湖南省土木建筑学会给排水专业委员会第三十二次学术年会-马军教授课件

1、 饮用水厂升级改造与深度处理技术进展 马军哈尔滨工业大学市政环境工程学院内容水质问题预氧化技术常规工艺强化技术臭氧催化氧化技术过硫酸盐催化氧化技术膜技术 饮用水水质问题预氧化技术氧化剂臭氧高锰酸盐高铁酸盐二氧化氯过硫酸盐氯高级氧化 (AOPs)高锰酸盐预氧化预氧化技术 EDCs/PPCPsPseudo-PersistentContaining Some Electron-Rich Moieties氧化有机污染物Shao and Ma, J Water ST-Aqua, 2010Impact of background constituentsHe, Guan , Ma

2、, Environ. Sci. & Technol., 2009,43,8332-8337Identification of manganese intermediates Ligands significantly inhibit the disproportionation of Mn(III) into MnO2(i.e., enhance the stability of Mn(III)Jiang, Pang, Ma. Environ. Sci. Technol. 2010, 44, 4270-4275Application:Enhanced removal of algae by p

3、ermanganate preoxidation 藻含量：2.5106个/L，pH7.2-7.5, 水温27oCWith preoxidationPAC dose (mg/L)PAC(mg/L)PAC(mg/l)Removal of algae (%） Enhanced removal of algae by permanganate preoxidationPermanganateComposite permanganateconcenmtration (g/L)AlgaeWavelength (nm)Removal of taste and odor by permanganate pre

4、oxidationIntensity of odour Full scale application of permananate preoxidation for algae removal (200000m3/d)Without PPCpreoxidationWith PPCpreoxidationAlgae after sedimentation (Cell/L)With permanganaste preoxidationPAC coagualtion only 高铁酸盐预氧化预氧化技术高铁酸盐预氧化除藻 湖泊水 浊度 10-30NTU；含藻量 8106-2107个/升；pH 7.5-

5、7.7.Ma and Liu, Water Research, 2002Enhanced removal of turbidity by preoxidation with ferrate preoxidation a)Al2(SO4)318H2OMa and Liu, Water Research, 2002Turbidity in settled water(NTU)Turbidity in filtered water(NTU)Enhanced removal of Fe and Mn from surface waters Ma and Liu, Water Research, 200

6、2Enhanced color and turbity reduction by ferrate proxidationFerrate Dosage (K2FeO4, mg/L)Ferrate Dosage (K2FeO4, mg/L)Enhanced removal of heavy metals Ferrate Dosage (K2FeO4, mg/L)Ferrate Dosage (K2FeO4, mg/L)Cd Removal(%)Pb Removal(%)各种预氧化技术效能比较预氧化技术Oxidation of E2 in surface water (a) and wastewat

7、er (b) backgroundLogarithm of the relative residual concentration of E2 during oxidative treatment as a function of oxidant dose in surface water (a) and wastewater effluent (b) at pH 8, and the consumption kinetics of the selective oxidants ( 12 M) in these two waters (c for surface water and d for

8、 wastewater effluent). Effect of permanganate oxidation on algae cells Xie and Ma, Environm Sci & Technol., 2013Effect of ozone oxidation on algae cells Xie and Ma, Environmental Science & Technology, 201332Comparison of permanganate and ozone preoxidation of algae on its BDPs formationNo influenceM

9、uch Increase臭氧预氧化和高锰酸钾预氧化对藻代谢有机物预处理后续消毒副产物比较Comparison of permanganate and ozone preoxidation of AOM of algae on its BDPs formationNo InfluenceMuch increaseComparison of permanganate and ozone preoxidation of AOM of algae on fluorescence absorption KMnO4 O3 Xie and Ma, Environmental Science & Techno

10、logy, 2013Comparison of permanganate and ozone preoxidation of AOM from algae on formation of high molecular weight organic matters Xie and Ma, Environmental Science & Technology, 2013 Xie and Ma, Environmental Science & Technology, 2013Comparison of permanganate and ozone preoxidation of algae on i

11、ts DBPs formation 常规工艺强化技术-强化混凝技术混凝工艺问题Difficulty in treating the water with low temperature and low turibidityDifficulty in treating the water with high organic content, particular humic bearing waters39强化混凝Enhanced coagulationConventinal coagulationRFloc SizeXiao and MaWater Research,2008剩余铝浓度降低En

12、hanced cogalutionConventional coagulationXiao and MaWater Research,200841 强化除色除浊效果Enhanced coagulationConventional ccoagulationXiao and MaWater Research,200842PACEnhanced coagulationRaw water 43强化混凝处理高色度地表水PAC 强化混凝原水 PAC 强化混凝原水 生产性应用结果Temperature 3-5 COD Reduction 68%生产性应用结果COD Reduction：77.3%After

13、sedimentationBefore filtration-强化沉淀强化常规处理工艺现行沉淀技术存在问题Horizontal flow tank Low efficiency, high length (100-120m)Inclined tube settling tank High efficiency, less space required, inferior flow condition, inferior finished water quality 54新型沉淀池双向流平流斜板沉淀池沉淀效率高、适应能力强、抗冲击负荷能力强克服了平流沉淀池的异重流问题5758气浮除有机物效能Ma

14、 and Jiang, Environ. Sci. Technol , 200759沉淀与气浮联用技术60生产性应用效果利用沉淀与气浮技术进行平流沉淀池升级改造浊度去除效果TurbidityOperation days63Reduction of organics（CODMn)64Reduction of algaeAlgae65臭氧催化氧化深度处理技术66Hydrous MnO2Catalysts developed in our groupCeramic honeycomb(CH)FeOOH Surface bound-OH- ions play a key roleTiO2Mn-TiO2

15、Co-TiO2BimetalliccatalysisFormed in situdifficult to recycleMnOx/GACNano-sizecatalystCarbon nanotubeNobel metal catalyst Reduced by-productsImproved stability of supportPt/Carbon nanotubeSupported TiO2Nano-size particlesdifficult to separateMn-Fe-K/CHMn-Cu-K/CHMultiple metal oxides supportedZnO/CH N

16、iO/CH Fe2O3/CH MnO2/CH CuO/CH metal oxide supportedAmorphous MnOx easy to leachCeO2Minimizing bromate formation during catalyzed ozonationMn catalysts-MnOx formed in situT=294 K, pH=7.0 (1 mM PO43- buffered), O3=2.28 mg/L, Mn dosage=1 mg/L, Atrazine0=3uM1) A high catalytic activity of MnOx2) Surface

17、 bound-OH- ions play a key roleMa, Ozone Sci. Eng. (1997)227Ma, Water Res. (1999) 785Ma, Water Res. (2000) 3822Heterogeneous catalytic ozonation of refractory organics: 1. conceptSurface hydroxyl groups initiating ozone decomposition into highly active hydroxyl radicalsMa J and Graham N., Water Rese

18、arch, 1999；2000Hydroxyl on surfaceMn catalysts-MnOx /GACBatch testContinuous test(MnOx formed in situ difficult to recycle)Ozone Sci. Eng. (2004) 3Water Res. (2005)779Mn catalysts-MnO2/Ceramic honeycombT= 293 K, pH=6.92, NB0=50 ug/L, total applied ozone=1.00 mg/L; CH dose= 58.3 mg/L, 2% MnO2/CH dose

19、=60.3 g/LO3CH/O3MnO2-CH/O3(Amorphous MnOx on GAC easy to leach)Appl. Catal. B: Environ. (2008)256Fe catalysts-FeOOHA highly hydroxylated surface J. Mol. Catal. A: Chem. (2008) 82Appl. Catal. B: Environ. (2008)131Nano-sized catalyst - TiO2 and supportedCatalyzed ozonation of nitrobenzene with differe

20、nt catalyst mass (O30=0.367 mg/L, NB0= 60 ug/L, T=293 K )J. Mol. Catal. A: Chem. (2007) 41Ozone Sci. Eng. (2009) 45TiO2/Silica-GelO30=0.9 mg/minCeramic honeycomb supported catalystT= 293 K, pH=6.92, NB0=50 ug/L, total applied ozone=1.00 mg/LEnviron. Sci. Technol. (2009) 2047Environ. Sci. Technol. (2

21、009) 4157ZnONiOFe2O3CuOInitiation of OH profoundly depends on the density of surface-OH2+ of ceramic honeycomb supported catalyst Catalytic ozone: FeNi Zn HO initiation is related to surface hydroxyl densityEnviron. Sci. Technol., 2008; 2009Ceramic honeycomb supported catalyst -Multiple elements met

22、al oxides T= 293 K, pH=6.92, NB0=50 ug/L, total applied ozone=1.00 mg/LJ. Environ. Sci:China. (2006) 1065Mn-CuMn-Fe-KAppl. Catal. B: Environ. (2009)326能够彻底分解破坏Degradation of Nitrobenzene by Cata-ozonationDegradation of organics by ultrasonic wavesZhao, Sun & Ma, et al. Environ. Sci. Technol. (2009)

23、Initiation of OH. by USZhao, Sun & Ma, et al. Environ. Sci. Technol. (2009) Mineralization by US - Effect of types of US fields Zhao, Sun & Ma, et al. Environ. Sci. Technol. (2009)US-assisted catalytic ozonation：Adsorption by CH；：US；：US/CH；：Ozone；：Ozone/US；：Ozone/CH；：US/Ozone/CH臭氧催化氧化工程应用Permanganat

24、e proxidation prior to ozonationEnhanced coagulation and pretreatment by preoxidation with permanganate Ozonation and catalytic ozonation after filtrationCatalytic ozonation contactorComparative study of cata-O3/BAC and BAC with O3/BAC Ozonation/BAC Catalytic ozonation/BACMonitoring pointsOzone Ozon

25、e/BACCat ozone Cat ozone/BACDOC reductions by catalytic ozonation过硫酸盐高级氧化降解水中有机污染物脱氢电子转移SO4- +有机物2.5-3.1VHO 1.8-2.7V加成SO42-+产物饮用水水质标准限值 250mg/L简介选择性稳态浓度高SO4-有机污染物除草剂酚类水体修复水处理Antoniou, et al., 2010;Lau, et al., 2007; Waldemer et al., 2007; Chan et al., 2007; Hori, et al. 2005; Anipsitakis, et al., 20

26、04藻毒素简介持久性有机物内分泌干扰物卤代有机物消毒工艺93热过渡金属辐射碱醌SO4- 简介过氧单硫酸盐（PMS）过氧二硫酸盐（PDS）94基于硫酸根自由基新型高级氧化技术与理论紫外催化活化过氧单硫酸盐磁性金属材料活化过氧单硫酸盐羟胺强化亚铁活化过氧单硫酸盐近期研究结果951 紫外催化活化PMS提出并验证了紫外催化PMS体系中HO和SO4-产生与转化途径。建立了紫外催化PMS体系中HO、SO4-以及有机污染物的降解动力学表达式。961 紫外催化活化PMS通过自由基抑制实验和电子顺磁共振(EPR)技术验证了过氧单硫酸盐在=254nm紫外辐射下主要发生-O-O-键断裂，产生羟基自由基(HO)和SO

27、4-SO4-HO1 紫外催化活化PMS1 紫外催化活化PMS引用32次99HCO3-Cl-NO3-NOM水质参数的影响1 紫外催化活化PMS表明各种参数取值为在天然水体存在的浓度时，该工艺仍应该具有较好的除污染效果。100与UV/ H2O2 和UV/PDS对比：H2O2 ：固体药剂， 相对于H2O2容易运输和保存PDS： 相对于UV/PDS ， UV/PMS在pH8-10自由基产率高，除污染效果好更适用于碱性条件1 紫外催化活化PMS101基于硫酸根自由基新型高级氧化技术与理论紫外催化活化过氧单硫酸盐磁性金属材料活化过氧单硫酸盐羟胺强化亚铁活化过氧单硫酸盐2 磁性金属材料活化PMS合成了一种对

28、过氧单硫酸盐具有高活化特性的磁性金属材料，CuFe2O4。进一步研究其活化过氧单硫酸盐降解有机污染物的活性物种和自由基的形成机理。分析了不同水质参数如pH、碱度、天然有机物、无机盐类以及不同水质背景水体对降解污染物效果的影响。发现SO4-比HO具有更强的选择性，受水体背景成份影响更小，因而稳态浓度更高、氧化效率更高。2 磁性金属材料活化PMSNOMHCO3-PMSCuFe2O4pH2 磁性金属材料活化PMS水质参数和操作条件的影响1052 磁性金属材料活化PMS实际水体背景下的去除效果106对比了不同金属的铁酸盐活化PMS去除污染物的效果：CoFe2O4 CuFe2O4MnFe2O4 ZnFe2O4.金属的铁酸盐活化PMS机理实质为电子在M2+/M3+, O2/O2 和 PMS之间的转移。2 磁性金属材料活化PMSApplied Catalysis B:Environmental，2014107与 H2O2 和PDS对比：更容易被固体金属催化剂活化适用于碱性条件可用于地表水和地下水的净化与修复工艺2 磁