Peracetic acid (PAA) and performic acid (PFA) for water … · 2020-02-09 · Does not form toxic...
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Peracetic acid (PAA) and performic acid (PFA) for water disinfection
Ravi Kumar Chhetri Postdoc
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Introduction
Peracetic acid (PAA) is one of the most used disinfectants inwastewater treatment. Also used in food industry andaquaculture.
Peracetic acid is used as commercial solution in equilibrium withhydrogen peroxide:
𝐶𝐶𝐻𝐻3𝐶𝐶𝐶𝐶𝐶𝐶𝐻𝐻 + 𝐻𝐻2𝐶𝐶2↔ 𝐶𝐶𝐻𝐻3𝐶𝐶𝐶𝐶3𝐻𝐻 + 𝐻𝐻2𝐶𝐶
Does not form toxic byproducts
Hydrogen peroxide is a weak disinfectant.
(Acetic acid) (Hydrogen peroxide) (peracetic acid) (water)
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Introduction
Performic acid (PFA) is one of the most used disinfectants infood and medical industries.
Performic acid is unstable and need to synthesis before use:
𝐶𝐶𝐻𝐻2𝐶𝐶2 + 𝐻𝐻2𝐶𝐶2↔ 𝐶𝐶𝐻𝐻2𝐶𝐶3 + 𝐻𝐻2𝐶𝐶
Newly introduced disinfectant to wastewater industy Recently used in Combined Sewer Overflow (CSO) disinfection Does not form toxic byproducts
(Formic acid) (Hydrogen peroxide) (performic acid) (water)
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Combined sewer overflow
-500 E.coli/100mL-200 Enterococcus/100mL
Disinfectant profile in CSO
0 5 10 15 20 250
2
4
6 C0
Ct (t=HRT)
C·t = area under curve
dilution onrelease to surface water
Ct = Ceffluent
Reaction time (min)
Disin
fect
ant (
mg/
L)
3 design parameters
• C·t=effect concentration= area under curve
• Ct =concentration after retention time (t)=Ceffluent
• Residual toxicity
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• Modified spectrophotometric method with ABTS* for less H2O2interference. – Mixing reagent A (ABTS) and reagent B (acetic acid buffer)
*= (2, 2’’-azino-bis [3-ethylbenzothiazoline-6-sulfonic acid] diammonium salt)
Quantification method of Peracetic acid (PAA) and performic acid (PFA)
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Quantification of Peracetic acid (PAA) and performic acid (PFA)
0 10 20 30 400.0
0.2
0.4
0.6
PFAH2O2
Tid (min)
Abso
rban
s (4
05nm
)
• PAA-ABTS reaction=10 min• Color development
kinetics 2.5 mg/L PAA & 2.5 mg/L H2O2
0 1 2 3 4 5 6 7 8 9 100.0
0.2
0.4
0.6
PFAH2O2
y= 0,2452x+0,01211R2= 0.9809
mg/L
Abs
orba
ns (4
05nm
)
• PFA-ABTS reaction=20 min• Color development
kinetics 2.5 mg/L PFA & 2.5 mg/L H2O2
Kinetics of color development Calibration curve
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0 100 200 3000
2
4
6
8
10
pH 5.18
pH 4.16
pH 8.0
pH 7.5
pH 7.5
A
Time (min)
PAA
(mg/
L)
0 100 200 3000
2
4
6
8
pH 3.78
pH 3.97
pH 6.39
pH 8.0pH 7.5
B
Time (min)
PFA
(mg/
L)
0 100 200 3000
2
4
6
8
10
5% raw WW15% raw WW40% raw WW
C
Time (min)PA
A (m
g/L)
0 100 200 3000
1
2
3
4
5% raw WW15% raw WW40% raw WW
D
Time (min)
PFA
(mg/
L)0 50 100 150 200
0
1
2
E
Sea water
Time (min)
PAA
(mg/
L)
0 50 100 150 2000
1
2
F
Sea water
Time (min)
PFA
(mg/
L)
Concentration profiles
PAA PFA
Slow degradation Fast degradation
Matrix dependent Matrix independent
pH effect Matrix effect
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• 10 min contact time for Enterococcus inactivation. Reasonable robust to
matrix at 5% to 15% WW.
• Light CSO was simulated with 5% wastewater PFA is effective on
Enterococcus removal, PAA efficiency increases much more with long contact times (treatment exposure time).
Disinfection efficiency of PAA and PFA
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0 10 20 30 40 50 60 70 80 90 1000.00
0.25
0.50
0.75
1.00
1.25
0
25
50
75
100
125
150
y = - 0.003 x + 1.1R2 = 0.936
PAAHP
mg(KMnO4)/L
PAA
(g/L
)
H2 O
2 (mg/L)
• Different concentration of KMnO4was used for titration
• Stability of PAA was observed for 48 h
• Re-apperance of H2O2 was studied
Solution’s characteristics before and after titration procedure.
PAA (mg/L) H2O2 (mg/L)
Initial concentration 1160 150
Concentration after titration 1010 1.5
Removal 12.9% 99%
PAA and H2O2 measured at the end of titration with differentconcentrations of KMnO4
Optimization of PAA without H2O2
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Schematic diagram of RAS