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Precipitation Processes
Presentation Prepared by:
Joe Chwirka - Camp Dresser & McKee
(chwirkajd@cdm.com)
Bruce Thomson - University of New Mexico
(bthomson@unm.edu)
Presented by: YuJung Chang HDR Engineering, Inc.
Introduction
Arsenic removal by coagulation & filtration is effective for
many applications
Presentation will discuss:
Chemistry of the process
Variables affecting process performance (especially pH
& coagulant dose)
Process variations
Coagulation & granular media filtration
Coagulation & membrane filtration
Design considerations
1.2
1.0
H3AsO4
Fraction
0.8
2-
HAsO4
H2AsO4
3-
AsO4
0.6
0.4
0.2
0.0
0
10
12
14
pH
Coagulation-Filtration - Chwirka & Thomson
1.2
AsO 3
1.0
3-
H3AsO3
Fraction
0.8
H2 AsO3
0.6
HAsO3
2-
0.4
0.2
0.0
0
10
12
14
pH
Coagulation-Filtration - Chwirka & Thomson
Redox Chemistry of As
20
1 .0
15
H 3A sO
H 2A sO
10
.5
5
H A sO
pe
H 3A sO
2-
E h (v o lts )
A sO
34
A s 2 S 3 (s )
-5
-.5
H 2A sO
-1 0
H A sO
23
A sO
33
-1 5
0
Coagulation-Filtrationp H-
10
12
14
0
-1
log Concentration
-2
Arsenolite (As2O3)
-3
Claudetite (As2O3)
-4
Orpiment (As2S3)
-5
-6
-7
-8
-9
-10
0
10
12
14
pH
-2
log Concentration
-4
Fe3(AsO4)2
-6
Mn3(AsO4)2
AlAsO4
Ca3(AsO4)2
CrAsO4
Cu3(AsO4)2
Fe3(AsO4)2
FeAsO4
Mn3(AsO4)2
LaAsO4
-8
-10
-12
-14
0
FeAsO4
Cu3(AsO4)2
AlAsO4
CrAsO4
LaAsO4
6
10
12
14
pH
Important Points
As has two oxidation states - As(III) & As(V)
As(III)
Non-ionic (H3AsO3) at neutral pH
High solubility
More toxic to many organisms
As(V)
Ionic (H2AsO4-/HAsO42-) at neutral pH
Some phases are less soluble
More reactive in solution:
Membranes
IX
Adsorption
Coagulation-Filtration - Chwirka & Thomson
Coprecipitation
Coprecipitation involves removal of two or more
constituents by a precipitation reaction. Coprecipitation of
As with Fe(OH)3 is an effective treatment process:
FeCl3 + 3H2O = Fe(OH)3(s) + 3H+ + 3ClPoints:
Produces HCl which will lower pH
Typical Fe dose ~10-4 M, whereas As conc. ~10-7 M, hence
As is minor component within precipitate
As likely removed by adsorption onto Fe(OH)3 surface with
subsequent enmeshment as floc particle grows
Al(OH)3 also effective
Coagulation-Filtration - Chwirka & Thomson
Solubility of Fe(OH)3
0
-2
Solubility of Fe(OH)3
log Conc.
-4
-6
Fe(OH)4-
-8
Fe3+
-10
-12
Fe(OH)2+
FeOH2+
-14
0
10
12
14
pH
10
1.2
+
FeOH2
1.0
FeO
o
FeOH
0.8
Fraction
0.6
0.4
0.2
0.0
0
10
12
14
pH
11
Fe
O H
O
Fe
As
O
O H
O H
k1
G o e t h it e S u rf a c e
k -1
O H
Fe
As
O
O
k2
Fe
Fe
k -2
As
Fe
O H
O H
+ H 2O
M o n o d e n ta te
S u r f a c e C o m p le x
+ O H-
B id e n ta t e
S u r f a c e C o m p le x
Coagulation-Filtration - Chwirka & Thomson
12
13
K[Fe]
As Fraction Removed
1 K[Fe]
[Fe] = Iron Precip. Formed (mM)
14
100
90
As Removal (% )
80
70
60
50
40
30
[Fe]
20
[Fe]+[Al]
10
0
0
0.02
0.04
0.06
0.08
0.1
15
16
50
10
9.5
40
30
8
7.5
20
Filtrate pH
8.5
Residual Arsenic
Filtrate pH
6.5
10
6
5.5
5
0
10
15
20
17
100.0
10.00
90.0
9.00
80.0
8.00
70.0
7.00
60.0
6.00
50.0
5.00
40.0
4.00
30.0
3.00
20.0
2.00
10.0
1.00
0.0
0.00
0
20
40
60
80
100
As
pH
Arsenic, ug/L
pH
120
FeCl3, mg/L
18
25
8.5
Arsenic
pH
8
7.5
15
7
10
pH
20
6.5
6
5.5
0
0
10
15
20
25
30
35
40
19
80
70
60
pH 6.0
pH 6.8
50
40
30
20
10
0
0
10
12
14
16
20
25
pH 8.5
20
15
pH 6.5
pH 7.5
pH 8.5
pH 7.5
10
5
pH 6.5
0
0
10
20
30
40
50
60
Silicate, mg/L
1.0
H3SiO4-
Fraction
0.8
0.6
H2SiO420.4
0.2
0.0
0
10
12
14
pH
22
100
80
60
Surface Waters
40
Ground Waters
20
0
0
10
20
30
40
50
60
70
23
Polymeric Silica
100
80
50 mg/L
60
17 mg/L
40
5 mg/L
20
0
5.0
5.5
6.0
6.5
7.0 7.5
pH
8.0
8.5
9.0
9.5
24
Coagulation/ Filtration
Use pressure filters
Direct Filtration frequently used for iron and manganese
removal.
Limited to low ferric dose applications.
High coagulant dose will result in frequent backwash
requirements
Increased residuals production & handling costs
Increased production of wastewater
25
Pressure Filter
CO2
CO2
Treated
Water
Raw Water
Aeration
Rapid Mix
Solids to
Dewatering
Solids to Landfill
26
27
28
10
11
12
13
14
15
29
Wastewater, %
12.0%
10.0%
8.0%
6.0%
4.0%
2.0%
0.0%
0
10
12
14
16
30
31
Particle size
Particle breakthrough
backwash requirements
filter ripening
Backup Filters
32
Coagulation/ Microfiltration
Pilot tested in Albuquerque, 1998
Pilot tested in NAS Fallon, NV, 2001
Pilot tested in El Paso, TX, 2001/2002
Fallon Paiute Shoshone Tribe: 0.5 mgd
City of Albuquerque: 2.3 mgd
33
34
What is C/MF?
FeCl3
Microfiltration
Unit
CO2
CO2
Treated
Water
Raw Water
Aeration
Rapid Mix
Solids to
Dewatering
Solids to Landfill
35
0.01
0. 1
1.0
10
100
1000
Sand
Dissolved Organics
Bacteria
Viruses
Salts
Colloids
Cysts
Media Filtration
Microfiltration
Ultrafiltration
Nanofiltration
Reverse Osmosis
36
MF Process Operates in
Direct Filtration Mode
Filtrate
Feed
Feedwater
(with
contaminants)
Filtrate
37
Air
Air
(100
psig)
Feedwater
3
38
Coagulation/ Microfiltration
Pilot tested in Albuquerque, 1998
Pilot tested in NAS Fallon, NV, 2001
Pilot tested in El Paso, TX, 2001/2002
Fallon Paiute Shoshone Tribe: 0.5 mgd
City of Albuquerque: 2.3 mgd
39
What is C/MF?
FeCl3
Microfiltration
Unit
CO2
CO2
Treated
Water
Raw Water
Aeration
Rapid Mix
Solids to
Dewatering
Solids to Landfill
41
0.01
0. 1
1.0
10
100
1000
Sand
Dissolved Organics
Bacteria
Viruses
Salts
Colloids
Cysts
Media Filtration
Microfiltration
Ultrafiltration
Nanofiltration
Reverse Osmosis
42
MF Process Operates in
Direct Filtration Mode
Filtrate
Feed
Feedwater
(with
contaminants)
Filtrate
43
Air
Air
(100
psig)
Feedwater
3
44
Pall Microfilter
45
Memcor Performance
NAS Fallon, 15 mg/L FeCl3
Transmembrane Pressure
25
32 GFD
20
15
psi
27 GFD
27 GFD
38 GFD
(No FeCl3)
10
0
0
20
40
60
80
Elapsed Time [days]
100
120
46
TM P [psi]
7
6
5
Start-Up
Post Clean
3
2
1
0
0
10
20
30
40
50
47
Pall Performance
NAS Fallon, FeCl3 45 mg/L
20
54 GFD
TMP, psi
15
54 GFD
42GFD
10
5
0
0
10
20
30
40
50
60
70
80
90
48
49
50
El Paso
Pall Performance
24
20
Well Shutdown for
Repair
TMP (psi)
16
12
10 mg/L FeCl3, pH 6.8,
74.9 gfd, >100 Day CIP
0
0
500
1000
1500
2000
2500
Operational Hours
3000
3500
4000
51
Cl2
Treated
Water to
Distribution
System
Rapid Mix
M
CO2
Well 1
Microfilter
Well 2
Static Mixer
Lowry
Aeration
System
Ferric
Chloride
Finished
Water
Sump
Solids
Recycle
Recycle
Sump
Lamella
Plate
Thickener
Liquids to
Sewer
Dewatered
Solids to
Landfill
Filter
Bottom
Dumpster
52
53
54
55
C/MF Summary
Emerging Technology for Arsenic Treatment
Can be designed for high flux rates with Low TOC
groundwater
Optimize solids loading by pH pre-treatment
Cost competitive with other technologies
56
57
58
Pressure Filters
$1,252,998
C/MF
$987,898
$71,436
$0.77
$82,392
$0.89
$2,087,000
$125,220
1.38
$1,948,000
$116,880
1.29
59
60
Residuals Handling
Mechanical dewatering will be complicated: Ferric sludge is
difficult to dewater
Need body additives, Diatomaceous Earth
Filter Bottom Dumpsters and polymer for small applications.
Solids drying ponds:
Ponds need to be lined.
Anaerobic conditions may release the As.
Provide access for sludge removal equipment.
61
62
63
64