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© Matias Vanotti,
ARS-USDA
Recovery of Phosphate and Ammonia from Animal
Waste: A New Paradigm in Agriculture
USDA-ARS Coastal Plains Research Center
Florence, South Carolina, USA
Matias Vanotti
ReUseWaste Kick Off Meeting
University of Copenhagen, Sept 24-26, 2012
© Matias Vanotti,
ARS-USDA
© Matias Vanotti,
ARS-USDA
Concentration of swine production
Concentration of pig production in USA
North Carolina produces
approximately 750 million
chickens, 40 million turkeys,
3.5 billion table eggs, and
19 million hogs per year.
Animal Manure – Surplus N and P in North Carolina, USA
© Matias Vanotti,
ARS-USDA
Percent of Agronomic Crop and Forage Phosphorus Needs
Supplied by Recoverable Plant Available Manure Phosphorus at the County
Level in North Carolina
0 - 10
10 - 40
40 - 70
70 - 100
> 100 Source: Barker & Zublena
Animal Manure – Excess P in North Carolina
© Matias Vanotti,
ARS-USDA
P
N K
Source: IFDC
Global Fertilizer Prices
© Matias Vanotti,
ARS-USDA
Fertilizers
28%
Diesel
27%
Electricity
21%
Natural Gas
4%
Gasoline
9%
Pesticides
6%
LP Gas
5%
Escalating U.S. Fertilizer Costs
20
10
20
00
19
90
19
80
19
70
19
60
19
500
100
200
300
400
500
600
Year
Cost
per
ton (
$) Anhydrous
nitrogen
Potash
Energy and Agriculture
© Matias Vanotti,
ARS-USDA
Presentation outline: Nutrient recovery
technologies at USDA-ARS
• Soluble P extraction after buffer removal
• Solids-liquid separation with polymers
• Quick wash P recovery from solid manures
• Biochar P fertilizer
• N recovery with membranes
Recovery of Phosphate from Wastewater
On-farm
Phosphorus Mining
from Manure
© Matias Vanotti,
ARS-USDA
Phosphorus Removal Process
Buffer Systems in Animal Manure
Urea Hydrolysis
CO(NH2)2 + 2H2O ---> 2NH4+ + CO3
2-
Alkalinity
Ammoniacal
Nitrogen
© Matias Vanotti,
ARS-USDA
Buffer Systems Make Difficult the
Precipitation of Phosphorus
in Liquid Manure:
Carbonate Buffer System prevents calcium
phosphate formation
Ca(OH)2 + Ca(HCO3)2 2CaCO3 + 2H2O (2)
Ammonium – Ammonia Buffer System prevents
calcium phosphate formation
Ca(OH)2 + 2NH4
+ NH3 + Ca++ + 2H2O (3)
High Amount of Chemical Required © Matias Vanotti,
ARS-USDA
Phosphorus Removal Process
• The addition of Ca(OH)2 (or Mg) after
removal of natural buffers rapidly increases
the pH, which promotes precipitation of
phosphate with small amounts of chemical
added.
Vanotti et al. Extraction of soluble phosphorus from swine wastewater. Trans.
ASAE 46:1665-1674. © Matias Vanotti,
ARS-USDA
Phosphorus Removal Concept: Elimination of Buffer System with Biological Treatment
NITRIFICATION
BIOREACTOR
LIME OR
CA/MG HYDROXIDE
DISPENSER
PHOSPHORUS
SEPARATION
REACTOR EFFLUENT
WITH
NITRATE
PHOSPHATE
PRECIPITATE
INFLUENT WITH
AMMONIA
PHOSPHORUS
ALKALINITY
Wastewater Treatment System Vanotti et al. U.S. Patent 6,893,567 B1
© Matias Vanotti,
ARS-USDA
Phosphorus recovery from swine wastewaterusing Calcium Hydroxide
1 5 10
Calcium hydroxide rates (Moles of Ca added/ mol P)
0
10
20
30
40
50
60
P removed from liquid (mg/L)
with nitrification control
100%
© Matias Vanotti,
ARS-USDA
Calcium
Phosphate
Solid-liquid
Separation
Module
Nitrification
Denitrification
Module
Phosphorus
Removal
Module
Swine
Houses Separated
solids Reuse
Effluent
On-Farm Treatment System
© Matias Vanotti,
ARS-USDA
Goshen Ridge Farm, Duplin Co., NC
4,360-finishing pig production unit
Solid-liquid
Separation
N treatment
Phosphorus
Recovery Module
Raw ManureTreated: 39 m3/day
Manure treatment system developed to replace swine lagoons in
North Carolina. NC Attorney General – Smithfield Foods/PSF
Agreement
© Matias Vanotti,
ARS-USDA
Soluble phosphorus separation and
bagging of the calcium phosphate
P separation module
© Matias Vanotti,
ARS-USDA
Dewatering and bagging of calcium phosphate
Recovered P from sludge = 99.5%
Vanotti et al., Biores. Technol. 98:3184-3194
Constituent Percentage
P2O5 24.4% ± 4.5%
Calcium 27.3 %
Potassium 0.9 %
Magnesium 1.8 %
Chemical Composition
Recovered Phosphates
99% plant available (standard citrate test)
© Matias Vanotti,
ARS-USDA
Agronomic Effectiveness of Phosphates
Recovered from Manure
Green-house testing at Florence Interaction with Industry
Production of fertilizer pellets
Concentration of pathogen indicator in manure liquid (bacterial
count/mL)
1
10
100
1000
10000
100000
1000000
Manure flush Separated
liquid
Biological N
removal
P effluent
EnterococciTotal Coliforms
THE HIGH PROCESS pH DISINFECTS THE EFFLUENT
SUMMARY
• Phosphorus is selectively precipitated using lime after
carbonate and ammonia buffers are reduced with
biological N removal.
• The precipitate is calcium phosphate (~ 24% P2O5)
that can be reused as plant fertilizer.
• The high process pH also disinfects the effluent (> 4
logs)
Environmentally Superior Technology (EST)
Standards for New Swine Operations in NC
Substantially eliminate:
1. ammonia emissions
2. odor emissions
3. pathogens
4. nutrient (N & P) surplus
5. heavy metal contamination
Lessons learned after testing 18 technologies at full-scale:
a combination of two or more simple processes
are needed to meet all environmental standards
Diet Manipulation Liquid System
Solid Separation
Screen 5-25%
Enhanced Separation
Polymer Flocculation> 90%
Vermicompost
High Solids
Anaerobic Digestion
Pelletize
Plastic composites
Biochars
Oil
Composting
Plant Growth Media
Dry Systems
High Rise/ Deep bedding/
Belt System
Methane Digestion
Algae Biomass (biodiesel)
Phosphorus Precipitation
(Struvite, Calcium Phosphate)
Constructed Wetland
Rice/ Soybeans
Nitrification, DN, Anammox
(Transform Ammonia to Nitrate, N2)
Gasification
On Farm Liquid Treatment and
Application to Cropland
Solid & Nutrients Moved
from Farm, Value-added Products Ethanol
Phosphorus Products
Ammonia Recovery
(Membranes)
Liquid
Ammonia
NPPC Task Force Other Utilization Activities, Vanotti 2001, revised 2009
EST
EST © Matias Vanotti,
ARS-USDA
Lower Cost, Second Generation
Technology
NC Attorney General – Smithfield Foods
Environmental Enhancement Program
TREATED
EFFLUENT
PHOSPHORUS SEPARATION
REACTOR UNIT
B
BLOWER
PAM
P
DENITRIFICATION
UNIT
CLARIFICATION
UNIT
NITRIFICATION
BIOREACTOR UNIT
RETURN SLUDGE
CONFINED LIVESTOCK
SWINE
MANURE (SM)
SOLID SEPARATION
UNIT 1
RECYCLE
PHOSPHATE
PRECIPITATE
SLUDGE (PS)
P
M
HOMOGENIZATION
TANK
MIXER
PAM
DEWATERED PHOSPHORUS
SLUDGE
DEWATERED SWINE MANURE
& PHOSPHORUS
PRECIPITATE
SOLID SEPARATION
UNIT 2
P
SECOND GENERATION WITH SIMULTANEOUS SOLID-LIQUID
SEPARATION OF SWINE MANURE AND PHOSPHORUS PRECIPITATE
Vanotti et al. (2010), U.S. Patent 7674379
Phosphorus removal module - continuous flow
Application of lime to pH 9.5 and settling of calcium phosphate
Small P reactor (~ 1 m3 for 5400 pigs)
© Matias Vanotti,
ARS-USDA
Solid-liquid separation of manure and
phosphorus with flocculation
High-capacity rotary press
Capture of P, organic N, Cu & Zn
Solids
N
P © Matias Vanotti,
ARS-USDA
FLOCCULATION WITH POLYMERS INCREASES
SOLIDS SEPARATION EFFICIENCIES
• PAM Applications: municipal, food processing, soil erosion, animal waste
• Absorb and bridge colloidal suspended particles into flocs
• Effective at low dosage
• Natural Polymers: Chitosan, Tanins
+
+
+
+
+
+
+
++
+
+
+
+
+
+
+
+
+
+
+
+
+
+
++
+
++
++
PAM Flocculation
Vanotti et al., Transactions of the ASAE, 1999, 2002, 2005 © Matias Vanotti,
ARS-USDA
Model: Centralized Plant for Processing of Separated Manure Solids
Generation of Value Added Products though Composting
© Matias Vanotti,
ARS-USDA
Centralized Solids Processing Facility (Composting)
• Conserved the separated N and P
• Manure transformed into Class A compost
• Processed into plant growth media
Mass
Balance
%
Loss
% Recovery
Nitrogen 3.5 96.5
Phosphorus 0 100
Nutrient Stabilization & Recovery
Solids Processing Facility
95.6Total Copper
99.6Total Zinc
101.2Total Phosphorus
97Total Nitrogen
56.6 %Total Carbon
28.4Material Volume
55.5 %Material Weight
© Matias Vanotti,
ARS-USDA
Production of high-value plant growth media
and organic fertilizers from composted
manure
© Matias Vanotti,
ARS-USDA
Another Phosphorus Recovery Technology
Quick Wash Process
Manure is washed with mild acids and then
the phosphorus is recovered as solid
© Matias Vanotti,
ARS-USDA
Poultry Litter
Phosphorus Removal and Recovery Quick Wash Process
USDA - ARS
Washed
Litter
P extraction
Acidic solution
Poultry
Litter
P removal
Alkaline pH
P precipitation
enhancement
Recovered P
Liquid
Effluent
1 2 3
© Matias Vanotti,
ARS-USDA
Manure Wash Pilot Experiment
Solid Manure
+ Water
+ Acid
Washed
Solids
Lime
Extracted
Phosphorus
Solids
Liquid with Low
Suspended Solids
+ Soluble Phosphorus
Liquid to
Recycle
1 2
Flocculant
3
© Matias Vanotti,
ARS-USDA
.
P recovered from
poultry litter Poultry litter after
quick wash
Quick Wash
Products
© Matias Vanotti,
ARS-USDA
Quick Wash for Pig Manure (Steps 2 & 3)
Process was optimized at pH 8
0 2 4 6 8 10 12 140
100
200
300
0
20
40
60
80
100
TP RecoveredTP in Liquid Extract
pH
To
tal P
, m
g/L
To
tal P
Reco
vere
d, %
pH after step 1 = 4.3, then adjusted by addition of hydrated lime [2% Ca(OH)2] % TP Recovered = (P recovered /Initial P in fresh swine manure) x 100 Initial P in pig manure = 7.1 g/kg (30% solids)
© Matias Vanotti,
ARS-USDA
Quick Wash for Pig Manure – Steps 2 & 3
TP recovery was greatly improved with anionic
PAM application
Flocculant = anionic polyacrylamide polymer applied at 7 mg/L
3 4 5 6 7 8 9 10 11 12 13 140
20
40
60
80
100No Flocculant
With Flocculant
pH
To
tal P
Reco
vere
d,
%
Quick Wash Process
Component of a Manure Management System
Land application
• Washed manure residue with higher N:P ratio
Nutrient transfer program
• Transport of a concentrated P material is more
effective
5-year Project at USDA-ARS Florence, SC (2010-2015): Innovative Bioresource Management Technologies for Enhanced Environmental Quality and Value Optimization.
P-Fertilizer
Treated Water
CH4, CO, H2, etc.
Obj. 3: Impacted Riparian Buffers
3a. N2O Emission Assessment 3b. Microbial Assessment
3c. Biochar Treatment
Obj. 2: Thermochemical
Conversion Technologies
2b. Combustible Gas & Biochar Production 2d. “Designer Biochar” Production
Manure
2a. Feedstock Conditioning
2a. Feedstock Characterization
1h. Microbial Assessment
2b. Structure & Materials Testing
1b. Solid-Liquid Separation 1c. N-removal 1e. P-extraction
Obj. 1: Advanced Management
Systems
1g. NH3 and GHG Assessment
1d. NH3 Recovery
Obj. 4: Byproduct Uses
4b. Improve Soil Fertility 4c. Improve Crop Production
4a. Contaminant Adsorbant
Legend
Method/Assessment
Physical Process
Information
Separated Swine Solids 1a. Facilitate Adoption
2b. Pelletizing
N-Fertilizer
Pelleted Fertilizer
Biochars produced from different feedstocks
and at high/low temperatures
• Biochar pyrolyzed at high/low temperatures will have different structural chemistries
13C Nuclear Magnetic
Resonance spectra of
Pecan biochar
Ground pecan shell
•Biochar can be made
from various crop and manure feedstocks
Pyrolysis Reactor Swine manure
© Matias Vanotti,
ARS-USDA
Figure 1. Ryegrass growth response curve to chemical P fertilization
and yield response to P added via livestock biochar (From Hunt and
Cantrell, USDA-ARS, Florence. )
Manure Biochars as P fertilizer
5.0
5.5
6.0
6.5
7.0
7.5
8.0
8.5
9.0
9.5
10.0
0 50 100 150
Cu
mu
lati
ve R
yegr
ass
Dry
Mat
ter,
g
P, mg P kg soil-1
Chemical Fertilizer
Biochar Mean (350 & 700°C)
Min - Swine 350°C
Max - Chicken 350°C
© Matias Vanotti,
ARS-USDA
Nitrogen Recovery Technology
with Gas Membranes
© Matias Vanotti,
ARS-USDA
Recovery and Concentration of Ammonia
o Ammonia permeation through microporous, hydrophobic
membranes
oReduced ammonia emissions from livestock operations
oProduct is ammonia solution with > 50,000 ppm N
N Recovery from Swine Wastewater
0 5 10 150
1000
2000
3000
4000
5000
6000
7000Decreasing N inSwine Wastewater
Recovered Ammonia Solution
Sampling Day
Am
mo
nia
Co
ncen
trati
on
(p
pm
)
© Matias Vanotti,
ARS-USDA
Liquid Manure Strip solution
(Aqueous acid)
NH4+
H+ + NH3 NH3 + H+
NH4+
Gas-filled pore Hydrophobic
Polymer (e-PTFE)
Microporous gas-permeable membrane:
The ammonia gas (NH3) passes through
For this research we used gas-permeable membranes
made of expanded polytetrafluoroethylene (ePTFE)
(Teflon)
Gas Permeable Membrane Microscopic structure (SEM)
Manufacture of Gas Permeable Membrane
PTFE is stretched to form a strong, porous material
© Matias Vanotti,
ARS-USDA
Tubular or Flat Membrane
Manifold
Air with Ammonia
Acidic Liquid
Membrane pores NH
3
H + NH 4
+
Tubular or Flat Membrane
Manifold Submerged in the
Wastewater
Dirty Liquid with Ammonia
Acidic Liquid Ammonium Salt Fertilizer
Membrane Pores NH
3
H + NH 4 +
Concept of Ammonia Capture from
Wastewater using Gas Permeable Membrane
© Matias Vanotti,
ARS-USDA
TUBULAR MEMBRANES Removal of NH3 from Liquid Manure Using Gas-Permeable
Membranes
Swine
Manure
© Matias Vanotti,
ARS-USDA
© Matias Vanotti,
ARS-USDA 0 14 28 42 56 70 84 98
0500
10001500
5000
15000
25000
35000
45000
55000
NH4-N Recovered in membrane manifold
NH4-N Removed from liquid swine manure
Sampling Time (days)
NH
4-N
co
ncen
trati
on
(mg
L-1
)
Recovery and Concentration of Ammonia from
Liquid Swine Manure using Gas Membranes
(10 batches using same stripping solution)
CONFINEDLIVESTOCK
RAWWASTE
MEMBRANE MANIFOLD SYSTEM
Anaerobic Livestock Wastewater Lagoon withAmmonia Recovery System
RECOVEREDAMMONIA
pH
FLOAT
Retrofit of manure storage units to harvest the ammonia
Vanotti et al. 2011. US Patent SN 13/164,363
© Matias Vanotti, ARS-USDA
Nutrient Recovery System (N and P)
TREATED
EFFLUENT
AMMONIA &
PHOSPHORUS
SEPARATION REACTOR
P
PHOSPHORUS
PRECIPITATEDSLUDGE
CONFINEDLIVESTOCK
SWINE
MANURE(SM)
SOLID SEPARATION
UNIT
P
M
HOMOGENEIZATION
TANK
MIXER
DEWATERED MANURE SOLIDS,
PHOSPHORUS & EXTRACTED NITROGEN
P
P
RAW
WASTE
LIME OR
ALKALI
DISPENSER
MEMBRANE
MANIFOLD
RECOVERED AMMONIA
pH
DO
T
© Matias Vanotti, ARS-USDA
© Matias Vanotti,
ARS-USDA
1. The use of gas-permeable membrane technology could
be an effective approach to recover ammonia from
livestock wastewater.
2. A concentrated liquid nitrogen is obtained that can be
re-used in agriculture as a valued fertilizer.
Conclusions – N recovery from liquid
manure
© Matias Vanotti,
ARS-USDA
http://www.ars.usda.gov/saa/cpswprc
© Matias Vanotti,
ARS-USDA