絮凝—反渗透耦合过程深度处理DOP化工废水
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摘要
高浓度邻苯二甲酸二辛酯(DOP)有机化工废水生物毒性强,采用常规处理手段很难完全降解,对环境存在较高危害性。如何有效地深度处理高浓度化工废水并回用于生产之中,一直是国内外研究的热点。
本实验采用絮凝-反渗透耦合过程对DOP化工厂二级生化出水进行深度处理研究。考察了絮凝预处理的最佳条件,研究了三种反渗透复合膜(BW30、CPA2和CSM-RE)对该实际废水的处理性能,并利用扫描电子显微镜分析了废水处理过程前后膜面结构的变化。研究结果表明:絮凝预处理可有效降低废水的浊度和部分COD,为反渗透处理提供良好的进水水质,其最佳絮凝条件为PAC投加量为750mg/L、pH值为8。虽然产水通量相对较低,但BW30膜能提供更加稳定的通量和较高的截留率,且对目前废水的抗污染性能优于CPA2膜和CSM-RE膜,因而,BW30膜更适用于现有废水的工业化处理。三种反渗透膜均可有效去除废水中的盐类和COD,从而大大提高出水水质,其中BW30膜对COD的去除率大于93%,CPA2膜和CSM-RE膜达75%,三种反渗透膜的产水COD分别为5.89、32.0和36mg/L,Cl~-分别为35.25、150.16和148.55mg/L,SO_4~(2-)分别为7.12、23.07和18.04mg/L,浊度去除率均达到100%,表明其产水完全达到循环冷却水的水质标准,可以满足化工废水回用的目的。通过对三种反渗透膜实验前后的SEM结果分析表明,简单的水力清洗即可恢复较高的通量,因而,絮凝作为反渗透的预处理是完全可行的。
以上研究显示,絮凝-反渗透耦合过程深度处理工艺,对DOP化工行业的节能减排、废水资源化回用具有很好的实际应用价值和前景。
High concentration organic wastewater of dioctyl phthalate (DOP) is very difficult to degrade completely by conventional treatments and leads to serious problems to the environment due to its strong biological toxicity. The effective way to treat high concentration industrial wastewater for reutilization is eagerly investigated by researchers all over the world in recent years.
In this paper, reverse osmosis (RO) coupling with coagulation was used in advanced treatment of secondary effluent from DOP chemical plant for reutilization. To prevent membrane fouling effectively, the optimal operating conditions for coagulation process were investigated at first. Performance of three different kinds of composite RO membranes BW30, CPA2 and CSM-RE were compared and the membrane surface structure variation during wastewater treatment was analyzed by SEM. Results showed that coagulation as pre-treatment had good performance on removal of turbidity and COD, which could guarantee good quality of feed water for RO. The optimum operating conditions for coagulation process were found at pH 8 and 750 mg/L of PAC. It was also found that permeate flux of CPA2 was higher than CSM-RE and BW30, but BW30 provided better stabilization of flux, lower fouling tendency, and better rejection rate than the others in practical waste treatment. Therefore, the BW30 membrane was better than others in industrial application. All three RO membranes presented good performance in rejecting salt and COD effectively to improve product water quality. The removal of COD can be achieved more than 93% for BW30, compared with more than 75% for CPA2 and CSM-RE. After advanced treatment, the product water quality from the coupling process satisfied State Reuse Qualification and could be successfully reused as cooling water in chemical industry. SEM micrographs were used to compare the membrane properties of surface morphology before and after the treatment during membrane treatment. It was predicted that most pollution could be removed by simple hydraulic cleaning due to coagulation as pretreatment before reverse osmosis.
In conclusion, advanced treatment aimed at reutilization by coagulation and membrane coupling process has good value and promising prospect for energy-saving and emission reduction in chemical industry.
本实验采用絮凝-反渗透耦合过程对DOP化工厂二级生化出水进行深度处理研究。考察了絮凝预处理的最佳条件,研究了三种反渗透复合膜(BW30、CPA2和CSM-RE)对该实际废水的处理性能,并利用扫描电子显微镜分析了废水处理过程前后膜面结构的变化。研究结果表明:絮凝预处理可有效降低废水的浊度和部分COD,为反渗透处理提供良好的进水水质,其最佳絮凝条件为PAC投加量为750mg/L、pH值为8。虽然产水通量相对较低,但BW30膜能提供更加稳定的通量和较高的截留率,且对目前废水的抗污染性能优于CPA2膜和CSM-RE膜,因而,BW30膜更适用于现有废水的工业化处理。三种反渗透膜均可有效去除废水中的盐类和COD,从而大大提高出水水质,其中BW30膜对COD的去除率大于93%,CPA2膜和CSM-RE膜达75%,三种反渗透膜的产水COD分别为5.89、32.0和36mg/L,Cl~-分别为35.25、150.16和148.55mg/L,SO_4~(2-)分别为7.12、23.07和18.04mg/L,浊度去除率均达到100%,表明其产水完全达到循环冷却水的水质标准,可以满足化工废水回用的目的。通过对三种反渗透膜实验前后的SEM结果分析表明,简单的水力清洗即可恢复较高的通量,因而,絮凝作为反渗透的预处理是完全可行的。
以上研究显示,絮凝-反渗透耦合过程深度处理工艺,对DOP化工行业的节能减排、废水资源化回用具有很好的实际应用价值和前景。
High concentration organic wastewater of dioctyl phthalate (DOP) is very difficult to degrade completely by conventional treatments and leads to serious problems to the environment due to its strong biological toxicity. The effective way to treat high concentration industrial wastewater for reutilization is eagerly investigated by researchers all over the world in recent years.
In this paper, reverse osmosis (RO) coupling with coagulation was used in advanced treatment of secondary effluent from DOP chemical plant for reutilization. To prevent membrane fouling effectively, the optimal operating conditions for coagulation process were investigated at first. Performance of three different kinds of composite RO membranes BW30, CPA2 and CSM-RE were compared and the membrane surface structure variation during wastewater treatment was analyzed by SEM. Results showed that coagulation as pre-treatment had good performance on removal of turbidity and COD, which could guarantee good quality of feed water for RO. The optimum operating conditions for coagulation process were found at pH 8 and 750 mg/L of PAC. It was also found that permeate flux of CPA2 was higher than CSM-RE and BW30, but BW30 provided better stabilization of flux, lower fouling tendency, and better rejection rate than the others in practical waste treatment. Therefore, the BW30 membrane was better than others in industrial application. All three RO membranes presented good performance in rejecting salt and COD effectively to improve product water quality. The removal of COD can be achieved more than 93% for BW30, compared with more than 75% for CPA2 and CSM-RE. After advanced treatment, the product water quality from the coupling process satisfied State Reuse Qualification and could be successfully reused as cooling water in chemical industry. SEM micrographs were used to compare the membrane properties of surface morphology before and after the treatment during membrane treatment. It was predicted that most pollution could be removed by simple hydraulic cleaning due to coagulation as pretreatment before reverse osmosis.
In conclusion, advanced treatment aimed at reutilization by coagulation and membrane coupling process has good value and promising prospect for energy-saving and emission reduction in chemical industry.
引文
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[2]李玉林.化工废水的治理[J].内蒙古油化工,2002,04(54):116-117
[3]彭松.蒋克彬.陈红艳.化工废水治理措施综述[J].江苏环境科技.2008.21(1):122-124
[4]丁春生,李达钱.化工废水处理技术与发展[J].浙江工业大学学报,2005.33(6):647-650
[5]丁春生.气浮/水解/二级AO处理精细化工废水[J].中国给水排水,2005.21(1):79-81
[6]Chen L,Sheng H Treatment of chemical mechanical polishing wastewater by electrocoagulation:system performances and sludge settling characteristics[J].Chemosphere,2004,54(3):235-242
[7]孙琳,苗群,刘忠强.混凝沉淀预处理包装印刷废水的试验研究[J].水资源保护.2005(2):75-78
[8]Chedly T,Latifa B,Loubna M Landfill Ieachate treatment with ozone and ozone/hydrogen peroxide systems[J].Journal of Hazardous Materials,2007,140(1-2):316-324
[9]Koparal A,Yavuz Y,Gurel C Electrochemical degradation and toxicity reduction of C.l.Basic Red 29 solution and textile wastewater by using diamond anode[J].Journal of Hazardous Materials.2007,145(1-2):100-108
[10]张林生,蒋岚岚,肖璐宁等.石墨极板电解气浮法的脱色效果[J].中国给水排水,2002.04(18):75-77
[11]Kotsou M,Kyriacou A,Lasaridi K,et al.Integrated aerobic biological treatment and chemical oxidation with Fenton's reagent for the processing of green table olive wastewater[J].Process Biochemistry,2004,39(4):1653-1660
[12]Windey K,De B,Verstraete W Oxygen-limited autotrophic nitrification-denitrification (OLAND) in a rotating biological contactor treating high-salinity wastewater[J].Water Research,2005(39):4512-4520
[13]李咏梅,顾国维,赵建夫.焦化废水中儿种含氮杂环化合物缺氧降解机理[J].同济大学学报,2001,29(6):720-723
[14]Villacanas F,Pereira M,Orfao J,et al.Adsorption of simple aromatic compounds on activated carbons[J].Journal of Colloid and Interface Science,2006,293(1):128-136
[15]Nakai T,Sato Y,Takahashi N,et al.Supercritical CO_2 extraction treatment of organic compound in aqueous solution by countercurrent extraction[J].Journal of Japan society on water environment,1999,22(10):854-858
[16]Li H,Liu L,Zhang R,et al.Application of Catalytic Wet Air Oxidation to treatment of landfill leachate on Co/Bi catalyst[J].Chemical Research in Chinese Universities,2004,20(6):711-716
[17]邓小红.铁屑内电解法处理电镀含铬废水的实验研究及应用[J].环境工程学报,2008,2(10):1349-1352
[18]许振良.膜法水处理技术[M].北京:化学工业出版社,2001
[19]John A.国际同用水的应用实例研究[J].21世纪国际城市污水处理及资源化发展战略研讨会与展览会,北京,2001
[20]林兰,张国亮,孟琴等..膜技术住电镀废水资源化过程中的应用[M].化工生化技术与生物质能源,北京,化工出版社,2006
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