Fenton氧化法去除制革废水中难降解鞣剂的研究
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摘要
制革废水是典型的高污染难生物降解的废水,随着污水排放标准的提高,仅仅生物法降解制革废水已经难以满足日益提高的污水排放标准要求。动物生皮经化学药剂和机械物理加工形成皮革,这个过程中生皮中的大量的脂质、蛋白会溶于水中,为了让皮革获得光滑,耐磨等一系列优质性状,制革工艺中会大量添加纯碱、工业盐、硫化物、各种合成鞣剂、加脂剂、染料等化工原料,这些部分也会形成废物排出。这其中,皮革生产过程中采用的大量鞣剂、助鞣剂结构稳定,是主要的难生物降解物质。
本文以单宁、β-萘磺酸钠为难降解鞣剂、助鞣剂的代表,研究了Fenton氧化法对两种物质的降解情况。首先通过单因素试验了解了Fenton氧化单宁、β-萘磺酸钠的效果,分析了初始pH值、过氧化氢投加量、亚铁投加量、曝气量、反应温度、反应时间对Fenton氧化降解单宁、β-萘磺酸钠的影响效果和原因,并对反应后加碱沉淀进一步去除COD效果进行了试验。并采用ESI-MS分析了Fenton氧化单宁、β-萘磺酸钠的产物,对Fenton氧化两种物质的机理进行了探讨。通过响应曲面试验检验了初始pH值、反应时间、过氧化氢投加量与反应物浓度的交互作用,简要分析了交互作用产生的原因。建立了污染物响应曲面模型,通过方差分析以及假设检验分析了模型的适用性,在确定模型拟合度良好的条件下进行了反应条件优化和验证。在优化的基础上将响应模型应用于实际废水,取得了良好的效果。
Fenton氧化单宁、β-萘磺酸钠的单因素试验表明相对于反应温度、曝气程度,反应的初始pH值、过氧化氢投加量、亚铁盐投加量、以及反应时间是Fenton氧化的重要影响因素。最佳pH值在2.5至3左右,过氧化氢投加量与COD值摩尔比接近1:1,亚铁盐投加量为过氧化氢投加量的1/20至1/5(摩尔比),反应时间60min。单因素试验中同时考察了反应过程中pH值的变化情况,通过pH值的变化从一个侧面分析了污染物、过氧化氢、铁盐的存在形式和对反应的影响,解释了各因素影响Fenton氧化的原因。这其中,亚铁离子和铁离子的存在形式对Fenton氧化的影响很大。最后通过反应后加碱沉淀,进一步提高了单宁和β-萘磺酸钠的去除效果,去除率的提高普遍在5%以上,最高达到13%。
经ESI-MS分析,Fenton氧化单宁和β-萘磺酸钠主要是羟基自由基优先进攻含有官能团的苯环形成醌,之后使苯环断裂生成羧酸、酮等中间产物。这些中间产物会被氧化成苯酚,苯酚经历对苯醌,顺丁烯二酸最终被完全矿化。
响应曲面法分析各因素交互作用发现污染物浓度、pH值以及过氧化氢投加量之间交互作用显著。拟合模型相关系数R2达0.9以上,置信度为99%,试验精度Adeq Precision高。模型优化得到Fenton氧化的最优条件进行实验室验证,单宁和β-萘磺酸钠的误差分别为0.84%和1.38%。将模型应用于实际废水预测,效果良好。现场皮革废水生物处理后经Fenton氧化,COD降至60mg/L以下。
Tanning effluent is conventional high contamination and non-biodegradation waste water, Traditional treatment method cannot be in keeping with the improvement of emission standard. A great deal of tanning agents and auxiliary tanning agents are adopted in tannery production process. They are mainly the non-biodegradation materials with stable structure.
In this paper, selecting tannin and Sodiumβ-naphthalenesulfonate as model (auxiliary) tanning agent, the efficiency and mechanism of Fenton degradation on tannin andβ-NaSS were studied. Effect and reasons of initial pH, hydrogen peroxide dose, ferrous salt dose, aeration rate, reaction temperature and reaction time on the Fenton Oxidation were analysed. Then studied on the effect of coagulation and sedimentation with residual ferric salt after Fenton OxidationThe interaction of initial pH, reaction time, hydrogen peroxide dose and concentration of the pollutant was research by response surface method in order to make a brief analysis of the reasons. After creating response surface models of the two kind pollutants, It showed that the models were fitting well with analysis of variance and hypothesis testing. Reaction conditions were optimized by the models and lab testing results were accordance to the optimization conditions. Experiment with actual waste water in optimization condition gained good effect. ESI-MS was used to analyse the products generated by Fenton Oxidation of tannin andβ-NaSS so as to study the mechanisms of Fenton Oxidation of tannin andβ-NaSS. Single factor experiment indicated that initial pH, H2O2 dose, ferrous salt dose and reaction time are more important to Fenton Oxidation than reaction temperature, aeration rate. The optimal conditions are pH about2.5 to 3, the mol ratio of H2O2 dose and COD≈1:1, the mol ratio of Fe2+ and H2O2 from 1/20 to 1/5, reaction time=60min.The pH changs during Fenton Oxidation was also researched by single factor test. It can reflect the exist form of tannin,β-NaSS, H2O2 and iron ion, and explain how these factors affect the Fenton oxidation. the greater affection is ferrous ion and ferric ion s exist form . Removal ratios of tannin andβ-NaSS by coagulation and sedimentation after Fenton were improved above 5% generally, some up to 13%.ESI-MS analysis showed that during Fenton oxidation of tannin andβ-NaSS process, the hydroxy free radicals priority attack benzene ring with functional group and form quinone. Quinone was easily lead benzene rings to breaking into carboxylic acid, ketone and other intermediate products .If free radicals are enough, these intermediate products can be oxidated to phenol. Phenol was mineralized totally by way of p-benzoquinone, maleate, CO2 and H2O.
Response surface method verified that interaction of concentration of pollutant, H2O2 dose, and pH was outstanding. oefficients of correlation(R2)of fitting models were above 0.9, meanwhile the models’confidence level was 99% with high signal to noise ratio.It could be obtained optimal conditions using model optimize. Taking laboratory experiment in optimal conditions, tannin and NaSS error was only 0.84%and 1.38%. Experiment with actual waste water in optimization condition also gained good effect.After Fenton oxidation of biological treatment effluent of tanning waste water, COD could be blow 60mg/L and meet emission standard.
本文以单宁、β-萘磺酸钠为难降解鞣剂、助鞣剂的代表,研究了Fenton氧化法对两种物质的降解情况。首先通过单因素试验了解了Fenton氧化单宁、β-萘磺酸钠的效果,分析了初始pH值、过氧化氢投加量、亚铁投加量、曝气量、反应温度、反应时间对Fenton氧化降解单宁、β-萘磺酸钠的影响效果和原因,并对反应后加碱沉淀进一步去除COD效果进行了试验。并采用ESI-MS分析了Fenton氧化单宁、β-萘磺酸钠的产物,对Fenton氧化两种物质的机理进行了探讨。通过响应曲面试验检验了初始pH值、反应时间、过氧化氢投加量与反应物浓度的交互作用,简要分析了交互作用产生的原因。建立了污染物响应曲面模型,通过方差分析以及假设检验分析了模型的适用性,在确定模型拟合度良好的条件下进行了反应条件优化和验证。在优化的基础上将响应模型应用于实际废水,取得了良好的效果。
Fenton氧化单宁、β-萘磺酸钠的单因素试验表明相对于反应温度、曝气程度,反应的初始pH值、过氧化氢投加量、亚铁盐投加量、以及反应时间是Fenton氧化的重要影响因素。最佳pH值在2.5至3左右,过氧化氢投加量与COD值摩尔比接近1:1,亚铁盐投加量为过氧化氢投加量的1/20至1/5(摩尔比),反应时间60min。单因素试验中同时考察了反应过程中pH值的变化情况,通过pH值的变化从一个侧面分析了污染物、过氧化氢、铁盐的存在形式和对反应的影响,解释了各因素影响Fenton氧化的原因。这其中,亚铁离子和铁离子的存在形式对Fenton氧化的影响很大。最后通过反应后加碱沉淀,进一步提高了单宁和β-萘磺酸钠的去除效果,去除率的提高普遍在5%以上,最高达到13%。
经ESI-MS分析,Fenton氧化单宁和β-萘磺酸钠主要是羟基自由基优先进攻含有官能团的苯环形成醌,之后使苯环断裂生成羧酸、酮等中间产物。这些中间产物会被氧化成苯酚,苯酚经历对苯醌,顺丁烯二酸最终被完全矿化。
响应曲面法分析各因素交互作用发现污染物浓度、pH值以及过氧化氢投加量之间交互作用显著。拟合模型相关系数R2达0.9以上,置信度为99%,试验精度Adeq Precision高。模型优化得到Fenton氧化的最优条件进行实验室验证,单宁和β-萘磺酸钠的误差分别为0.84%和1.38%。将模型应用于实际废水预测,效果良好。现场皮革废水生物处理后经Fenton氧化,COD降至60mg/L以下。
Tanning effluent is conventional high contamination and non-biodegradation waste water, Traditional treatment method cannot be in keeping with the improvement of emission standard. A great deal of tanning agents and auxiliary tanning agents are adopted in tannery production process. They are mainly the non-biodegradation materials with stable structure.
In this paper, selecting tannin and Sodiumβ-naphthalenesulfonate as model (auxiliary) tanning agent, the efficiency and mechanism of Fenton degradation on tannin andβ-NaSS were studied. Effect and reasons of initial pH, hydrogen peroxide dose, ferrous salt dose, aeration rate, reaction temperature and reaction time on the Fenton Oxidation were analysed. Then studied on the effect of coagulation and sedimentation with residual ferric salt after Fenton OxidationThe interaction of initial pH, reaction time, hydrogen peroxide dose and concentration of the pollutant was research by response surface method in order to make a brief analysis of the reasons. After creating response surface models of the two kind pollutants, It showed that the models were fitting well with analysis of variance and hypothesis testing. Reaction conditions were optimized by the models and lab testing results were accordance to the optimization conditions. Experiment with actual waste water in optimization condition gained good effect. ESI-MS was used to analyse the products generated by Fenton Oxidation of tannin andβ-NaSS so as to study the mechanisms of Fenton Oxidation of tannin andβ-NaSS. Single factor experiment indicated that initial pH, H2O2 dose, ferrous salt dose and reaction time are more important to Fenton Oxidation than reaction temperature, aeration rate. The optimal conditions are pH about2.5 to 3, the mol ratio of H2O2 dose and COD≈1:1, the mol ratio of Fe2+ and H2O2 from 1/20 to 1/5, reaction time=60min.The pH changs during Fenton Oxidation was also researched by single factor test. It can reflect the exist form of tannin,β-NaSS, H2O2 and iron ion, and explain how these factors affect the Fenton oxidation. the greater affection is ferrous ion and ferric ion s exist form . Removal ratios of tannin andβ-NaSS by coagulation and sedimentation after Fenton were improved above 5% generally, some up to 13%.ESI-MS analysis showed that during Fenton oxidation of tannin andβ-NaSS process, the hydroxy free radicals priority attack benzene ring with functional group and form quinone. Quinone was easily lead benzene rings to breaking into carboxylic acid, ketone and other intermediate products .If free radicals are enough, these intermediate products can be oxidated to phenol. Phenol was mineralized totally by way of p-benzoquinone, maleate, CO2 and H2O.
Response surface method verified that interaction of concentration of pollutant, H2O2 dose, and pH was outstanding. oefficients of correlation(R2)of fitting models were above 0.9, meanwhile the models’confidence level was 99% with high signal to noise ratio.It could be obtained optimal conditions using model optimize. Taking laboratory experiment in optimal conditions, tannin and NaSS error was only 0.84%and 1.38%. Experiment with actual waste water in optimization condition also gained good effect.After Fenton oxidation of biological treatment effluent of tanning waste water, COD could be blow 60mg/L and meet emission standard.
引文
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