Pyrolysis of

Low Grade Biomass and WasteDr. Marion Carrier

m.carrier@aston.ac.uk

Fuel and Energy Research Forum – 27th June 2017 – Leeds

Primary processing

Combustion

Gasification

Pyrolysis

Liquefaction

Thermochemical conversionBiochemical conversion

Fermentation Enzymatic hydrolysis

Anaerobic digestion

2

Thermal behaviour

Larrain et al., Journal of Analytical and Applied Pyrolysis, https://doi.org/10.1016/j.jaap.2017.05.0115

Pyrolysis reactors

X oo

oo o

ooX X

X X

XX

X

X

X

XX

XX

X

XX

X

X

X

X

FuelGas

oo oooo

ooo

o

oooo ooBed material

Fixed bed Fluidized bed Entrained-flow

6

Pyrolysis oil – Chemicals

Plastics

-mixture of aliphatic and aromatic compounds C5-C8/low molecular weight compounds.- hydrocarbons: Benzene, Toluene, Xylene.-water

Coal

- light-benzene, toluene, xylenes, styrene, phenols, pyridine, anilines and quinolones- water

Biomass

-acids, alcohols, aldehydes, esters, ketones, phenols, guaiacols, syringols, sugars, furans, alkenes, PAHs, nitrogen compounds, and miscellaneous oxygenates-water

Wiser’s model of coal

Lignin’s unitscellulose

glucomannan

PMMA

PET

OH

O

OH

OH OHO

O

O

O

OH

OH

OH

O

O

O

O

OH

OHOH OH

O

O

1

2

3

R1, R2 = OCH3 or H

PE

β-1,4 bonds

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Low Grade Biomass and WasteForest residues & pulp and paper residuesDry urban wastes (construction and demolition waste); Logs;

Shrubs and wood residues; Sawdust; Bark; Wood chips; Damaged wood from plantation fires; sludges

Sugar Cane Bagasse

Vineyardsprunings

Black Wattle

Maize cob

Corn stover

Agricultural residues

Municipal waste

Electronic wasteManure

Waste tires

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Challenges for waste pyrolysis

• Collection and transport

• Heterogeneity

• Ash and water contents

• Physical preparation (on-site storage and blending, mixing and shredding)

• Presence of contaminants (alkali metals, halides, sulfur, nitrogen)

• Choice of the reactor

• Feeding

• Quality assessment of products

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Agricultural residues

Carrier et al., Journal of Analytical and Applied Pyrolysis, 96 (2012) 24-32. Uras et al., Journal of Analytical and Applied Pyrolysis, 98(2012) 207-213.

• surface functional groups on biochar surfaces• high cation capacities• mostly alkaline in nature• high aromatic carbon contents• high surface areas and micro-porosities

CparaffinicCsubstitutedCaromaticCphenolic

Ccarboxyl

Ccarbonyl

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Postulated mechanisms of the interactions of biochar with organic

contaminantsPostulated mechanisms of biochar interactions with inorganic contaminants

Adsorption mechanisms

13

Pulp and Paper sludges

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Pulp and Paper sludges

Energy conversion Chemicals

Biomaterials

Ridout et al., Journal of Analytical and Applied Pyrolysis 111 (2015) 64–75.Ridout et al., Energy Conversion and Management 111 (2016) 103–114.

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Municipal solid waste

Major dry MSW fractions in Mauritius are:-paper, -plastic,-and yard waste.

Pyrolysis of MSW:

•Producing fewer toxins due to the absence of oxygen;•Handling mixed plastic waste alternative to landfilling; 16

Municipal solid wasteA mixture (MX) between polypropylene (PP), cardboard (CB) and branches (BR) at a mass ratio 1:1:1.

Sample Ychar(%)

DTG Tpeak (°C)

DTG max(1/s)

Tonset(°C)

T range(°C)

PP 2.8 479 -0.0099 454 370-500CB 16.7 370 -0.0039 333 230-600BR 18.7 375 -0.0025 320 201-500MX 9.8 375, 481 -0.02, -0.03 327 200-415, 415-525

Gunasee et al., Journal of Analytical and Applied Pyrolysis 121 (2016) 50–61.

H2O

CH4

CO

CxHy

CO2

H2

DTG

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Synergism

BTXBIOMASS PE, PP

Dorado et al., Applied Catalysis B: Environmental 162 (2015) 338–345.18

Take-home messages

• Pyrolysis – chemistry and thermodynamics

• Design of reactor adapted to the type of feedstocks

• Control of products yields (e.i. bio-oil / tar / waxe, char and gas) possible

• Production of commodity and fine chemicals according to the nature of feedstocks

• Co-pyrolysis may provide a solution when it comes to increase yield of valuable products.

• Pyrolysis of low grade biomass and waste - A Win-Win-Win scenario• Volume reduction, alternative to landfilling (for MSW) and combustion• Production of high-value products (biomaterials and bio-chemicals)• ‘Permanently’ sequestering carbon and nitrogen / Carbon and mineral recycling

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AcknowledgementsCurrently working on an European Union and Horizon 2020 program

to financially support the

Action H2020-MSCA-IF-2014, Pyrochem, grant number 656967 entitled:

‘Biopolymers 13C tracking during fast pyrolysis of biomass-A 2-level mechanistic

investigation’.

And the EBRI team

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AcknowledgementsProf. Anthony Bridgwater

Dr. François-Xavier Collard

Prof. Johann Gorgens

Sanjana Gunasee

Dr. Ailsa G. Hardie

Jan-Erns Joubert

Prof. Hansie Knoetze

Tomas Larrain

Prof. Romeela Mohee

Prof. Ljubisa Radovic

Dr. Angelo Ridout

Umit Uras