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LITTER GENERATED
AMMONIA CAPTURED BY
ACTIVATED CARBON
DERIVED FROM BROILER
LITTER
Kari Fitzmorris Brisolara, ScD, MSPH
Louisiana State University,
Health Sciences Center
Dana M. Miles, PhD and Isabel M. Lima, PhD
USDA Agricultural Research Service
RESEARCH OBJECTIVES
 Analyze waste sources for their potential as activated
carbons
 Create activated carbons and char from broiler litter
using steam activation to minimize cost and waste
production.
 Assess the physical properties of the carbons
 Determine the efficacy of the activated carbon and
char with regard to ammonia adsorption using
laboratory-based direct-measurement experiments
followed by manure emissions studies.
COLLECTION
CARBON
ACTIVATED
CARBONS
Poultry Cake Carbon 2500x Poultry Litter Carbon 250x
COST OF SOURCE MATERIAL FOR
ACTIVATED CARBON
Biosolid cost $3 to 10 / ton plus binder - pelletized.
Bituminous coal $60 to 80 / ton plus binder -
pelletized.
 (2010 average $60.88/ton)
Saving of >6 times in source material for activated
carbon
Litter Generated Ammonia Captured by Activated Carbon Derived from Broiler Litter
ACTIVATED CARBON MARKET
It is anticipated world demand for virgin activated carbon will rise 9.9 -
17 percent yearly through 2014.
The global market for activated carbon is forecast to reach a market
size of 2.3 million metric tons by the year 2017
One of the main drivers of growth is mercury control technology for
industrial air purification applications to meet new emissions
standards
The primary uses are currently water treatment and air purification
3 largest players in the industry – Calgon, Norit & MeadWestvaco.
Calgon reported cost of products sold increased 8.4% to $95.5 million in the third
quarter of 2011.
There are NO carbons with good metals adsorbing properties
currently on the market.
Current value for a high quality carbon is about $1.50+/lb.
COMMON SOURCES FOR ACTIVATED
CARBON
Bituminous coal
Coconut shells
Alternative Sources
 Nut shells (pecan, walnut)
 Sugarcane bagasse
 Soybean hulls
ACTIVATED CARBON FROM WASTE
Biosolids
 Most studies only examined pyrolyzed municipal
wastes – no activation
Other wastes
 Tires
 Paper mill waste
COMPARISON WITH OTHER
CARBONS
Sample Sample Description
Our carbons Made from pelletized manure, steam activated under N2
Coal, coconut
shell or wood
based
PUR RF Replacement Filter, coal derived, 10x20 mesh, originally in block for
Calgon F300 Filtrasorb 300, GAC by Calgon Carbon for removal of organic
pollutants from munic/indust wastewaters. Made from
bituminous coal.
Made from pelletized coal, ground coconut
shells/sawdust, steam activated under N2
Norit Darco Hg Powdered (<45 μm)
activated carbon made
from lignite coal.
ACTIVATED CARBON
Sources
 Poultry Litter
 Mississippi State University
 Includes bedding material (pine shavings)
 Pre-windrowed Poultry Litter
 North Louisiana private farm
 Includes bedding material (rice hulls)
ACTIVATED CARBON RESULTS
Pyrolysis and Activation
Chemical and Physical Properties
Ammonia:
Preliminary Study
Recent Results
CARBON CHARACTERIZATION
Physical properties
• Carbon yields, surface area, attrition resistance, bulk
density, particle size distribution, SEM characterization
Chemical properties
 Total surface
charge, pH, compositional
analysis, ash content, X-ray
analysis, NMR
Adsorptive properties
 Adsorption isotherms, kinetic studies, batch and column modes, for several
compounds
Pellet Mill FurnacePelletized Manure
PYROLYSIS AND ACTIVATION
700oC under nitrogen gas for 1 hr
Steam activation
 Flow rate 3 mL/min
800oC for 45 min
Acid washed (1hr 0.1M HCl)
Ground to 18 x 40 mesh
PHYSICAL/CHEMICAL PROPERTIES
Percent yield
Bulk density
Surface area
Surface charge
Elemental
analysis
Carbon
Nitrogen
Phosphorus
Sulfur
PHYSICAL/
CHEMICAL
PROPERTIES
OF MANURE
AND
RESULTING
ACTIVATED
CARBONS.
MS
Litter
LA
Litter
% Yield (%) 22.2 20.0
BET Surface Area (m2/g) 461.2 523.8
Element mg/g
Calcium Raw 23.3 37.3
Activated
Carbon
62.8 114
Copper Raw 0.47 0.56
Activated
Carbon
2.20 3.06
Iron Raw 1.98 2.09
Activated
Carbon
7.42 12.3
Magnesium Raw 6.39 14.5
Activated
Carbon
15.3 47.4
Phosphoru
s
Raw 13.9 12.1
Activated
Carbon
34.8 48.2
Sulfur Raw 7.73 19.1
Activated 13.7 49.0
CARBON PHYSICAL
PROPERTIES
Yield Surface Area Attrition
% m2
/ g %
Broiler Litter 22.7 441 17.9
Broiler Cake 11.0 395 24.0
Turkey Litter 21.1 414 20.0
Turkey Cake 16.4 394 25.8
PUR RF - 474 32.0
Coal 70.0 0 13.8
Coconut Shell 22.7 843 22.3
Wood 17.9 849 15.6
Swine 17.0 419 20.6
Dairy 26.8 318 22.1
pH
7.9
8.2
8.0
8.1
4.9
3.1
2.9
6.9
9.0
6.4
PRELIMINARY AMMONIA STUDY
 Preliminary studies show the carbon from broiler litter (BAC)
performed better than the commercial carbon with regard to NH3
adsorption
 The broiler litter carbon resisted breakthrough 21% longer than
the Vapure 612, the commercial carbon.
 The concentration of the NH3 gas was 7.05 mg N/min for the
broiler litter assessment and 6.87 mg N/min for the Vapure trial.
 The removal rates were 0.98 mg N/min for the BAC which was
the maximum allowed by the experimental flow rates for 20
minutes.
 The rate of adsorption of the Vapure carbon at 0.42 mg N/min was
less than half of that of the BAC.
Litter Generated Ammonia Captured by Activated Carbon Derived from Broiler Litter
Litter Generated Ammonia Captured by Activated Carbon Derived from Broiler Litter
PRELIMINARY AMMONIA RESULTS
Sample ID Total
Adsorption
(mg N)
mg N
Adsorbed/
gram
Carbon
Breakthrough
Time
(seconds)
BAC 19.6 2.07 63
Vapure 8.3 1.02 50
CUMULATIVE LITTER AMMONIA EMISSION FOR THE LITTER ONLY
(CONTROL), BROILER ACTIVATED CARBON COLUMN (BAC), AND
COMMERCIAL CARBON COLUMN (VAPURE).
A,B MEANS HAVING DIFFERENT SUPERSCRIPTS DIFFER SIGNIFICANTLY BASED ON LSD COMPARISONS
(P≤0.05).
0
2
4
6
8
10
12
14
0 24 48 72
Time (hr)
CumulativeLitterAmmoniaEmitted(mgN)
Control
BAC
Vapure
a
b
a
b
a
b
a
a
b
b
c
RECENT RESULTS - SCHEMATIC
PRE-WINDROW CARBON ADSORPTION
PERFORMANCE WITH 1000 PPM
AMMONIA
0
100
200
300
400
500
600
700
800
900
1,000
0 50 100 150 200
Ammonia(ppm)
Time (minutes)
10g 5g 2g 1g
CONCLUSIONS
Waste sources tested result in carbons with
low surface areas and low percent yields as
compared to commercial grade carbons
Activated carbon made from broiler litter is
efficacious for NH3 adsorption originating from
litter
Broiler activated carbon performed better than
commercial Vapure carbon in preliminary
tests, but was comparable to the commercial
carbon in the litter emission study
The BAC represents the re-use of a waste
material, deriving inherent value not only from
its role as a carbon, but also as a disposal
mechanism for the poultry waste itself
RECOMMENDATIONS
Analysis of the surface properties of the
carbons
Surface functional groups
Equalize the driving force for accurate
comparison
Assessment of the feasibility of the use of
the carbons in granular form
 Adsorption
 Regeneration/attrition

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Litter Generated Ammonia Captured by Activated Carbon Derived from Broiler Litter

  • 1. LITTER GENERATED AMMONIA CAPTURED BY ACTIVATED CARBON DERIVED FROM BROILER LITTER Kari Fitzmorris Brisolara, ScD, MSPH Louisiana State University, Health Sciences Center Dana M. Miles, PhD and Isabel M. Lima, PhD USDA Agricultural Research Service
  • 2. RESEARCH OBJECTIVES  Analyze waste sources for their potential as activated carbons  Create activated carbons and char from broiler litter using steam activation to minimize cost and waste production.  Assess the physical properties of the carbons  Determine the efficacy of the activated carbon and char with regard to ammonia adsorption using laboratory-based direct-measurement experiments followed by manure emissions studies.
  • 5. ACTIVATED CARBONS Poultry Cake Carbon 2500x Poultry Litter Carbon 250x
  • 6. COST OF SOURCE MATERIAL FOR ACTIVATED CARBON Biosolid cost $3 to 10 / ton plus binder - pelletized. Bituminous coal $60 to 80 / ton plus binder - pelletized.  (2010 average $60.88/ton) Saving of >6 times in source material for activated carbon
  • 8. ACTIVATED CARBON MARKET It is anticipated world demand for virgin activated carbon will rise 9.9 - 17 percent yearly through 2014. The global market for activated carbon is forecast to reach a market size of 2.3 million metric tons by the year 2017 One of the main drivers of growth is mercury control technology for industrial air purification applications to meet new emissions standards The primary uses are currently water treatment and air purification 3 largest players in the industry – Calgon, Norit & MeadWestvaco. Calgon reported cost of products sold increased 8.4% to $95.5 million in the third quarter of 2011. There are NO carbons with good metals adsorbing properties currently on the market. Current value for a high quality carbon is about $1.50+/lb.
  • 9. COMMON SOURCES FOR ACTIVATED CARBON Bituminous coal Coconut shells Alternative Sources  Nut shells (pecan, walnut)  Sugarcane bagasse  Soybean hulls
  • 10. ACTIVATED CARBON FROM WASTE Biosolids  Most studies only examined pyrolyzed municipal wastes – no activation Other wastes  Tires  Paper mill waste
  • 11. COMPARISON WITH OTHER CARBONS Sample Sample Description Our carbons Made from pelletized manure, steam activated under N2 Coal, coconut shell or wood based PUR RF Replacement Filter, coal derived, 10x20 mesh, originally in block for Calgon F300 Filtrasorb 300, GAC by Calgon Carbon for removal of organic pollutants from munic/indust wastewaters. Made from bituminous coal. Made from pelletized coal, ground coconut shells/sawdust, steam activated under N2 Norit Darco Hg Powdered (<45 μm) activated carbon made from lignite coal.
  • 12. ACTIVATED CARBON Sources  Poultry Litter  Mississippi State University  Includes bedding material (pine shavings)  Pre-windrowed Poultry Litter  North Louisiana private farm  Includes bedding material (rice hulls)
  • 13. ACTIVATED CARBON RESULTS Pyrolysis and Activation Chemical and Physical Properties Ammonia: Preliminary Study Recent Results
  • 14. CARBON CHARACTERIZATION Physical properties • Carbon yields, surface area, attrition resistance, bulk density, particle size distribution, SEM characterization Chemical properties  Total surface charge, pH, compositional analysis, ash content, X-ray analysis, NMR Adsorptive properties  Adsorption isotherms, kinetic studies, batch and column modes, for several compounds
  • 16. PYROLYSIS AND ACTIVATION 700oC under nitrogen gas for 1 hr Steam activation  Flow rate 3 mL/min 800oC for 45 min Acid washed (1hr 0.1M HCl) Ground to 18 x 40 mesh
  • 17. PHYSICAL/CHEMICAL PROPERTIES Percent yield Bulk density Surface area Surface charge Elemental analysis Carbon Nitrogen Phosphorus Sulfur
  • 18. PHYSICAL/ CHEMICAL PROPERTIES OF MANURE AND RESULTING ACTIVATED CARBONS. MS Litter LA Litter % Yield (%) 22.2 20.0 BET Surface Area (m2/g) 461.2 523.8 Element mg/g Calcium Raw 23.3 37.3 Activated Carbon 62.8 114 Copper Raw 0.47 0.56 Activated Carbon 2.20 3.06 Iron Raw 1.98 2.09 Activated Carbon 7.42 12.3 Magnesium Raw 6.39 14.5 Activated Carbon 15.3 47.4 Phosphoru s Raw 13.9 12.1 Activated Carbon 34.8 48.2 Sulfur Raw 7.73 19.1 Activated 13.7 49.0
  • 19. CARBON PHYSICAL PROPERTIES Yield Surface Area Attrition % m2 / g % Broiler Litter 22.7 441 17.9 Broiler Cake 11.0 395 24.0 Turkey Litter 21.1 414 20.0 Turkey Cake 16.4 394 25.8 PUR RF - 474 32.0 Coal 70.0 0 13.8 Coconut Shell 22.7 843 22.3 Wood 17.9 849 15.6 Swine 17.0 419 20.6 Dairy 26.8 318 22.1 pH 7.9 8.2 8.0 8.1 4.9 3.1 2.9 6.9 9.0 6.4
  • 20. PRELIMINARY AMMONIA STUDY  Preliminary studies show the carbon from broiler litter (BAC) performed better than the commercial carbon with regard to NH3 adsorption  The broiler litter carbon resisted breakthrough 21% longer than the Vapure 612, the commercial carbon.  The concentration of the NH3 gas was 7.05 mg N/min for the broiler litter assessment and 6.87 mg N/min for the Vapure trial.  The removal rates were 0.98 mg N/min for the BAC which was the maximum allowed by the experimental flow rates for 20 minutes.  The rate of adsorption of the Vapure carbon at 0.42 mg N/min was less than half of that of the BAC.
  • 23. PRELIMINARY AMMONIA RESULTS Sample ID Total Adsorption (mg N) mg N Adsorbed/ gram Carbon Breakthrough Time (seconds) BAC 19.6 2.07 63 Vapure 8.3 1.02 50
  • 24. CUMULATIVE LITTER AMMONIA EMISSION FOR THE LITTER ONLY (CONTROL), BROILER ACTIVATED CARBON COLUMN (BAC), AND COMMERCIAL CARBON COLUMN (VAPURE). A,B MEANS HAVING DIFFERENT SUPERSCRIPTS DIFFER SIGNIFICANTLY BASED ON LSD COMPARISONS (P≤0.05). 0 2 4 6 8 10 12 14 0 24 48 72 Time (hr) CumulativeLitterAmmoniaEmitted(mgN) Control BAC Vapure a b a b a b a a b b c
  • 25. RECENT RESULTS - SCHEMATIC
  • 26. PRE-WINDROW CARBON ADSORPTION PERFORMANCE WITH 1000 PPM AMMONIA 0 100 200 300 400 500 600 700 800 900 1,000 0 50 100 150 200 Ammonia(ppm) Time (minutes) 10g 5g 2g 1g
  • 27. CONCLUSIONS Waste sources tested result in carbons with low surface areas and low percent yields as compared to commercial grade carbons Activated carbon made from broiler litter is efficacious for NH3 adsorption originating from litter Broiler activated carbon performed better than commercial Vapure carbon in preliminary tests, but was comparable to the commercial carbon in the litter emission study The BAC represents the re-use of a waste material, deriving inherent value not only from its role as a carbon, but also as a disposal mechanism for the poultry waste itself
  • 28. RECOMMENDATIONS Analysis of the surface properties of the carbons Surface functional groups Equalize the driving force for accurate comparison Assessment of the feasibility of the use of the carbons in granular form  Adsorption  Regeneration/attrition

Hinweis der Redaktion

  1. Bituminous coal contains 45-86% carbon and has two to three times the heating value of lignite. Bituminous coal was formed under high heat and pressure It is the most abundant rank of coal found in the United States, accounting for about half of U.S. coal production.
  2. In Figure 4 below, the similarities between the two carbon sources should be noted. The control generated more NH3 than when the litter emission was captured using either activated carbon column. Though the BAC achieved breakthrough later than the Vapure, which indicates better initial performance, the Vapure carbon was able to surpass the BAC over time. However, the two did not appear statistically different until the final measurement at 62 hours (p=0.0234).