008.
[20]张林生.印染废水处理技术及典型工程[M].北京,化学工业出版社,2005.44-171.
[21]Nollet H, Roels M, Lutgen P, et al. Removal of PCBs from wastewater using fly ash[J]. Chemosphere,2003,53:655-665.
[22]洪爱珍.氨基化壳聚糖微球吸附阴离子偶氮染料研究[D].[硕士学位论文].福州：福建师范大学.2003.
[23]Ho Y S, Chiu W T, Wang C C. Regression analysis for the sorption isotherms of basic dyes on sugarcane dust[J]. Bioresource Technology,2005,96(11):1285-1291.
[24]Lorenc-Grabowska E, Gryglewicz G. Adsorption of lignite-derived humic acids on coal-based mesoporous activated carbons[J]. Journal of Colloid and Interface Science,2005, 284(2):416-423.
[25]Mohana S V, Raoa N C, Karthikeyan J. Adsorptive removal of direct azo dye from aqueous phase onto coal based sorbents, a kinetic and mechanistic study[J]. Journal of Hazardous Materials,2002,90(2):189-204.
[26]Sparks D L, Carski T H. Kinetics of potassium exchange in heterogeneous systems[J]. Applied Clay Science,1985,1(1-2):89-101.
[27]Chatterjee S, Chatterjee S, Chatterjee B P, et al. Adsorptive removal of congo red, a carcinogenic textile dye by chitosan hydrobeads:Binding mechanism, equilibrium and kinetics[J]. Colloids and Surfaces A,2007,299(1-3):146-152.
[2]Crini G. Non-conventional low-cost adsorbents for dye removal:A review[J]. Bioresource Technology,2005,97(2006):1061-1085.
[3]明欲晓,曹敬华.压力生物氧化法处理印染废水试验研究[J].中国给水排水,1996,12(4)：6-9.
[4]刘文琦.一种新型壳聚糖絮凝剂的合成及其对印染废水的脱色研究[D].[硕士学位论文].南昌：南昌大学,2006.
[5]徐肖邢,曾小君,陆雪良.采用高效脱色剂处理染料废水的研究[J].工业用水与废水,2003,34(1)：39-42.
[6]胡俊生,任雪冬,马广韬等.臭氧高级氧化技术处理酸性红B染料废水[J].沈阳建筑大学学报(自然科学版),2009,25(2)：320-324.
[7]张乃东,林秀,郑威.UV-vis/H2O2/草酸铁络合物法光解焦化含酚废水的研究[J].黑龙江大学自然科学学报,2002,19(1)：103-105.
[8]陈季华.纺织染整废水处理技术及工程实例[M].北京,化学工业出版社,2008.14-15.
[9]汤义武,舒余德,蒋汉濒.活性炭处理冶炼厂废水的基础研究[J].湘潭矿业学院学报,1997,2(4)：69-73.
[10]Kuma K V, Ramamurthi V, Sivanesan S. Modeling the mechanism involved during the sorption of methylene blue onto fly ash[J]. Journal of Colloid Interface Science,2005, 284:14-21.
[11]Janos P, Buchtova H, Ryznarov M. Sorption of dyes from aqueoussolutions onto fly ash[J]. Water Research,2003,37:4938-4944.
[12]山本良一.环境材料[M].北京：化学工业出版社,1997.
[13]王泽民.利用硅藻土复合净水剂处理造纸废水的研究[J].非金属矿,1993,(3)：33-35.
[14]曾清华,王栋知,王淀佐.粘土-无机层间化合物的制备、表征和应用[J].非金属矿,1998,123(3)：8-28.
[15]Aksu Z. Application of biosorption for the removal of organic pollutants:a review[J]. Process Biochemistry.2005,40(3-4):997-1026.
[16]李亚峰,佟玉衡,陈立杰.实用废水处理技术[M].第二版,北京,化学工业出版社,2007.112-115.
[17]王爱琴.甲壳素化学[M].北京,科学出版社,2008,1-443.
[18]Shigemasa Y, Ishida A, Sashiwa H, et al. Synthesis of a new chitin derivative, (1-carboxyethy) chitosan[J]. Chemistry Letters,1995,24(8):623-624
[19]许晨,卢灿辉.壳聚糖季铵化衍生物的吸湿与保湿性[J].应用化学,1996,13(5)：94-95.
[20]俞继华,冯才旺,唐有根.甲壳素和壳聚糖的化学改性及其应用[J].广西化工,1997,26(3)：28-32.
[21]张亚静,朱瑞芬,童兴龙.壳聚糖季铵盐对味精废水絮凝作用[J].水处理技术,2001,27(5)：281-283.
[22]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,2005,46(7)：385-388
[23]卜洪忠,于文涛.壳聚糖与凹凸棒土对金属离子吸附作用研究[J].化学世界,2005,46(8)：468-470.
[24]Knorr D. Dye binding properties of chitin and chitosan[J]. Journal of Food Science,1983, 48(1):36-37.
[25]McKay G, Blair H S, J Gardner. The adsoprtion of dyes in chitin. Equilibrium studies[J]. Journal of Applied Polymer Science,1982,27:3043-3057.
[26]徐景华,鲁越青,李益民等.壳聚糖对重金属离子吸附作用的研究[J].水处理技术,1998,24(6)：359-362.
[27]杨洪.壳聚糖对重金属离子的吸附行为[J].烟台大学学报(自然科学与工程版),1999,12(4)：309-312.
[28]李静,高玉杰,任继春.天然高分子絮凝剂壳聚糖[J].天津造纸,2003,25(1)：33-34.
[29]周能,蒋先明,黎庆涛等.壳聚糖净化味精废水的研究[J].广西化工,1999,28(3)：57-60.
[30]邢锋,丁浩,冯乃谦.活化处理提高天然沸石吸附能力的研究[J].矿产保护与利用,2000,(2)：17-21.
[31]周明达,张晖,邵凯等.改性沸石处理含磷废水的实验研究[J].环境污染与防治,2005,27(2)：137-138.
[32]程晓维,汪靖,张枚等.CXN天然沸石的研究Ⅶ骨架高硅超稳化改性[J].化学学报,2006,64(1)：1-8.
[33]曹建劲.沸石改性及其吸附性能研究[J].化工矿物与加工,2002,(12)：10-11.
[34]谢晓凤.改性沸石应用于废水处理的研究[D].[硕士学位论文].北京：北京化工大学,2003.
[35]潘嘉芬.天然斜发沸石吸附高浓度氨氮废水实验研究[J].中国矿业,2008,17(2)：87-89.
[36]蔡青青.改性沸石吸附废水中磷污染物的研究[J].环境科学与管理,2008,33(7)：92-94
[37]罗道成,易平贵,陈安国.改性沸石对电镀废水中的Pb、Zn、Ni的吸附[J].材料保护,2002,35(7)：20-22.
[38]李曼尼,刘晓飞,江雅新等.改性斜发沸石在水处理中的应用[J].环境化学,2007,26(1)：21-26.
[39]程明,袁凤英.改性沸石在废水处理中的应用[J].工业水处理,2004,24(12)：6-8.
[40]葛学贵,太玉明,李大好等.沸石在环境治理工程中的应用[J].环境科学与技术,2001,24(6)：21-24.
[41]李增新,梁强,段春生等.天然沸石负载壳聚糖去除废水中铜离子的研究[J].非金属 矿,2007,30(1)：57-59.
[42]李增新,李俊,王国明等.天然沸石负载壳聚糖去除水中砷的研究[J].现代化工,2007,27(增2)：196-197.
[43]李增新,段春生,王彤等.天然沸石负载壳聚糖去除水中Cr6+的研究[J].非金属矿,2006,29(4)：46-49.
[44]王擎.壳聚糖包覆粉煤灰对模拟染料废水的脱色实验研究[D].[硕士学位论文].成都：西南交通大学,2006.
[45]卢晓岩,朱琨,梁莹等.改性沸石对水中铬酸盐的吸附和解吸性能研究[J].兰州交通大学学报(自然科学版),2005,24(4)：72-74.
[1]郑光洪,冯西宁.染料化学[M].北京：中国纺织出版社,2001.
[2]王擎.壳聚糖包覆粉煤灰对模拟染料废水的脱色实验研究[D].[硕士学位论文].成都：西南交通大学,2006.
[3]Han R P, Zhang J J, Han P, et al. Study of equilibrium, kinetic and thermodynamic parameters about methylene blue adsorption onto natural zeolite[J]. Chemical Engineering Journal,2009,145(3):496-504.
[4]何永祥.天然沸石对水体中甲基橙和亚甲基蓝的吸附研究[D].[硕士学位论文].郑州：郑州大学,2007.
[5]Han R P, Zou L N, Zhao X, et al. Characterization and properties of iron oxide-coated zeolite as adsorbent for removal of copper (Ⅱ) from solution in fixed bed column[J]. Chemical Engineering Journal,2009,149(1-3):123-131.
[6]Farmer V C.矿物的红外光谱(应育浦等译)[M].北京：科学出版社,1982,289.
[7]邹卫华.锰氧化物改性过滤材料对铜和铅离子的吸附研究[D].[博士学位论文].长沙：湖南大学,2006.
[1]Faria P, Orfao J, Pereira M. Adsorption of anionic and cationic dyes on activated carbons with different surface chemistries[J]. Water Research,2004,38(8):2043-2052.
[2]Al-Degs Y, Khraisheh M, Allen S, et al. Effect of carbon surface chemistry on the removal of reactive dyes from textile effluents[J]. Water Research,2000,34(3):927-935.
[3]王丽，王爱琴.壳聚糖/蒙脱土纳米复合材料的制备及对染料的吸附性能[J].高分子材料科学与工程.2007,23(5)：104-107.
[4]Alberghina G, Bianchini R, Fichera M, et al. Dimerization of Cibacron Blue F3GA and other dyes:influence of salts and temperature[J]. Dyes and Pigments,2000,46(3):129-137.
[5]Crini G. Non-conventional low-cost adsorbents for dye removal:A review[J]. Bioresource Technology,2005,97(2006):1061-1085.
[6]Strawn D G, Scheidegger A M, Sparks D L. Kinetics and mechanisms of Pb(Ⅱ) sorption and desorption at the aluminum oxide-water interface[J]. Environmental Science and Technology, 1998,32(17):2596-2601.
[7]Han R P, Zhu L, Zou W H, et al. Removal of copper(Ⅱ) and lead(Ⅱ) from aqueous solution by manganese oxide coated sand-II. Equilibrium study and competitive adsorption[J]. Journal of Hazardous materials,2006,137(1):480-488.
[8]卢丽霞,雷彤,林群龙等.壳聚糖复合微球的制备及其对F-的吸附[J].化工时刊,2004,18(2)：45-46.
[9]洪爱真,魏燕芳,陈盛.磁性壳聚糖微球对酸性偶氮染料废水的脱色研究[J].福建轻纺,2003,(2)：1-5.
[10]Al-Degs Y S, El-Barghouthi M I, El-Sheikh A H, et al. Effect of solution pH, ionic strength, and temperature on adsorption behavior of reactive dyes on activated carbon[J]. Dyes and pigments,2007,77(2008):16-23.
[11]Majeti N V, Kumar R. A review of chitin and chitosan applications[J]. Reactive and Functional Polymers,2000,46(1):1-27.
[12]Harry S. The theory of coloration of textiles. In:Johnson A, editor. Thermodynamics of dye adsorption.2nd ed. West Yorkshire, UK:Society of Dyers and Colorists; 1989.255.
[13]Rathinam A, Jonnalagadda R R, Balachandran U N. Removal of basic yellow dye from aqueous solution by sorption on green alga Caulerpa scalpelliformis[J]. Reactive and Functional Polymers,2007,142(1-2):68-76.
[14]邹宗柏,傅大放,张璐.用微波辐照消除磺基水杨酸污染物[J].环境污染与防治,1999,21(1)：22-24.
[15]Chiou M S, Li H Y. Adsorption behavior of reactive dye in aqueous solution on chemical cross-linked chitosan beads[J]. Chemosphere,2003,50(8):1095-1105.
[16]朱启忠,赵亮云,赵宏等.壳聚糖处理印染废水的研究[J].四川环境,2006,25(1)：17-19.
[17]高晓荣,任广军.糠醛渣对刚果红的吸附性能研究[J].当代化工,2008,37(6)：575-578.
[18]蔡冬鸣,任南琪.酸改性δ-MnO2去除水中染料的特性和机理[J].环境化学,2007,26(2)：171-174.
[19]李乐勇,王毅力,廖柏寒.官厅水库底泥对染料的吸附特征研究[J].安全与环境学报,2006,6(1)：91-95.
[20]詹予忠,杨向东,李玉博.刚果红和结晶紫在锯末上的吸附性能研究[J].离子交换与吸附,2006,22(2)：134-139.
[21]马淞江,李方文,磁性磺化煤吸附水溶性有机染料的研究[J].湖南科技大学学报,2006,21(3)：90-92.
[22]许卉,申景强,杨昕.石莼吸附脱色处理水溶性染料[J].化学研究与应用,2002,14(4)：394-396.
[23]郭黎平.钙基膨润土的改性以及对刚果红染料的吸附研究[D].[硕士学位论文].哈尔滨：东北师范大学,2008.
[24]王元凤.谷壳和梧桐树叶对水体中亚甲基蓝和刚果红的吸附研究[D].[硕士学位论文].郑州：郑州大学,2007.
[25]孙影芝,龚仁敏,张小平等.苤蓝皮生物吸附去除水体中的阴离子染料[J].安徽师范 大学学报(自然科学版),2005,28(1)：80-83.
[26]马延军,王修林,范典高.水溶液中有机染料分子在甲基(苯乙基)键合硅胶上的吸附[J].海洋湖沼通报,1994,(4)：24-29.
[27]孙迎芝.稻壳吸附剂去除水体中的离子型染料及其吸附机理研究[D].[硕士学位论文].芜湖：安徽师范大学硕士学位论文,2005.
[28]申震,唐先进,刘超等.焙烧态镁铝水滑石处理阴离子染料废水研究[J].环境科学与技术,2006,29(3)：89-91.
[1]Langmuir I. The constitution and fundamental properties of solids and liquids[J]. Journal of the Franklin Institute,1917,183(1):102-105.
[2]Freundlich H M F. Uber die adsorption in lasungen[J]. Physical Chemistry,1906,57: 385-470.
[3]Guibal E, Saucedo I, Roussy J. Uptake of uranyl ions by new sorbing polymers:discussion of adsorption isotherms and pH effect[J]. Reactive Polymers,1994,23(2-3):147-156.
[4]Redlich O, Peterson D L. A useful adsorption isotherm[J]. Physical Chemistry,1959,63(6): 1024.
[5]Jossens L, Prausnitz J M, Fritz W, et al. Thermodynamics of multi-solute adsorption from dilute aqueous solutions[J]. Chemical Engineering Science,1978,33(8):1097-1106.
[6]Unlu N, Ersoz M. Adsorption characteristics of heavy metal ions onto a low cost biopolymeric sorbent from aqueous solutions[J]. Journal of Hazardous Materials,2006,136(2):272-280.
[7]Butler J A V, Ockrent C. Studies in electrocapillarity:Part Ⅲ[J]. Physical Chemistry,1930, 34(12):2841-2859.
[8]Fritz W, Schuender E U. Simultaneous adsorption equilibria of organic solution in dilute aqueous solution on activated carbon[J]. Chemical Engineer Science,1974,29(5): 1279-1288.
[9]Sheidrof C, Rebhum M, Sheintuch M. Organic pollutants adsorption from multicomponent systems modeled by Freundlich type isotherm[J]. Water Research,1982,16(3):357-362.
[10]Murali V, Aylmore A G. Competitive adsorption during solute transport in soils:1. Mathematical models[J]. Soil Science,1983,135(3),143-150.
[11]Fritz W, Schuender E U. Simultaneous adsorption equilibria of organic solution in dilute aqueous solution on activated carbon[J]. Chemical Engineer Science,1974,29(5): 1279-1288.
[12]Aksu Z, Akpinar D. Competitive biosorption of phenol and chromium(Ⅵ) from binary mixtures onto dried anaerobic activated sludge[J]. Biochemical Engineering Journal,2001, 7(3):183-193.
[13]Cavazzini A, Felinger A, Guiochon G. Study of the adsorption equilibria of the enantiomers of 1-phenyl-1-propanol on cellulose tribenzoate using a microbore column[J]. Journal of chromatography,2002,953(1-2):55-66.
[14]Critenden J C, Luft P, Hand D W. Prediction of multicomponent adsorption equilibria using Ideal Adsorbed Solution theory[J]. Environmental Science and Technology,1985,19(11): 1037-1043.
[15]Aksu Z. Determination of the equilibrium, kinetic and thermodynamic parameters of the batch biosorption of lead(Ⅱ) ions onto Chlorella vulgaris[J]. Process Biochemistry,2002, 38(1):89-99.
[16]Han R P, Wang Y, Zou W H, et al. Comparison of linear and nonlinear analysis in estimating the Thomas model parameters for methylene blue adsorption onto natural zeolite in fixed-bed column[J]. Journal of Hazardous Materials,2007,145:331-335.
[17]Ho Y S, Porter J F, McKay G. Equilibrium isotherm studies for the sorption of divalent metal ions onto peat:copper, nickel and lead single component systems[J]. Water, Air, and Soil Pollution,2002,141:1-33.
[18]Kundu S, Gupta A K. Arsenic adsorption onto iron oxide-coated cement (IOCC):regression analysis of equilibrium data with several isotherm models and their optimization[J]. Chemical Engineering Journal,2006,122:93-106.
[19]王爱琴.甲壳素化学[M].北京,科学出版社,2008.
[20]张林生.印染废水处理技术及典型工程[M].北京,化学工业出版社,2005.44-171.
[21]Nollet H, Roels M, Lutgen P, et al. Removal of PCBs from wastewater using fly ash[J]. Chemosphere,2003,53:655-665.
[22]洪爱珍.氨基化壳聚糖微球吸附阴离子偶氮染料研究[D].[硕士学位论文].福州：福建师范大学.2003.
[23]Ho Y S, Chiu W T, Wang C C. Regression analysis for the sorption isotherms of basic dyes on sugarcane dust[J]. Bioresource Technology,2005,96(11):1285-1291.
[24]Lorenc-Grabowska E, Gryglewicz G. Adsorption of lignite-derived humic acids on coal-based mesoporous activated carbons[J]. Journal of Colloid and Interface Science,2005, 284(2):416-423.
[25]Mohana S V, Raoa N C, Karthikeyan J. Adsorptive removal of direct azo dye from aqueous phase onto coal based sorbents, a kinetic and mechanistic study[J]. Journal of Hazardous Materials,2002,90(2):189-204.
[26]Sparks D L, Carski T H. Kinetics of potassium exchange in heterogeneous systems[J]. Applied Clay Science,1985,1(1-2):89-101.
[27]Chatterjee S, Chatterjee S, Chatterjee B P, et al. Adsorptive removal of congo red, a carcinogenic textile dye by chitosan hydrobeads:Binding mechanism, equilibrium and kinetics[J]. Colloids and Surfaces A,2007,299(1-3):146-152.