Fenton法处理含植物多酚类废水的作用机制及在槟榔废水中的应用

发布时间：2018-01-15 06:26

本文关键词：Fenton法处理含植物多酚类废水的作用机制及在槟榔废水中的应用　出处：《湖南农业大学》2015年硕士论文　论文类型：学位论文

更多相关文章： 槟榔废水 植物多酚 Fenton试剂 机理

【摘要】：槟榔煮籽废水是一种高浓度、高色度的有机酸性废水,属于难生物降解废水。目前,国内外针对槟榔煮籽废水处理的专项研究少有报道,仅有针对槟榔加工企业排放的综合废水的报道,然而由于没有专门的工艺研究,目前开发的处理工艺操作繁琐,成本高昂,影响了其在槟榔加工废水处理领域的推广应用。本论文基于槟榔废水含有难降解成分,造成可生化性下降,以此探究槟榔煮籽废水中抑制微生物生长的有效成分,以Fenton试剂氧化法处理模拟废水并应用于实际废水,采用响应面法优化工艺条件,利用LC-MS联用技术测定Fenton试剂处理含有效成分的模拟废水中的化合物,探讨Fenton试剂作用槟榔废水的机理,以期为槟榔煮籽废水的处理提供新的思路和设计依据。(1)探索了高效液相色谱法测定表儿茶素与芦丁的液相色谱条件,测定了槟榔废水中表儿茶素与芦丁的含量。液相色谱条件为：以甲醇与0.1%的磷酸溶液为流动相,梯度洗脱程序为：Omin:20%B,8min:100%B,9min:20%B, 10min:20%B,检测波长236nm,柱温40℃,流速1.0mL/min,进样量为10ul,在此条件下,表儿茶素与芦丁能够得到很好的分离,表儿茶素与芦丁的线性回归方程分别为y=5.6126x-0.1248(R2=0.9997), y=12.237+0.2929 (R2=0.9994),平均回收率为100.9%、97.48%,精密度RSD为1.7%、1.9%。表儿茶素、芦丁的保留时间分别为：756min、8.82min。(2) Fenton试剂氧化技术具有较强的氧化能力,且反应条件较易控制,能够去除模拟废水中的TOC与COD,实验研究了Fenton试剂法处理含表儿茶素模拟废水的最优工艺条件,以废水中的TOC与COD的去除率为指标,根据单因素实验结果确定响应面分析法的影响因子。基于Box-Behnken响应曲面法,考察了初始pH值、双氧水投加量、硫酸亚铁投加量和反应时间的单独作用和交互作用,并建立了TOC去除率数学模型。当表儿茶素的浓度为2OOmg/L时,取模拟水样200m1置于烧杯中进行Fento n氧化反应,实验表明,在初始pH值为4,双氧水投加量为7.5ml/L,硫酸亚铁投加量为1.25g/L,反应时间为12Omin, PAM加入量为0.2%时,整个反应过程对TOC去除率可达到67%。通过Box-Behnken响应曲面可知,初始pH值、硫酸亚铁投加量的交互作用对TOC去除率有显著影响,其中双氧水投加量、硫酸亚铁投加量与反应时间对TOC去除率的影响极显著。Fenton试剂处理模拟废水最佳的工艺条件为：双氧水投加量为10.6ml/L,硫酸亚铁投加量2.25g/L,初始pH值为4.59,反应时间为74min。在此条件下TOC去除率为82%。(3)实验研究了Fenton试剂法处理含芦丁的模拟废水的最优工艺条件,以废水中的TOC与COD的去除率为指标,根据单因素实验结果确定响应面分析法的影响因子。采用Design-expert8.0软件进行响应面试验设计,当芦丁的浓度为200mg/L时,取模拟水样200ml置于烧杯中进行Fenton氧化反应,实验表明,在初始pH值为4,双氧水投加量为7.5mL/L,硫酸亚铁投加量为1.5g/L,反应时间为120min, PAM加入量为0.5%时,整个反应过程对TOC去除率可达到68.3%。通过Box-Behnken响应曲面可知,初始pH值、硫酸亚铁投加量与反应时间的交互作用对TOC去除率有显著影响,其中硫酸亚铁投加量、反应时间对TOC去除率的影响极显著。最佳反应条件为双氧水投加量7.6ml/L,硫酸亚铁投加量2.05g/L,初始pH值3.83,反应时间73min,在此反应条件下TOC去除率为74.6%。(4)实验研究了Fenton试剂法处理槟榔废水的最优工艺条件,以废水中的TOC与COD的去除率为指标,根据单因素实验结果确定响应面分析法的影响因子。基于Box-Behnken响应曲面法,当槟榔废水中COD浓度为6300mg/L时,实验表明,在初始pH值为5,双氧水投加量为50mg/L,硫酸亚铁投加量为12.5g/L,反应时间为120min,PAM加入量为0.2%时,整个反应过程对TOC去除率可达到65%。通过Box-Behnken响应曲面可知,双氧水投加量、硫酸亚铁投加量的交互作用对TOC去除率有显著影响,其中双氧水投加量对TOC去除率的影响极显著。Fenton试剂处理槟榔废水最佳的工艺条件为：双氧水投加量为54.2ml/L,硫酸亚铁投加量12.55g/L,初始pH值为4.98,反应时间为103min。在此条件下TOC去除率为70%。(5)利用液质联用技术分析Fenton试剂氧化含多酚类物质芦丁的模拟废水的产物,从结果可以看出,Fenton试剂氧化芦丁的主要途径有两种：一种是在酸性条件下水解芦丁为槲皮素与芸香糖,槲皮素在羟基自由基的作用下,B环上的羟基被氧化为酮基,再进一步氧化为小分子化合物；另一种是羟基自由基直接攻击B环与C环之间的氧原子,产生两种氧化物,最终被进一步氧化为二氧化碳或者小分子化合物。
[Abstract]:Areca cooked seed wastewater is a kind of high concentration, high chroma of the organic acid wastewater, which belongs to the wastewater. At present, domestic and foreign to the areca cook special research of wastewater treatment seeds were rarely reported, only for wastewater discharge enterprises areca processing reports, however due to the lack of specialized research process, process operation at present the development of complex, high cost, affects its application in the field of areca processing wastewater. This paper based on areca wastewater containing refractory components, resulting in biodegradability decreased, in order to explore areca cooking waste water by inhibiting microbial effective components of seed growth, with Fenton reagent oxidation of simulated wastewater and Application in wastewater. Under the optimized condition by response surface method, combined compound Fenton reagent treatment of simulated wastewater containing active ingredients in the determination by LC-MS technique, to investigate the Fenton reagent The mechanism of areca wastewater, in order to provide new ideas and design basis for the treatment of wastewater. Areca cooked seeds (1) to explore the HPLC method for the determination of epicatechin and rutin by HPLC, catechin and rutin content in wastewater by areca. A liquid chromatography with 0.1% phosphoric acid solution and methanol as mobile phase, gradient elution program: Omin:20%B, 8min:100%B, 9min:20%B, 10min:20%B, the detection wavelength of 236nm, the column temperature was 40 degrees, 1.0mL/min flow rate, sample volume was 10ul, under this condition, epicatechin and rutin can be well separated, linear regression equation. Catechin were y=5.6126x-0.1248 and rutin (R2=0.9997), y=12.237+0.2929 (R2=0.9994), the average recovery rate was 100.9%, 97.48%, RSD of precision was 1.7%, 1.9%. epicatechin, rutin retention time were: 756min, 8.82min. (2) Fenton oxidation technology Strong oxidation ability, and the reaction condition is easy to control, can TOC and COD removal from simulated wastewater, experimental study on Fenton reagent optimal conditions containing epicatechin in simulated wastewater, with TOC and COD in wastewater removal rate as the index, according to the single factor test results to determine the response method the impact factor analysis. The response surface method based on Box-Behnken, the influence of initial pH value, h2o2dosage, single action and interaction of ferrous sulfate dosage and reaction time, and establishes a mathematical model of the removal rate of TOC. When the epicatechin concentration is 2OOmg/L, the Fento n oxidation reaction. Simulation of water 200m1 placed in a beaker experiment showed that in the initial pH value is 4, the hydrogen peroxide dosage was 7.5ml/L, ferrous sulfate dosage is 1.25g/L, the reaction time is 12Omin, the PAM content is 0.2%, the removal rate of TOC reaction process To 67%. through the Box-Behnken response surface shows that the initial pH value, FeSO 4 interaction dosage on TOC removal rate has a significant effect, the hydrogen peroxide dosage, ferrous sulfate dosage and reaction time on the removal rate of TOC was significantly.Fenton reagent treatment of simulated wastewater the best process conditions: hydrogen peroxide dosage the amount of 10.6ml/L, ferrous sulfate dosage of 2.25g/L, initial pH value is 4.59, the reaction time was 74min. under this condition, the removal rate of TOC is 82%. (3) experiment of Fenton reagent optimal conditions of simulated wastewater containing rutin, TOC and COD in wastewater removal rate as the index, according to the single the experimental results to determine the factors of the impact factor response surface analysis method. The response surface experimental design by using Design-expert8.0 software, when the rutin concentration is 200mg/L, the Fenton oxidation of simulated water sample 200ml is placed in a beaker Should the experiments show that in the initial pH value is 4, the hydrogen peroxide dosage was 7.5mL/L, ferrous sulfate dosage is 1.5g/L, the reaction time is 120min, the PAM content is 0.5%, the reaction process of 68.3%. removal rate can reach Box-Behnken by response surface according to TOC, the initial pH value, FeSO 4 interaction dosage and reaction time on the removal rate of TOC has a significant effect, the ferrous sulfate dosage, reaction time on the removal rate of TOC had significant effect. The optimum reaction conditions for hydrogen peroxide dosage 7.6ml/L, ferrous sulfate dosage of 2.05g/L, initial pH value 3.83, reaction time 73min, the removal rate under the reaction conditions TOC 74.6%. (4) experiment of Fenton reagent optimal conditions of areca wastewater, with TOC and COD in wastewater removal rate as the index, according to the results of single factor experiments to determine the response surface analysis of the impact factor based on Box-Behnken. The response surface method, when the areca COD in the effluent concentration of 6300mg/L, experiments show that the initial pH value is 5, the hydrogen peroxide dosage was 50mg/L, ferrous sulfate dosage is 12.5g/L, the reaction time is 120min, the PAM content is 0.2%, the reaction process of removal rate can reach 65 by response surface Box-Behnken%. According to TOC, the dosage of hydrogen peroxide and ferrous sulfate plus the amount of investment and interaction on the TOC removal rate has a significant effect, the effect of hydrogen peroxide dosage on the removal rate of TOC was significantly.Fenton reagent treatment conditions for areca wastewater: hydrogen peroxide dosage is 54.2ml/L, ferrous sulfate dosage of 12.55g/L, initial the pH value is 4.98, the reaction time was 103min. under this condition, the removal rate of TOC is 70%. (5) simulated wastewater containing polyphenol rutin product combined with technical analysis of Fenton oxidation by liquid substances, can be seen from the results, Fenton reagent The main way of oxidation of rutin has two kinds: one kind is hydrolyzed under acidic conditions for quercetin and rutin rutinose, quercetin in hydroxyl radicals under the action of B on the oxidation of hydroxyl ring ketone, and further oxidation of small molecule compounds; the other is between the oxygen atoms of hydroxyl radical attack B and C rings, produced two kinds of oxides, was further oxidized to carbon dioxide or small molecular compounds.

【学位授予单位】：湖南农业大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：X792

【相似文献】