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)

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