壳聚糖/明胶微球对活性染料吸附净洗性能研究
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摘要
在印染行业中，活性染料由于染色工艺简单、色谱齐全、价格适中、色牢度较高等优点被广泛应用于纤维素纤维纺织品的印染工艺。然而，在染色工艺中，会有高达20%～40%的浮色染料未能上染固色，这些浮色染料源于已吸附于纤维而未参与共价反应的染料和大部分水解染料，它的存在会大大降低染色织物的色牢度，需要通过净洗工艺将其除去。据统计，活性染料净洗工艺消耗的净洗剂以及洗下的浮色染料产生的COD占整个染色加工产生COD的1/3；所消耗的大量水、能源及后续废水处理的成本占其染色成本的50%以上。水体中的染料，影响水生植物的光合作用、能够致癌、致畸、危害人类健康。
解决活性染料印染废水的水体污染问题通常有两种方式：一是终端治理，在染料废水排放前通过各种水污染治理手段，使染料废水达到国家排放标准；二是源头治理，在活性染料印染加工过程中，通过清洁化工艺，尽量减少染料废水的产生。
而染料作为着色物质，常规的生化法难于彻底脱色，因此吸附法是工业上染料废水深度处理的主要方法之一。该方法目前存在的主要问题是吸附剂吸附量偏低，成本高，产生二次固废，而且解吸困难，难于循环利用。
针对以上问题，根据壳聚糖的阳离子性，明胶的两性特点，以二者为原料，戊二醛为交联剂，通过反相悬浮交联法，制备出壳聚糖/明胶复合微球（CGMSs）。一方面，CGMSs吸附剂具有优异吸附与解吸性能，可用于活性染料为代表的阴离子型染料废水处理之中；另一方面，将该CGMSs用于活性染料水洗工艺，取得了节水、省时、降低COD、实现了染料回收利用等多种良好效果。
过单因素优选法，逐个研究了壳聚糖、明胶的用量、交联剂的种类、乳化剂的种类及用量、内外相比例、搅拌速率、乳化时间及温度等因素对CGMSs制备的影响，通过扫描电子显微镜和激光粒径分析仪的表征，分析了各因素对CGMSs粒径与形貌的影响规律。结果表明：以戊二醛为交联剂，壳聚糖浓度为0.02g/mL，明胶浓度为0.08g/mL，乳化剂Span-80的用量为0.04g/mL，水油比为1/6、搅拌速度为900r/min，乳化温度为60℃，乳化20min的条件下，可制得形态圆整，色泽均匀，流动性好，表面粗糙不平、体积平均径为23.53μm、等电点为6.0的壳聚糖/明胶复合微球。
以CGMSs为吸附剂，选用活性艳橙RO1、活性红RR24两种活性染料，研究了各种实验参数对染料吸附性能的影响。这些参数包括：吸附工艺（温度、时间、pH）、吸附剂性质、离子强度、振荡速率、CGMSs解吸重复利用等。结果显示：(1)增加振荡速率能够提高CGMSs的吸附量，而电解质硫酸钠使CGMSs的吸附量下降，但影响不太明显。(2)CGMSs最佳吸附条件为：pH2～3，温度30℃，吸附时间为80min；当染料初始浓度为0.4g/L，CGMSs的用量分别为0.8g/L和1.0g/L时，活性艳橙RO1与活性红RR24的去除率分别为98.7%和99.1%。(3)CGMSs的解吸性能：CGMSs反复使用7次后，活性艳橙RO1与活性红RR24的吸附量下降率分别为8.6%与9.7%。因此CGMSs是活性染料去除的理想吸附剂之一，具有潜在的应用前景。
为了阐明CGMSs吸附途径和吸附机理，研究了吸附剂对活性染料的吸附动力学模型、吸附等温模型及热力学行为。实验结果表明：准二级动力学方程比较适合描述CGMSs对活性染料的吸附动力学，此外粒子内扩散与外在质量扩散同时影响吸附速率，但粒子内扩散是速控步骤；CGMSs对活性染料的吸附平衡数据比较符合Langmuir吸附等温方程，这说明吸附为单分子层化学吸附，同时根据D－R方程计算得出的吸附平均自由能也表明，CGMSs对活性染料的吸附是以化学吸附为主的；吸附剂对两种活性染料的焓变ΔH>0，说明CGMSs对染料的吸附为吸热过程，温度升高有利于染料吸附；熵变ΔS为正值，说明吸附过程中CGMSs与染料溶液的界面上，体系的熵是增加的，即水分子脱附引起的熵增加大于染料分子吸附引起的熵减少，所以体系无序度增加；吸附吉布斯函变ΔG都小于0，表明CGMSs对活性染料的吸附过程是自发的。
本课题首次研究将CGMSs用作活性染料净洗剂。在净洗工艺中，浮色染料在溶液与纤维之间存在分配平衡，CGMSs通过不断吸附溶液中的染料来打破这种平衡，从而使纤维上的浮色染料不断通过水溶液被CGMSs吸附，从而达到净洗活性染料的目的。CGMSs在水洗工艺中具有较强的抗硬水性、较好的耐电解质性、优异的pH缓冲性、其净洗效果随着CGMSs中壳聚糖百分含量的增加，CGMSs粒径的减少而提高。CGMSs净洗剂的最佳应用条件为pH4.0，时间15min，CGMSs浓度0.2g/L，温度95℃。 CGMSs的净洗效果与常规净洗剂净洗效果基本一致，但其净洗残液COD值约为常规净洗剂的1/16，因此显著降低了活性染料废水处理成本；与常规净洗工艺相比，CGMSs净洗工艺省去皂洗前1道冷水洗和1道酸洗工艺，为活性染料水洗工艺节约了用水用汽，降低了活性染料染色成本。
因为浮色染料中吸附于纤维而未参与共价反应的部分活性染料仍具有染色功能，而CGMSs净洗剂上浮色染料的解吸pH条件与活性染料的染色工艺pH条件基本一致。为确定CGMSs净洗剂上未反应活性染料的循环利用，本课题以商品活性染料为模拟物，初步研究了活性染料负载CGMSs在纤维素纤维织物染色工艺中的应用性能。实验结果表明：染料负载CGMSs可以实现小浴比染色、染色织物的匀染性要优于常规染色工艺。试验确定其最佳染色工艺为：染色时间70min，浴比为1:30， Na2SO4用量为30g/L时织物表观色深值最大；活性红RR24染料Na2CO3的最佳用量为20g/L，染色温度70℃，对于活性艳蓝RBE19Na2CO3的最佳用量为15g/L，染色温度60℃。
壳聚糖、明胶是自然界中存在的一类可再生的生物质资源，以二者为原料所制备的壳聚糖/明胶复合微球对活性染料具有良好的吸附、解吸性能。用复合微球代替传统基于表面活性剂复配的活性染料净洗剂，能够取得节水、节能、降低COD等良好效果，而且可以在染色工艺中同时实现CGMSs的再生和未水解活性染料的二次利用。这一基于吸附理念设计制备出的活性染料净洗剂，拓展了活性染料净洗途径，为解决活性染料印染环保问题提供了新的技术支持。
In dyeing and finishing industry, the reactive dyes are widely usedto dye and print the cellulose fabrics for their reasonable price, ease ofapplication, good color values and excellent fastness properties.However, the reactive dyes suffer disadvantage of incompleteexhaustion up to20%～40%during dyeing. The vagrant dye consistedof unreacted and mainly hydrolyzed dyes can sharply decrease thefastness of fabrics. Generally, this vagrant dyes are wiped off through awash-off process with a great deal of dyeing wastewater producing.According to incomplete statistics, one-third of the effluent (COD)derived from the total dyeing technics are related to the washingprocedures since the vagrant dyes and auxiliaries existing. Moreover, agreat of energy and water consumption, as well as the treatment of theresulting effluent, typically accounts for the major part of the totaldyeing cost (about50%). The polluted water badly affects thephotosynthesis of hydrophyte and can also cause severe damage tohuman beings because of their mutagenic effect and carcinogenicity.
There are two ways to solve the dyeing pollution, one is theend-of-pipe control, recovering the wastewater through various disposalmeasurements before the discharge; the other is to decrease thewastewater outflow from sources by means of clean productiontechnics.
Dyes are chromogenic organic compounds, so the routinebiological and chemical treatments cannot reach the aim of disposingdyeing wastewater. At present, adsorption is one of the best choices forindustrial dyes wastewater advanced disposal. But the adsorptiontreatment has the disadvantages of low adsorption capacity, high-cost,second solid rejectamenta producing and difficulty to recycle for the weak desorption character.
According to the problem mentioned above, Chitosan-gelatincomposite microspheres were prepared by the inverse suspensioncrosslinking reaction， using cationic chitosan (CS) and amphotericgelatin as the raw materials and taking glutaraldehyde as thecross-linking agent. The chitosan/gelatin microspheres(CGMSs)prepared have the excellent adsorption and desorption quality andsuitable for disposing the anionic dyeing wastewater especially reactivedyes. In addition, CGMSs display the merits of saving water, sparingtime, decreasing COD and reclaiming dyes during the wash-offtechnology.
When CGMSs were prepared, the factors such as dosage ofchitosan, gelatin and emulsion, selection of emulsion and crosslinkingagents, the ratio of water-oil, agitation speed, emulsification time andtemperature were investigated. The products were characterized bySEM and laser particle size analyzer. The CGMSs obtained wereindicated spherical, irregular surface morphology, and good fluidnesswith23.53μm of volume mean diameter and6.0of isoeletric point. Theoptimal conditions were as follows: chitosan was0.02g/L, gelatin was0.08g/L, Span-80was0.04g/L, the ratio of water–oil was1/6, thetemperature was60℃emulsifed at900r/min for20min.
The effect of the experiment parameters on the adsorption ofReactive Orange1(RO1) and Reactive Red24(RR24) onto CGMSs werestudied. These parameters included the adsorption technology, such astemperature, time and pH, the adsorbent properties, ionic strength,shaking speed and recycling application. It was found that (1) theadsorption capacity increased with increasing shaking speed anddecreased with increasing the dosage of electrolyte;(2) The optimalconditions were pH2～3, temperature of30℃, adsorption for80min.Meanwhile, the dye removal rate can achieve to98.7%and99.1%forRO1and RR24at the condition of initial dye concentration of0.4g/L,the CGMSs concentration of0.8g/L and1.0g/L, respectively;(3)Theadsorption capacity decreased by only8.6%of RO1and9.7%of RR24 separately after the CGMSs was used for7times. These resultssuggested that CGMSs can be used repeatedly without losing adsorptioncapacities significantly. So the CGMSs are proved to be a kind ofpromising excellent adsorption material.
In order to illustrate the mechanism of CGMSs adsorbing reactivedyes, the adsorption kinetics and isotherm models as well asthermodynamic parameters were researched. The results indicated thatthe adsorption kinetics followed the pseudo-second-order model. Boththe external mass transfer and the intraparticle diffusion had the ratelimiting influences on the removal process, but intraparticle diffusionwas the rate determining step. The isotherm models revealed that theadsorption process of reactive dyes onto CGMSs fited well with theLangmuir model which suggested the adsorption was monomolecularlayer chemisorption. The mean adsorption energy (E) calculated fromthe Dubinin-Radushkevich isotherm manifested that the adsorption wasmainly chemisorption as well. The positive values of ΔH indicated thatthe adsorption was endothermic and the process would benefit from thetemperature increasing. The positive values of ΔS implied that therandomness increased at the microsphere/solution surface. It can beexplained that the randomness gains by water desorption were exceedthe randomness reduces by dye adsorption. Whereas, the negative ΔGvalues showed that the adsorption was spontaneous in the experimentalconditions.
The CGMSs are taken as the reactive wash-off agent, which are theinnovation of this research. The function of CGMSs wash-off can becompleted by the vagrant dye shifting from fabric to CGMSs whichbreak the dye balance between fabric and dye solution by adsorption.The CGMSs have the properties of pH buffering, resistance to thehardness water and the electrolyte as a wash-off agent. The efficiencyof wash-off can be improved with the increase of chitosan content andthe decrease of diameter of CGMSs. With regard to the technologycondition, the optimal wash-off parameters were as follows: the CGMSsdosage was0.2g/L, temperature was95℃and pH was4washing for15 min. The efficiency of CGMSs can rival routinely detergent in colorfastness, while the COD of CGMSs wash-off residue accounts for1/16of that of detergent wash-off residue. Compared with the traditionallytechnology, CGMSs method saved once room temperature wash-off andonce acid wash-off. The use of CGMSs will sharply alleviate the burdenof dyeing wastewater and can save water and energy and cut the cost ofdyeing process.
The dyes unfixed to fabric are still capable of dyeing, meanwhile,the pH of dye desorption from CGMSs coincides with that of reactivedye dyeing technics. In order to value the unfixed dyes recycling, theapplication of CGMSs loaded reactive dye in cellulose fabric dyeingtechnics were studied. The results showed that CGMSs loaded reactivedyes were suitable to low liquor ratio dyeing with the superior levellingproperty to the general dyeing technics. The best RR24dyeingproduction will be achieved in condition that the liquor ratio was1:30,time was70min, temperature was70℃, sodium sulfate was30g/L andsodium carbonate was20g/L. For the RBE19dye, the optimal conditionwas temperature of60℃, sodium carbonate of15g/L and the othersections were the same as RR24.
Chitosan and gelatin are the natural renewable bioresources. TheCGMSs showed excellent performances on adsorption and desorption ofreactive dyes. It can achieve many good effects such as water-saving,energy-saving and reducing COD of effluents using CGMSs as awash-off agent for reactive dyes instead of the traditional surfactantcombinations. The regeneration of CGMSs can be obtained at the sametime with the reutilization of unhydrolyzed reactive dyes in dyeingprocess. This wash-off agent designed on the basis of adsorptionmechanism expanded the way of wash-off for reactive dyeing, providinga new technology to resolve the problem of reactive dye dyeingwastewater and environmental pollution.
解决活性染料印染废水的水体污染问题通常有两种方式：一是终端治理，在染料废水排放前通过各种水污染治理手段，使染料废水达到国家排放标准；二是源头治理，在活性染料印染加工过程中，通过清洁化工艺，尽量减少染料废水的产生。
而染料作为着色物质，常规的生化法难于彻底脱色，因此吸附法是工业上染料废水深度处理的主要方法之一。该方法目前存在的主要问题是吸附剂吸附量偏低，成本高，产生二次固废，而且解吸困难，难于循环利用。
针对以上问题，根据壳聚糖的阳离子性，明胶的两性特点，以二者为原料，戊二醛为交联剂，通过反相悬浮交联法，制备出壳聚糖/明胶复合微球（CGMSs）。一方面，CGMSs吸附剂具有优异吸附与解吸性能，可用于活性染料为代表的阴离子型染料废水处理之中；另一方面，将该CGMSs用于活性染料水洗工艺，取得了节水、省时、降低COD、实现了染料回收利用等多种良好效果。
过单因素优选法，逐个研究了壳聚糖、明胶的用量、交联剂的种类、乳化剂的种类及用量、内外相比例、搅拌速率、乳化时间及温度等因素对CGMSs制备的影响，通过扫描电子显微镜和激光粒径分析仪的表征，分析了各因素对CGMSs粒径与形貌的影响规律。结果表明：以戊二醛为交联剂，壳聚糖浓度为0.02g/mL，明胶浓度为0.08g/mL，乳化剂Span-80的用量为0.04g/mL，水油比为1/6、搅拌速度为900r/min，乳化温度为60℃，乳化20min的条件下，可制得形态圆整，色泽均匀，流动性好，表面粗糙不平、体积平均径为23.53μm、等电点为6.0的壳聚糖/明胶复合微球。
以CGMSs为吸附剂，选用活性艳橙RO1、活性红RR24两种活性染料，研究了各种实验参数对染料吸附性能的影响。这些参数包括：吸附工艺（温度、时间、pH）、吸附剂性质、离子强度、振荡速率、CGMSs解吸重复利用等。结果显示：(1)增加振荡速率能够提高CGMSs的吸附量，而电解质硫酸钠使CGMSs的吸附量下降，但影响不太明显。(2)CGMSs最佳吸附条件为：pH2～3，温度30℃，吸附时间为80min；当染料初始浓度为0.4g/L，CGMSs的用量分别为0.8g/L和1.0g/L时，活性艳橙RO1与活性红RR24的去除率分别为98.7%和99.1%。(3)CGMSs的解吸性能：CGMSs反复使用7次后，活性艳橙RO1与活性红RR24的吸附量下降率分别为8.6%与9.7%。因此CGMSs是活性染料去除的理想吸附剂之一，具有潜在的应用前景。
为了阐明CGMSs吸附途径和吸附机理，研究了吸附剂对活性染料的吸附动力学模型、吸附等温模型及热力学行为。实验结果表明：准二级动力学方程比较适合描述CGMSs对活性染料的吸附动力学，此外粒子内扩散与外在质量扩散同时影响吸附速率，但粒子内扩散是速控步骤；CGMSs对活性染料的吸附平衡数据比较符合Langmuir吸附等温方程，这说明吸附为单分子层化学吸附，同时根据D－R方程计算得出的吸附平均自由能也表明，CGMSs对活性染料的吸附是以化学吸附为主的；吸附剂对两种活性染料的焓变ΔH>0，说明CGMSs对染料的吸附为吸热过程，温度升高有利于染料吸附；熵变ΔS为正值，说明吸附过程中CGMSs与染料溶液的界面上，体系的熵是增加的，即水分子脱附引起的熵增加大于染料分子吸附引起的熵减少，所以体系无序度增加；吸附吉布斯函变ΔG都小于0，表明CGMSs对活性染料的吸附过程是自发的。
本课题首次研究将CGMSs用作活性染料净洗剂。在净洗工艺中，浮色染料在溶液与纤维之间存在分配平衡，CGMSs通过不断吸附溶液中的染料来打破这种平衡，从而使纤维上的浮色染料不断通过水溶液被CGMSs吸附，从而达到净洗活性染料的目的。CGMSs在水洗工艺中具有较强的抗硬水性、较好的耐电解质性、优异的pH缓冲性、其净洗效果随着CGMSs中壳聚糖百分含量的增加，CGMSs粒径的减少而提高。CGMSs净洗剂的最佳应用条件为pH4.0，时间15min，CGMSs浓度0.2g/L，温度95℃。 CGMSs的净洗效果与常规净洗剂净洗效果基本一致，但其净洗残液COD值约为常规净洗剂的1/16，因此显著降低了活性染料废水处理成本；与常规净洗工艺相比，CGMSs净洗工艺省去皂洗前1道冷水洗和1道酸洗工艺，为活性染料水洗工艺节约了用水用汽，降低了活性染料染色成本。
因为浮色染料中吸附于纤维而未参与共价反应的部分活性染料仍具有染色功能，而CGMSs净洗剂上浮色染料的解吸pH条件与活性染料的染色工艺pH条件基本一致。为确定CGMSs净洗剂上未反应活性染料的循环利用，本课题以商品活性染料为模拟物，初步研究了活性染料负载CGMSs在纤维素纤维织物染色工艺中的应用性能。实验结果表明：染料负载CGMSs可以实现小浴比染色、染色织物的匀染性要优于常规染色工艺。试验确定其最佳染色工艺为：染色时间70min，浴比为1:30， Na2SO4用量为30g/L时织物表观色深值最大；活性红RR24染料Na2CO3的最佳用量为20g/L，染色温度70℃，对于活性艳蓝RBE19Na2CO3的最佳用量为15g/L，染色温度60℃。
壳聚糖、明胶是自然界中存在的一类可再生的生物质资源，以二者为原料所制备的壳聚糖/明胶复合微球对活性染料具有良好的吸附、解吸性能。用复合微球代替传统基于表面活性剂复配的活性染料净洗剂，能够取得节水、节能、降低COD等良好效果，而且可以在染色工艺中同时实现CGMSs的再生和未水解活性染料的二次利用。这一基于吸附理念设计制备出的活性染料净洗剂，拓展了活性染料净洗途径，为解决活性染料印染环保问题提供了新的技术支持。
In dyeing and finishing industry, the reactive dyes are widely usedto dye and print the cellulose fabrics for their reasonable price, ease ofapplication, good color values and excellent fastness properties.However, the reactive dyes suffer disadvantage of incompleteexhaustion up to20%～40%during dyeing. The vagrant dye consistedof unreacted and mainly hydrolyzed dyes can sharply decrease thefastness of fabrics. Generally, this vagrant dyes are wiped off through awash-off process with a great deal of dyeing wastewater producing.According to incomplete statistics, one-third of the effluent (COD)derived from the total dyeing technics are related to the washingprocedures since the vagrant dyes and auxiliaries existing. Moreover, agreat of energy and water consumption, as well as the treatment of theresulting effluent, typically accounts for the major part of the totaldyeing cost (about50%). The polluted water badly affects thephotosynthesis of hydrophyte and can also cause severe damage tohuman beings because of their mutagenic effect and carcinogenicity.
There are two ways to solve the dyeing pollution, one is theend-of-pipe control, recovering the wastewater through various disposalmeasurements before the discharge; the other is to decrease thewastewater outflow from sources by means of clean productiontechnics.
Dyes are chromogenic organic compounds, so the routinebiological and chemical treatments cannot reach the aim of disposingdyeing wastewater. At present, adsorption is one of the best choices forindustrial dyes wastewater advanced disposal. But the adsorptiontreatment has the disadvantages of low adsorption capacity, high-cost,second solid rejectamenta producing and difficulty to recycle for the weak desorption character.
According to the problem mentioned above, Chitosan-gelatincomposite microspheres were prepared by the inverse suspensioncrosslinking reaction， using cationic chitosan (CS) and amphotericgelatin as the raw materials and taking glutaraldehyde as thecross-linking agent. The chitosan/gelatin microspheres(CGMSs)prepared have the excellent adsorption and desorption quality andsuitable for disposing the anionic dyeing wastewater especially reactivedyes. In addition, CGMSs display the merits of saving water, sparingtime, decreasing COD and reclaiming dyes during the wash-offtechnology.
When CGMSs were prepared, the factors such as dosage ofchitosan, gelatin and emulsion, selection of emulsion and crosslinkingagents, the ratio of water-oil, agitation speed, emulsification time andtemperature were investigated. The products were characterized bySEM and laser particle size analyzer. The CGMSs obtained wereindicated spherical, irregular surface morphology, and good fluidnesswith23.53μm of volume mean diameter and6.0of isoeletric point. Theoptimal conditions were as follows: chitosan was0.02g/L, gelatin was0.08g/L, Span-80was0.04g/L, the ratio of water–oil was1/6, thetemperature was60℃emulsifed at900r/min for20min.
The effect of the experiment parameters on the adsorption ofReactive Orange1(RO1) and Reactive Red24(RR24) onto CGMSs werestudied. These parameters included the adsorption technology, such astemperature, time and pH, the adsorbent properties, ionic strength,shaking speed and recycling application. It was found that (1) theadsorption capacity increased with increasing shaking speed anddecreased with increasing the dosage of electrolyte;(2) The optimalconditions were pH2～3, temperature of30℃, adsorption for80min.Meanwhile, the dye removal rate can achieve to98.7%and99.1%forRO1and RR24at the condition of initial dye concentration of0.4g/L,the CGMSs concentration of0.8g/L and1.0g/L, respectively;(3)Theadsorption capacity decreased by only8.6%of RO1and9.7%of RR24 separately after the CGMSs was used for7times. These resultssuggested that CGMSs can be used repeatedly without losing adsorptioncapacities significantly. So the CGMSs are proved to be a kind ofpromising excellent adsorption material.
In order to illustrate the mechanism of CGMSs adsorbing reactivedyes, the adsorption kinetics and isotherm models as well asthermodynamic parameters were researched. The results indicated thatthe adsorption kinetics followed the pseudo-second-order model. Boththe external mass transfer and the intraparticle diffusion had the ratelimiting influences on the removal process, but intraparticle diffusionwas the rate determining step. The isotherm models revealed that theadsorption process of reactive dyes onto CGMSs fited well with theLangmuir model which suggested the adsorption was monomolecularlayer chemisorption. The mean adsorption energy (E) calculated fromthe Dubinin-Radushkevich isotherm manifested that the adsorption wasmainly chemisorption as well. The positive values of ΔH indicated thatthe adsorption was endothermic and the process would benefit from thetemperature increasing. The positive values of ΔS implied that therandomness increased at the microsphere/solution surface. It can beexplained that the randomness gains by water desorption were exceedthe randomness reduces by dye adsorption. Whereas, the negative ΔGvalues showed that the adsorption was spontaneous in the experimentalconditions.
The CGMSs are taken as the reactive wash-off agent, which are theinnovation of this research. The function of CGMSs wash-off can becompleted by the vagrant dye shifting from fabric to CGMSs whichbreak the dye balance between fabric and dye solution by adsorption.The CGMSs have the properties of pH buffering, resistance to thehardness water and the electrolyte as a wash-off agent. The efficiencyof wash-off can be improved with the increase of chitosan content andthe decrease of diameter of CGMSs. With regard to the technologycondition, the optimal wash-off parameters were as follows: the CGMSsdosage was0.2g/L, temperature was95℃and pH was4washing for15 min. The efficiency of CGMSs can rival routinely detergent in colorfastness, while the COD of CGMSs wash-off residue accounts for1/16of that of detergent wash-off residue. Compared with the traditionallytechnology, CGMSs method saved once room temperature wash-off andonce acid wash-off. The use of CGMSs will sharply alleviate the burdenof dyeing wastewater and can save water and energy and cut the cost ofdyeing process.
The dyes unfixed to fabric are still capable of dyeing, meanwhile,the pH of dye desorption from CGMSs coincides with that of reactivedye dyeing technics. In order to value the unfixed dyes recycling, theapplication of CGMSs loaded reactive dye in cellulose fabric dyeingtechnics were studied. The results showed that CGMSs loaded reactivedyes were suitable to low liquor ratio dyeing with the superior levellingproperty to the general dyeing technics. The best RR24dyeingproduction will be achieved in condition that the liquor ratio was1:30,time was70min, temperature was70℃, sodium sulfate was30g/L andsodium carbonate was20g/L. For the RBE19dye, the optimal conditionwas temperature of60℃, sodium carbonate of15g/L and the othersections were the same as RR24.
Chitosan and gelatin are the natural renewable bioresources. TheCGMSs showed excellent performances on adsorption and desorption ofreactive dyes. It can achieve many good effects such as water-saving,energy-saving and reducing COD of effluents using CGMSs as awash-off agent for reactive dyes instead of the traditional surfactantcombinations. The regeneration of CGMSs can be obtained at the sametime with the reutilization of unhydrolyzed reactive dyes in dyeingprocess. This wash-off agent designed on the basis of adsorptionmechanism expanded the way of wash-off for reactive dyeing, providinga new technology to resolve the problem of reactive dye dyeingwastewater and environmental pollution.
引文
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