摘要
随着现代工业的快速发展,许多生产企业所排放的废水污染问题也日益严重。其中,重金属离子废水的特点是毒效期长、持续、生物不可降解等,它可以通过食物链在生物体内累积而导致生物体致癌、致残、致畸;印染废水成份比较复杂,所含的有毒、有害物质会严重污染环境。因此,这些有害废水的处理显得十分迫切,有关废水处理研究已经受到关注。吸附法是其中一类重要的处理方法。
膨润土因具有较强的离子交换能力和大的表面积而表现出较强的吸附性能,因此可用于废水处理。为了大幅度提高天然膨润土的吸附能力和拓宽应用领域,本论文采用原位聚合法制备了共聚物改性膨润土--丙烯酸共聚物/膨润土复合物,并研究其对不同类型废水(即含金属离子或含染料化合物水溶液)的吸附作用首先介绍了废水处理的方法,对膨润土的改性及其改性产物在重金属废水和染料废水处理中应用研究进展进行了综述,同时总结了目前膨润土、有机改性中存在的问题。
其次,以钠基膨润土(NaB)为原料,首次通过原位聚合法,将亲水性单体与疏水性单体在膨润土分散液中进行共聚,制备了两种新型双亲性丙烯酸共聚物/膨润土复合物,即共聚物P(MAV)/NaB复合物与交联共聚物P(MAVM)/NaB复合物。采用红外光谱(FT-IR)、X-射线衍射(XRD)、扫描电镜(SEM)等仪器分析方法,研究了其组成、微观结构、形貌和表面官能团等。
第三,以P(MAVM)/NaB为吸附剂,分别处理含Pb~(2+)、Cd~(2+)废水,考查了废水pH值、吸附剂用量、金属离子初始浓度,以及吸附温度与吸附时间对其吸附性能的影响。发现吸附处理Pb~(2+)废水时,25°C,当pH=5,P(MAVM)/NaB=0.2 g/L,[Pb~(2+)]=50.0mg/L时,振荡30min条件下吸附效果最好,Pb~(2+)去除率达94.40% ;处理Cd~(2+)废水时, 25°C , pH=6 , P(MAVM)/NaB=1.0g/L ,[Cd~(2+)]=200.0mg/L,振荡60min条件下,去除率为89.54%。进一步对其吸附等温模型和动力学进行了探讨。发现吸附动力学特性符合准二级动力学模型,吸附等温模型较好地符合Freundlich等温式。
第四,将P(MAV)/NaB复合物用于吸附染料化合物--亚甲基蓝(MB)、品红(BF),考查了水溶液pH值、吸附剂用量、染料初始浓度,以及吸附温度与吸附时间对其吸附性能的影响。发现吸附处理MB废水时,25°C,pH=6-7,[MB]=20.0mg/L, [P(MAVM)/NaB]=0.1 g/L,振荡吸附5 min条件下,MB溶液的脱色率可达为97.73%。发现吸附处理BF废水时,pH=6-7, 25°C,[BF]=100.0 mg/L;[P(MAVM)/NaB]=1.0 g/L,振荡5min条件下,脱色率为95.96%。进一步对其吸附等温模型和动力学进行了探讨。发现吸附动力学特性符合准二级动力学模型,吸附等温模型较好地符合Freundlich等温式。
总之,将制备的双亲性丙烯酸共聚物/膨润土复合物分别用于金属离子与染料化合物的吸附。发现具有较高的吸附性能,有望用于不同金属离子和染料的处理或富集。
With the rapid development of modern industry, the wastewater discharge pollution problem by many production enterprises is getting worse. The characteristics of heavy metal ions wastewater is valid, lasting, and biological non-degradable. It can accumulate through the food chain resulting in biological organisms, cancer, disability, teratogenic. Printing and dyeing wastewater ingredients are complex, contains poisonous and harmful material can seriously pollute the environment. Therefore, these harmful wastewater treatment appears very urgent, relevant wastewater treatment research has been concerned. Adsorption is one kind of important processing method.
Due to strong ion-exchange capacity and large surface area, Bentonite shows strong adsorption, it can be used for wastewater treatment. In order to dramatically improve natural bentonite adsorption ability and expand the application field, this paper prepared two new amphiphilic acrylic acid copolymer/bentonite composite by in-situ polymerization, and researched on its adsorption function for the different types of wastewater (contain metal ions or dye compound aqueous)
Firstly, this paper introduced wastewater treatment methods, bentonite modification, the application of their modified products in heavy metal waste and dye wastewater treatment is reviewed. And summarized the problems of current bentonite, organic modify.
Secondly, based on sodium base bentonite (NaB) as raw material, the hydrophilic monomer and hydrophobic were dispersed with bentonite in aquous solution and copolymerized by in-situ polymerization. Two kind of new amphiphilic acrylic acid copolymer/bentonite composite were prepared, The copolymer P(MAV)/NaB composite and cross-linked copolymer P(MAVM)/NaB composite. Using infrared spectrometry (FT-IR)、X-ray diffraction (XRD), scanning electron microscopy (SEM) instrument analysis methods to study the composition, microstructure, morphology and surface functional group, and so on
Thirdly, we have treated the Pb~(2+)、Cd~(2+) wastewater using P(MAVM)/NaB as adsorbent. Examine the effect of pH of wastewater, adsorbent dosage, initial concentration of metal ions, adsorption temperature and time on adsorption properties. We have treated the Pb~(2+) wastewater, The optimal condition is as following: pH=5, [Pb~(2+)]=50.0 mg/L, P(MAVM)/NaB=0.2 g/L, oscillating 30 min in 25oC. The removal rate reached to 94.40%. We have treated the Cd~(2+) wastewater. The optimal condition is as following: pH=6, [Cd~(2+)]=200.0mg/L, P(MAVM)/NaB=1.0g/L, oscillating 60 min in 25°C. the removal rate reached to 89.54%。And its adsorption isotherm and kinetic models were discussed. Adsorption kinetics consistent with quasi-second order kinetic model, adsorption isotherm model was fitted to Freundlich isotherm.
Fourthly, we have treated the MB、BF wastewater using P(MAVM)/NaB as adsorbent. Examine the effect of pH of wastewater, adsorbent dosage, initial concentration of metal ions, adsorption temperature and time on adsorption properties. We have treated the MB wastewater, The optimal condition is as following: pH: 6-7, [MB]=20.0 mg/L, P(MAVM)/NaB=0.1g/L, , oscillating 5 min in 25 oC. Under the condition, the decolorization rate reached to 97.73%. We have treated the BF wastewater. The optimal condition is as following: pH: 6-7, [BF]=100.0mg/L, P(MAVM)/NaB=1.0g/L, oscillating 5 min in 25°C. Under the condition, the decolorization rate reached to 95.96%.And its adsorption isotherm and kinetic models were discussed. Adsorption kinetics consistent with quasi-second order kinetic model, adsorption isotherm model was fitted to Freundlich isotherm.
In short, the prepared amphiphilic acrylic acid copolymer/bentonite composite were used for dye compounds and the metal ions adsorption. Found to have high adsorption properties, it is expected to be used for different metal ions and dye processing or enrichment
引文
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