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Improved Recovery of Ammonia From Swine Manure Using
Gas-Permeable Membrane Technology and Aeration
Waste-to-Worth Confere...
North Carolina produces approximately 750
million chickens, 40 million turkeys, 3.5 billion
table eggs, and 19 million hog...
Escalating U.S. Fertilizer Costs
USDA-NRCS
Why recover N?
0
100
200
300
400
500
600
700
800
900
1950
1960
1970
1980
1990
2...
Escalating U.S. Fertilizer Costs
Why recover N?
0
100
200
300
400
500
600
700
800
900
1950
1960
1970
1980
1990
2000
2010
2...
Recovery of Ammonia from Manure
 Ammonia is separated using gas-permeable membranes
 Applications include liquid manures...
WHAT IS INTENDED TO DO?
• Removal of ammonia gas from the liquid
manures before it escapes into the air.
• Nitrogen is rec...
Recovery of Ammonia from Liquid Manure with
Gas-permeable Membranes
• Technology recovers ammonia from liquid manure
• Pro...
For this research we used gas-permeable membranes
made of expanded polytetrafluoroethylene (ePTFE)
Gas Permeable Membrane
...
Tubular or Flat Membrane
Manifold
Air with Ammonia
Acidic Liquid
Membrane pores
NH 3
H + NH 4
+
Tubular or Flat Membrane
M...
Liquid Manure Strip solution
(Aqueous acid)
NH4+
H+ + NH3 NH3 + H+
NH4+
Gas-filled poreHydrophobic
Polymer (e-PTFE)
Gas-pe...
Synthetic
Wastewater
Strip solution
(water)
Glucose
(500 ppm COD)
KHP
(1000 ppm COD)
H2O
Gas-filled poreHydrophobic
Polyme...
Design Parameter: Effect of waste strength
Swine manure characteristics (ITACyL, Spain)
Manure
strength Swine Farm
Type pH...
Ammonia recovery rate increases with manure strength
0
500
1000
1500
2000
2500
3000
0 4 8 12 16 20 24 28 32
Nrecoveredinth...
Wastewater Strip solution
(Aqueous acid)
NH4+ + OH-
H2O + NH3 NH3 + H+
NH4+
Gas-filled poreHydrophobic
Polymer (e-PTFE)
Ga...
Two ways can be used to increase manure pH
and N recovery efficiency by the gas-permeable
membrane system:
1. Add alkali c...
Two ways can be used to increase manure pH
and N recovery efficiency by the gas-permeable
membrane system:
1. Add alkali c...
Experimental device for ammonia capture from manure using gas-
permeable membranes (closed loop).
pH
Pump
pH
Acidic soluti...
Design Parameter: Effect of aeration
Swine manure characteristics (Segovia, Spain)
ManureType Swine Farm
Type
pH
NH4-N
mg/...
Experiment with raw swine manure using gas-permeable
membrane system with aeration and nitrification inhibition
7.00
7.50
...
Operational costs of NH3 recovery using
gas-permeable membranes ($/4000 pigs/year)
Costs of ammonia recovery are reduced b...
N recovery: Effect of low-rate aeration
Covered lagoon effluent, North Carolina
Research by Dr. Patrick Dube, ARS-Florence...
7
7.5
8
8.5
9
9.5
0 5 10 15 20 25 30
pH
Time (d)
Manure pH
Aerated
Non Aerated
Changes in pH of manure during N recovery p...
0
2500
5000
7500
10000
12500
15000
0
500
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0 1 2 3 4 5 6
NH4-Ninacidtank(mgN/L)
NH4-Ninmanure(mgN/L)
Tim...
0
500
1000
1500
2000
2500
3000
3500
0 5 10 15 20 25 30
NH4+-NinManure(mgN)
Time (d)
Ammonia Removed from Manure
Aerated
No...
Treatment
Time
Initial
NH4
+
in
Manure
Remaining NH4
+
in Manure
NH4
+
removed
from
Manure
NH4
+
recovered
in acidic
solut...
Recovery of Ammonia from Liquid Manure
with Gas-permeable Membranes
• Technology captures ammonia emissions
• Produces liq...
N recovery in swine Ongoing demonstration (NCSU and ARS cooperation)
• NRCS CIG grant awarded in 2012 (PI: Dr. John Classe...
http://www.ars.usda.gov/saa/cpswprc
Treatment Technologies for Nitrogen
Management in Liquid Manure
1. Biological nitrogen removal
(conversion of ammonia into...
Treatment Technologies for Nitrogen
Management in Liquid Manure
1. Biological nitrogen removal
(conversion of ammonia into...
Ammonia was removed but carbon (volatile solids)
was not removed
Technology can be combined with anaerobic digestion to
re...
Improved Recovery of Ammonia From Swine Manure Using Gas-Permeable Membrane Technology and Aeration
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Improved Recovery of Ammonia From Swine Manure Using Gas-Permeable Membrane Technology and Aeration

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The full proceedings paper is at: www.extension.org/72883

Significant efforts are required to abate NH3 emissions from livestock operations. In addition, the costs of fertilizers have rapidly increased in recent years, especially nitrogen fertilizer such as anhydrous ammonia which is made from natural gas. Thus, new technologies for abatement of ammonia emissions in livestock operations are being focused on N recovery. This presentation shows a novel system that uses gas-permeable membranes to capture and recover ammonia from liquid manure, reducing ammonia emissions from livestock operations, and recovering concentrated liquid nitrogen that could be sold as fertilizer.

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Improved Recovery of Ammonia From Swine Manure Using Gas-Permeable Membrane Technology and Aeration

  1. 1. Improved Recovery of Ammonia From Swine Manure Using Gas-Permeable Membrane Technology and Aeration Waste-to-Worth Conference, Seattle, WA. April 2nd , 2015 1. USDA-ARS Coastal Plains Research Center, Florence, South Carolina, USA 2. Agriculture Technological Institute of Castilla y León (ITACyL), Valladolid, Spain Matias Vanotti1, María Cruz García2, Patrick Dube1, Ariel Szogi1
  2. 2. 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 Ammonia Emissions in many regions of USA (and the world) Walker et al., Atmos. Environ. 38:1235-1246 Ammonia Emissions
  3. 3. Escalating U.S. Fertilizer Costs USDA-NRCS Why recover N? 0 100 200 300 400 500 600 700 800 900 1950 1960 1970 1980 1990 2000 2010 2020 AverageFarmPrice($ton-1) Year Anhydrous Ammonia Urea 44-46% Nitrogen USDA-ERS
  4. 4. Escalating U.S. Fertilizer Costs Why recover N? 0 100 200 300 400 500 600 700 800 900 1950 1960 1970 1980 1990 2000 2010 2020 AverageFarmPrice($ton-1) Year Anhydrous Ammonia Urea 44-46% Nitrogen USDA-ERS Energy and Agriculture
  5. 5. Recovery of Ammonia from Manure  Ammonia is separated using gas-permeable membranes  Applications include liquid manures and air in livestock houses Product is liquid fertilizer with 50,000 to 100,000 ppm N Poultry Litter (Air) Liquid Manure
  6. 6. WHAT IS INTENDED TO DO? • Removal of ammonia gas from the liquid manures before it escapes into the air. • Nitrogen is recovered from liquid manures in a concentrated, purified form
  7. 7. Recovery of Ammonia from Liquid Manure with Gas-permeable Membranes • Technology recovers ammonia from liquid manure • Produces liquid fertilizer with > 50,000 ppm nitrogen • US Patent granted in 2015: “Systems and Methods for Reducing Ammonia Emissions from Liquid Effluents and for Recovering Ammonia” SN 13/164,363, filed June 20, 2011 ( Vanotti,M.B., and Szogi,A.A) Ammonia (NH3) recovery using gas-permeable membrane systemRaw waste Membrane module Recovered ammonia Low aeration pH Concentrator tank North Carolina Spain
  8. 8. For this research we used gas-permeable membranes made of expanded polytetrafluoroethylene (ePTFE) Gas Permeable Membrane Microscopic structure (SEM) Manufacture of Gas Permeable Membrane in South Carolina PTFE is stretched to form a strong, porous material
  9. 9. 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 NH3 H+ NH4 + Concept of Ammonia Capture from Wastewater using Gas Permeable Membrane
  10. 10. Liquid Manure Strip solution (Aqueous acid) NH4+ H+ + NH3 NH3 + H+ NH4+ Gas-filled poreHydrophobic Polymer (e-PTFE) Gas-permeable membrane system: The ammonia gas (NH3) passes through
  11. 11. Synthetic Wastewater Strip solution (water) Glucose (500 ppm COD) KHP (1000 ppm COD) H2O Gas-filled poreHydrophobic Polymer (e-PTFE) Microporous gas-permeable membrane : In tests, the soluble carbon did not pass through 0 ppm COD
  12. 12. Design Parameter: Effect of waste strength Swine manure characteristics (ITACyL, Spain) Manure strength Swine Farm Type pH NH4-N mg/l TKN mg/L EC (mS) COD mg/L TS g/L VS g/L Low Piglet 8.64 1065 1345 8.470 4519 4.89 2.58 Medium Farrow-finish w/ separation 7.57 1680 2743 14.080 24405 17.41 10.33 High Finishing 7.52 2285 3699 16.980 34081 29.87 20.13
  13. 13. Ammonia recovery rate increases with manure strength 0 500 1000 1500 2000 2500 3000 0 4 8 12 16 20 24 28 32 Nrecoveredintheacidtank(mg) time (days) Medium Low High Manure strength Initial NH4 mg N/L NH4 removed % NH4 recovery % NH4 recovery rate (mg/L/d) low 1390 94 87 74 medium 2180 90 90 92 high 2970 88 91 194 M.C. Garcia and M.B. Vanotti, Waste Management 38 (2015) 455–461 2015 Process pH adjusted with alkali (7.7 to 9) 7.00 7.50 8.00 8.50 9.00 9.50 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 pH Time (d) medium low high
  14. 14. Wastewater Strip solution (Aqueous acid) NH4+ + OH- H2O + NH3 NH3 + H+ NH4+ Gas-filled poreHydrophobic Polymer (e-PTFE) Gas-permeable membrane used for separation of free ammonia (NH3)
  15. 15. Two ways can be used to increase manure pH and N recovery efficiency by the gas-permeable membrane system: 1. Add alkali chemicals (OH-) 2. Low-rate aeration HCO3 - + air  OH- + CO2 NH4 + + OH-  NH3 + H2O Design Parameter: Effect of aeration
  16. 16. Two ways can be used to increase manure pH and N recovery efficiency by the gas-permeable membrane system: 1. Add alkali chemicals (OH-) 2. Low-rate aeration HCO3 - + air  OH- + CO2 NH4 + + OH-  NH3 + H2O  Aeration increases manure pH about 1 unit  The aeration rate must be low to inhibit nitrification  Nitrification inhibitor can be used (< 10 ppm) Vanotti and Szogi. US 13/143,363 Treated effluent DO Influent with ammonia pH Acid addition Nitrification Inhibitor P Aeration Design Parameter: Effect of aeration
  17. 17. Experimental device for ammonia capture from manure using gas- permeable membranes (closed loop). pH Pump pH Acidic solution Manure Gas-permeable membrane Sample Air Pump Airflow meter pH Pump pHpH Acidic solution Manure Gas-permeable membrane Sample Air Pump Airflow meter
  18. 18. Design Parameter: Effect of aeration Swine manure characteristics (Segovia, Spain) ManureType Swine Farm Type pH NH4-N mg/l TKN mg/L COD mg/L TS g/L VS g/L Raw from pit under slatted floor Farrowing sow house 7.57 2390 2700 16780 14.4 7.5
  19. 19. Experiment with raw swine manure using gas-permeable membrane system with aeration and nitrification inhibition 7.00 7.50 8.00 8.50 9.00 9.50 0 2 4 6 8 10 12 14 16 18 20 Time (days) ManurepH aerated manure (no alkali) no air applied (no alkali) 0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000 0 2 4 6 8 10 12 14 16 18 20 Time (days) NH4-Nrecovered(mg) aerated manure no air 99% recovery 65% recovery Aeration increased the pH of manure. As a result, the ammonia recovery by the membrane system was enhanced. M.C. Garcia, M.B. Vanotti, A.A. Szogi. 2015. Journal Environmental Management 152:19-26
  20. 20. Operational costs of NH3 recovery using gas-permeable membranes ($/4000 pigs/year) Costs of ammonia recovery are reduced by replacing alkali chemicals with low-rate aeration to speed-up the process. 0 1000 2000 3000 4000 5000 6000 7000 8000 9000 Alkali Chemical Low-rate Aeration
  21. 21. N recovery: Effect of low-rate aeration Covered lagoon effluent, North Carolina Research by Dr. Patrick Dube, ARS-Florence Manure Type Swine Farm Type pH NH4-N mg/l TKN mg/L COD mg/L TS g/L VS g/L Anaerobic digestion Finishing 8.71 2090 2460 1695 8.5 1.5
  22. 22. 7 7.5 8 8.5 9 9.5 0 5 10 15 20 25 30 pH Time (d) Manure pH Aerated Non Aerated Changes in pH of manure during N recovery process Covered lagoon effluent, NC 0 2000 4000 6000 8000 10000 12000 0 5 10 15 20 25 30 Alkalinity(mgCaCO3/L) Time (d) Alkalinity Aerated Non Aerated
  23. 23. 0 2500 5000 7500 10000 12500 15000 0 500 1000 1500 2000 2500 0 1 2 3 4 5 6 NH4-Ninacidtank(mgN/L) NH4-Ninmanure(mgN/L) Time (d) Aerated Manure Acid Tank 0 2500 5000 7500 10000 12500 15000 0 500 1000 1500 2000 2500 0 5 10 15 20 25 NH4-Ninacidtank(mgN/L) NH4-Ninmanure(mgN/L) Time (d) Non Aerated Manure Acid Tank Changes in ammonia concentration in manure and the N recovery tank Covered lagoon effluent, NC
  24. 24. 0 500 1000 1500 2000 2500 3000 3500 0 5 10 15 20 25 30 NH4+-NinManure(mgN) Time (d) Ammonia Removed from Manure Aerated Non Aerated 0 500 1000 1500 2000 2500 3000 3500 0 5 10 15 20 25 30 NH4+-Nrecovered(mgN) Time (d) Ammonia Recovered in Acid Tank Aerated Non Aerated Mass of ammonia removed from manure vs. Mass of ammonia recovered Covered lagoon effluent, NC
  25. 25. Treatment Time Initial NH4 + in Manure Remaining NH4 + in Manure NH4 + removed from Manure NH4 + recovered in acidic solution NH4 + removal efficiency NH4 + recovery efficiency NH4 + Volatilized in air (days) -----------------------------mg N------------------------ -----------------%------------------ Aerated 5 3133 (151) 96 (29) 3037 2979 (2) 97 98 2 Non Aerated 25 3157 (132) 71 (19) 3086 2936 (40) 98 95 5 Mass Balances of the Recovery of Ammonia - Covered lagoon effluent, NC
  26. 26. Recovery of Ammonia from Liquid Manure with Gas-permeable Membranes • Technology captures ammonia emissions • Produces liquid fertilizer with > 50,000 ppm nitrogen • Low-rate aeration effectively substitutes for chemical 5 6 13 14 7 4 2 1 28 15 Acidic solution Concentrator tank pH Ammonium salt Liquid manure Membrane module NH3 Pump Acidic solution Concentrator tank pHpH Ammonium salt Liquid manure Membrane module NH3 Pump CONFINED LIVESTOCK RAW WASTE ANAEROBIC DIGESTER WITH AMMONIA RECOVERY SYSTEM BIOGAS TREATED EFFLUENT CONCENTRATOR TANK RECOVERED AMMONIA Improvement of Anaerobic Digestion
  27. 27. N recovery in swine Ongoing demonstration (NCSU and ARS cooperation) • NRCS CIG grant awarded in 2012 (PI: Dr. John Classen): • Field demonstration: a pilot module for NH3 recovery was constructed at NCSU and it i being tested in 2015 in 3 manure management systems : - anaerobic digester, scraper & belt.
  28. 28. http://www.ars.usda.gov/saa/cpswprc
  29. 29. Treatment Technologies for Nitrogen Management in Liquid Manure 1. Biological nitrogen removal (conversion of ammonia into N2) Nitrification-Denitrification Anammox deammonification (Carbon needed) (Carbon not needed) Nitrification with HPNS bacteria in swine operation in North Carolina Brocadia caroliniensis (ARS- Florence)
  30. 30. Treatment Technologies for Nitrogen Management in Liquid Manure 1. Biological nitrogen removal (conversion of ammonia into N2) 2. Ammonia removal and recovery
  31. 31. Ammonia was removed but carbon (volatile solids) was not removed Technology can be combined with anaerobic digestion to recover both the ammonia and the energy from manure. M.C. Garcia and M.B. Vanotti, Waste Management 38 (2015) 455–461 2015

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