WaterTech 2011 Edmonton, AB
April 13‐15, 2011
Patented AmmEL Process for the Treatment of Ammonia in
Low Temperature Mine Wastewater;
Ammonia Converted to Environmentally–Friendly
Nitrogen Gas
Gene S. Shelp, Leonard P. Seed, Daren Yetman and John M. Motto
ENPAR Technologies Inc., Guelph, Ontario, Canada
WaterTech 2011 Edmonton, AB
April 13‐15, 2011
Introduction • Ammonia listed as a toxic substance by
Environment Canada
• One approach employed by the mining industry has been to lower the pH of the wastewater to render it less toxic (due to a shift in the NH3/NH4+ equilibrium)
• While this approach has assisted in meeting acute lethality discharge requirements, the total ammonia‐N released into the environment is not reduced
• Current technology for treating ammonia relies heavily on biological activity (e.g. nitrification) to convert ammonia to nitrate
WaterTech 2011 Edmonton, AB
April 13‐15, 2011
Introduction • Total nitrogen removal requires additional
biological processes to remove nitrate from wastewater prior to discharge
• Biological treatment systems are adversely affected by cold temperatures and changes in effluent composition
• A novel and patented ion‐exchange/electrochemical treatment technology (the AmmEL system) has been developed by Enpar Technologies, Inc. which is not adversely affected by low temperature
WaterTech 2011 Edmonton, AB
April 13‐15, 2011
The AmmEL Process
Electrochemical Reactor
IX
Wastewater (NH4)
Loading
(Phase 1)
Treated Effluent
Regeneration
(Phase 2)
Conversion
(Phase 3)
Regenerant Tank
IX
NH4 N2 NH4
WaterTech 2011 Edmonton, AB
April 13‐15, 2011
AmmEL Reactions
2NH4+ → N2 + 8H+ + 6e‐
2Cl‐ → Cl2 + 2e‐
Cl2 + H2O → HOCl + HCl
2NH4+ + 3HOCl → N2 + 3H2O + 5H+ + 3Cl‐
WaterTech 2011 Edmonton, AB
April 13‐15, 2011
The AmmEL Advantage
• Eliminates nitrogen loading by converting ammonia directly into innocuous N2
• Does not produce nitrate and the GHG nitrous oxide associated with biological treatment
• Not affected by low temperature
• Intermittent operation ‐‐ no start‐up delays
• Can be fully automated ‐‐ low maintenance
WaterTech 2011 Edmonton, AB
April 13‐15, 2011
System Applications
• Mining effluent or process streams containing ammonia derived from the use of ammonia based blasting powder and/or the oxidation of cyanide
• Tertiary treatment for municipal waste water treatment plants (MWTP) and lagoon systems
• Process streams related to steel, fertilizer and
chemical industries
WaterTech 2011 Edmonton, AB
April 13‐15, 2011
Pilot Study The AmmEL‐LC System
WaterTech 2011 Edmonton, AB
April 13‐15, 2011
AmmEL‐LC Pilot Unit Specifications
• 3‐20 cm x 3.05m fluidized bed IX columns, BV = 59.3L
• 1.5 kW electrochemical reactor
• pH adjustment station for the inlet water stream • The main operating conditions for the system were as
follows: – Wastewater flow rate: 18‐20 L/min – Recharge brine flow rate: 8‐10 L/min – Brine NaCl concentration: 3‐4% – Cell current: 150 A
WaterTech 2011 Edmonton, AB
April 13‐15, 2011
• Designed to allow for single column operation as well as series column operation
• Typical treatment mode was to operate the system with two columns in series in a lead‐lag arrangement
• Third column was either involved in a regeneration cycle or was in standby
• Following a regeneration cycle, the regenerated column was rinsed with a small amount of treated water to remove any extraneous brine
• The rinse stream was directed into a 200L holding tank for testing prior to release back into the holding pond
WaterTech 2011 Edmonton, AB
April 13‐15, 2011
IX 1 IX 1 IX 2 IX 2 IX 3 IX 3
Reactor Reactor
WaterTech 2011 Edmonton, AB
April 13‐15, 2011
Single Column Results
Breakthrough Curve at 18 L/min
99 98 97 9692
90 88 86 8479
75
67
5853
2728 28
29 29
27
3132
31 3130
2928
30
0.3 0.5 0.81.2
2.2 2.73.7 4.5
5.16.5
7.69.6
11.6
14.2
0
10
20
30
40
50
60
70
80
90
100
0
5
10
15
20
25
30
35
1 2 3 4 5 6 7 8 9 10 11 12 13 14
Amm
onia
Rem
oved
(%)
Amm
onia
Con
cent
ratio
n (m
g/L)
Run Time (h)
% Removed Inlet Ammonia Outlet Ammonia
99 98 97 9692
90 88 86 8479
75
67
5853
2728 28
29 29
27
3132
31 3130
2928
30
0.3 0.5 0.81.2
2.2 2.73.7 4.5
5.16.5
7.69.6
11.6
14.2
0
10
20
30
40
50
60
70
80
90
100
0
5
10
15
20
25
30
35
1 2 3 4 5 6 7 8 9 10 11 12 13 14
Amm
onia
Rem
oved
(%)
Amm
onia
Con
cent
ratio
n (m
g/L)
Run Time (h)
% Removed Inlet Ammonia Outlet Ammonia
WaterTech 2011 Edmonton, AB
April 13‐15, 2011
Typical Single Column Results
Flow rate (L/min) 18.0 Total run time (h) 14 Total volume treated (L) 15,120 Water temperature (°C) 5.7 Inlet pH 7.76 Outlet pH 7.85 Avg inlet ammonia (mg/L) 29.1 Avg outlet ammonia (mg/L) 5.1
WaterTech 2011 Edmonton, AB
April 13‐15, 2011
Series Column Results
Ammonia Loading, Columns C2 & C1
96 96 96 96 94 92 9087
85 8480
76
6863
58
50
27
24
2725
2423
24
2021
2223
2120
2122 22
1.1 1.0 1.0 1.1 1.51.8 2.4
2.53.3 3.6
4.6 5.16.3
7.89.3
11.1
0
10
20
30
40
50
60
70
80
90
100
0
5
10
15
20
25
30
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
Amm
onia
Rem
oved
(%)
Amm
onia
Con
cent
ratio
n (m
g/L)
Time (h)
% Removed Inlet Ammonia Outlet Ammonia
96 96 96 96 94 92 9087
85 8480
76
6863
58
50
27
24
2725
2423
24
2021
2223
2120
2122 22
1.1 1.0 1.0 1.1 1.51.8 2.4
2.53.3 3.6
4.6 5.16.3
7.89.3
11.1
0
10
20
30
40
50
60
70
80
90
100
0
5
10
15
20
25
30
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
Amm
onia
Rem
oved
(%)
Amm
onia
Con
cent
ratio
n (m
g/L)
Time (h)
% Removed Inlet Ammonia Outlet Ammonia
WaterTech 2011 Edmonton, AB
April 13‐15, 2011
Series Column Results
Ammonia Loading, Columns C1 & C3
99 99 99 98 97 96 9491
88 90 8782
7872
6624
3032 32 32 32
3032
3032
3332
3332 32
0 .1 0 .3 0 .4 0 .6 0 .91 .3 1 .9
2 .8 3 .5 3 .24 .2
5 .77 .3
8 .710.8
0
10
20
30
40
50
60
70
80
90
100
0
5
10
15
20
25
30
35
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ammonia Removed (%)
Ammonia Concentration (mg/L)
T im e (h )
% R em oved In le t Am m onia O utle t Am m onia
99 99 99 98 97 96 9491
88 90 8782
7872
6624
3032 32 32 32
3032
3032
3332
3332 32
0 .1 0 .3 0 .4 0 .6 0 .91 .3 1 .9
2 .8 3 .5 3 .24 .2
5 .77 .3
8 .710.8
0
10
20
30
40
50
60
70
80
90
100
0
5
10
15
20
25
30
35
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Ammonia Removed (%)
Ammonia Concentration (mg/L)
T im e (h )
% R em oved In le t Am m onia O utle t Am m onia
WaterTech 2011 Edmonton, AB
April 13‐15, 2011
Series Column Results
Ammonia Loading, Columns C3 & C2
96 97 96 95 9491 90
8582
7982
7673
32 32
35 35 3537
3534
37 37 3735
37
1.1 1.1 1.4 1.72.2
3.2 3.75.0
6.57.7 6.8
8.410.0
0
10
20
30
40
50
60
70
80
90
100
0
5
10
15
20
25
30
35
40
1 2 3 4 5 6 7 8 9 10 11 12 13
Amm
onia
Rem
oved
(%)
Amm
onia
Con
cent
ratio
n (m
g/L)
Time (h)
% Removed Inlet Ammonia Outlet Ammonia
96 97 96 95 9491 90
8582
7982
7673
32 32
35 35 3537
3534
37 37 3735
37
1.1 1.1 1.4 1.72.2
3.2 3.75.0
6.57.7 6.8
8.410.0
0
10
20
30
40
50
60
70
80
90
100
0
5
10
15
20
25
30
35
40
1 2 3 4 5 6 7 8 9 10 11 12 13
Amm
onia
Rem
oved
(%)
Amm
onia
Con
cent
ratio
n (m
g/L)
Time (h)
% Removed Inlet Ammonia Outlet Ammonia
WaterTech 2011 Edmonton, AB
April 13‐15, 2011
Series Column Results C2 & C1 C1 & C3 C3 & C2
Flow Rate (L/min) 18.2 18.1 18.3
Total Run Time (h) 16 15 13
Water Temperature (°C) 5.9 6.0 5.9
Inlet pH 7.79 7.84 7.82
Outlet pH 7.86 7.86 7.91
Average Inlet NH3 (mg/L) 23.0 31.0 35.3
Average Outlet NH3 (mg/L) 4.0 3.4 4.5
WaterTech 2011 Edmonton, AB
April 13‐15, 2011
Pilot Study Conclusions
• The AmmEL‐LC system can readily remove ammonia from mine waste water to below the discharge requirement of 10 mg/L
• No pretreatment of the stream was required
• The efficiency of the AmmEL‐LC was not affected by low water temperatures (>6°C)
• Operating costs were relatively low ($0.10/m3 of water treated)
WaterTech 2011 Edmonton, AB
April 13‐15, 2011
Full‐Scale Installation • Full‐scale installation commissioned March 10, 2010 in Timmins,
Ontario
• Three zeolite filled 30 cm (i.d.) x 6 m ion exchange columns
• Electrochemical reactor → 18 m2 of anode surface area; 16V, 2000A DC rectifier
• Chlorine gas scrubber to comply with Ontario MoE chlorine emission levels
• The system is designed to treat 400 m3 of mine waste per day containing an average of 30 mg of ammonia‐nitrogen/L
• Emission levels are 10 mg NH3‐N/L year round including during the winter months when mine water can reach temperatures slightly above freezing
WaterTech 2011 Edmonton, AB
April 13‐15, 2011
Ion Exchange Columns
WaterTech 2011 Edmonton, AB
April 13‐15, 2011
Electrochemical Reactor
WaterTech 2011 Edmonton, AB
April 13‐15, 2011
DC Rectifier Chlorine Gas Scrubber
WaterTech 2011 Edmonton, AB
April 13‐15, 2011