insight into the oxidation mechanism of uv/free chlorine process · 2018-08-27 · insight into the...
TRANSCRIPT
Insight Into the Oxidation Mechanism
of UV/Free Chlorine Process
Weiqiu Zhang a, Shiqing Zhou b, Jinming Luo a, John Crittenden a
256th ACS Conference, Aug 21th 2018
a Brook Byers Institute for Sustainable Systems
Department of Civil and Environmental Engineering
Georgia Institute of Technology
b Department of Water Engineering and Science
College of Civil Engineering
Hunan University
2
OUTLINE
Introduction
Approach
Results and Discussion
Summary
Future Work
3
INTRODUCTION: Concerns about organic contaminants in water
Organic contaminants in aqueous
phase: Global Challenging
Environmental risks of organic
contaminants:
• persistence in aqueous phase
• bioaccumulation in fish
• toxicity for human health
How to destory organic contaminants in aqueous phase
Fang, C., M. Megharaj, and R. Naidu. "Electrochemical Advanced Oxidation Processes (EAOP) to degrade per-and polyfluoroalkyl substances (PFASs)." Journal of Advanced Oxidation Technologies 20.2 (2017).
Bonito, Lindsay T., Amro Hamdoun, and Stuart A. Sandin. "Evaluation of the global impacts of mitigation on persistent, bioaccumulative and toxic pollutants in marine fish." PeerJ 4 (2016): e1573.
?
CHLDDT
PBDEPCB
4
INTRODUCTION: Current treatment processes
• Adsorption
• Air Stripping
• Biological treatment: refractory contaminants (e.g. antibiotics)
phase transfer
Complex radical chain reactions
AOPs yield highly reactive radicals at room temperature and pressure
(e.g. HO∙, SO4-∙, Cl∙)
Organic
Contaminants
CO2
H2O
• Advanced oxidation processes (AOPs): effective for refractory organic contaminants
5
INTRODUCTION: Application of AOPs technologies
• O3/H2O2 process
Conventional AOPs Major Concerns
3 2 2 22O H O 2HO 3O
2 2H O h 2HO
Production of O3 is expensive & inefficient process
H2O2 is expensive, market price $500/ton
residual H2O2 need to be quenched
low energy efficiency (∅H2O2 = 0.5, εH2O2 = 19.6M-1cm-1)
• UV/H2O2 process
Von Gunten, Urs. "Ozonation of drinking water: Part II. Disinfection and by-product formation in presence of bromide, iodide or chlorine." Water Research 37.7 (2003): 1469-1487.
Low Pressure UV/H2O2
O3/H2O2
6
INTRODUCTION: Application of AOPs technologies
Alternative AOPs
• UV/Persulfate (PS) process
2
2 8 4S O h 2SO
4 2 4HSO O HO HSO
Major Concerns
Most common inorganic anions in water
https://chemlegin.wordpress.com/2012/07/
Cl- reduces the perfluorinated compounds (e.g. PFOA) destruction rate (experimental observe)
Experimental Condition: [R]=150μM, [PS]=15mM
Cl- + SO4-∙ SO4
2- + C𝐥∙ ∙ ∙ ∙ ClO3-
PFOA starts to be destroyed until all Cl- convert into ClO3-
7
INTRODUCTION: Impact of Chloride Ions on UV/Persulfate Process
Organic compounds (R) can react with SO4-∙, HO∙, Cl∙
Elementary Reactions Network4
4
' ' 'Cl
4 HO /R Cl /RSO /RR
R 4 HO /RSO /R
k [SO ][R] k [HO ][R] k [Cl ] [R]r
r k [SO ][R] k [HO ][R]
Simulation Conditions: [R]=10-4M, [PS]=0.01M, pH=7
SO4
-.
R
H2O
PSSO4
-.
R
H2O
RPS
PS SO4
-.No Cl-
Cl-
H2O
SO4
-.
Cl.
PS
R
Cl-
H2O
PS
R
Cl-
H2O
SO4
-.
Cl.
PS
R
Cl-
H2O
PS
R
R
PS SO4
-.
Cl2
-.Cl.
PS
ClO-3
ClO2
.ClOH-. HO.
Cl- is present
Maximum
Cl
Rr
: Destruction rate of organic contaminant when Cl- is present
(e.g. 0.001 M Cl-)Rr : Destruction rate of organic contaminant when Cl- is not present
8
C/C0=exp (−kobs×t)
0M Cl- kobs=0.0092s-1
0.01M Cl- kobs=0.0043s-1
0.1M Cl- kobs=0.0023s-1
e.g. Benzoic acid degradation in UV/PS
[R]=10-4M, [PS]=0.01M, pH = 7, [Cl-] = 0M ~ 0.1M
Model Validation
INTRODUCTION: Impact of Chloride Ions on UV/Persulfate Process
Cl- has inhibition impact on UV/Persulfate Process vs. Cl- has negligible impact on UV/H2O2
Zhang, W., Zhou, S., Sun, J., Meng, X., Luo, J., Zhou, D., & Crittenden, J. C. Impact of Chloride Ions on UV/H2O2
and UV/Persulfate Advanced Oxidation Processes. Environmental science & technology. (2018).
9
INTRODUCTION: UV/Free Chlorine Process
Promising AOPs: UV/Free Chlorine process
Major Advantages
NaOCl is much cheaper, market price $250/ton
No need to quench residual free chlorine
High energy efficiency than UV/H2O2 and UV/PS
(∅HOCl = 0.9, εHOCl = 59M-1cm-1, ∅OCl- = 0.8, εOCl- = 66M-1cm-1)
• H2O2: $500/ton, NaS2O8: $800/ton
Kinetic behavior and mechanism of organic contaminants destruction in UV/Free Chlorine process
(∅H2O2 = 0.5, εH2O2 = 19.6M-1cm-1, ∅PS = 0.5, εPS = 20.8M-1cm-1)
How to appropriately design UV/Free Chlorine process
HOCl / OCl h HO /O Cl 2Cl Cl Cl 2O Cl / H OCl /HO HOCl Cl
Cl- has negligible impact on UV/Free Chlorine
(e.g. Benzoic acid, Clofibric acid, Ibuprofen, Carbamazepine, Caffeine)
Understand
10
APPROACHES: Modeling Study
AOPs Modeling Study
1. Interpret AOPs
mechanism
2. Predict AOPs
performance
3. Optimize AOPs
operation
11
APPROACHES- Modeling Methodologies
Identified Elementary Reactions
Reaction Rate Constant
Estimator
ODEs solver
Time-dependent Concentration
Profiles of parent compounds,
byproducts and intermediates
Experimental
Validation
Energy
Efficiency
Estimator
Electrical energy
required
* Elementary Reactions
(Literature Reported)
* Rate Constants Estimator
(Genetic Algorithm)
* Ordinary Differential Equations
(ODEs) Generator and Solver
(Gear’s Algorithm)
12
Genetic Algorithm
Minimize Objective Function
Fit Experimental Data
2
exp cal exp
1OF C C / C
n 1
OFmin = 0.0732
9 1 1
Cl /R
4 1 1
Cl /R
6 1 1
ClO /R
k 1.03 10 M s
k 5.17 10 M s
k 1.23 10 M s
3-Methylbenzoic Acid
Solve both constrained and
unconstrained optimization
problem based on a natural
selection process that mimics
biological evolution3-Methylbenzoic Acid degradation in UV/Free Chlorine
Experimental Condition:
[BA]= 5×10-6M, pH=7.2
APPROACHES: Determining rate constants
kCl./R kCl2
-./R kClO./R
13
Stiff ODEs Solver Gear’s Method
'
s
k n k n s n s
k 0
0 0
y f (t, y)
a y h f (t , y )
initial condition : y(t ) y
Experimental Condition:
[BA]= 5×10-6M, pH=7.2
Most Stable Algorithm
Model validation
by comparing with
experimental data
APPROACHES: Ordinary Differential Equations Solver
14
Results & Discussion
Rate constants of reactive chlorine species (a) 4-Fluorobenzoic Acid concentration vs. time
(b) Concentration Profiles of
2-Chlorobenzoic Acid
(c) Concentration Profiles of
2-Iodorobenzoic Acid
(d) Concentration Profiles of
3-Cyanobenzoic Acid
(e) Concentration Profiles of
3-Nitrobenzoic Acid
Experimental Condition:
[BA]= 5×10-6M, pH=7.2
15
Results & Discussion
Quantitative Structure Activity Relationship (QSAR)
(a) Linear relationship for kCl./R and σ (c) Linear relationship for kClO./R and σ(b) Linear relationship for kCl2
-./R and σ
Hammett constants (σ) vs. Rate constants
Chemical ActivityChemical Descriptor
logkCl./R =9.05-1.86σ
R2=0.95logkCl2
-./R =4.64-0.84σ
R2=0.83
logkClO./R =6.08-0.48σ
R2=0.82
16
Results & Discussion
Relative contribution of reactive radicals
dominant contribution
[HO∙] vs. time [Cl∙] vs. time
[ClO∙] vs. time[Cl2-∙] vs. time
17
Results & Discussion
Elementary reaction network
Experimental Condition:
[R]= 5×10-6 M, [Free Chlorine] = 5×10-6 M − 5.6 ×10-5 M
[Cl-] = 5×10-6 M − 5.6 ×10-5 M, pH = 7.2
Kinetic Data:
2
2 2 2
10 1 1 8 1 1 9 1 1
HO /free chlorine HO /R
9 1 1 9 1 1
Cl / free chlorine Cl /Cl
3 1 7 1 1 9 1 1
Cl /H O 2 Cl /R
4 1
2Cl Cl Cl /H O
k 8.8 10 M s k 10 M s 10 M s
k 8.2 10 M s k 8 10 M s
k [H O] 1.3 10 s k 10 M s 10 M s
k 5.3 10 s k [H O] 1.3
2
3 1
4 1 1 5 1 1 5 1 1 6 1 1
ClO /RCl /R
10 s
k 10 M s 10 M s k 10 M s 10 M s
18
Energy Efficiency
Electrical Efficiency per log order (EE/O)
0.0022lbgram
i f i f
C EP tEE \ O
V log(C / C ) log(C / C )
Minimize EE/O (0.0009 KWh/L)
Free Chlorine Dosage 0.4mM
UV Intensity 1.2×10-5 Einstein/L.sExperimental Condition:
[BA]= 5×10-6M, pH=7.2
Results & Discussion
19
SUMMARY
First Principle Kinetic Model for UV/Free Chlorine Process
3. Interpret degradation
mechanisms - radicals make
dominant contribution
1. Estimated reactivities of
reactive chlorine species
4. Optimize UV/free chlorine
process operational process
2. Predict UV/free chlorine
process performance
QSAR models
20
UV/H2O2 Pretreatment Subsequent Chlorination (Example)
o 70% of Thiamphenicol
(THA) was destroyed by
UV/H2O2 during 90
minutes
o The yields of THMs for
THA kept decreasing for
UV/H2O2 pretreatment
Future Work: What controls the design for practical water treatment?
Micropollutants removal or DBPs formation potential decreases ?
Which AOPs: UV/ H2O2 vs. UV/Free Chlorine processes(1) requires less energy for micropollutants & DBPs formation potential destruction?
(2) chlorate production?
UV/H2O2 & UV/Free Chlorine processes may increase DBPs formation potential Concern
Micropollutants removal controls
(a) Degradation of THA in UV/H2O2 process
Experimental Condition:
[Thiamphenicol]0 = 3 μM, [H2O2] = 0.3 mM
[Cl2] = 1.0 mM
(b) THMs yields for THA with UV/H2O2 process pretreatment
Yin, Kai et. al 2018
21
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Thank you!
Question?
Authors contacts:
Weiqiu Zhang
Georgia Institute of Technology
Email: [email protected]
John Crittenden
Georgia Institute of Technology
Email: [email protected]