湖南省土木建筑學(xué)會給排水專業(yè)委員會第三十二次學(xué)術(shù)年會-馬軍教授課件

1、 飲用水廠升級改造與深度處理技術(shù)進展 馬軍哈爾濱工業(yè)大學(xué)市政環(huán)境工程學(xué)院內(nèi)容水質(zhì)問題預(yù)氧化技術(shù)常規(guī)工藝強化技術(shù)臭氧催化氧化技術(shù)過硫酸鹽催化氧化技術(shù)膜技術(shù) 飲用水水質(zhì)問題預(yù)氧化技術(shù)氧化劑臭氧高錳酸鹽高鐵酸鹽二氧化氯過硫酸鹽氯高級氧化 (AOPs)高錳酸鹽預(yù)氧化預(yù)氧化技術(shù) EDCs/PPCPsPseudo-PersistentContaining Some Electron-Rich Moieties氧化有機污染物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個/L，pH7.2-7.5, 水溫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 高鐵酸鹽預(yù)氧化預(yù)氧化技術(shù)高鐵酸鹽預(yù)氧化除藻 湖泊水 濁度 10-30NTU；含藻量 8106-2107個/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(%)各種預(yù)氧化技術(shù)效能比較預(yù)氧化技術(shù)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臭氧預(yù)氧化和高錳酸鉀預(yù)氧化對藻代謝有機物預(yù)處理后續(xù)消毒副產(chǎn)物比較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 常規(guī)工藝強化技術(shù)-強化混凝技術(shù)混凝工藝問題Difficulty in treating the water with low temperature and low turibidityDifficulty in treating the water with high organic content, particular humic bearing waters39強化混凝Enhanced coagulationConventinal coagulationRFloc SizeXiao and MaWater Research,2008剩余鋁濃度降低En

12、hanced cogalutionConventional coagulationXiao and MaWater Research,200841 強化除色除濁效果Enhanced coagulationConventional ccoagulationXiao and MaWater Research,200842PACEnhanced coagulationRaw water 43強化混凝處理高色度地表水PAC 強化混凝原水 PAC 強化混凝原水 生產(chǎn)性應(yīng)用結(jié)果Temperature 3-5 COD Reduction 68%生產(chǎn)性應(yīng)用結(jié)果COD Reduction：77.3%After

13、sedimentationBefore filtration-強化沉淀強化常規(guī)處理工藝現(xiàn)行沉淀技術(shù)存在問題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新型沉淀池雙向流平流斜板沉淀池沉淀效率高、適應(yīng)能力強、抗沖擊負荷能力強克服了平流沉淀池的異重流問題5758氣浮除有機物效能Ma

14、 and Jiang, Environ. Sci. Technol , 200759沉淀與氣浮聯(lián)用技術(shù)60生產(chǎn)性應(yīng)用效果利用沉淀與氣浮技術(shù)進行平流沉淀池升級改造濁度去除效果TurbidityOperation days63Reduction of organics（CODMn)64Reduction of algaeAlgae65臭氧催化氧化深度處理技術(shù)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能夠徹底分解破壞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臭氧催化氧化工程應(yīng)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過硫酸鹽高級氧化降解水中有機污染物脫氫電子轉(zhuǎn)移SO4- +有機物2.5-3.1VHO 1.8-2.7V加成SO42-+產(chǎn)物飲用水水質(zhì)標(biāo)準限值 250mg/L簡介選擇性穩(wěn)態(tài)濃度高SO4-有機污染物除草劑酚類水體修復(fù)水處理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藻毒素簡介持久性有機物內(nèi)分泌干擾物鹵代有機物消毒工藝93熱過渡金屬輻射堿醌SO4- 簡介過氧單硫酸鹽（PMS）過氧二硫酸鹽（PDS）94基于硫酸根自由基新型高級氧化技術(shù)與理論紫外催化活化過氧單硫酸鹽磁性金屬材料活化過氧單硫酸鹽羥胺強化亞鐵活化過氧單硫酸鹽近期研究結(jié)果951 紫外催化活化PMS提出并驗證了紫外催化PMS體系中HO和SO4-產(chǎn)生與轉(zhuǎn)化途徑。建立了紫外催化PMS體系中HO、SO4-以及有機污染物的降解動力學(xué)表達式。961 紫外催化活化PMS通過自由基抑制實驗和電子順磁共振(EPR)技術(shù)驗證了過氧單硫酸鹽在=254nm紫外輻射下主要發(fā)生-O-O-鍵斷裂，產(chǎn)生羥基自由基(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水質(zhì)參數(shù)的影響1 紫外催化活化PMS表明各種參數(shù)取值為在天然水體存在的濃度時，該工藝仍應(yīng)該具有較好的除污染效果。100與UV/ H2O2 和UV/PDS對比：H2O2 ：固體藥劑， 相對于H2O2容易運輸和保存PDS： 相對于UV/PDS ， UV/PMS在pH8-10自由基產(chǎn)率高，除污染效果好更適用于堿性條件1 紫外催化活化PMS101基于硫酸根自由基新型高級氧化技術(shù)與理論紫外催化活化過氧單硫酸鹽磁性金屬材料活化過氧單硫酸鹽羥胺強化亞鐵活化過氧單硫酸鹽2 磁性金屬材料活化PMS合成了一種對

28、過氧單硫酸鹽具有高活化特性的磁性金屬材料，CuFe2O4。進一步研究其活化過氧單硫酸鹽降解有機污染物的活性物種和自由基的形成機理。分析了不同水質(zhì)參數(shù)如pH、堿度、天然有機物、無機鹽類以及不同水質(zhì)背景水體對降解污染物效果的影響。發(fā)現(xiàn)SO4-比HO具有更強的選擇性，受水體背景成份影響更小，因而穩(wěn)態(tài)濃度更高、氧化效率更高。2 磁性金屬材料活化PMSNOMHCO3-PMSCuFe2O4pH2 磁性金屬材料活化PMS水質(zhì)參數(shù)和操作條件的影響1052 磁性金屬材料活化PMS實際水體背景下的去除效果106對比了不同金屬的鐵酸鹽活化PMS去除污染物的效果：CoFe2O4 CuFe2O4MnFe2O4 ZnFe2O4.金屬的鐵酸鹽活化PMS機理實質(zhì)為電子在M2+/M3+, O2/O2 和 PMS之間的轉(zhuǎn)移。2 磁性金屬材料活化PMSApplied Catalysis B:Environmental，2014107與 H2O2 和PDS對比：更容易被固體金屬催化劑活化適用于堿性條件可用于地表水和地下水的凈化與修復(fù)工藝2 磁