中空纤维更新液膜技术用于含铬废水处理的研究
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摘要
Cr(Ⅵ)对人体毒性较大,含铬废水,尤其是含六价铬废水对环境污染十分严重。随着现代工业的发展,产生越来越多含六价铬废水,必须严格处理方可排放。传统的含六价铬废水处理方法多存在二次污染严重和资源浪费问题。液膜技术作为一种新型的分离手段,可以实现萃取与反萃过程的耦合,具有传质效率高,选择性好等优点,对处理含重金属废水具有良好的应用前景。
本文首先对Cr(Ⅵ)的分析方法进行了显著性研究,随后进行了溶剂萃取和大块液膜(BLM)实验,确定实验体系,再利用中空纤维更新液膜技术处理模拟含铬废水。选用K_2Cr_2O_7溶液模拟含六价铬废水,以磷酸三丁酯(TBP)作为流动载体,煤油为稀释剂,NaOH溶液为反萃剂,考察了各操作条件对传质的影响,在最佳条件下进行小试实验研究,建立了中空纤维更新液膜过程的传质模型,并对模型进行了验证。
1、使用改进后的二苯碳酰二肼分光光度法测量水相中Cr(Ⅵ),该方法操作简单、灵敏度高、准确度好。根据最小二乘法回归标准曲线,对其剩余标准偏差、斜率、截距进行显著性检验。结果表明,标准曲线之间无显著性差异,采用改进后的二苯碳酰二肼分光光度法分析Cr(Ⅵ)浓度,方法稳定、可靠。
2、萃取实验考察载体浓度和料液相pH值对分配系数的影响,并分别选用工业煤油和正庚烷为稀释剂进行萃取实验,其对萃取过程几乎无影响。通过大块液膜,确定了K_2Cr_2O_7-TBP/Kerosene-NaOH的液膜体系,并考察了液膜相用量、反萃剂浓度对传质的影响。
3、利用中空纤维更新液膜技术处理模拟含六价铬废水,首先进行单因素影响的考察,分别通过单程实验和循环实验进行了载体浓度、稀释剂种类、相比、料液相初始浓度、料液相pH值、反萃剂浓度对传质的影响。实验结果表明,Cr(Ⅵ)在反萃剂中可以达到富集,富集因子可达30。
4、建立了中空纤维更新液膜过程的传质模型,对模型进行了验证,模型预测值与实验数据吻合情况良好。
中空纤维更新液膜技术具有选择性好、传质效率高、无二次污染等优点。根据研究结果,该技术在处理含六价铬废水上具有很好的应用前景。
Hexavalent chromium is great toxic,wastewater laden chromium especially hexavalent chromium is very dangerous to our environment.With the development of modern industry,a great deal of hexavalent chromium laden wastewater discharg into environment every year.It must be disposed strictly before discharged.At present,the traditional technology of deal with the chromium laden wastewater exists some problemes such as secondary pollutant,the waste of resource,and so on.As a new separation instrumentality,liquid membrane technology can achieve the coupling between extraction and back-extraction.Liquid membrane technology has the advantage of high transport efficiency and good selection.And it has the better applied foreground in deal with wastewater contain heavy metal.
This paper study the distinct difference of the analysis method of Cr(Ⅵ) firstly.And then,the extraction experiment and bulk liquid membrane experiment carried respectively.After make sure the system,the stimulant wastewater laden hexavalent chromium dealed with using hollow fiber renewal liquid membrane.The system is K_2Cr_2O_7-TBP/Kerosene-NaOH, observe the effect of operation conditions,and magnify the experiment in best operation conditions,and the transport model is established.
1、The determination of hexavalent chromium in aqueous solution was investigated by UV-visspectrophotometer using the mixture of 1,5-diphenylcarbonydrazide and hybrid acids as chromogenic agent.The standard lines were obtained and the significance test was carried out by F-test and t-test.The results show that there is no significance difference between the standard lines and this analysis method is stability and reliability.
2、The effect of carrier concentration and pH in feed phase is study in extraction experiment.Using the thinner of kerosene or n-heptant has almost no impaction.The system that K_2Cr_2O_7-TBP/Kerosene-NaOH is used in bulk liquid membrane,and the volume of liquid membrane and stripping concentration are studied in bulk liquid membrane.
3、The study on deal with simulation wastewater laden hexavalent chromium using hollow fiber renewal liquid membrane.The single factors are studied firstly in recycling mode and single mode,it contains carrier concentration,kind of thinner,o/w volume ratio,the initial Cr(Ⅵ) concentration in feed phase,pH in feed phase,stripping concentration.The effect of velocity using two kinds of contactor.Cr(Ⅵ) can be concentrated in stripping phase,the enrichment factor is almost 30.
4、The transport model of the transport process in hollow fiber renewal liquid membrane is established.It was verified that the model has a good agreement with experimental results.
Hollow fiber renewal liquid membrane has the advantage of good selection,high transport efficiency and no-secondary pollutant.It has the better applied foreground in deal with wastewater contain heavy metal.
本文首先对Cr(Ⅵ)的分析方法进行了显著性研究,随后进行了溶剂萃取和大块液膜(BLM)实验,确定实验体系,再利用中空纤维更新液膜技术处理模拟含铬废水。选用K_2Cr_2O_7溶液模拟含六价铬废水,以磷酸三丁酯(TBP)作为流动载体,煤油为稀释剂,NaOH溶液为反萃剂,考察了各操作条件对传质的影响,在最佳条件下进行小试实验研究,建立了中空纤维更新液膜过程的传质模型,并对模型进行了验证。
1、使用改进后的二苯碳酰二肼分光光度法测量水相中Cr(Ⅵ),该方法操作简单、灵敏度高、准确度好。根据最小二乘法回归标准曲线,对其剩余标准偏差、斜率、截距进行显著性检验。结果表明,标准曲线之间无显著性差异,采用改进后的二苯碳酰二肼分光光度法分析Cr(Ⅵ)浓度,方法稳定、可靠。
2、萃取实验考察载体浓度和料液相pH值对分配系数的影响,并分别选用工业煤油和正庚烷为稀释剂进行萃取实验,其对萃取过程几乎无影响。通过大块液膜,确定了K_2Cr_2O_7-TBP/Kerosene-NaOH的液膜体系,并考察了液膜相用量、反萃剂浓度对传质的影响。
3、利用中空纤维更新液膜技术处理模拟含六价铬废水,首先进行单因素影响的考察,分别通过单程实验和循环实验进行了载体浓度、稀释剂种类、相比、料液相初始浓度、料液相pH值、反萃剂浓度对传质的影响。实验结果表明,Cr(Ⅵ)在反萃剂中可以达到富集,富集因子可达30。
4、建立了中空纤维更新液膜过程的传质模型,对模型进行了验证,模型预测值与实验数据吻合情况良好。
中空纤维更新液膜技术具有选择性好、传质效率高、无二次污染等优点。根据研究结果,该技术在处理含六价铬废水上具有很好的应用前景。
Hexavalent chromium is great toxic,wastewater laden chromium especially hexavalent chromium is very dangerous to our environment.With the development of modern industry,a great deal of hexavalent chromium laden wastewater discharg into environment every year.It must be disposed strictly before discharged.At present,the traditional technology of deal with the chromium laden wastewater exists some problemes such as secondary pollutant,the waste of resource,and so on.As a new separation instrumentality,liquid membrane technology can achieve the coupling between extraction and back-extraction.Liquid membrane technology has the advantage of high transport efficiency and good selection.And it has the better applied foreground in deal with wastewater contain heavy metal.
This paper study the distinct difference of the analysis method of Cr(Ⅵ) firstly.And then,the extraction experiment and bulk liquid membrane experiment carried respectively.After make sure the system,the stimulant wastewater laden hexavalent chromium dealed with using hollow fiber renewal liquid membrane.The system is K_2Cr_2O_7-TBP/Kerosene-NaOH, observe the effect of operation conditions,and magnify the experiment in best operation conditions,and the transport model is established.
1、The determination of hexavalent chromium in aqueous solution was investigated by UV-visspectrophotometer using the mixture of 1,5-diphenylcarbonydrazide and hybrid acids as chromogenic agent.The standard lines were obtained and the significance test was carried out by F-test and t-test.The results show that there is no significance difference between the standard lines and this analysis method is stability and reliability.
2、The effect of carrier concentration and pH in feed phase is study in extraction experiment.Using the thinner of kerosene or n-heptant has almost no impaction.The system that K_2Cr_2O_7-TBP/Kerosene-NaOH is used in bulk liquid membrane,and the volume of liquid membrane and stripping concentration are studied in bulk liquid membrane.
3、The study on deal with simulation wastewater laden hexavalent chromium using hollow fiber renewal liquid membrane.The single factors are studied firstly in recycling mode and single mode,it contains carrier concentration,kind of thinner,o/w volume ratio,the initial Cr(Ⅵ) concentration in feed phase,pH in feed phase,stripping concentration.The effect of velocity using two kinds of contactor.Cr(Ⅵ) can be concentrated in stripping phase,the enrichment factor is almost 30.
4、The transport model of the transport process in hollow fiber renewal liquid membrane is established.It was verified that the model has a good agreement with experimental results.
Hollow fiber renewal liquid membrane has the advantage of good selection,high transport efficiency and no-secondary pollutant.It has the better applied foreground in deal with wastewater contain heavy metal.
引文
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