Separation of Ammonia and Phosphate Minerals from

Wastewater using Gas-Permeable Membranes

WRRI Water Sustainability Through Nanotechnology Symposium
March 15, 2017 – Raleigh, NC

Matias Vanotti
Collaborators: Patrick Dube, Ariel Szogi
United States Department of Agriculture, ARS
Florence, SC
 Presentation outline

Recent development at USDA of systems and methods to

recover N, P and value-added materials from wastes

1. Improved ammonia recovery from liquid with gas-

membranes

2. Simultaneous N and P recovery with membranes

3. Recovery of ammonia without chemicals

 Why recover N?

Escalating U.S. Fertilizer Costs

900
USDA-ERS
800
Average Farm Price ($ ton-1)

700
Anhydrous
600 Ammonia

500
Urea 44-46%
400 Nitrogen

300 USDA-NRCS

200

100

0
1950
1960
1970
1980
1990
2000
2010
2020

Year
 Why recover N?

Escalating U.S. Fertilizer Costs

900
USDA-ERS
800
Average Farm Price ($ ton-1)

700
Energy and Agriculture
Anhydrous
600 Ammonia

500
Urea 44-46%
400 Nitrogen

300

200

100

0
1950
1960
1970
1980
1990
2000
2010
2020

Year
 Why recover phosphorus?

Cordell, D., et al., Chemosphere 84:747-758

Animal Manure – Surplus N & P , Ammonia emissions
in areas of concentrated animal production
Surplus Phosphorus
North Carolina produces
approximately 750 million
chickens, 40 million turkeys,
3.5 billion table eggs, and
19 million hogs per year.

Ammonia Emissions

Walker et al., Atmos. Environ. 38:1235-1246

 Value Chain without Solution

Key Material Livestock

Wastewater
Key Material
(Manure)

Lagoons
Land Application
Hauling
 The Technology
What do you do?
• Our technology simultaneously removes and recovers both
nitrogen and phosphorus from manures and wastewaters.

Why do you do it?

• This creates value added products from wastes and helps
society with a cleaner environment.
Phosphorus
Products

Wastewater Nitrogen Phosphorus

(Manure) Recovery Recovery Nitrogen
Treatment Treatment Products

Clean Water
 Value Chain with Solution

Key Material Livestock

Wastewater
Key Material Phosphorus
(Manure)
Products
Nitrogen Phosphorus
Key Material Equipment Recovery Recovery Nitrogen
Treatment Treatment Products

Key Material Chemicals Clean Water

 Ecosystem Map With Solution
How your product interacts with the world once it is in the hands of the customer
Engineering
Companies

Suppliers Equipment Service Providers Environmental

-Pumps Manufacturers Impact/Regulations
-Mixers -Clean Water
-Membrane -Reduced Emissions
modules

Customers
Tourism Industry -Swine
(fishing/recreation) -Dairy
-Municipal Wastewater
-Aquaculture?
Water Quality
Clean water Nutrient Credits

-Homeowner Nitrogen Product Phosphorus

-Farmers Manufacturer Product
-Greenhouse Manufacturer
Animal Feed
Liquid N Fertilizer
Phosphorus Pellets
New technology: Recovery of Ammonia from Manure

Swine
Manure

Poultry Litter (Air)

 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

 Recovery and Concentration of Ammonia
N Recovery from Swine Wastewater

Ammonia Concentration (ppm)

7000
Decreasing N in
6000 Swine Wastewater
5000 Recovered Ammonia
4000 Solution

3000
2000
1000
0
0 5 10 15
Sampling Day

o Ammonia permeation through microporous, hydrophobic

membranes

oReduced ammonia emissions from livestock operations

oProduct is ammonia solution with > 50,000 ppm N

 Gas-permeable membranes

• Medical uses: Used in membrane oxygenators to imitate

the function of the lungs in cardiopulmonary bypass, to add
oxygen to, and to remove carbon dioxide from the blood
(Gaylor, 1988).

• Clothing & shoe industries: Used to provide waterproof

and breathable fabrics in sportswear and footware (i.e.
GORE-TEX® Products, 1968)
 For this research we used gas-permeable membranes
made of expanded polytetrafluoroethylene (ePTFE)

PTFE is stretched to form a strong, porous material

Gas Permeable Membrane

Microscopic structure (SEM)

Manufacture of Gas Permeable Membrane

 Recovery of Ammonia from Liquid Manure
with Gas-permeable Membranes
• Technology captures ammonia emissions
• Produces liquid fertilizer with > 50,000 ppm nitrogen

Improvement of Anaerobic Digestion

CONFINED
LIVESTOCK ANAEROBIC DIGESTER
WITH AMMONIA RECOVERY SYSTEM
BIOGAS
RAW
WASTE
TREATED EFFLUENT

CONCENTRATOR
TANK

15 RECOVERED
AMMONIA

28
4
13
14
5
7
2
6
1
 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
Concept of Ammonia Capture from Wastewater using
Gas Permeable Membrane

Air with Ammonia

Dirty Liquid with Ammonia
Membrane Pores pores
Membrane
NH
NH 33

H+
H NH 4 +
NH

Acidic Liquid
Acidic Liquid Ammonium Salt Fertilizer

Tubular or Flat
Tubular Membrane
or Flat Membrane
Manifold
Manifold Submerged in the
Wastewater
Gas-permeable membrane system:
The ammonia gas (NH3) passes through

Liquid Manure Strip solution

(Aqueous acid)

H+ + NH3 NH3 + H+

NH4+ NH4+

Hydrophobic Gas-filled pore

Polymer (e-PTFE)
 Does it work?
Ammonia removal from animal waste using gas permeable membranes

SWINE LAGOON
302 mg NH4-N/L, pH 8.3

Rate = 153 mg N/L/day

R2 = 0.998
Retrofit of manure storage units to harvest the ammonia
CONFINED
LIVESTOCK

RAW
WASTE
MEMBRANE MANIFOLD SYSTEM
pH

FLOAT

RECOVERED
AMMONIA

Anaerobic Livestock Wastewater Lagoon with

Ammonia Recovery System
 Recovery and Concentration of Ammonia from
Liquid Swine Manure using Gas Membranes
(10 batches using same stripping solution)
55000
NH4-N concentration

NH4-N Recovered in membrane manifold

45000
NH4-N Removed from liquid swine manure
35000
(mg L-1)

25000

15000

5000
1500
1000
500
0
0 14 28 42 56 70 84 98
Sampling Time (days)

Recovered NH4-N was concentrated to 53,000 ppm

 Microporous gas-permeable membrane :
In tests, the soluble carbon did not pass through
Synthetic Strip solution
Wastewater (water)
Glucose
(500 ppm COD) H2O

KHP 0 ppm COD

(1000 ppm COD)

Hydrophobic Gas-filled pore

Polymer (e-PTFE)
 Design Parameter: Effect of wastewater pH:

Initial Source pH = 8.3 Initial Source pH = 10.0

NH4-N NH4-N
Mass NH4-N Recovery from pH of Mass NH4-N Recovery
Time in Trap Source Trap in Trap from Source pH of Trap
(hours) (mg) (%) (mg) (%)
0 0 0 1.08 0 0 1.08
1 0.86 1.0 1.11 7.82 8.7 0.99
2 2.44 2.7 0.98 26.51 29.4 1.16
3 3.72 4.1 0.99 38.60 42.9 1.28
4 4.77 5.3 1.1 48.86 54.3 1.6
5 5.39 6.0 1.0 56.40 62.7 1.8

N Recovery was ~ 1.2 % per hour at pH 8.3 and 13% per

hour at pH 10 (increased 10 times)
Gas-permeable membrane
used for separation of free ammonia (NH3)
Strip solution
Wastewater (Aqueous acid)

H2O + NH3 NH3 + H+

NH4+ + OH- NH4+

Hydrophobic
Polymer (e-PTFE) Gas-filled pore
 Design Parameter: Effect of waste strength
Swine manure characteristics

Manure
strength Swine Farm NH4-N TKN EC COD TS VS
Type pH mg/l mg/L (mS) mg/L g/L g/L

Low Piglet 8.64 1065 1345 8.470 4519 4.89 2.58

Farrow-finish
Medium 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

Ammonia recovery from livestock manure using gas-permeable
membrane module and concentrator tank (Closed loop system).

pH

Acidic
Liquid manure
solution
NH3 Ammonium salt
Pump
Membrane module Concentrator tank
Experimental device for ammonia capture from manure using gas-
permeable membranes (closed loop).

Pump
pH
sample
pH

Gas-permeable
membrane

Acidic solution Manure

Process pH adjusted with alkali (7.7 to 9)
9.50

9.00

8.50
pH

8.00

7.50

7.00
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32

Time (d)

medium low high

 Removal of ammonia in the manures and recovery
in the acid tank
LOW STRENGTH

1400 5000 HIGH STRENGTH

ammonia in acid tank (mg/L)

1200 4500
4000
ammonia in manure (mg/L)

1000 3000 9000

3500
800 3000 8000

ammonia in acid tank (mg/L)

ammonia in manure (mg/L)
2500
600 2500 7000
400 2000
1500 2000 6000
200
1000 5000
0 500 1500
0 1 2 3 4 5 7 9 101114151718212324252930 4000
-200 0
time (days) 1000 3000
2000
500
MEDIUM STRENGTH 1000
0 0
1800 7000 0 1 2 3 4 5 7 9 10 11 14 15 17 18 21 23 24 25 29 30
amonia in manure (mg/L)

1600 6000 time (days)

amonia in acid tank (mg/L)

1400
5000
1200
1000 4000
800 3000
600
2000
400
200 1000
0 0

Time (days)
Ammonia recovery rate increases with manure strength

N recovered in the acid tank (mg)

3000

2500

2000

1500

1000

500

0
0 4 8 12 16 20 24 28 32
time (days)
Medium Low High

Manure Initial NH4 NH4 NH4 NH4

strength mg N/L removed recovery recovery
% % rate
(mg/L/d)
low 1385 94 87 74
medium 2184 90 90 92
high 2971 88 90 194
M.C. Garcia and M.B. Vanotti, Waste Management 2014 (in press)
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.
 Ammonia Recovery System with Anaerobic Digestion

CONFINED
LIVESTOCK

ANAEROBIC DIGESTER
AMMONIA REMOVAL UNIT WITH WITHOUT INHIBITORY AMMONIA
MEMBRANE MANIFOLD SYSTEM BIOGAS
RAW BEFORE ANAEROBIC DIGESTION
WASTE

RAW WASTE STRIPPED

OF AMMONIA TREATED EFFLUENT

MEMBRANE
MANIFOLD SYSTEM
STRIPPING ACID
SOLUTION TANK / RESERVOIR

MIXER

RECOVERED
AMMONIA
Zarebska et al. (2015) Ammonium fertilizers production from manure: A critical review.

The gas-permeable membrane method had very

low energy demand
Energy consumption of ammonia
recovery methods (manure)
5 kWh/m3 feed
4.5 NF= nanofiltration
4 RO = reverse osmosis
3.5 GPM = gas permeable memb.
3
AS = air stripping
2.5
2
IE = ion exchange/ zeolites
1.5 CP = Chemical precipitation
1
0.5
0
NF RO GPM AS IE CP
 The gas-permeable membrane method (MD) had
high chemical demand (NaOH to increase pH)
Chemical cost ($/m3 feed)
14

12
NF= nanofiltration
RO = reverse osmosis
10
GPM = gas permeable memb.
8 AS = air stripping
6 IE = ion exchange/ zeolites
4 CP = Chemical precipitation
2

0
NF RO GPM AS IE CP

Zarebska et al. (2015) Ammonium fertilizers production from manure: A critical review.
 Design Parameter: Effect of aeration
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
Two ways can be used to increase manure pH
and N recovery efficiency by the gas-permeable
membrane system:
Acid
addition
1. Add alkali chemicals (OH-)
pH
P
Nitrification
Inhibitor
DO

Influent Treated
2. Low-rate aeration with effluent
ammonia

HCO3- + air  OH- + CO2

NH4+ + OH-  NH3 + H2O Aeration

 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 9,005,333
 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 in 2015: “Systems and Methods for Reducing Ammonia Emissions from Liquid Effluents and
for Recovering the Ammonia” (US 9,005,333, Vanotti,M.B., and Szogi,A.A)

Ammonia (NH3) recovery

using gas-permeable
Raw waste membrane system

pH

Membrane module
Recovered
ammonia

Low aeration Concentrator tank

 Experimental device for ammonia capture from manure using gas-
permeable membranes (closed loop).

Pump

Air Flow
Meter pH pH
Air Sampling Probe
and Probe
Pump Valve Port

Air
Escape
Port
Stripping
Solution

Gas Permeable
Membrane

Aquarium
Aeration
Stone Manure
 N recovery: Effect of low-rate aeration
Covered lagoon effluent, North Carolina

Liquid with 2,100 mg/L NH4-N

 Ammonia (NH3) recovery gas-
permeable membrane system
pH
Raw
Manure Pump Recovered
Ammonia
Concentrator
Anaerobic Tank
Digester

Digested
Effluent Gas-permeable
Membrane
NH3 Module
Low Aeration
Changes in ammonia concentration in manure and the N recovery tank
Covered anaerobic lagoon effluent, NC
2500 15000

NH4-N in manure (mgN/L)

NH4-N in acid tank (mgN/L)

2000
Non Aerated 12500
10000
1500
Manure 7500
1000 Acid Tank 5000
500 2500
0 0
0 5 10 15 20 25
Time (d)

2500 15000
Aerated
NH4-N in manure (mgN/L)

NH4-N in acid tank (mgN/L)

2000 12500
10000
1500
Manure
7500
1000 Acid Tank
5000
500 2500
0 0
0 1 2 3 4 5 6
Time (d)
Mass Balances of the Recovery of Ammonia - anaerobic digester effluent

NH4+ NH4+
Initial NH4+ NH4+ NH4+
Treatment Remaining NH4+ removed recovered
NH4+ in removal recovery Volatilized
Time in Manure from in acidic
Manure efficiency efficiency in air
Manure solution

(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

Significant cost reductions can be achieved with new concepts
and research
Operational cost of NH3 recovery using
gas-permeable membranes ($/4000 pigs/year)
9000
8000
7000
6000
5000
4000
3000
2000
1000
0
Alkali Chemical Low-rate Aeration
Changes in pH and alkalinity of manure during N recovery process
Covered anaerobic lagoon effluent, NC

9.5

9.0

8.5
pH

8.0

7.5

Alkalinity (mg CaCO3/L)

7.0 10000
0 10 20 30
Time (d)

5000
Farm 1 Aerated Farm 2 Aerated
Farm 1 Non Aerated Farm 2 Non Aerated
0
0 10 20 30
Time (d)

Farm 1 Aerated Farm 2 Aerated

Farm 1 Non Aerated Farm 2 Non Aerated
 Key finding

• The process removes ammonia and alkalinity and

increases pH.

• These are ideal conditions for phosphorus

precipitation and recovery
 Recovery of ammonia and phosphorus
from animal manure
Configuration 1 Configuration 2
Stripping
Stripping
Solution
Solution
Liquid Reservoir
Reservoir
Liquid Manure
Manure Recovered
Recovered Ammonia
Magnesium
Ammonia
Chloride
Anaerobic
Anaerobic Digester
Digester Magnesium
Chloride
Treated
Effluent with ammonia
Effluent with ammonia Treated Effluent
and phosphorus
and phosphorus Effluent
Gas-permeable
Gas-permeable
Membrane
Membrane
Module
Module
BB
BB
Blower
Blower

Recovered
Recovered Phosphorus
Phosphorus Solids
Solids

Influent P concentration: 150-200 mg/L

Influent N concentration: 1500-2000 mg/L
US Pat. Appl. 62/169,387 (USDA 6/1/2015)
For Mg phosphates, two potential forms that can precipitate
in liquid systems that contain Mg2+–NH4+–PO43− and a high
Mg/Ca ratio are struvite and newberyite
(Boistelle et al., 1983; Abbona et al., 1988; Muster et al., 2013).

Struvite
Mg2+ + H2PO4- + NH3  MgNH4PO4 + H+

Newberyite
Mg2+ + H2PO4-  MgHPO4 + H+
Digester Strip
Gas-permeable
MgCl2 Solution (H+)
Effluent membrane
Hydrophobic Gas-filled
polymer pore

NH4+ NH3 NH3 + H+

-
High
HCO3 OH- pH
Mg2+ NH4+
PO43- NH4+
System 1

System 2

Recovered
Low rate MgHPO4 MgNH4PO4 ammonium
aeration Recovered phosphate solids salts
 Nitrogen and Phosphorus Recovery
Configuration 2: MgCl2 added to N reactor
(no alkali added)
Stripping
Solution
Liquid Reservoir
Manure
Recovered
Magnesium Ammonia

Anaerobic Chloride
Digester Influent P = 446 mg/L
Effluent with ammonia Treated Influent pH =8.4
and phosphorus Effluent

Gas-permeable
Membrane
Module
pH after aeration = 9.5
BB
Blower
N recovery = 91%
P recovery = 100%
Recovered
Phosphorus
Solids
Configuration 2 with MgCl2 added (without NaOH)
Concentrations MASS BALANCE
Recovered
Influent Effluent Initial Recovered Total
Nutrient by Effluent
Concentration Concentration Manure Solid Recovery
Membrane

mg/L Percentages

N 2354 69.2 100% 7.7% 83.1% 2.9% 90.5%

P 446 23.5 100% 104.3% 0% 5.3% 104.3%

Configuration 2 with MgCl2 added (without NaOH)
Concentrations MASS BALANCE
Recovered
Influent Effluent Initial Recovered Total
Nutrient by Effluent
Concentration Concentration Manure Solid Recovery
Membrane

mg/L Percentages

N 2354 69.2 100% 7.7% 83.1% 2.9% 90.5%

P 446 23.5 100% 104.3% 0% 5.3% 104.3%

Composition of Recovered Solid

Plant Available P
N P2O 5 Mg Ca K
(Citrate soluble)
Percentages, %
4.5 26.4 10.0 2.0 1.7 99.00
Struvite = 5.7 N : 29 P2O5 : 10 Mg
 Configuration 2
16.45 mmol / L MgCl2
Mg:P = 1.2:1
0 mmol / L NaOH
Recovered by N = 1949 mg (82.8 %)
Membrane P = 0 mg (0.0 %)

Nutrient
Influent Recovery Effluent
System
N = 2354 mg (100.0 %) N = 69 mg (2.9 %)
P = 446 mg (100.0 %) P = 24 mg (5.4 %)
Recovered N = 184 mg (7.8 %)
Solid P = 472 mg (105.9 %)
 Nitrogen and Phosphorus Recovery
Configuration 1: MgCl2 added after N removal
(no alkali added)
Stripping
Solution
Reservoir
Liquid
Manure
Recovered
Ammonia

Anaerobic
Digester Magnesium
Chloride

Effluent with ammonia and Treated

phosphorus Effluent

Gas-permeable
Membrane Influent P = 446 mg/L
Module
Influent pH =8.4
BB
Blower
pH effluent after N
Recovered
Phosphorus recovery = 9.3
Solids
P recovery = 93.2%
US Pat. Appl. 62/169,387 (USDA 6/1/2015)
Recovered Phosphates (Configuration 1)

• P recovered as High-Grade Magnesium Phosphate

• 99.7% plant available (standard citrate test)
Chemical Composition
Constituent Percentage
P2O5 46.4%
Magnesium 17.1%
Calcium 0.4 %
Newberyite (MgHPO4.3H2O)
Potassium 1.7 % 41% P2O5 and 14% Mg
Nitrogen 1.8 %
Triple superphosphate = 46% P2O5; Rock phosphate = 27-36% P2O5
 Configuration 1 with Municipal Side
Stream Wastewater (after AD of
sludges)

Concentrations MASS BALANCE

Recovered
Influent Effluent Initial Recovered Total
Nutrient by Effluent
Concentration Concentration Manure Solid Recovery
Membrane

mg/L Percentages

N 731 123 100% 2.4% 90.5% 16.7% 92.3%

P 147 6 100% 79.2% 0% 4.1% 79.2%

 Results obtained were consistent using swine and municipal side-stream digester
effluents
 Composition similar to rare bio-mineral NEWBERYITE
that is found in guano deposits

Composition of Recovered Phosphate Minerals (Swine Effluent)

Plant Available
N P2O 5 Mg Ca K
P
Percentages, %
1.8 46.4 17.1 0.4 1.8 99.7

Composition of Recovered Phosphate Minerals (Municipal Centrate)

James River WWTP, Virginia

Plant
N P2O 5 Mg Ca K
Available P)

Percentages, %
2.8 44.1 13.6 0.9 0.7 98.5

Struvite = 5.7 N : 29 P2O5 : 10 Mg Newberyite 41 P2O5 : 14 Mg

 Recovered N Nutrient
Ecosystem Recovered
P Credits
P Nutrient
N Credits
Cost Map
Treated
Manure Wastewater
N and P removal
technology

5200-head swine farm Power Equipment

(finishing) Chemical
Capital and Operational Costs
Equipment, Chemical, Power $57,168.47 / year
Potential Revenue
Sale of fertilizer products (N & P) $58,538.63 / year

Additional Revenue: Sale of Non-

point Nutrient Credits (2:1 trading $ 61,449.93 / year
ratio)
 Conclusions
• Phosphorus recovery was combined with ammonia
recovery using gas-permeable membranes

• Aeration destroyed carbonates, increased pH, and

enhanced N capture

• The process provided approximately 100% phosphorus

recovery efficiencies

• With substantial ammonia capture, the recovered P

contained very-high phosphate grade (biomineral
newberyite)
https://www.ars.usda.gov/southeast-area/florence-sc/coastal-plain-soil-water-and-
plant-conservation-research/