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Filamentous Sludge Bulking Control
by Nano Zero-valent Iron in
Activated Sludge Treatment Systems
East China University of Science and Technology
Presenter: Yue Liu
Advisor: Dr. Zhiqiang Hu
Professor Shuguang Lu
Outline
 Introduction
 Materials and Methods
 Results and Discussion
 Conclusions
2
Introduction
3
Activated Sludge Process
The most used biological wastewater treatment
method in the world.
A process using air and a biological floc composed
of bacteria and protozoa.
Settling tank to allow the biological flocs to settle,
thus separating the biological sludge from the clear
treated water.
4
Fig. 1. A generalized, schematic diagram of an activated sludge process
Sludge Bulking
 When: The sludge fails to separate out in the
sedimentation tanks.
 Causes: Foaming
Pin-point flocs
Viscous bulking
 Results: Looser and less settleable sludge flocs and in
serve cases, the whole operation may fail.
 Control: specific & non-specific methods
5
Fig. 2. Sludge bulking
Filamentous bulking
Control Methods
6
Fig. 3. Control methods
Nano Zero-valent Iron (NZVI)
 Size: 55 ± 11 nm
 Applied for nitrogen and phosphate removal in
wastewater treatment;
 A new type of antimicrobial agents with its
mode of action through reductive decomposition
of cell membrane;
 Can help sludge flocculation and settling due to
oxidative dissolution of NZVI;
 A highly selective agent.
7
Fig. 4. Transmission electron microscopic images of NZVI
Objectives
 To explore the use of NZVI for sludge bulking control
 Try to reduce the side effect of the use of NZVI
8
9
Materials and Methods
Nano Zero-valent Iron Synthesis
10
Fig. 5. The schematic configuration diagram of NZVI fabrication.
(1-NaBH4 2-CMC+FeCl2∙4H2O 3-N2 gas)
Fig. 6. The process of NZVI preparation
 NZVI concentration: 0.11 M (6060 mg/L)
CSTR Setup and Operation
 Two identical lab-scale activated sludge systems
(Tank #1 and #2)
 The volume of aeration chamber: 6.7 L
 The volume of settling chamber: 1.57 L
 Influent flow rate: 7.6 L/d
 HRT: 0.88 d
 SRT: 10 d
 Activated sludge source: Columbia WWTP (MO, U.S.)
11
Fig. 6. Schematic diagram of operation process (1- Influent; 2-
Pump; 3, 4- Mixed liquor; 5- Bubble diffuser; 6- A glass baffle; 7-
Magnetic stirring apparatus; 8- Effluent).
Synthetic Wastewater
Chemical agents Concentration (mg/L)
Non-fat dry milk powder (COD) 500
NH4Cl 89.18
Na2HPO4∙7H2O 51.89
MgSO4 44
CaCl2∙2H2O 14
FeCl2∙4H2O 2
MnSO4 3
(NH4)6Mo7O24∙4H2O 1.2
CuSO4 0.8
Zn(NO3)2∙6H2O 1.8
12
Table 2. Feedstock for CSTR systems
Experimental Process
13
Batch Study Day 50
Analysis methods
Sludge COD Live and dead staining
Mixed Liquor Suspended Solids (MLSS) Effluent COD
Specific Oxygen Uptake Rate (SOUR) Effluent NO3
-
-N
Sludge Volume Index (SVI)/ Sludge Volume (SV30) Effluent NO2
-
-N
Microscopic observations Effluent NH4
+
-N
14
Table 3. Experimental methods involved in the experiment
15
Results and Discussion
Initial Bioreactor Performance
 Initial SVI (mL/g) measurement:
After nearly 15 days and before 1st
time NZVI dosing:
Sludge started bulking when SVI was above 150 mg/L.
16
Fig. 7. SVI values in Tank #1 ( ) and Tank #2 (○ ◇) before NZVI dosing and
in Tank #1 ( ) and Tank #2 (● ◆) after NZVI dosing in Tank #2 and Tank #1
as control on day 68, 81, 90, respectively.
Tank #1 Tank #2
311 → 106 308 → 99
Tank #1 Tank #2
282 → 629 99 → 481
1st
dosing 2nd
dosing 3rd
dosing
Biomass COD (Cont’d)
 The degree of loss sludge differed between the
two bioreactors during sludge bulking.
 Initial Biomass COD (mg/L)
At early stage of sludge bulking:
 The biomass concentration gradually reduced
due to a significant sludge loss in the effluent.
17
Fig. 8. Biomass COD in Tank #1 ( ) and Tank #2 (○ ◇) before NZVI dosing and in Tank
#1 ( ) and Tank #2 (● ◆) after NZVI dosing in Tank #2 and Tank #1 as control on day
68, 81, 90, respectively.
Tank #1 Tank #2
2,430 ± 425 2,475 ± 497
Tank #1 Tank #2
1,582 ± 171 1,744 ± 218
Effluent Water Quality (Cont’d)
 Sludge bulking affected effluent water quality.
 From Day 1—Day 67:
Effluent COD concentration (mg/L):
COD Removal efficiency: 92 %
18
Fig. 9. Effluent COD in Tank #1 ( ) and Tank #2 (○ ◇) before NZVI dosing and in Tank
#1 ( ) and Tank #2 (● ◆) after NZVI dosing in Tank #2 and Tank #1 as control on day
68, 81, 90, respectively.
Tank #1 Tank #2
36 ± 20 33 ± 21
Effluent Water Quality (Cont’d)
19
Effluent
(mg/L)
NO3
-
-N NO2
-
-N NH4
+
-N
Tank #1 35 ± 3 0.22 ± 0.23 0.39 ± 0.03 (99% removal)
Tank #2 36 ± 3 0.13 ± 0.02 0.28 ± 0.02 (99% removal)
Fig. 10. Effluent NO3
-
-N (a), NO2
-
-N (b) and NH4
+
-N (c) in Tank #1 ( ) and Tank #2 (○ ◇)
before NZVI dosing and in Tank #1 ( ) and Tank #2 (● ◆) after NZVI dosing in Tank #2
and Tank #1 as control on day 68, 81, 90, respectively.
(a)
(b)
(c)
1ST
TIME DOSING 2ND
TIME DOSING
Fig. 10. SVI values from Tank #2 for the first time one-time dosing with
NZVI dosing concentration of 37.5 mg/L. Fig. 11. SVI vales from Tank #2 for the second-time dosing with NZVI
dosing concentration of 75 mg/L.
Bioreactor performance and
benefits associated with NZVI
dosing
20
0h 2h 6h 10h 20h 24h 0h 4h 16h 22h 4h 16h 24h 48h
Before AfterBefore dosing After dosing
Reason Analysis
 The concentration of NZVI was too low to make difference.
 The form existed in the system transferred from nano zero-valent iron to oxidized iron, which had
less reducing capacity.
 The contact time was not long enough before washing out.
21
Improvement:
 Increase the concentration of NZVI dosing in the Tank
 Reduce the dissolved oxygen concentration just before dosing
3rd
Time NZVI Dosing (Cont’d)
22
Fig. 12. SVI vales from Tank #2 for the third time one-
time dosing with NZVI dosing concentration of 112.5
mg/L.
 The use of NZVI for the 3rd dosing caused a significant increase in effluent COD, NH4
+
-N and NO2
-
-N
concentrations, a slight decrease in NO3
-
-N.
Fig. 13. NH4
+
-N concentration from Tank #2 for the
third time one-time dosing with NZVI dosing
concentration of 112.5 mg/L.
Fig. 14. NO2
-
-N concentration from Tank #2 for the
third time one-time dosing with NZVI dosing
concentration of 112.5 mg/L.
0h 4h 8h 18h 24h 42h 48h 0h 4h 8h 18h 24h 42h 48h 0h 4h 8h 18h 24h 42h 48h
After dosingBefore dosing
Impact of NZVI Dosing on Nitrifying
Bacterial Activity
 The autotrophic SOUR values in Tanks#2 were
decreased by 40 ± 4 % due to sludge bulking.
 After 1st
time dosing, the nitrifying bacteria
activity was not affected.
 After 3rd
time dosing, the nitrifying bacteria
activity decreased.
 With enough dosage, the nitrification would be
influenced by the dosing of NZVI.
23
Fig. 15. Autotrophic SOUR values in Tank #2 before ( ) and after dosing○
( ).Error bars represent standard deviation of the duplicate experiments●
from the mean of duplicate samples.
24
Conclusions
Conclusions
 NZVI was successfully used to kill the filamentous bacteria.
 Positive effect on sludge bulking control with NZVI dosing concentration of 112.5 mg/L
 The slight side effect of the NZVI dosing on nitrification and effluent water quality
25
Acknowledgements
 My deepest gratitude goes first to Dr. Zhiqiang Hu, my supervisor in University of Missouri, for
his constant encouragement and guidance.
 Besides, I am grateful to all the faculty of School of Resources and Environmental Engineering
at East China University of Science and Technology, for their patience, motivation, enthusiasm
and immense knowledge. Their guidance helped me in all of my campus life.
 Last my thanks would go to my beloved family for their loving considerations and great
confidence in me all through these years.
 I also owe my sincere gratitude to my friends and my fellow classmates who gave me their
help and time helping me work out my difficulties.
26
Thank you!
27

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NZVI Controls Sludge Bulking in Activated Sludge

  • 1. Filamentous Sludge Bulking Control by Nano Zero-valent Iron in Activated Sludge Treatment Systems East China University of Science and Technology Presenter: Yue Liu Advisor: Dr. Zhiqiang Hu Professor Shuguang Lu
  • 2. Outline  Introduction  Materials and Methods  Results and Discussion  Conclusions 2
  • 4. Activated Sludge Process The most used biological wastewater treatment method in the world. A process using air and a biological floc composed of bacteria and protozoa. Settling tank to allow the biological flocs to settle, thus separating the biological sludge from the clear treated water. 4 Fig. 1. A generalized, schematic diagram of an activated sludge process
  • 5. Sludge Bulking  When: The sludge fails to separate out in the sedimentation tanks.  Causes: Foaming Pin-point flocs Viscous bulking  Results: Looser and less settleable sludge flocs and in serve cases, the whole operation may fail.  Control: specific & non-specific methods 5 Fig. 2. Sludge bulking Filamentous bulking
  • 6. Control Methods 6 Fig. 3. Control methods
  • 7. Nano Zero-valent Iron (NZVI)  Size: 55 ± 11 nm  Applied for nitrogen and phosphate removal in wastewater treatment;  A new type of antimicrobial agents with its mode of action through reductive decomposition of cell membrane;  Can help sludge flocculation and settling due to oxidative dissolution of NZVI;  A highly selective agent. 7 Fig. 4. Transmission electron microscopic images of NZVI
  • 8. Objectives  To explore the use of NZVI for sludge bulking control  Try to reduce the side effect of the use of NZVI 8
  • 10. Nano Zero-valent Iron Synthesis 10 Fig. 5. The schematic configuration diagram of NZVI fabrication. (1-NaBH4 2-CMC+FeCl2∙4H2O 3-N2 gas) Fig. 6. The process of NZVI preparation  NZVI concentration: 0.11 M (6060 mg/L)
  • 11. CSTR Setup and Operation  Two identical lab-scale activated sludge systems (Tank #1 and #2)  The volume of aeration chamber: 6.7 L  The volume of settling chamber: 1.57 L  Influent flow rate: 7.6 L/d  HRT: 0.88 d  SRT: 10 d  Activated sludge source: Columbia WWTP (MO, U.S.) 11 Fig. 6. Schematic diagram of operation process (1- Influent; 2- Pump; 3, 4- Mixed liquor; 5- Bubble diffuser; 6- A glass baffle; 7- Magnetic stirring apparatus; 8- Effluent).
  • 12. Synthetic Wastewater Chemical agents Concentration (mg/L) Non-fat dry milk powder (COD) 500 NH4Cl 89.18 Na2HPO4∙7H2O 51.89 MgSO4 44 CaCl2∙2H2O 14 FeCl2∙4H2O 2 MnSO4 3 (NH4)6Mo7O24∙4H2O 1.2 CuSO4 0.8 Zn(NO3)2∙6H2O 1.8 12 Table 2. Feedstock for CSTR systems
  • 14. Analysis methods Sludge COD Live and dead staining Mixed Liquor Suspended Solids (MLSS) Effluent COD Specific Oxygen Uptake Rate (SOUR) Effluent NO3 - -N Sludge Volume Index (SVI)/ Sludge Volume (SV30) Effluent NO2 - -N Microscopic observations Effluent NH4 + -N 14 Table 3. Experimental methods involved in the experiment
  • 16. Initial Bioreactor Performance  Initial SVI (mL/g) measurement: After nearly 15 days and before 1st time NZVI dosing: Sludge started bulking when SVI was above 150 mg/L. 16 Fig. 7. SVI values in Tank #1 ( ) and Tank #2 (○ ◇) before NZVI dosing and in Tank #1 ( ) and Tank #2 (● ◆) after NZVI dosing in Tank #2 and Tank #1 as control on day 68, 81, 90, respectively. Tank #1 Tank #2 311 → 106 308 → 99 Tank #1 Tank #2 282 → 629 99 → 481 1st dosing 2nd dosing 3rd dosing
  • 17. Biomass COD (Cont’d)  The degree of loss sludge differed between the two bioreactors during sludge bulking.  Initial Biomass COD (mg/L) At early stage of sludge bulking:  The biomass concentration gradually reduced due to a significant sludge loss in the effluent. 17 Fig. 8. Biomass COD in Tank #1 ( ) and Tank #2 (○ ◇) before NZVI dosing and in Tank #1 ( ) and Tank #2 (● ◆) after NZVI dosing in Tank #2 and Tank #1 as control on day 68, 81, 90, respectively. Tank #1 Tank #2 2,430 ± 425 2,475 ± 497 Tank #1 Tank #2 1,582 ± 171 1,744 ± 218
  • 18. Effluent Water Quality (Cont’d)  Sludge bulking affected effluent water quality.  From Day 1—Day 67: Effluent COD concentration (mg/L): COD Removal efficiency: 92 % 18 Fig. 9. Effluent COD in Tank #1 ( ) and Tank #2 (○ ◇) before NZVI dosing and in Tank #1 ( ) and Tank #2 (● ◆) after NZVI dosing in Tank #2 and Tank #1 as control on day 68, 81, 90, respectively. Tank #1 Tank #2 36 ± 20 33 ± 21
  • 19. Effluent Water Quality (Cont’d) 19 Effluent (mg/L) NO3 - -N NO2 - -N NH4 + -N Tank #1 35 ± 3 0.22 ± 0.23 0.39 ± 0.03 (99% removal) Tank #2 36 ± 3 0.13 ± 0.02 0.28 ± 0.02 (99% removal) Fig. 10. Effluent NO3 - -N (a), NO2 - -N (b) and NH4 + -N (c) in Tank #1 ( ) and Tank #2 (○ ◇) before NZVI dosing and in Tank #1 ( ) and Tank #2 (● ◆) after NZVI dosing in Tank #2 and Tank #1 as control on day 68, 81, 90, respectively. (a) (b) (c)
  • 20. 1ST TIME DOSING 2ND TIME DOSING Fig. 10. SVI values from Tank #2 for the first time one-time dosing with NZVI dosing concentration of 37.5 mg/L. Fig. 11. SVI vales from Tank #2 for the second-time dosing with NZVI dosing concentration of 75 mg/L. Bioreactor performance and benefits associated with NZVI dosing 20 0h 2h 6h 10h 20h 24h 0h 4h 16h 22h 4h 16h 24h 48h Before AfterBefore dosing After dosing
  • 21. Reason Analysis  The concentration of NZVI was too low to make difference.  The form existed in the system transferred from nano zero-valent iron to oxidized iron, which had less reducing capacity.  The contact time was not long enough before washing out. 21 Improvement:  Increase the concentration of NZVI dosing in the Tank  Reduce the dissolved oxygen concentration just before dosing
  • 22. 3rd Time NZVI Dosing (Cont’d) 22 Fig. 12. SVI vales from Tank #2 for the third time one- time dosing with NZVI dosing concentration of 112.5 mg/L.  The use of NZVI for the 3rd dosing caused a significant increase in effluent COD, NH4 + -N and NO2 - -N concentrations, a slight decrease in NO3 - -N. Fig. 13. NH4 + -N concentration from Tank #2 for the third time one-time dosing with NZVI dosing concentration of 112.5 mg/L. Fig. 14. NO2 - -N concentration from Tank #2 for the third time one-time dosing with NZVI dosing concentration of 112.5 mg/L. 0h 4h 8h 18h 24h 42h 48h 0h 4h 8h 18h 24h 42h 48h 0h 4h 8h 18h 24h 42h 48h After dosingBefore dosing
  • 23. Impact of NZVI Dosing on Nitrifying Bacterial Activity  The autotrophic SOUR values in Tanks#2 were decreased by 40 ± 4 % due to sludge bulking.  After 1st time dosing, the nitrifying bacteria activity was not affected.  After 3rd time dosing, the nitrifying bacteria activity decreased.  With enough dosage, the nitrification would be influenced by the dosing of NZVI. 23 Fig. 15. Autotrophic SOUR values in Tank #2 before ( ) and after dosing○ ( ).Error bars represent standard deviation of the duplicate experiments● from the mean of duplicate samples.
  • 25. Conclusions  NZVI was successfully used to kill the filamentous bacteria.  Positive effect on sludge bulking control with NZVI dosing concentration of 112.5 mg/L  The slight side effect of the NZVI dosing on nitrification and effluent water quality 25
  • 26. Acknowledgements  My deepest gratitude goes first to Dr. Zhiqiang Hu, my supervisor in University of Missouri, for his constant encouragement and guidance.  Besides, I am grateful to all the faculty of School of Resources and Environmental Engineering at East China University of Science and Technology, for their patience, motivation, enthusiasm and immense knowledge. Their guidance helped me in all of my campus life.  Last my thanks would go to my beloved family for their loving considerations and great confidence in me all through these years.  I also owe my sincere gratitude to my friends and my fellow classmates who gave me their help and time helping me work out my difficulties. 26

Editor's Notes

  1. 各位老师,下午好,我是刘玥。我的论文题目是《利用纳米零价铁处理控制活性污泥系统中丝状菌污泥膨胀问题》。下面我将本论文设计的主要内容向各位老师作简要的展示
  2. 这是我今天要展示的四个部分。首先我将向大家大致介绍一下本次实验的研究背景和研究意义。然后是实验目标,以及整个实验的实验材料和实验方法的选择,实验结果与讨论,最后总结实验结论。
  3. 第一部分,实验背景和实验意义的介绍。
  4. 第一个关键词:活性污泥处理系统。 众所周知,活性污泥系统是生物法污水处理方法中最常用的一种形式。它的性能在很大程度上依赖于好的泥水分离。然而在实际生产应用中,常常会由于各种不同的因素导致污泥沉降性能降低,从而影响整个污水处理系统的运行。这样就出现了污泥膨胀的现象。
  5. 污泥膨胀发生在泥水分离能力变差,污泥沉降性能降低的时候。主要有以下四种类型,包括泥水混合物表面产生大量泡沫,针点型絮体,黏性污泥膨胀,以及最后的最广泛存在的丝状菌污泥膨胀。它是由于过度的丝状微生物的生长导致的污泥膨胀。最终会使污泥絮体蓬松,沉降性能减弱。而目前的控制方法分为特异性和非特异性控制。
  6. 特异性方法旨在特异性消除适宜丝状菌生长的各种因素。然而由于丝状菌可以在大部分环境条件下生存,因此很难营造一种环境是适宜菌胶团细菌的生长而选择性压迫丝状菌的生长。并且,即使要这样做修改工艺操作流程或工艺的结构,成本也非常高。因而通常情况下,非特异性的控制方法多被采用。右边为三种常见的治理污泥膨胀的添加试剂,分别为杀菌剂,压载剂和混凝絮凝剂。
  7. 这种新型试剂就是纳米零价铁,左图为它的投射电子显微镜图像。它被选做投加试剂,有以下几点原因。纳米铁已可应用于污水处理中的氮磷去除,并且纳米铁是一种新型杀菌剂,由于铁具有非常强还原能力,可以将细胞膜进行还原性分解,从而杀菌。再者,纳米铁在水中溶解后释放出二价铁离子后,可以与污泥作用后絮凝沉降。最后一个特点是,有文献说明纳米铁可以选择性杀死相关细菌。丝状菌和NZVI两者都具有很大的比表面,因而我们可以大胆猜测丝状菌将会比菌胶团更易于接触到NZVI,这样就能选择性杀死丝状菌了。
  8. 本次实验的主要实验目的是探索研究纳米零价铁在污泥膨胀中的应用,并在一定程度上减少由此产生的副作用。
  9. 第二部分为实验材料和方法的选择。
  10. 纳米零价铁的制备。左图为制备纳米铁的简易装置示意图。反应过程中二价铁离子被还原,而硼氢根则被氧化,并最终还生成了氢气。由此化学计量比例,我们最终得到了浓度为0.11 mol/L的纳米零价铁。6060mg/L
  11. 该实验的装置如下图所示,由两个完全相同的反应器组成CSTR(连续搅拌反应器)系统,分别分为好氧曝气部分和沉淀区,水力停留了时间为0.88天,污泥龄为10天。进水为合成废水。
  12. 这是合成废水的成分列表,目标COD进水为500 mg/L,并添加了一些大量和微量营养物质。
  13. 两个CSTR总共反应运行了95天,人为地分为了以下四个阶段,在其中共进行了三次NZVI的投加。
  14. 此表罗列的是在本实验中所涉及的所有实验指标。包括污泥COD,MLSS, 检测污泥浓度,SOUR 监测污泥活性,SVI 和 SV30 监测污泥沉降性能,死活染色和显微镜观察可以直观地体现污泥的形态变化,还对处理过后出水的水质进行检测,包括COD, 硝态氮,亚硝态氮和氨氮含量,体现污泥的硝化作用情况。
  15. 虽然两个反应器都在同等条件下相同SRT和HRT的情况下进行运行,但是产生了不同的膨胀趋势,这也体现了污泥系统中污泥膨胀机理的不确定性和复杂变化
  16. Complete nitrification
  17. 由图我们可以得知在投加了第一次NZVI后,SVI数值并没有明显的降低或变化。并且水质中硝态氮、亚硝态氮、氨氮浓度都几乎没有变化。这说明在对于外界投加的物质,活性污泥系统具有一定的缓冲作用,保持原有的运行状态。 而在第二次增加NZVI浓度投加后,仍旧没有明显变化,污泥持续膨胀中。