新生态型聚硅酸铁锰处理染料废水的优化
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摘要
为了提高混凝剂对染料废水的净化效率,本文利用硅酸钠、硫酸亚铁和高锰酸钾为原料合成了新型复配混凝剂聚硅酸铁锰(PSFM),分别以直接大红、分散蓝和活性黄染料废水为处理对象进行混凝模拟实验,研究了碱度和浊度等因素对PSFM混凝去除染料性能影响.结果表明,PSFM对直接大红和分散蓝染料废水具有较好的混凝净化效能,其色度和TOC去除率分别可达99.2%、95.4%和98.5%、93.8%,效果优于聚硅酸铁(PSF)、Al2(SO4)3和Fe Cl3等常规混凝剂,PSFM对活性黄染料废水色度和TOC去除率分别为56.3%和51.3%.浊度对PSFM混凝效能无明显影响.在碱度分别为50、0和75 mg·L~(-1)时,PSFM对直接大红、分散蓝和活性黄去除率分别达到最高.此外,利用扫描电子显微镜(SEM)、傅里叶红外(FTIR)和X射线衍射仪(XRD)等高级表征手段对PSFM进行了表征,对混凝过程中的混合液和絮体分别进行Zeta电位和絮体粒径在线监测,探索得PSFM混凝主要机制为Fe+与Mn+水解产生的带正电的多核配合物和聚硅的桥联聚合,同时还包括新生态水合二氧化锰和羟基氧化铁的吸附助凝作用.
To improve the efficiency of the removal of dye wastewater,a new type of coagulant"polysilicate ferromanganese(PSFM) "has been synthesized using sodium silicate,ferrous sulfate,and potassium permanganate.Three dyes(direct red,disperse blue,and active yellow) were used for the coagulation tests.The effects of the alkalinity and turbidity on the performance of PSFM were studied.The experimental results show that PSFM performs well with respect to the coagulation of the direct red and disperse blue dyes.The color and TOC removal efficiencies reach 99.2%,95.4% and 98.5%,and 93.8%,respectively.The coagulation performance is better than that of the conventional coagulants polysilicate iron(PSF),Al2(SO4)3,and Fe Cl3.The color and TOC removal rates of PSFM for the active yellow dye reach 56% and 51%,respectively.Turbidity has no significant effect on the coagulation efficiency of PSFM.The purification efficiency and alkalinity depend on the amount of dye to be removed.The best alkalinity for the direct red,disperse blue,and active yellow dyes is 50 mg·L~(-1),0 mg·L~(-1),and 75 mg·L~(-1),respectively.In addition,PSFM has been characterized by scanning electron microscopy(SEM),Fourier transform infrared spectroscopy(FTIR),and X-ray diffraction(XRD).The Zeta potentials of the mixed solutions and flocs during coagulation were also determined.The main indicators of PSFM coagulation are positively charged polynuclear complexes produced by hydrolysis of Fe+and Mn+and the bridging polymerization of polysilicon.The adsorption of hydrated manganese dioxide and hydroxyl oxide may also be included.
To improve the efficiency of the removal of dye wastewater,a new type of coagulant"polysilicate ferromanganese(PSFM) "has been synthesized using sodium silicate,ferrous sulfate,and potassium permanganate.Three dyes(direct red,disperse blue,and active yellow) were used for the coagulation tests.The effects of the alkalinity and turbidity on the performance of PSFM were studied.The experimental results show that PSFM performs well with respect to the coagulation of the direct red and disperse blue dyes.The color and TOC removal efficiencies reach 99.2%,95.4% and 98.5%,and 93.8%,respectively.The coagulation performance is better than that of the conventional coagulants polysilicate iron(PSF),Al2(SO4)3,and Fe Cl3.The color and TOC removal rates of PSFM for the active yellow dye reach 56% and 51%,respectively.Turbidity has no significant effect on the coagulation efficiency of PSFM.The purification efficiency and alkalinity depend on the amount of dye to be removed.The best alkalinity for the direct red,disperse blue,and active yellow dyes is 50 mg·L~(-1),0 mg·L~(-1),and 75 mg·L~(-1),respectively.In addition,PSFM has been characterized by scanning electron microscopy(SEM),Fourier transform infrared spectroscopy(FTIR),and X-ray diffraction(XRD).The Zeta potentials of the mixed solutions and flocs during coagulation were also determined.The main indicators of PSFM coagulation are positively charged polynuclear complexes produced by hydrolysis of Fe+and Mn+and the bridging polymerization of polysilicon.The adsorption of hydrated manganese dioxide and hydroxyl oxide may also be included.
引文
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[14]Xu H,Jiao R Y,Xiao F,et al.Effects of different coagulants in treatment of Ti O2-humic acid(HA)water and the aggregate characterization in different coagulation conditions[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2014,446:213-223.
[15]Xu H,Jiang W,Xiao F,et al.The characteristics of flocs and zeta potential in nano-TiO2system under different coagulation conditions[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2014,452:181-188.
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[17]Liao Y,Tang X M,Yang Q Q,et al.Characterization of an inorganic polymer coagulant and coagulation behavior for humic acid/algae-polluted water treatment:polymeric zinc-ferricsilicate-sulfate coagulant[J].RSC Advances,2017,7(32):19856-19862.
[18]Li H S,Chen Y H,Long J Y,et al.Removal of thallium from aqueous solutions using Fe-Mn binary oxides[J].Journal of Hazardous Materials,2017,338:296-305.
[19]郑晓青,韦安磊,张一璇,等.铁锰氧化物/生物炭复合材料对水中硝酸根的吸附特性[J].环境科学,2018,39(3):1220-1232.Zheng X Q,Wei A L,Zhang Y X,et al.Characteristic of nitrate adsorption in aqueous solution by iron and manganese oxide/biochar composites[J].Environmental Science,2018,39(3):1220-1232.
[20]Wu K,Wang H J,Liu R P,et al.Arsenic removal from a higharsenic wastewater using in situ formed Fe-Mn binary oxide combined with coagulation by poly-aluminum chloride[J].Journal of Hazardous Materials,2011,185(2-3):990-995.
[21]Xu X,Yu S L,Shi W X,et al.Effect of acid medium on the coagulation efficiency of polysilicate-ferric(PSF)-A new kind of inorganic polymer coagulant[J].Separation and Purification Technology,2009,66(3):486-491.
[22]Zhu G C,Zheng H L,Zhang Z,et al.Characterization and coagulation-flocculation behavior of polymeric aluminum ferric sulfate(PAFS)[J].Chemical Engineering Journal,2011,178:50-59.
[23]杨雪,张景成,关小红.新生态铁的混凝作用探索[J].环境科学,2012,33(4):1221-1226.Yang X,Zhang J C,Guan X H,et al.Exploration of newlyformed ferric as the coagulant[J].Environmental Science,2012,33(4):1221-1226.
[24]Lan W,Qiu H Q,Zhang J,et al.Characteristic of a novel composite inorganic polymer coagulant-PFAC prepared by hydrochloric pickle liquor[J].Journal of Hazardous Materials,2009,162(1):174-179.
[25]张钢,范先媛,朱小丽,等.聚硅酸铝铁复合絮凝剂性能的研究[J].环境科学与技术,2012,35(8):185-188.Zhang G,Fan X Y,Zhu X L,et al.Coagulation behavior of polysilicate aluminum ferric sulfate composite flocculant[J].Environmental Science&Technology,2012,35(8):185-188.
[26]Moussas P A,Zouboulis A I.A study on the properties and coagulation behaviour of modified inorganic polymeric coagulant-Polyferric silicate sulphate(PFSiS)[J].Separation and Purification Technology,2008,63(2):475-483.
[27]Julien F,Güeroux B,Mazet M.Comparison of organic compounds removal by coagulation-flocculation and by adsorption onto preformed hydroxide flocs[J].Water Research,1994,28(12):2567-2574.
[28]张伟超,魏群山,罗专溪,等.碱度和浊度对混凝去除磺胺甲唑与土霉素的影响[J].环境科学研究,2015,28(5):802-807.Zhang W C,Wei Q S,Luo Z X,et al.Effects of alkalinity and turbidity on SMZ and OTC removal by coagulation[J].Research of Environmental Sciences,2015,28(5):802-807.
[2]舒小铭,徐灿灿,文晓刚,等.铁刨花-Fenton-絮凝工艺对染料生产废水中AOX、色度和TOC的去除效果研究[J].环境科学,2016,37(7):2618-2624.Shu X M,Xu C C,Wen X G,et al.Removal of AOX,chroma and TOC in chemical dyestuff wastewater with iron ScrapsFenton-Coagulation combined process[J].Environmental Science,2016,37(7):2618-2624.
[3]Lopez-Lopez C,Martín-Pascual J,Martínez-Toledo M V,et al.Kinetic modelling of TOC removal by H2O2/UV,photo-Fenton and heterogeneous photocatalysis processes to treat dye-containing wastewater[J].International Journal of Environmental Science and Technology,2015,12(10):3255-3262.
[4]Pourjavadi A,Nazari M,Kabiri B,et al.Preparation of porous graphene oxide/hydrogel nanocomposites and their ability for efficient adsorption of methylene blue[J].RSC Advances,2016,6(13):10430-10437.
[5]Mokhtar N M,Lau W J,Ng B C,et al.Preparation and characterization of PVDF membranes incorporated with different additives for dyeing solution treatment using membrane distillation[J].Desalination and Water Treatment,2015,56(8):1999-2012.
[6]郭玥,杜磊,李庆,等.不同铝系混凝剂处理印染废水[J].环境工程学报,2016,10(4):1847-1852.Guo Y,Du L,Li Q,et al.Coagulation process using different Al-based coagulants in treatment of dyeing wastewater[J].Chinese Journal of Environmental Engineering,2016,10(4):1847-1852.
[7]羊小玉,周律,王倩.复合混凝剂的制备及活性染料的去除[J].化工环保,2017,37(1):43-48.Yang X Y,Zhou L,Wang Q.Preparation of composite coagulant and removal of reactive dye[J].Environmental Protection of Chemical Industry,2017,37(1):43-48.
[8]隋智慧,刘安军.复合混凝剂的制备及其对印染废水的处理[J].纺织学报,2007,28(11):69-72.Sui Z H,Liu A J.Preparation of inorganic compound coagulant and its application in the treatment of dyeing effluent[J].Journal of Textile Research,2007,28(11):69-72.
[9]Tang S F,Yuan D L,Zhang Q,et al.Fe-Mn bi-metallic oxides loaded on granular activated carbon to enhance dye removal by catalytic ozonation[J].Environmental Science and Pollution Research,2016,23(18):18800-18808.
[10]李天舒,马燕,郭睿,等.铁锰复合氧化物吸附活性黑染料的性能研究[J].环境工程,2014,32(S1):44-47.Li T S,Ma Y,Guo R,et al.The research on efficiency of reactive black adsorbed by Fe-Mn binary oxide[J].Environmental Engineering,2014,32(S1):44-47.
[11]刘可,马军,关小红,等.新生态铁锰氧化物混凝除磷效果研究[J].中国给水排水,2009,25(21):89-90,94.Liu K,Ma J,Guan X H,et al.Study on phosphorus removal by freshly formed Fe/Mn oxide coagulation[J].China Water&Wastewater,2009,25(21):89-90,94.
[12]付军,范芳,李海宁,等.铁锰复合氧化物/壳聚糖珠:一种环境友好型除磷吸附剂[J].环境科学,2016,37(12):4882-4890.Fu J,Fan F,Li H N,et al.Fe-Mn binary oxide impregnated chitosan bead(FMCB):An environmental friendly sorbent for phosphate removal[J].Environmental Science,2016,37(12):4882-4890.
[13]张大为,徐慧,王希,等.藻形态及混凝剂组成对混凝-超滤过程的影响[J].环境科学,2017,38(8):3281-3289.Zhang D W,Xu H,Wang X,et al.Effects of algal morphology and Al species distribution on the coagulation-ultrafiltration process[J].Environmental Science,2017,38(8):3281-3289.
[14]Xu H,Jiao R Y,Xiao F,et al.Effects of different coagulants in treatment of Ti O2-humic acid(HA)water and the aggregate characterization in different coagulation conditions[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2014,446:213-223.
[15]Xu H,Jiang W,Xiao F,et al.The characteristics of flocs and zeta potential in nano-TiO2system under different coagulation conditions[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2014,452:181-188.
[16]王元宏,魏群山,季有知,等.聚硅酸铝镁锌混凝剂的制备及去除抗生素性能和机理初探[J].安全与环境学报,2017,17(3):1057-1063.Wang Y H,Wei Q S,Ji Y Z,et al.Preparation of inorganic polymer coagulant-PSAMZ and the mechanism for its antibiotics removing performance[J].Journal of Safety and Environment,2017,17(3):1057-1063.
[17]Liao Y,Tang X M,Yang Q Q,et al.Characterization of an inorganic polymer coagulant and coagulation behavior for humic acid/algae-polluted water treatment:polymeric zinc-ferricsilicate-sulfate coagulant[J].RSC Advances,2017,7(32):19856-19862.
[18]Li H S,Chen Y H,Long J Y,et al.Removal of thallium from aqueous solutions using Fe-Mn binary oxides[J].Journal of Hazardous Materials,2017,338:296-305.
[19]郑晓青,韦安磊,张一璇,等.铁锰氧化物/生物炭复合材料对水中硝酸根的吸附特性[J].环境科学,2018,39(3):1220-1232.Zheng X Q,Wei A L,Zhang Y X,et al.Characteristic of nitrate adsorption in aqueous solution by iron and manganese oxide/biochar composites[J].Environmental Science,2018,39(3):1220-1232.
[20]Wu K,Wang H J,Liu R P,et al.Arsenic removal from a higharsenic wastewater using in situ formed Fe-Mn binary oxide combined with coagulation by poly-aluminum chloride[J].Journal of Hazardous Materials,2011,185(2-3):990-995.
[21]Xu X,Yu S L,Shi W X,et al.Effect of acid medium on the coagulation efficiency of polysilicate-ferric(PSF)-A new kind of inorganic polymer coagulant[J].Separation and Purification Technology,2009,66(3):486-491.
[22]Zhu G C,Zheng H L,Zhang Z,et al.Characterization and coagulation-flocculation behavior of polymeric aluminum ferric sulfate(PAFS)[J].Chemical Engineering Journal,2011,178:50-59.
[23]杨雪,张景成,关小红.新生态铁的混凝作用探索[J].环境科学,2012,33(4):1221-1226.Yang X,Zhang J C,Guan X H,et al.Exploration of newlyformed ferric as the coagulant[J].Environmental Science,2012,33(4):1221-1226.
[24]Lan W,Qiu H Q,Zhang J,et al.Characteristic of a novel composite inorganic polymer coagulant-PFAC prepared by hydrochloric pickle liquor[J].Journal of Hazardous Materials,2009,162(1):174-179.
[25]张钢,范先媛,朱小丽,等.聚硅酸铝铁复合絮凝剂性能的研究[J].环境科学与技术,2012,35(8):185-188.Zhang G,Fan X Y,Zhu X L,et al.Coagulation behavior of polysilicate aluminum ferric sulfate composite flocculant[J].Environmental Science&Technology,2012,35(8):185-188.
[26]Moussas P A,Zouboulis A I.A study on the properties and coagulation behaviour of modified inorganic polymeric coagulant-Polyferric silicate sulphate(PFSiS)[J].Separation and Purification Technology,2008,63(2):475-483.
[27]Julien F,Güeroux B,Mazet M.Comparison of organic compounds removal by coagulation-flocculation and by adsorption onto preformed hydroxide flocs[J].Water Research,1994,28(12):2567-2574.
[28]张伟超,魏群山,罗专溪,等.碱度和浊度对混凝去除磺胺甲唑与土霉素的影响[J].环境科学研究,2015,28(5):802-807.Zhang W C,Wei Q S,Luo Z X,et al.Effects of alkalinity and turbidity on SMZ and OTC removal by coagulation[J].Research of Environmental Sciences,2015,28(5):802-807.