iron and manganese removal processeshydratechnm.org/...removal_by_iron_removal.pdf · iron-based...
TRANSCRIPT
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Iron and Manganese Removal Processes
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Presentation Agenda• Arsenic Background: chemistry
and treatment options• Treatment selection
considerations • Treatment options
– Iron removal• Case studies• Conclusions
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Arsenic Chemistry• Arsenic has two primary valence states:
• Arsenic Occurrence by valence state– Surface waters - predominately As (V)– Ground waters – usually found as As (III),
however, concentrations of As (V) or a combination of As (III) and As (V) can be found
As (III) As +3 Arsenite
As (V) As +5 Arsenate
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Iron-based Arsenic Removal Processes
• Adsorptive properties of iron mineral toward arsenic are well known
• That knowledge is the basis for many arsenic treatment processes– Coagulation with iron coagulant– Iron-based adsorption media– Iron removal processes
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Arsenic Removal by IronAs(III) vs As(V)
As(III) is removed during iron removal and other iron-based processes, but just not as well as As(V)
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As (III) OxidationAs (III) OxidationEffective!
Free ChlorinePotassium PermanganateOzoneSolid Oxidizing Media (MnO2 solids)
IneffectiveChloramineChlorine Dioxide UV Radiation + SulfideOxygen
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Arsenic Treatment Issues• Treatment complexity/cost• Pre- and Post-treatment needs• Residuals –Disposal Issues
– Ion exchange & RO produce liquid wastes– Adsorbent media produce wasted solids– Coagulation/filtration and iron removal
processes produce solids• Filter backwash waste• Sediment in contactor (pass TCLP test)
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Arsenic Treatment Simplified Process Selection Guide
Iron - mg/L0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Ars
enic
- ug
/L
0
5
10
15
20
25
30
35
40
45
50
As MCL
Fe -
SMC
L
AIron Removal Process
(Optimized for Maximium As Removal)
BModified Iron Removal Process
C
Media AdsorptionIron Coag/FiltIon ExchangeIron Removal(M)RO / NF
20 - 1 Fe/As ra
tio
or above
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Removal of 1 mg/L of iron
achieves
removal of 50 ug/L arsenic(0ptimized conditions and As[V])
Arsenic Removal by Iron Removal Processes
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Arsenic Removal During Iron Removal Considerations
Iron in water (>20/1 Fe/As ratio)? • Form of arsenic, III or V?
Oxidation:– Type of oxidant: oxygen, chlorine, KMnO4…?– Point of application?
• Contact time?– Iron and As oxidation– Arsenic adsorption
• How can arsenic removal be predicted?• Ways to improve arsenic removal during iron
removal?
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Iron (and Mn) RemovalBasics
Filtrationparticle removal
Oxidation Contact Basin
AerationCl2,
KMnO4, other
Oxidation, Particle Development
15 – 30 minutes
Fe(OH)3 (S)MnO2 (S)
Fe IIMn II
Fe IIIMn IV
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Iron and Arsenic (and Mn) Removal
AerationCl2,
KMnO4,other
Fe IIAs III
Oxidation
Fe IIIAs V
Note: Aeration will not oxidize As III to As V
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Iron and Arsenic (and Mn) Removal
Contact Basin
Oxidation, particle
development
Fe(III)/As particles+
arsenic
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Iron and Arsenic (and Mn) Removal
FiltrationFe III/ As Particle Removal
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Oxidant Selection
• Depends on As, Fe (and Mn)• Aeration
– Will not oxidize Mn II and As III (-) – May need contact basin (-)– Iron particles have less surface area (-)– Longer filter run lengths (+)
• Strong oxidants (chlorine, permanganate, etc)– Address Mn and As oxidation (+)– More particle surface area (+)– Probably no contactor needed (+)– Difficult to feed (-)– Shorter filter run lengths (-)
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Assessment ToolJar Test
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OxidationOxidation-- Point of ApplicationPoint of ApplicationCase Study Case Study -- MichiganMichigan
Parameter ConcentrationArsenic – ug/L 19 - 24
As III 95 %As V 5 %
Calcium – mg/L 74 - 84Magnesium – mg/L 30 - 33Iron – mg/L 0.5 - 0.6Manganese –mg/L 0.02Sulfate – mg/L 50 - 60Silica – mg/L 12 - 13pH - units 7.1 - 7.3
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OxidationOxidation-- Point of ApplicationPoint of ApplicationCase Study Case Study -- MichiganMichigan
20 min CT
WellsWells
Aeration towerAeration towerPressure filtersPressure filters
Cl2
50 % removal
As = 19-24 ug/LFe = 0.5 -0.6 mg/L
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Oxidation- Point of ApplicationCase Study - Michigan
20 min CT
Wells
Aeration towerPressure filtersCl2
50 % removal
As = 19-24 ug/LFe = 0.5 -0.6 mg/L
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Oxidation- Point of ApplicationCase Study - Michigan
20 min CT
Wells
Aeration towerPressure filters
Cl2
75 % removalAs = 19-24 ug/LFe = 0.5 -0.6 mg/L
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Oxidant Selection• Depends on As, Fe (and Mn)• Aeration
– Will not oxidize Mn II and As III (-) – May need contact basin (-)– Iron particles have less surface area (-)– Longer filter run lengths (+)
• Strong oxidants (chlorine, permanganate, etc)– Address Mn and As oxidation (+)– More particle surface area (+)– Probably no contactor needed (+)– Difficult to feed (-)– Shorter filter run lengths (-)
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The Effect of Oxidant on Visual Properties of Iron Particles
pH
7.0 7.5 8.0 8.5 9.0 9.5 10.0
Colo
r, P
tCo
unit
s
0
50
100
150
200
250
300PO2= 0.122 atm
PO2=saturated
0.122 atm PO2+5 mg Cl2/L
ClO2 (2 mg/L)
Fe[III] Linear regression
The effect of oxidant type on colorFetot= 5 mg/L, DIC= 5 mg C/L, 0.122 atm O2, 23oC.
The effect of oxidant type on the color of iron particles collected from filter backwash.
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Process ModificationsIncreasing As RemovalIncreasing As Removal
Utility with iron removal in place or willbe in place but can not meet MCL:
•Change point of oxidant addition•Increase iron concentration•Adjust pH•Replace media w/ As adsorption media
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Climax, MN Iron Removal System
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Climax, MN Iron Removal Process
Date - 2004/2005
Aug Sep Oct Nov Dec Jan Feb Mar
Ars
enic
con
cent
ratio
n - u
g/L
0
5
10
15
20
25
30
35
40
45
50
55
Iron
conc
entra
tion
- mg/
L
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
Raw Water ArsenicTreated Water Arsenic Raw Water Iron
2004 2005
MCL
0.8 mg/L Fe added
Climax, MN Iron Removal System
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The Effect of Initial Arsenic(V) Concentration on the Capacity of Iron to
Remove Arsenic(Fe(II)init=1 mg/L, DIC=10 mg C/L, pH=8, 24oC)
Initial As, μg/L
0 50 100 150 200 250
μg A
s/m
g Fe
0
20
40
60
80
100
120
140
160
180
200
1 mg Fe/L reduces 150 ug As/L by 115 ug As/L to 35 ug As/L
1 mg Fe/L reduces 35 ug As/L by 23 ug As/L to 12 ug As/L
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The Effect of pH, Iron and Free Chlorine on Arsenic Removal
1 mg Fe/L, 100 mg As(V)/L, 5 mg C/L DIC, PO2= 0.122
atm, 24 OC
pH
6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5
Ars
enic r
emov
ed, %
0
20
40
60
80
100
No chlorine1 mg Cl2/L
RegressionFe(III), no chlorine
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Effect of Water Quality1 mg Fe/L, 100 ug As(V)/L, 5 mg C/L DIC, pH=8, 24 OC
Phosphate, mg/L
0.0 0.5 1.0 1.5 2.0 2.5 3.0
% A
rsen
ic R
emov
al
0
20
40
60
80
1001 mg/L Chlorine0 mg/L Chlorine
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Lidgerwood, NDTwo Wells:
•100 feet deep
•As Raw 135 – 150 ug/L (mostly As III)
•As Finished 35 ug/L
•Fe Raw 1.3 – 1.6 mg/L (9/11:1)
•Superfund site – arsenic for grasshopper control
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Lidgerwood, NDExisting Treatment:
•Pre-chlorination
•Aeration
•Oxidation – KMnO4
•Filtration Aid – polymer
•Filtration – Antrasand (2 gpm/ft2)
•Post chlorination and fluoridation
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Lidgerwood, ND
Mixing Tank
Detention Tank
Aeration Tower
Well 1
Well 2
Filters
Clearwell
Backwash tank Sludge Tank
KMn04
Filter AidChlorine
Chlorine
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Lidgerwood, ND
EPA Demonstration Project:
•Turbidmeters
•Additional polymer feed
•FeCl3 Coagulation (~1 mg/L)
•As Finished 7-8 ug/L
•Cost - $55,740
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Lidgerwood, ND
Mixing Tank
Detention Tank
Aeration Tower
Well 1
Well 2
Filters
Clearwell
Backwash tank Sludge Tank
KMn04
Filter Aid (2)Ferric chloride
Chlorine
Chlorine
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Sabin, MN
Two Wells:
•As Raw 45 ug/L
•As Finished 40 ug/L (20-25 ug/L
Plant is falling apart!!
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Sabin, MNExisting Treatment:
•Chlorination
•Aeration
•Sand filtration
•Fluoridation
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Sabin, MNMajor Capital Improvement:
•Population 400
•$1,200,000 Total cost
•$800,000 low interest loan
•$160,000 grant
•EPA Demonstration Project
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Conclusions• Iron removal = arsenic removal• Arsenic speciation is important• Oxidant type is important• Point of oxidant application is
important– Arsenic removal impacted – Plant operation impacted
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Thank-you
QUESTIONS TO DARREN LYTLE
EPA/ORD
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