The Potential Role of Ammonia Electrolysis

in the Treatment of Ammonium-Containing

Wastewaters Gerardine Botte Ohio University
Gregory Bowden AECOM Water
Presentation Overview

g Introduction

g Ammonia Removal
g Biological processes

g Physical-Chemical processes
g Ammonia Electrolysis
 Biological Wastewater Treatment

Influent Primary Settling

Activated Final Effluent
Tank Settling
Sludge
Tank

RAS

Primary Sludge WAS

Gravity
Thickener Anaerobic
Digestion

Ammonium Conc. = 15-35 mg/L

Centrate Dewatering

Biosolids

1% of Plant Influent Flow

15 to 40% of the TN load to the Plant
Ammonium Conc. = 1,000 to 3,000 mg/L
Similar to landfill leachate and liquid stream from
animal manure digestion
Nitrification Denitrification in the Main Plant

1 mol Nitrate
(NO3- ) Organic Carbon
(40%)

te rs
a c iz e
r)
o b id
it r x
( N it e O
O2

tr
(25%)

Ni
1 mol Nitrite 1 mol Nitrite Organic Carbon
(NO2- ) (NO2- ) (60%)
a s rs
o n iz e
)
o m id
os Ox
it r ia
(N o n

O2
m

(75%)
Am

1 mol Ammonia mol Nitrogen Gas

(N2 )
(NH3 / NH4+)

Autotrophic Bacteria Heterotrophic Bacteria

Aerobic Environment Anoxic Environment
 Nitritation Denitritation Process for Centrate Treatment
in a Separate Bioreactor

1 mol Nitrate
(NO3- )
40% Carbon
25% Reduction in Oxygen Demand
40% Reduction in Carbon Demand
30% Reduced Biomass Production
25% O2

1 mol Nitrite 1 mol Nitrite

(NO2- ) (NO2- ) 60% Carbon

75% O2

1 mol Ammonia mol Nitrogen Gas

(NH3/ NH4 +) (N2 )

Autotrophic Heterotrophic
Aerobic Environment Anoxic Environment
 Partial Nitritation ANAMMOX Process for Centrate
Treatment in a Separate Bioreactor
NH4+ + 1.32 NO2- + 0.066 HCO
1 mol 3 + 0.13 H
-
Nitrate +

(NO3- ) 40% Carbon

0.26 NO3- + 1.02N2 + 0.066 CH2O0.5N0.15 + 2.03 H2O

25% O2

1 mol NO - - 1 mol Nitrite

0.57 mol NO
2 2
(NO2- ) 60% Carbon
ANAMMOX
Anaerobic Ammonia Oxidation
Partial
75% Nitrification
O2 Autotrophic Nitrite Reduction
40% O2
CO2 (New Planctomycete,
Strous et al. 1999)
1 mol NH4 + 0.44
0.5 mol
molNN
22
+ 0.11 NO3-
Benefits;
60% Reduction in Oxygen Demand
Almost 100% Reduction in Carbon (e- donor) Demand
> 80% Reduced Biomass Production Bernhard Wett, 2005
Energy and Chemical Requirements for the Nitrification
Denitrification Process
Case Study: Centrate Treatment at the District of Columbia
Water and Sewer Authority Blue Plains Advanced
Wastewater Treatment Plant

310 million gallons per day (average

dry weather flow)
Two-stage biological reactor system
consisting of organic substrate
removal following by nitrification-
denitrification

Plant effluent ammonia and nitrate concentrations 0.5

mg/L, each, by 2014
Centrate ammonia loading (projected 2014 value) of
12,200 kg/day (26,800 lbs/day)
Energy and Chemical Requirements for the Nitrification
Denitrification Process

If centrate is treated in the main plant:

Power demand for aeration (fine bubble diffusers):
~ 36,800 kW-hr/day or ~ 3 kW-hr/kg-ammonia
Annual power cost @ $0.10/kW-hr: $1.34MM/year
Methanol demand for denitrification:
8,600 gal/day
Annual methanol cost @ $1.20/gal: $3.77MM/year

If centrate is treated in a separate bioreactor:

Nitritation denitritation or partial nitritation
ANAMMOX can be used to reduce power and
chemical consumption
~ 6 million gallons of tank volume required
Alternatives to Biological Treatment
Recover and beneficially reuse both ammonia
& phosphate
Only 100 years of Phosphorus resources available

Product recovery technologies

Air Stripping/Acid Absorption
Vacuum flash distillation / acid absorption
Magnesium ammonium phosphate (struvite)
precipitation

Use nutrient-rich products as fertilizers

Utilize NH3 as a fuel source

Ammonia Electrolysis to generate H2
DCWASA Centrate: potential to generate up
to 2,150 kg/day (4,730 lb/day) of H2
Ammonia Electrolysis Technology
 Technology

catalyst catalyst H H
electrolyte H H
hydrogen
exhaust
N N OH- H H
OH-
OH-
e-
OH-
Low energy consumption e-
(1.55 kWh-kg H2) OH- -
e- OH- OH
OH -
e- OH-
N e-
H H N OH- -
H e- OH
H H OH-
H
Invented at Ohio
University by Dr. Botte
ammonia and her research group
Electrochemical from tank (US patent # 7,485,211).
Engineering Research
Center, Ohio University 0.059 V
 Ammonia Electrolysis

Reactions

Anode: Ammonia Oxidation

2NH 3 + 6OH ! " N 2 + 6H 2O + 6e! E0 =-0.77 vs SHE
Cathode: Water Reduction
2H 2O + 2e! " H 2 + 2OH ! E0 = !0.82 V vs SHE
Overall Reaction

2NH 3 ! N 2 + 3H 2 E0 = 0.059 V H2
H2O N2
NH3
Electrochemical KOH
Engineering Research
Center, Ohio University
 Advantages of Technology

Minimization of hydrogen storage problem

Zero Hazards emissions
Fuel Flexibility
Low temperature operation
Compatibility with renewal energy sources (e.g.
solar, wind)
Works a variety concentration values of
ammonia
Fertilizer plants and municipal waste water
treatment stations could potentially produce
their own energy from waste

Electrochemical
Engineering Research
Center, Ohio University
 Results

The feasibility of the technology for the

removal of ammonia has been demonstrated.
Ammonia concentrations can be reduced
under 1 mg/l.
Operating conditions for the use of the AEC
for the removal of ammonia has been
optimized.
Over 99.3% removal of ammonia has been
achieved.

Electrochemical
Engineering Research
Center, Ohio University
Case Study 1: Without Recovery
Hydrogen
Nitrogen

Centrate

water
Electrochemical
Engineering Research
Center, Ohio University
 Case Study 1: Without Recovery
Nitrogen Hydrogen Variable/Parameter Value
NH3 removal (kg/day)= 12,200
Unit Size (kW)= 1,600
Centrate
Energy (kW-h per kg NH3)= 3.2
N2 (kg/day)= 420
water H2 (kg/day)= 90
Cost Electricity ($ per kW- 0.1
h)=
Electricity Cost ($ per year)= 1.42 MM

35% cheaper pH Adjustment ($ per year)= 1.89 MM

Electrochemical
Engineering Research
Total Cost ($ per year)= 3.31 MM
Center, Ohio University
Savings ($ per year)= 1.88 MM
Case Study 2: Combined Heat and Power

Hydrogen
Nitrogen

Centrate

water

water
Electrochemical
Engineering Research
Center, Ohio University
 Case Study 2: Combined Heat and Power
Variable/Parameter Value
NH3 removal (kg/day)= 12,200
Unit Size (kW)= 1,600
Efficiency Power (%)= 40
Energy Consumed (kW-h per kg NH3)= 3.2
Energy Produced (kW-h per kg NH3)= 2.4
Net Energy Consumed (kW-h per kg 0.8
NH3)=
Cost Electricity ($ per kW-h)= 0.1
Electricity Cost ($ per year)= 0.36 MM
56% cheaper
pH Adjustment ($ per year)= 1.89 MM
Electrochemical
Engineering Research
Center, Ohio University Total Cost ($ per year)= 2.25 MM
Savings ($ per year)= 2.86 MM
 Conclusions

Ammonia Electrolysis is more efficient for the

removal of ammonia from waste, direct
conversion to benign nitrogen
Ammonia concentrations can be reduced
under 1 mg/l.
Process can generate heat and power
Operational costs at least 56% lower than
traditional methods
Easy to operate (on/off access)
No Nitrous and nitric oxides produced
 QUESTIONS

Gerri Botte at botte@ohio.edu

Gregory Bowden at
gregory.bowden@aecom.com