Thermal treatment technologies for low moisture and dehydrated
manure feedstock
Natalie Taupe Supervisors: JJ Leahy, Witold Kwapinsky 13.05.2013
Contents
• Product characterization - pyrolysis and gasification
• Biochar volatile matter (VM) analysis and evaluation of toxicity
• Future plans
Thermo-chemical conversion of biomass
McKendry 2002
O2 Limited O2 Zero O2
Gasification of poultry litter
Yield [wt%]
Char 23
Oil 33
Gas* 44
Table: Product yields (* By difference)
End of March, Monaghan Ireland
5
Chicken litter gasification processes
6
Chicken litter farm Monaghan
7
Chicken litter gasification processes
Pyrolysis
Feedstock
• Organic chicken litter (Kantoher)
• Chicken litter (Monaghan)
• Cow manure (fodder silage)
• Pig manure char (ECN)
Sample preparation
• drying at 60°C, grinding,
sieving, mixing
Slow Pyrolysis process conditions
• Fixed bed reactor: 250 g/batch
• Heating rate: 20°C/min
• Max. Temperature: 400, 600°C
• Residence time: 1h
• Determined in triplicates
Moisture content (RSD) [% w/w]
as received air dried 60°C
PL 24.25 (0.47) 1.55 (0.10)
COW 86.27 (1.19) 9.86 (2.00) 1.36 (0.44)
Char recoveries db
average (RSD) [% w/w]
PL M 100
PL M 400 51.37 (0.89)
PL M 600 32.61 (1.75)
PL gasification 22.50
PL K 100
PL K 400 47.17 (1.30)
PL K 600 32.59 (0.28)
Cow 100
Cow 400 41.16 (0.88)
Cow 600 30.85 (1.80)
Table: Drying process
Table: Char recoveries (oven dry basis)
HHV (RSD) [MJ/kg]
Feedstock Char 400°C Char 600°C
PL M 16.12 (0.29) PLM 19.89 (0.56) PLM 19.48 (0.17)
PL K 16.53 (0.06) PLK 20.79 (0.69) PLK 20.08 (0.18)
Cow 16.92 (0.32) Cow 23.59 (0.22) Cow 23.62 (0.41)
PL Char gasification 14.26 (0.16) Pig 20.52 (0.22) Pig 20.20 (0.34)
Heating value High heating value (HHV): “the amount of heat produced by the complete combustion of a unit quantity of fuel”
Gas composition [%vol]
PL1 PL2 PL3
O2 5.46 4.18 5.82
N2 51.6 63.1 53.3
CH4 0.00 1.50 1.44
CO2 19.9 23.8 19.9
CO 0.00 20.9 17.5
H2 8.56 9.71 7.07
Ethane C2H6 14.5 19.8 16.2
Ethylene C2H4 0.00 0.00 0.00
Acetylene C2H2 0.00 0.00 0.00
Heating value [MJ/Nm3] 11.3 18.4 15.1
Table: HHV obtained from oxygen bomb calorimeter
Table: Gas concentration obtained from gasification of poultry litter using Micro GC
Collected gas in Tedlar gas sampling bags NH3 ~ 1% (Kitagawa AP-1 gas detector tube)
Elemental composition [wt.%db] Molar ratio polarity
H C N S O Ash H/C O/C (O+N)/C
PL M 6.1 38.5 4.3 0.5 32.5 18.2 1.9 0.6 0.9
PLM 400 3.1 46.8 6.4 0.7 14.3 28.8 0.8 0.2 0.6
PLM 600 1.2 50.5 4.2 0.8 1.5 41.9 0.3 0.0 0.3
PL gas 1.6 48.6 3.9 0.6 3.2 42.2 0.4 0.0 0.3
PL oil 0.9 55.6 13.2 0.0 30.3 ? 0.2 0.4 1.3
PL K 6.7 42.6 4.2 0.2 33.0 13.3 1.9 0.6 0.9
PLK 400 4.8 52.3 6.7 0.6 8.7 26.9 1.1 0.1 0.6
PLK 600 1.9 50.3 4.1 1.1 5.0 37.6 0.4 0.1 0.3
Cow 4.2 48.6 1.7 0.1 36.4 9.1 1.0 0.6 0.7
Cow 400 3.2 60.8 2.5 0.0 6.3 27.2 0.6 0.1 0.2
Cow 600 1.3 61.3 2.0 0.0 10.4 24.9 0.3 0.1 0.3
Pig 400 2.5 50.6 2.4 0.2 10.5 33.8 0.6 0.2 0.3
Pig 600 1.1 57.8 1.8 0.4 3.7 35.3 0.2 0.0 0.2
Elemental composition
Table: Elemental analysis (Vario EL Cube)
Conclusion C, Ash, S increases with increasing pyrolysis temperatures H, O, polarity decrease with increasing pyrolysis temperature
Biochar standardization
The goal of the guidelines is to ensure control of biochar production and quality based on well-researched, legally backed-up, economically viable and practically applicable processes.
15. May 2012
1. January 2013
European Biochar Certificate
Molar H/C ratio < 0.6 Molar O/C ratio < 0.4
Van Krevelen diagram
Fig: Van Krevelen diagram
Oil, pH
pH water content [% w/w] Oil 9.6 79.7-94.0
Table: Water content by Karl Fischer Titration and pH measurement
PL K 7.6
PL 400 10.5 PL 600 11.7 Pig 400 10.3
Pig 600 10.8
Volatile matter (VM) determination
• TGA (thermogravimatric analysis)
• 900°C (Oxygen free) 7min
Fixed carbon (FC) = 100% - VM - ash
Biochar volatile matter and toxicity
Deenik et al. 2010
Volatile matter (VM) in biochar
High volatile matter
Volatile matter
Macadamia nut shell charcoal extracted with deionized water
Polar compounds
Deenik et al. 2010
Non polar compounds (PAHs)
Biochar
Extraction Fractionation
http://www.chemguide.co.uk/analysis/chromatography/column.html
http://crescentok.com/staff/jaskew/ISR/chemistry/liquidkey.htm
Toxicity Seed germination (radish, lettuce )
Dilution (Minimal inhibition)
Volatile matter and toxicity
Plant growth
GC-MS
GC-MS results
6 . 0 0 8 . 0 01 0 . 0 01 2 . 0 01 4 . 0 01 6 . 0 01 8 . 0 02 0 . 0 02 2 . 0 02 4 . 0 0
2 0 0 0 0 0
4 0 0 0 0 0
6 0 0 0 0 0
8 0 0 0 0 0
1 0 0 0 0 0 0
1 2 0 0 0 0 0
1 4 0 0 0 0 0
1 6 0 0 0 0 0
1 8 0 0 0 0 0
2 0 0 0 0 0 0
2 2 0 0 0 0 0
2 4 0 0 0 0 0
2 6 0 0 0 0 0
2 8 0 0 0 0 0
3 0 0 0 0 0 0
T im e - - >
A b u n d a n c e
T I C : P A H _ S A M 1 _ H E X _ S O X . D \ d a t a . m s
6 . 0 0 8 . 0 0 1 0 . 0 01 2 . 0 01 4 . 0 01 6 . 0 01 8 . 0 02 0 . 0 02 2 . 0 02 4 . 0 0
1 0 0 0 0 0 0
2 0 0 0 0 0 0
3 0 0 0 0 0 0
4 0 0 0 0 0 0
5 0 0 0 0 0 0
6 0 0 0 0 0 0
7 0 0 0 0 0 0
8 0 0 0 0 0 0
9 0 0 0 0 0 0
1 e + 0 7
1 . 1 e + 0 7
T im e - ->
A b u n d a n c e
T I C : P A H _ S A M 1 _ T O L _ S O X . D \ d a t a . m s
hexane
toluene
Char: Pig manure Extraction method: Soxhlet Time: 24h Sample size: 0.5g biochar/ml Volume: 90ml Temperature: about 120°C
Cleanup!
GC-MS results
6 . 0 0 8 . 0 0 1 0 . 0 01 2 . 0 01 4 . 0 01 6 . 0 01 8 . 0 02 0 . 0 02 2 . 0 02 4 . 0 0
1 0 0 0 0 0 0
2 0 0 0 0 0 0
3 0 0 0 0 0 0
4 0 0 0 0 0 0
5 0 0 0 0 0 0
6 0 0 0 0 0 0
7 0 0 0 0 0 0
8 0 0 0 0 0 0
9 0 0 0 0 0 0
1 e + 0 7
1 . 1 e + 0 7
T im e - ->
A b u n d a n c e
T I C : P A H _ S A M 1 _ T O L _ S O X . D \ d a t a . m s
Soxhlet
6 . 0 0 8 . 0 01 0 . 0 01 2 . 0 01 4 . 0 01 6 . 0 01 8 . 0 02 0 . 0 02 2 . 0 02 4 . 0 00
1 0 0 0 0 0
2 0 0 0 0 0
3 0 0 0 0 0
4 0 0 0 0 0
5 0 0 0 0 0
6 0 0 0 0 0
7 0 0 0 0 0
8 0 0 0 0 0
9 0 0 0 0 0
1 0 0 0 0 0 0
1 1 0 0 0 0 0
1 2 0 0 0 0 0
1 3 0 0 0 0 0
1 4 0 0 0 0 0
1 5 0 0 0 0 0
T im e - - >
A b u n d a n c e
T I C : P A H _ S A M 1 _ T O L _ A S E . D \ d a t a . m s
Accelerated solvent extraction (ASE)
Some results
5 .0 05 .1 05 .2 05 .3 05 .4 05 .5 05 .6 05 .7 05 .8 05 .9 06 .0 06 .1 06 .2 06 .3 06 .4 06 .5 00
2 0 0 0 0 0
4 0 0 0 0 0
6 0 0 0 0 0
8 0 0 0 0 0
1 0 0 0 0 0 0
1 2 0 0 0 0 0
1 4 0 0 0 0 0
1 6 0 0 0 0 0
1 8 0 0 0 0 0
2 0 0 0 0 0 0
2 2 0 0 0 0 0
2 4 0 0 0 0 0
2 6 0 0 0 0 0
2 8 0 0 0 0 0
T im e -->
A b u n d a n c e
T IC : S A M _ A S E _ T O L _ S P L IT .D \ d a ta .m sT IC : N A P H T A L E N E D 1 6 .D \ d a ta .m s (*)
T IC : S A M _ A S E _ T O L _ S P L IT _ S P IK E .D \ d a ta .m s (*)
Biochar spiked with deut. Naphtalene
Feedstock and product characterization
Table: Analytical tools for feedstock and biochar characterisation
Property Analytical tools
Proximate analysis [wt.%]
Moisture content 105 °C
Ash content 575 °C
Volatile matter 950 °C
Fixed carbon 100-M-A-V
Ultimate analysis [wt.%]
Elemental analysis (C, H, N, O, S) Elemental analysis (Vario EL Cube)
Inorganic fraction
Al, As, Cd, Ca, Cr, Cu, Fe, K,
Mg, Mn, Mo, Na, Ni, P, Pb, Zn
ICP-AES / MS
Inductively coupled plasma
AAS
Atomic absorption
Texture characterization and morphology
Specific surface area (SBET)
[g/m2]
adsorption of N2
(Equ. of Brunauer, Emmett, Teller)
Morphology
SEM
Scanning electron microscopy
Property Analytical tools
Surface functionality
FTIR
Fourier transform infrared
spectroscopy
Aromatic character
13C-NMR
Solid state
nuclear magnetic resonance
Higher heating value [MJ/kg] Bomb calorimetry
pH Glas calomel electrode system
Thermal profile
TGA
Thermogravimetric analysis,
Differnetial scanning calorimetry
Cation exchange capacity Ammonium acetate extraction
method
Bulk density
Gas evolution
Pyro probe
Pyrolysis GC-MS (300-600°C)
Green -> complete Yellow -> almost complete Red -> still to come
Biochar production and characterization
Volatile matter
Schedule
Biochar
production
Biochar
characterization CPMAS 13C-NMR Plant growth
Extractions and
toxicity study
Data
collection
Statistical
analysis
March X X X
April X X
May X X X
June X X X X
July X X
August X X X
September X X X
October X
November X
Timetable
Table: Future Activities
Future work: • LCA • economic evaluation of combustion, gasification and pyrolysis
References D. P. Cole, E. a. Smith, and Y. J. Lee, “High-Resolution Mass Spectrometric Characterization of Molecules on Biochar from Pyrolysis and Gasification of Switchgrass,” Energy & Fuels, vol. 26, no. 6, pp. 3803–3809, Jun. 2012. J. L. Deenik, T. McClellan, G. Uehara, M. J. Antal, and S. Campbell, “Charcoal Volatile Matter Content Influences Plant Growth and Soil Nitrogen Transformations,” Soil Science Society of America Journal, vol. 74, no. 4, p. 1259, 2010. Freddo, Alessia, Chao Cai, and Brian J Reid. 2012. “Environmental Contextualisation of Potential Toxic Elements and Polycyclic Aromatic Hydrocarbons in Biochar.” Environmental Pollution (Barking, Essex : 1987) 171 (December) Hale, Sarah E, Johannes Lehmann, David Rutherford, Andrew R Zimmerman, Robert T Bachmann, Victor Shitumbanuma, Adam O’Toole, Kristina L Sundqvist, Hans Peter H Arp, and Gerard Cornelissen. 2012. “Quantifying the Total and Bioavailable Polycyclic Aromatic Hydrocarbons and Dioxins in Biochars.” Environmental Science & Technology 46 (5) (March 6) Hilber, Isabel, Franziska Blum, Jens Leifeld, Hans-Peter Schmidt, and Thomas D Bucheli. 2012. “Quantitative Determination of PAHs in Biochar: a Prerequisite to Ensure Its Quality and Safe Application.” Journal of Agricultural and Food Chemistry 60 (12) (March 28) Joseph S. D., M. Camps-Arbestain, Y. Lin, P. Munroe, C. H. Chia, J. Hook, L. van Zwieten, et al. 2010. “An Investigation into the Reactions of Biochar in Soil.” Australian Journal of Soil Research 48 (7) Keiluweit, Marco, Peter S Nico, Mark G Johnson, and Markus Kleber. 2010. “Dynamic Molecular Structure of Plant Biomass-derived Black Carbon (biochar).” Environmental Science & Technology 44 (4) (February 15) McGrath, Thomas, Ramesh Sharma, and Mohammad Hajaligol. 2001. “An Experimental Investigation into the Formation of Polycyclic-aromatic Hydrocarbons (PAH) from Pyrolysis of Biomass Materials.” Fuel 80 (12) (October) Sharma, Ramesh K, and Mohammad R Hajaligol. 2003. “Effect of Pyrolysis Conditions on the Formation of Polycyclic Aromatic Hydrocarbons (PAHs) from Polyphenolic Compounds.” Journal of Analytical and Applied Pyrolysis 66 (1-2) (January)
Thank you
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