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

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To reduce cost, the 2nd generation system incorporated new nitrifying bacteria sludge acclimated to low temperatures

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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)

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rifi

cati

on

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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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in

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n E

xhau

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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

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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%)

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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

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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

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ig W

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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)

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8999

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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

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NH

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oval

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(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