Thermal treatment technologies for low moisture and dehydrated

Thermal treatment technologies for low moisture and dehydrated

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
O2
Limited O2
Zero O2
McKendry 2002
Gasification of poultry litter
End of March, Monaghan Ireland
Table: Product yields (* By difference)
Yield [wt%]
Char
23
Oil
33
Gas*
44
Chicken litter gasification processes
5
Chicken litter farm Monaghan
6
Chicken litter gasification processes
7
Pyrolysis
Feedstock
•
•
•
•
Organic chicken litter (Kantoher)
Chicken litter (Monaghan)
Cow manure (fodder silage)
Pig manure char (ECN)
Table: Drying process
PL
COW
Moisture content (RSD) [% w/w]
as received
air dried
60°C
24.25 (0.47)
1.55 (0.10)
86.27 (1.19)
9.86 (2.00) 1.36 (0.44)
Table: Char recoveries (oven dry basis)
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
PL M
PL M 400
PL M 600
PL gasification
Char recoveries db
average (RSD) [% w/w]
100
51.37 (0.89)
32.61 (1.75)
22.50
PL K
PL K 400
PL K 600
100
47.17 (1.30)
32.59 (0.28)
Cow
Cow 400
Cow 600
100
41.16 (0.88)
30.85 (1.80)
Heating value
High heating value (HHV): “the amount of heat produced by the complete combustion
of a unit quantity of fuel”
Table: HHV obtained from oxygen bomb calorimeter
Feedstock
PL M
PL K
Cow
PL Char gasification
16.12 (0.29)
16.53 (0.06)
16.92 (0.32)
14.26 (0.16)
HHV (RSD) [MJ/kg]
Char 400°C
PLM
19.89 (0.56)
PLK
20.79 (0.69)
Cow
23.59 (0.22)
Pig
20.52 (0.22)
PLM
PLK
Cow
Pig
Char 600°C
19.48 (0.17)
20.08 (0.18)
23.62 (0.41)
20.20 (0.34)
Table: Gas concentration obtained from gasification of poultry litter using Micro GC
Gas composition [%vol]
PL1
PL2
O2
5.46
4.18
N2
51.6
63.1
CH4
0.00
1.50
CO2
19.9
23.8
CO
0.00
20.9
H2
8.56
9.71
Ethane C2H6
14.5
19.8
Ethylene C2H4
0.00
0.00
Acetylene C2H2
0.00
0.00
11.3
18.4
Heating value [MJ/Nm3]
PL3
5.82
53.3
1.44
19.9
17.5
7.07
16.2
0.00
0.00
15.1
Collected gas in Tedlar gas sampling bags
NH3 ~ 1%
(Kitagawa AP-1 gas detector tube)
Elemental composition
Table: Elemental analysis (Vario EL Cube)
Elemental composition [wt.%db]
Molar ratio
polarity
PL M
PLM 400
PLM 600
PL gas
PL oil
H
6.1
3.1
1.2
1.6
0.9
C
38.5
46.8
50.5
48.6
55.6
N
4.3
6.4
4.2
3.9
13.2
S
0.5
0.7
0.8
0.6
0.0
O
32.5
14.3
1.5
3.2
30.3
Ash
18.2
28.8
41.9
42.2
?
H/C
1.9
0.8
0.3
0.4
0.2
O/C
0.6
0.2
0.0
0.0
0.4
(O+N)/C
0.9
0.6
0.3
0.3
1.3
PL K
PLK 400
PLK 600
6.7
4.8
1.9
42.6
52.3
50.3
4.2
6.7
4.1
0.2
0.6
1.1
33.0
8.7
5.0
13.3
26.9
37.6
1.9
1.1
0.4
0.6
0.1
0.1
0.9
0.6
0.3
Cow
Cow 400
Cow 600
4.2
3.2
1.3
48.6
60.8
61.3
1.7
2.5
2.0
0.1
0.0
0.0
36.4
6.3
10.4
9.1
27.2
24.9
1.0
0.6
0.3
0.6
0.1
0.1
0.7
0.2
0.3
Pig 400
Pig 600
2.5
1.1
50.6
57.8
2.4
1.8
0.2
0.4
10.5
3.7
33.8
35.3
0.6
0.2
0.2
0.0
0.3
0.2
Conclusion
C, Ash, S
H, O, polarity
increases with increasing pyrolysis temperatures
decrease with increasing pyrolysis temperature
Biochar standardization
1. January 2013
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
European Biochar Certificate
Van Krevelen diagram
Molar H/C ratio < 0.6
Molar O/C ratio < 0.4
Fig: Van Krevelen diagram
Oil, pH
Table: Water content by Karl Fischer Titration and pH measurement
Oil
pH
9.6
PL K
PL 400
PL 600
Pig 400
Pig 600
7.6
10.5
11.7
10.3
10.8
water content [% w/w]
79.7-94.0
Biochar volatile matter and toxicity
Volatile matter (VM) determination
• TGA (thermogravimatric analysis)
• 900°C (Oxygen free) 7min
Fixed carbon (FC) = 100% - VM - ash
Volatile matter (VM) in biochar
Deenik et al. 2010
High volatile matter
Volatile matter
Polar compounds
Macadamia nut shell charcoal
extracted with deionized water
Deenik et al. 2010
Non polar compounds (PAHs)
Volatile matter and toxicity
Biochar
Extraction
Fractionation
Toxicity
Seed germination
(radish, lettuce )
Dilution
(Minimal inhibition)
Plant growth
GC-MS
http://www.chemguide.co.uk/analysis/chromatography/column.html
http://crescentok.com/staff/jaskew/ISR/chemistry/liquidkey.htm
GC-MS results
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
Char: Pig manure
Extraction method: Soxhlet
Time: 24h
Sample size: 0.5g biochar/ml
Volume: 90ml
Temperature: about 120°C
3 0 0 0 0 0 0
2 8 0 0 0 0 0
2 6 0 0 0 0 0
2 4 0 0 0 0 0
2 2 0 0 0 0 0
2 0 0 0 0 0 0
1 8 0 0 0 0 0
1 6 0 0 0 0 0
1 4 0 0 0 0 0
1 2 0 0 0 0 0
1 0 0 0 0 0 0
hexane
8 0 0 0 0 0
6 0 0 0 0 0
4 0 0 0 0 0
2 0 0 0 0 0
6 . 0 0
T
im
8 . 0 01 0 . 0 0
1 2 . 0 0
1 4 . 0 0
1 6 . 0 0
1 8 . 0 0
2 0 . 0 0
2 2 . 0 0
2 4 . 0 0
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
1 . 1 e + 0 7
1 e + 0 7
9 0 0 0 0 0 0
8 0 0 0 0 0 0
Cleanup!
7 0 0 0 0 0 0
6 0 0 0 0 0 0
5 0 0 0 0 0 0
4 0 0 0 0 0 0
3 0 0 0 0 0 0
toluene
2 0 0 0 0 0 0
1 0 0 0 0 0 0
6 . 0 0
T
im e - - >
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
GC-MS results
A
b
u
n
d
a
n
c
e
T
1
5
0
0
0
0
0
1
4
0
0
0
0
0
1
3
0
0
0
0
0
1
2
0
0
0
0
0
1
1
0
0
0
0
0
1
0
0
0
0
0
0
9
0
0
0
0
0
8
0
0
0
0
0
7
0
0
0
0
0
6
0
0
0
0
0
5
0
0
0
0
0
4
0
0
0
0
0
3
0
0
0
0
0
2
0
0
0
0
0
1
0
0
0
0
0
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)
0
6
T
im
e
. 0
0
8
. 0
01
0
. 0
0
1
2
. 0
0
1
4
. 0
0
1
6
. 0
0
1
8
. 0
0
2
0
. 0
0
2
2
. 0
0
2
4
. 0
0
- - >
A b u n d a n c e
T IC :
P A H
_ S A M
1 _ T O L _ S O X .D
\
d a ta .m s
1 .1 e + 0 7
1 e + 0 7
9 0 0 0 0 0 0
8 0 0 0 0 0 0
7 0 0 0 0 0 0
Soxhlet
6 0 0 0 0 0 0
5 0 0 0 0 0 0
4 0 0 0 0 0 0
3 0 0 0 0 0 0
2 0 0 0 0 0 0
1 0 0 0 0 0 0
6 .0 0
T im e - - >
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
Some results
Abundanc e
2800000
T IC : S A M _ A S E _ T O L _ S P L IT .D \ d a ta .m s
T I C : N A P H T A L E N E D 1 6 . D \ d a t a . m s (* )
T I C : S A M _ A S E _ T O L _ S P L I T _ S P I K E . D \ d a t a . m s (* )
2600000
2400000
2200000
2000000
1800000
1600000
1400000
1200000
1000000
Biochar spiked with deut. Naphtalene
800000
600000
400000
200000
0
5 .0 0
5 .1 0
5 .2 0
5 .3 0
5 .4 0
5 .5 0
5 .6 0
5 .7 0
5 .8 0
5 .9 0
6 .0 0
6 .1 0
6 .2 0
6 .3 0
6 .4 0
6 .5 0
T im e -->
Feedstock and product characterization
Table: Analytical tools for feedstock and biochar characterisation
Property
Analytical tools
Property
Proximate analysis [wt.%]
Analytical tools
FTIR
Moisture content
105 °C
Surface functionality
Ash content
575 °C
spectroscopy
Volatile matter
950 °C
13C-NMR
Fixed carbon
100-M-A-V
Aromatic character
Ultimate analysis [wt.%]
Elemental analysis (C, H, N, O, S)
Inorganic fraction
Al, As, Cd, Ca, Cr, Cu, Fe, K,
Mg, Mn, Mo, Na, Ni, P, Pb, Zn
Solid state
nuclear magnetic resonance
Elemental analysis (Vario EL Cube)
Higher heating value [MJ/kg]
Bomb calorimetry
ICP-AES / MS
pH
Glas calomel electrode system
TGA
Inductively coupled plasma
AAS
Thermal profile
Specific surface area (SBET)
adsorption of N2
[g/m2]
(Equ. of Brunauer, Emmett, Teller)
Cation exchange capacity
Green -> complete
Yellow -> almost complete
Red -> still to come
Ammonium acetate extraction
method
Bulk density
SEM
Scanning electron microscopy
Thermogravimetric analysis,
Differnetial scanning calorimetry
Atomic absorption
Texture characterization and morphology
Morphology
Fourier transform infrared
Pyro probe
Gas evolution
Pyrolysis GC-MS (300-600°C)
Timetable
Table: Future Activities
Biochar production and characterization
Volatile matter
Biochar
production
Biochar
characterization
X
X
X
April
X
X
May
X
June
X
Schedule
March
CPMAS
13C-NMR
Plant growth
Extractions and
toxicity study
Data
collection
X
X
Statistical
analysis
X
X
X
July
X
X
August
X
X
X
September
X
X
X
October
X
November
X
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 Polycyclicaromatic 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