Litter Generated Ammonia Captured by Activated Carbon Derived from Broiler Litter
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http://www.extension.org/67575 In 2011, the production rate of broilers was 8.6 billion with a value of $23.2 billion (USDA 2012). Both CERCLA and EPCRA have reporting requirements for ammonia (NH3) of 100 lb of NH3/d or 18.3 tons/yr, a level that may affect large animal production facilities (NRC 2003). Although USEPA (2009) has provided an exemption for animal waste producing farms under CERCLA for reporting hazardous air emissions, it is expected that this exemption will be revoked once valid methodologies are established for monitoring. Two of the 24 sites in the NAEMS monitoring study reported similar NH3 emissions of 3.6 – 5.3 tons of NH3 per house per year (Burns et al. 2009, Heber 2010). Emissions of this level indicate a need for developing technologies that can reduce the NH3 levels produced by broiler operations. This research is focused on the use of broiler litter as activated carbon (BAC) to reduce aerial NH3 generated by litter, an opportunity to not only reuse the manure, but also treat the emissions from or within broiler houses. The objective of this study was to evaluate the efficacy of BAC to remove NH3 volatilized from litter samples in a laboratory acid-trap system. Preliminary studies using NH3/air mixture indicated that the BAC capacity to adsorb NH3 was approximately double that of Vapure 612, a commercial carbon. In the litter emission study, the BAC and Vapure performance was comparable. Breakthrough for both carbons occurred within 14 hours of the test start. At the end of the 3 day test, the NH3 emission for BAC was 75% of the litter only control, whereas, the Vapure emission was 64% of the control. The results of the study demonstrate the potential for a cyclical waste utilization strategy in using broiler litter activated carbon to capture NH3 volatilized from litter.
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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.
- 3. COLLECTION
- 4. CARBON
- 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
- 15. Pellet Mill FurnacePelletized Manure
- 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
Notas do Editor
- 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.
- 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).