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Treatment Technologies for Ammonia in Liquid Manure: Nitrification/denitrification and Anammox Based
Deammonification
From Waste to Worth ConferenceDenver, Colorado, April 4, 2013
Matias Vanotti, Patrick Hunt, Ariel Szogi - USDA-ARS, Florence, SC, USAJose Martinez - IRSTEA, Rennes Centre, France
Airton Kunz - EMBRAPA Swine and Poultry, Concordia, Brazil Takao Fujii - Sojo University, Kumamoto, Japan Kenji Furukawa - Kumamoto University, Japan
North Carolina producesapproximately 750 million chickens, 40 million turkeys, 3.5 billion table eggs, and 19 million hogs per year.
Animal Manure – Surplus N and Ammonia Emissions in many regions of USA (and the world)
Walker et al., Atmos. Environ. 38:1235-1246
Ammonia Emissions
Treatment Technologies for Nitrogen Management in Liquid Manure
• Biological nitrogen removal (conversion of ammonia into N2)
1. Nitrification-Denitrification
• 2nd Generation system (lagoon replacement)• Full-scale treatment of 5,200 finishing pigs in North Carolina• Solid-liquid separation with polymer, then nitrification/denitrification
to remove the ammonia, and P recovery.
Bioresource Technology 100 (2009): 5406-5416
Solids
N
P
Biological nitrogen removal: Nitrification-Denitrification
NITRIFICATIONDENITRIFICATION
NH4+
NO2-
NO3-
N2
NOx
Organic-C
Organic-C
Organic-C
O2
O2
TREATEDEFFLUENT
PHOSPHORUS SEPARATION UNIT
BBLOWER
POLYMERFLOCCULANT
P
DENITRIFICATION
CLARIFICATION
NITRIFICATION
RETURNBIOLOGICAL SLUDGE
CONFINEDLIVESTOCK
SOLID-LIQUID SEPARATION UNIT
EXCESSBIOLOGICAL SLUDGE
RECYCLE
PHOSPHATE PRECIPITATE SLUDGE
P
M
HOMOGENIZATIONTANK LIME
DEWATERED SOLIDS,BIOLOGICAL SLUDGE & PHOSPHORUS SLUDGE
P
M
PREANOXIC BIOLOGICAL NITROGEN REMOVAL UNIT
Modified Ludzack-Ettinger (MLE)
P
SEPARATEDLIQUIDTANK
Denitrification
Nitrification
Denitrificationuses soluble carbonfrom manure
• 3rd Generation system (2012)• Full-scale treatment of 1,200-sow farrow-to-finish (producing 30,500
hogs/year) in North Carolina• Solid-liquid separation using settling and polymer, then
nitrification/denitrification to remove the ammonia
Terra Blue Inc., Clinton, NC
0
5
10
15
20
25
30
35
40
Feb Ma
Ap
rM
aJu
nJu
lA
ug
Sep
Oct
Nov
Dec
Jan
Feb
Wat
er T
emp
erat
ure
(o C
)Daily MAX
Daily MIN
Average
To reduce cost, the 2nd generation system incorporated new nitrifying bacteria sludge acclimated to low temperatures
0 5 10 15 20 25 300
500
1000
1500
2000
0
10
20
30
40
50HPNS; this invention
Marine; Furukawa et al.(1993)
On-site domestic, Chiemchaisriand Yamamoto (1993)
Municipal; Chudoba andPannier, (1994)
Enriched nitrifying for high-ammoniadigester; Shammas, (1986)
Livestock; Bae et al. (2001)
Municipal; Wild et al. (1971)
Nit
rifi
cati
on
Rat
eg
N/m
3 -rea
cto
r/d
Cold weather municipal; Anderssonand Rosen (1990)
y = 1.25 + 1.93xr2 = 0.998
Temperature, oC
mg
N /g
ML
VS
S /h
High Performance Nitrifying Sludge(HPNS): • Isolated from manure • High activity at low temperatures• Used for rapid start-up of plants
HPNS was deposited in Agriculture Research Culture Collection (Peoria, IL ) : NRRL B-50289
To start-up the plant, the nitrification tank (230 m3) was seeded with 1 liter of HPNS. In 40 days, it reached the optimum removal rate of 100 kg ammonia-N/day
Operation Simplicity Once a week, the operator measured the nitrifying biomass
and set the operation parameters for the week.
MLE Biological N Removal performanceInfluent
Conc. (After Solids Separation) (ppm)
EffluentConc. (ppm)
Efficiency%
TKN 1,428 ± 597 101 ± 145 92.9
NH4-N 1,182 ± 483 59 ± 124 95.0
COD 8,906 ± 4,933 1,016 ± 529 88.6
NH4-N removal efficiency: Warm Weather: 94.0% Cold Weather: 96.0%
Ammonia emissions reduction with this system compared to the anaerobic lagoon technology
Aneja et al., 2008. Atmospheric Environment, 42:3291-3300
Emissions reduction
Warm Season 94.7%
Cool Season 99.0%
TSS
N
P
Lagoon System
New System
The use of clean water to flush barns improved the air quality in the barns, pig health and economic returns
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May
Jun
Jul
Au
g
Sep
NH
3 C
on
cen
trat
ion
in
Bar
n E
xhau
st A
ir (
pp
m)
Lagoon SystemNew SystemAvg Lagoon Sytem Avg New System
NH3 in the barns
Benefits of cleaner environment on animal production
** Data compares five pig production cycles obtained with lagoon technology and five pig cycles obtained with the new technology (5200 pigs/cycle)
Treatment Technologies for Biological Nitrogen Removal in Liquid Manure
1. Nitrification-Denitrification
2. Partial Nitritation-Anammox
(Deammonification)Anammox
Deammonification ProcessTraditional Nitrogen Removal Processes
Uses external carbon addition for DN
( nitrification / denitrification )
NH4+
Anammox
NO2-
N2↑
Biological N removal processesBiological N removal processes
nitrification
denitrification nitrification
denitrification
MeOH
Q
4 Q
( partial nitritation / anammox)
Uses endogenous carbon for DN No carbon needed
Anammox: new shortcut for the biological removal of nitrogen
NITRIFICATIONDENITRIFICATION
NH4+
NO2-
NO3-
N2
NOx
Organic-C
ANAMMOX
Organic-C
Organic-C
O2
O2
Anammox bacteria for low-cost treatment of livestock wastewater
• Isolated from swine manure
in North Carolina
Brocadia caroliniensis
Anammox = Anaerobic ammonium oxidation
• ~ Half the aeration cost than
traditional method
Anammox biomass was grown in a parent reactor in Florence, South Carolina.
Brocadia caroliniensis was deposited in USDA Agriculture Research Culture Collection (Peoria, IL): NRRL B-50286
Partial nitritation + Anaerobic Ammonia Oxidation (ANAMMOX)
Partial Nitritation ANAMMOX
aeration
NH4+ + NO2
-
50 %
NH4+ in
-
N2
Treated effluent
Closed Anaerobic
Environment
• Two sequencing batch tractors (SBR)
• Treatment of swine wastewater (1400 mg N/L)
Anammox coupled with Partial Nitritation
Two-stage process:
Anammox SBR
Magrí, A.; Vanotti, M.B.; Szögi, A.A.; Cantrell, K.B. Partial nitritation of swine wastewater in view of its coupling with the anammox process. Journal of Environmental Quality (2012 doi:10.2135/jeq2012.0092)
Partial nitritation SBR
2010: anammox bacteria handled under anaerobic conditions
Completely anaerobic Chambers??
2011: Single tank deammonification process (nitritation-anammox)
Biofilm plastic carriers
Mixing of specialized bacterial cultures to start the one-stage process
Continuous flow, aerated reactor
Single-tank deammonification process start-up: 1. Mix of nitrification sludge with anammox,
2. start aeration and wastewater flow
Nitrification sludge HPNS
Anammox sludge B. Caroliniensisin the single-tank
Continuous flow, aerated fluidized reactor with biofilm carriers 30% v/v
Single-tank deammonification reactor setup (5-L reactor)
Another Single-tank deammonification reactor setup ( 1-L)
Air flowmeter and valve
Return Sludge
Single tank
Clarifier
DO monitor
pHmonitor
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 250
100
200
300
400
500
600
700
NH4-NinNH4-NoutNO2-NinNO2-NoutNO3-NinNO3-Nout
days
N C
once
ntra
tion
(mg/
L)
I II III
I = synthetic effluent (~360 mg NH4-/L), II = swine effluent ~340 mg NH4/L), III = swine effluent ~600 mg NH4-N/L).
Nitrogen Removal in Single Reactor
Single tank deammonification of swine wastewater
Stoichiometry obtained:1 NH4 + 0.87 O2 0.45 N2 + 0.11 NO3 + 1.41 H2O + 1.18 H+
Deammonification of swine wastewater
Parameter SW
Ammonia removal rate1034 mg N/L-
reactor/day
Ammonia removal efficiency 100%Total N removal efficiency 89.1%
Single tank deammonification process
Theory (partial nitritation + anammox):
NH4+ + 0.85 O2 → 0.44 N2 + 0.11 NO3
- + 1.41 H2O + 1.19 H+
Stoichiometric rates
NH4+ + 0.87 O2 → 0.45 N2 + 0.11 NO3
- + 1.41 H2O + 1.18 H+
Theoretical
Results of this study using digested swine manure
Deammonification reaction reduced 57% of the oxygen requirements and 100% of the carbon needs. (Compared to nitrification-denitrification, from 2.0 to 0.85 mol O2 / mol NH4)
NH4+ + 0.85 O2 → 0.44 N2 + 0.11 NOx
- + 1.41 H2O + 1.19 H+
Reactor 1 (5-L)
Reactor 2 (1-L)
•
•
New Deammonification Process for Manure Digester Effluents
Deammonification Treatment (compared to nitrification-denitrification)
• It is quick and efficient (high removal rate = 1 kg NH4-N/m3/day)
• Organic carbon is not needed (best option for anaerobic digestion effluents)• Aeration needs reduced by 57% (lower operational costs)
Conclusions
• Nitrification-denitrification of swine wastewater was optimized after solids-liquid separation using a pre-anoxic design and a high performance nitrification sludge (HPNS)
• Single-tank deammonification with anammox was feasible. It may be a key technology for efficient ammonia treatment in systems that consume carbon for energy production (AD)
http://www.ars.usda.gov/saa/cpswprc
Odor reduction in the liquid (99.9%)
0
500
1000
1500
2000
2500
3000
pp
b
Sample
Skatole
Homogenization Tank
Separated Water
Post Nitrogen Treatment
Post Phosphorus Treatment
Biological N treatment
Loughrin et al., JEQ 38:1739-1748
GHG Emissions reduced 97% with the replacement of the anaerobic lagoon with
the aerobic system
4430
542
18135
0500
100015002000250030003500400045005000
Ton
CO
2-eq
/yea
r
Baseline (lagoon) EST Project Activity
CH4 N2O
Vanotti et al., Waste Management 28:759-766
Greenhouse Gas (GHG) emission reduction using aerobic treatment (nitrification/denitrification and composting)
Vanotti et al., Waste Management 28:759-766
Baseline (lagoon)
Project Activity
De
cJ
an
Fe
bM
ar
Ap
rM
ay
Ju
nJ
ul
Au
gS
ep
Oc
tN
ov
De
cJ
an
Fe
b
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300
600
900
1200
0
20
40
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100
NitrogenPig Weight
To
tal P
ig W
eig
ht
(lb
* 10
00)
Flu
sh N
Lo
ad (kg
/d)
New systems need to be robust and withstand the large load changes during production (data show three production cycles)
Single-tank operation• Continuous flow• HRT 0.4-0.8 days• Return sludge 2Q• Ambient temperature (22 oC)• Aeration rate 60 mL/min (DO 0.5-
0.9 mg/L)• Plastic media 40% v/v• Reactor MLVSS ~2600 mg/L• Influent ammonia 365 to 600 mg
N/L• Carbonate alkalinity 1700 to 3000
mg/L
• Start-up with synthetic wastewater (10 days), then switch to swine wastewater (Effluent of anaerobic digestion)
Brocadia sp. (Candidatus AM285341)
Uncultured planctomycete Pla 5GA-8 (GQ356125)
Uncultured bacterium Asahi BRW (AB456583)
Brocadia caroliniensisCandidatus Brocadia fulgida (Candidatus EU478693)
Uncultured planctomycete HAuD-MB/2-35 (AB176696)
Brocadia anammoxidans (Candidatus AF375994)
Uncultured anoxic sludge bacterium KU1 (AB054006)
Anammoxoglobus propionicus (Candidatus DQ317601)
Jettenia asiatica (Candidatus DQ301513)
Uncultured planctomycete KSU-1 (AB057453)
Kuenenia stuttgartiensis (Candidatus AF375995)
Scalindua sorokinii (Candidatus AY257181)
100
100
100
8999
87
96
97
100
81
0.005
Similarity to Candidatus “B. caroliniensis” (JF487828)
Candidatus “Brocadia fulgida” 96%
Candidatus “Brocadia anammoxidans” 94%
Candidatus “Jettenia asiatica” 92%
Candidatus “Kuenia stuttgartiensis” 90%
Candidatus “Anammoxoglobus propionicus” 90%
Candidatus “Scalindua sorokinii” 86%
Single-tank reactor N removal at various N concentrations and loads
0102030405060708090100
0200400600800
100012001400160018002000
0 100 200 300 400 500
Rem
oval
effi
cien
cy (%
)
NH
4lo
ad o
r rem
oval
rate
(mg
N/L
-re
acto
r/d)
Influent NH4+ concentration (mg N/L)
NH4 load (mg N /L/d) NH4 removal (mg N/L/d) % Efficiency