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Technologies/systems for different manure and organic waste treatment options REMOVAL AND RECOVERY OF AMMONIA FROM LIQUID SWINE MANURE AND POULTRY LITTER USING GAS PERMEABLE MEMBRANES Vanotti M.B., Szogi A.A., Rothrock M.J. United States Department of Agriculture (USDA), Agricultural Research Service (ARS), Coastal Plains Research Center, 2611 W. Lucas St., Florence, South Carolina 29501, USA. Tel: +1 843 669 5203. [email protected] 1 INTRODUCTION New waste management methods are needed that can protect the environment and allow manure management to switch back to a recycling view of manure handling (Martinez et al., 2009). One of the largest environmental concerns associated with livestock and poultry production is the loss of ammonia gas (NH 3 ) from the manure (Aneja et al., 2001, Paerl, 1997). The Research Triangle Institute International (RTI, 2003) estimated the monetized economic benefits to North Carolina households of changes in environmental quality resulting from the generalized adoption of alternative waste technologies (2,300 swine operations). Results indicated that adoption of technologies that provides a 50% reduction of NH 3 emissions account for an estimated benefit of $190 million/year in avoided human health impacts (RTI, 2003). Similarly, volatilization of NH 3 inside poultry barns often results in an excessive accumulation of NH 3 in air, which can negatively affect the health of both workers and birds (Ritz et al., 2004). Although increased ventilation can lower the NH 3 in poultry houses to safe levels, it is expensive due to energy costs during winter months (Moore et al., 1995). Conservation and recovery of nitrogen (N) is also important in animal agriculture because of the high cost of commercial NH 3 fertilizers. Thus, there is major interest from producers and the public on implementing best control technologies that would abate NH 3 emissions from confined livestock and poultry operations by capturing and recovering N. We investigated the use of gas-permeable membranes as components of new processes to capture and recover ammonia from liquid manures as well as from the air in poultry houses and other livestock installations. Gas permeable membranes have been used in biomedical engineering applications in membrane oxygenator devices to imitate the function of the lungs in cardiopulmonary bypass and longer term life support, to add oxygen to, and to remove carbon dioxide from the blood (Gaylor, 1988). 2 MATERIALS AND METHODS The basic process includes the passage of gaseous ammonia through a microporous hydrophobic membrane and capture and concentration with circulating diluted acid on the other side of the membrane and production of a concentrated ammonium salt. The membranes can be assembled in modules or manifolds. We found that both tubular and flat gas-permeable membranes are useful extracting ammonia from manures, but in this paper we only show tubular configurations. They were used to remove ammonia of manure origin from both liquid and air. The enclosure consisted of a 2-L, polyethylene terephthalate (PET) plastic jar. The acid tank (Fig. 1) consisted of a 500- mL glass flask containing 300 mL 1N H 2 SO 4 . A peristaltic Manostat pump (Cole-Parmer,Vernon Hills, IL, USA) was used to continuously circulate the acid through the tubular membranes inside the chamber and back into the acid tank using flow rates of 70-80 mL day -1 . Gas-permeable tubing made of expanded polytetrafluoroethylene (ePTFE) (Phillips Scientific Inc., Rock Hill, SC) was used in the interior of the chamber for NH 3 capture. The length of the tubing used in all experiments was 66 cm with inner diameter 5.25 mm and wall thickness 1.00 mm. For liquid manure applications, the membrane manifolds were submerged in the manure liquid (1.8 L) and the ammonia was removed from the liquid matrix before it went into the air (Figure 1). The concept was successfully tested in ten batches using liquid swine manure containing about 1500 mg/L NH 4 -N. The same acidic solution was used in the consecutive batches. Concentrated acid was added to the acidic solution as needed when pH increased from <1 to about 2. For air applications, the membrane modules are placed exposed to the air close to the manure sources such

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Page 1: REMOVAL AND RECOVERY OF AMMONIA FROM LIQUID SWINE …ramiran.uvlf.sk/ramiran2010/docs/Ramiran2010_0190_final.pdf · Moore Jr, P A, Daniel T C, Edwards D R, Miller D M. 1995. Effect

Technologies/systems for different manure and organic waste treatment options

REMOVAL AND RECOVERY OF AMMONIA FROM

LIQUID SWINE MANURE AND POULTRY LITTER USING

GAS PERMEABLE MEMBRANES

Vanotti M.B., Szogi A.A., Rothrock M.J.

United States Department of Agriculture (USDA), Agricultural Research Service (ARS), Coastal Plains

Research Center, 2611 W. Lucas St., Florence, South Carolina 29501, USA. Tel: +1 843 669 5203.

[email protected]

1 INTRODUCTION

New waste management methods are needed that can protect the environment and allow manure management to

switch back to a recycling view of manure handling (Martinez et al., 2009). One of the largest environmental

concerns associated with livestock and poultry production is the loss of ammonia gas (NH3) from the manure (Aneja

et al., 2001, Paerl, 1997). The Research Triangle Institute International (RTI, 2003) estimated the monetized

economic benefits to North Carolina households of changes in environmental quality resulting from the generalized

adoption of alternative waste technologies (2,300 swine operations). Results indicated that adoption of technologies

that provides a 50% reduction of NH3 emissions account for an estimated benefit of $190 million/year in avoided

human health impacts (RTI, 2003). Similarly, volatilization of NH3 inside poultry barns often results in an excessive

accumulation of NH3 in air, which can negatively affect the health of both workers and birds (Ritz et al., 2004).

Although increased ventilation can lower the NH3 in poultry houses to safe levels, it is expensive due to energy costs

during winter months (Moore et al., 1995). Conservation and recovery of nitrogen (N) is also important in animal

agriculture because of the high cost of commercial NH3 fertilizers. Thus, there is major interest from producers and

the public on implementing best control technologies that would abate NH3 emissions from confined livestock and

poultry operations by capturing and recovering N. We investigated the use of gas-permeable membranes as

components of new processes to capture and recover ammonia from liquid manures as well as from the air in poultry

houses and other livestock installations. Gas permeable membranes have been used in biomedical engineering

applications in membrane oxygenator devices to imitate the function of the lungs in cardiopulmonary bypass and

longer term life support, to add oxygen to, and to remove carbon dioxide from the blood (Gaylor, 1988).

2 MATERIALS AND METHODS

The basic process includes the passage of gaseous ammonia through a microporous hydrophobic membrane and

capture and concentration with circulating diluted acid on the other side of the membrane and production of a

concentrated ammonium salt. The membranes can be assembled in modules or manifolds. We found that both

tubular and flat gas-permeable membranes are useful extracting ammonia from manures, but in this paper we only

show tubular configurations. They were used to remove ammonia of manure origin from both liquid and air. The

enclosure consisted of a 2-L, polyethylene terephthalate (PET) plastic jar. The acid tank (Fig. 1) consisted of a 500-

mL glass flask containing 300 mL 1N H2SO4. A peristaltic Manostat pump (Cole-Parmer,Vernon Hills, IL, USA)

was used to continuously circulate the acid through the tubular membranes inside the chamber and back into the acid

tank using flow rates of 70-80 mL day-1. Gas-permeable tubing made of expanded polytetrafluoroethylene (ePTFE)

(Phillips Scientific Inc., Rock Hill, SC) was used in the interior of the chamber for NH3 capture. The length of the

tubing used in all experiments was 66 cm with inner diameter 5.25 mm and wall thickness 1.00 mm. For liquid

manure applications, the membrane manifolds were submerged in the manure liquid (1.8 L) and the ammonia was

removed from the liquid matrix before it went into the air (Figure 1). The concept was successfully tested in ten

batches using liquid swine manure containing about 1500 mg/L NH4-N. The same acidic solution was used in the

consecutive batches. Concentrated acid was added to the acidic solution as needed when pH increased from <1 to

about 2. For air applications, the membrane modules are placed exposed to the air close to the manure sources such

Page 2: REMOVAL AND RECOVERY OF AMMONIA FROM LIQUID SWINE …ramiran.uvlf.sk/ramiran2010/docs/Ramiran2010_0190_final.pdf · Moore Jr, P A, Daniel T C, Edwards D R, Miller D M. 1995. Effect

Technologies/systems for different manure and organic waste treatment options

as poultry litter, composting pile, or the atmosphere above the liquid surface in manure tanks and pits. We tested

NH3 capture coming from solid poultry litter manures (Figure 2). The enclosure configuration was similar to the

one used for the liquid, except it contained 300 g of poultry litter with a height of about 5 cm. The membrane

manifolds were placed either above, on or below the poultry litter surface and its performance was compared (Figure

2).

FIGURE 1 Ammonia capture and concentration from liquid. A. Schematic of ammonia (NH3) capture from

liquid manure using hydrophobic gas-permeable tubular membrane: 1. Acid solution (NH3

Sink); 2. Container for acid solution; 3. Connecting tubing; 4. Fluid pump; 5. Tank with

wastewater; 6. Liquid manure (NH3 Emitting Source); 7. Hydrophobic, gas-permeable tubular

membrane. B and C. Pictures of bench reactor with submerged membrane tubing, one

submerged in water for illustration, and the other submerged in liquid swine manure used in

the experiments.

B CA B CA

FIGURE 2 Schematic of ammonia (NH3) capture from poultry litter using hydrophobic gas-permeable

membrane. The black tubing represents the impermeable Tygon® tubing and the light tubing

represents the gas-permeable tubing. Positioning of the tubular membranes with respect to the

litter surface were: Above (A), On (B) and Under (C) treatments. The dashed box in C

represents the nylon mesh pocket that supported the membrane tubing under the litter. Picture

shows the Above treatment.

3 RESULTS AND DISCUSSION

3.1 Removal and recovery of NH3 from liquid manures using gas permeable membranes

The idea of using gas permeable membranes to remove ammonia from liquid manure was successful. Although the

total ammonia concentration decreased slowly, the free ammonia (FA) decreased fast. Data in Fig. 3 show that as

ammonia was being removed from the liquid manure, the pH of the manure decreased. With the membrane

manifold installed, in 9 days the NH4-N concentration in the manure decreased about 50%, from 1,290 mg/L to 663

Page 3: REMOVAL AND RECOVERY OF AMMONIA FROM LIQUID SWINE …ramiran.uvlf.sk/ramiran2010/docs/Ramiran2010_0190_final.pdf · Moore Jr, P A, Daniel T C, Edwards D R, Miller D M. 1995. Effect

Technologies/systems for different manure and organic waste treatment options

mg/L. The pH decreased from 8.11 to 7.00. And the FA decreased 95%, from 1142 to 5.4 mg/L. Therefore, the

technology is useful to remove from liquid manure the free ammonia that is a portion of the total ammonia that has

been linked to ammonia emissions in swine farms (Szogi et al., 2006). We also evaluated application of alkali to

the manure to increase pH and accelerate ammonia removal by the membranes. The alkali was applied at the end of

batches 1-3 and at the beginning of batches 4-10 (Figure 4). We used various process pH in the range of 9 to 12.

With higher pH due to alkali addition, the ammonia in the liquid manure decreased faster and its recovery by the

membrane system was quicker. After ten batches, the ammonia was recovered and concentrated in a clear solution

containing 53,000 mg/L NH4-N (Fig. 4). Soluble compounds such as soluble COD did not pass through the gas

membrane, thus the concept represents an advantage for N removal from manure over biological systems.

0 2 4 6 8 10

0

50

100

150

6.5

7.0

7.5

8.0

8.5

9.0FA SWW

pH SWW

Sampling Time (days)

Fre

e A

mm

on

ia C

on

cen

trati

on

in S

WW

(m

g L

-1)

pH

0 2 4 6 8 100

50

100

150

0

500

1000

1500

2000

2500NH4N Trap (mg/L)

FA SWW (mg/L)

Sampling Time (days)

Fre

e A

mm

on

ia C

on

cen

trati

on

in S

WW

(m

g L

-1)

NH

4 -N c

on

cen

tratio

n

in A

cid

Tra

p (m

g/L

)

FIGURE 3 Removal of free ammonia (FA) from swine wastewater (SWW) and changes in pH of SWW

using gas permeable membranes.

0 14 28 42 56 70 84 980

500

1000

1500

4

6

8

10

12

14

5000

15000

25000

35000

45000

55000

NH4-N Recovered in Trap

pH SWW

NH4-N Removed from SWW

Sampling Time (days)

NH

4-N

co

ncen

trati

on

(mg

L-1

)

pH

FIGURE 4 Removal of NH4-N from swine wastewater (SWW) in ten consecutive batches using gas

permeable membranes. The same acid solution (trap) was used in all batches; the N

concentration in the solution increased from 0 to 53,000 mg/L.

3.2 Removal and recovery of NH3 from air in manure environments using gas permeable

membranes

The concept of using gas permeable membranes to remove ammonia from air in livestock facilities was also

successful. During the 21-day test, the NH4-N content in the litter decreased 58% by volatilization, from 1,369

mg/kg (± 9) to 792 (±7). In terms of recovery efficiency, 82% of the NH4-N was recovered during the first week of

the experiments, and 100% was recovered by the end of the third week. We found that the NH3 volatilized from the

litter can move down and below the litter layer and be effectively recovered with the membranes, as shown in the

Page 4: REMOVAL AND RECOVERY OF AMMONIA FROM LIQUID SWINE …ramiran.uvlf.sk/ramiran2010/docs/Ramiran2010_0190_final.pdf · Moore Jr, P A, Daniel T C, Edwards D R, Miller D M. 1995. Effect

Technologies/systems for different manure and organic waste treatment options

“under” treatment in Fig. 5. This provides flexibility in future membrane treatment system design. For example,

membrane manifolds may be placed below the bedding, or under caged production, thus minimizing exposure of

birds to NH3. Our results also show that aboveground placement of membrane manifolds is equally effective at

recovering NH3 from the litter, and these manifolds could be placed in grids near the surface or along waterer/feeder

lines, or even placed on the building walls. Considering the ammonia is captured inside the houses, this technology

help reduce ventilation and energy needs to lower ammonia levels in poultry houses.

1 3 5 7 9 11 13 15 17 19 210

100

200

300

400

Above

On

Under

Control

A

Sampling Time (days)

NH

3-N

Reco

vere

d (

mg

)

0 7 14 210

200

400

600

800

B

Sampling Time (days)

NH

4-N

co

nte

nt

of

PL

(m

g)

FIGURE 5 The mass of (A) NH3-N recovered with the membrane manifold and (B) NH4-N remaining in the

poultry litter manure (PL) from chambers comparing the effect of membrane positioning

(Figure 2). The bar represents the LSD0.05 value.

4 CONCLUSIONS

The results obtained in this study show that the use of gas-permeable membrane technology could be an effective

approach to recover ammonia from livestock wastewater and from the air in poultry litter and other livestock

operations. The final products are (1) reduced environmental emissions from livestock facilities, (2) cleaner air

inside the poultry and swine houses with benefits to bird/animal health, and (3) concentrated liquid nitrogen that can

be re-used in agriculture as a valued fertilizer.

REFERENCES

Aneja V P, Roelle P A, Murray G C, Southerland J, Erisman J W, Fowler D, Asman W A H, Patni N 2001.

Atmospheric nitrogen compounds II: emissions, transport, transformation, deposition and assessment.

Atmospheric Environment 35, 1903–1911.

Gaylor J D S 1988. Membrane oxygenators: Current developments in design and application. J. Biomedical

Engineering 10:541-547.

Martinez J, Dabert P, Barrington, S, Burton C 2009. Livestock waste treatment systems for environmental quality,

food safety, and sustainability. Bioresource Technology 100:5527-5536.

Moore Jr, P A, Daniel T C, Edwards D R, Miller D M. 1995. Effect of chemical amendments on ammonia

volatilization from poultry litter. Journal of Environmental Quality 24:293-300.

Paerl H W 1997. Coastal eutrophication and harmful algal blooms: importance of atmospheric deposition and

groundwater as ‘‘new’’ nitrogen and other nutrient sources. Limnology and Oceanography 42, 1154–1165.

Ritz C W, Fairchild B D, Lacy M P 2004. Implications of ammonia production and emissions from commercial

poultry facilities: A review. Journal of Applied Poultry Research 13:684-692.

RTI 2003. Benefits of adopting environmentally superior swine waste management technologies in North Carolina:

An environmental and economic assessment. Report prepared by RTI International, Research Triangle

Park, NC. RTI Project No 08251.000.

<www.cals.ncsu.edu/waste_mgt/smithfield_projects/phase1report04/appendix%20c-RTI.pdf>

Szogi A A, Vanotti M B, Stansbery A E 2006. Reduction of ammonia emissions from treated anaerobic swine

lagoons. Trans. ASABE 49(1):217-225.