Thermocatalytic-Reforming (TCR®) and TCR®-biochar …

Engineering Conferences InternationalECI Digital ArchivesBiochar: Production, Characterization andApplications Proceedings

8-20-2017

Thermocatalytic-Reforming (TCR®) and TCR®-biochar propertiesMarkus HeberleinFraunhofer Institute for Environmental, Safety, and Energy Technology UMSICHT, Germany

Fabian StenzelFraunhofer Institute for Environmental, Safety, and Energy Technology UMSICHT, Germany

Andreas HornungFraunhofer Institute for Environmental, Safety, and Energy Technology UMSICHT, Germany

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Recommended CitationMarkus Heberlein, Fabian Stenzel, and Andreas Hornung, "Thermocatalytic-Reforming (TCR®) and TCR®-biochar properties" in"Biochar: Production, Characterization and Applications", Franco Berruti, Western University, London, Ontario, Canada RaffaellaOcone, Heriot-Watt University, Edinburgh, UK Ondrej Masek, University of Edinburgh, Edinburgh, UK Eds, ECI Symposium Series,(2017). http://dc.engconfintl.org/biochar/82

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Sheet 1 © Fraunhofer UMSICHT

Thermo-catalytic Reforming (TCR®) and TCR®-biochar properties

Dipl.-Ing. Markus Heberlein

Fraunhofer Institute UMSICHT Department for Biological Process Technologies

Sulzbach-Rosenberg, Germany

Alba, Italy 21th of August 2017


Thermo-catalytic Reforming (TCR®) and TCR®-biochar properties Agenda

TCR®

TCR® process

TCR® product yields and quality for digestate

Biochar

General char usage possibilities

Motivation for substitution of fossil char

TCR®-biochar properties

Modification examples

Pore size distribution

Demineralisation and influence on BET surface

Summary and Outlook


2-stage process

Pyrolysis step: 350 – 500 °C

Reformation step: 500 – 750 °C

Input material:

Biogenic residues

Usable products:

Biochar

Gas

Oil

CO2 neutral products

Thermo-catalytic Reforming (TCR®) TCR® process


TCR®-Process Scheme

Catalytic Reforming

Carbonisation

Feedstock input

Biochar

Gas

Oil

Process water

Thermo-catalytic Reforming (TCR®) TCR® process


TCR® oil quality from digestate against beech

wood pyrolysis oil and biodiesel

Reformer temperature [°C]

Thermo-catalytic Reforming (TCR®) TCR® product yields and quality for digestate

Ga

s m

ixtu

re [%

]


TCR®-Biochar TCR®- Oil TCR®- Gas

C 50 - 65 wt.%

H <3 wt.%

N <2 wt.%

S <1 wt.%

O* <2 wt.%

Ash 30 - 45 wt.%

LHV 16 – 23 MJ/kg

C 70 - 80 wt.%

H <10 wt.%

N <5wt.%

S <1 wt.%

O* <7 wt.%

Asche <0.5 wt.%

LHV 31 - 34 MJ/kg

H2 35 - 50 v/v%

CO2 23 - 27 v/v%

CO 13 - 17 v/v%

CH4 5 - 9 v/v%

CxHy 1 - 3 v/v%

LHV 14 MJ/kg

Thermo-catalytic Reforming (TCR®) TCR® product yields and quality for digestate

* difference Typical TCR® temperatures for digestate: 400 - 500 °C pyrolysis and 700 °C reforming


Biochar Motivation for substitution of charcoal and fossil char

Conventionel supply sources:

Charcoal:

Forests; often Tropical and rainforest deforestation & often uncontrolled production conditions (intervention in flora and fauna, environment & natural

landscape GHG emissions).

Brown and hard coal:

Open-cast mining (intervention in flora and fauna, environment &

natural landscape GHG emissions). Underground mining (lowering of terrain).


Co-combustion (coal power plants, biomass power plants, waste-to-energy plants)

Lime and cement production (CO2–neutral secondary fuel)

Home use (small scale furnace, Barbecue Char)

Livestock farming (feed additive, bedding, manure treatment)

Filter material / Active Carbon (water or exhaust gas treatment)

Metallurgical processes

Soil amendment (nutrient carrier, additive in substrates, adsorption material, CO2 sequestration)

.

.

.

Higher prices in material use instead of energetic use !

Hans-Peter Schmidt 2013

Biochar General char usage possibilities


Sewage sludge

C 22.1 wt.-%

H 0.9 wt.-%

N 2.0 wt.-%

S 1.0 wt.-%

O* 0.0 wt.-%

Ash 74.0 wt.-%

LHV 8.2 MJ/kg

Biochar TCR®-Biochar properties

C 64.0 wt.-%

H 1.0 wt.-%

N 1.4 wt.-%

S 0.5 wt.-%

O* 1.1 wt.-%

Ash 32.0 wt.-%

LHV 23 MJ/kg

Digestate Brewer‘s spent grain

C 72.6 wt.-%

H 0.1 wt.-%

N 4.6 wt.-%

S 0.4 wt.-%

O* 4.8 wt.-%

Ash 17.5 wt.-%

LHV 26 MJ/kg

Wood

C 89.8 wt.-%

H 2.2 wt.-%

N 0.3 wt.-%

S 0.1 wt.-%

O* 4.5 wt.-%

Ash 3.1 wt.-%

LHV 34.4 MJ/kg

C 25.0 wt.-%

H 4.3 wt.-%

N 3.6 wt.-%

S 0.9 wt.-%

O* 19.7 wt.-%

Ash 46.5 wt.-%

LHV 8.1 MJ/kg

C 41.6 wt.-%

H 5.1 wt.-%

N 1.6 wt.-%

S 0.3 wt.-%

O* 31.6 wt.-%

Ash 8.7 wt.-%

LHV 15.8 MJ/kg

C 48.6 wt.-%

H 6.9 wt.-%

N 4.3 wt.-%

S 0.5 wt.-%

O* 36.2 wt.-%

Ash 3.5 wt.-%

LHV 20.5 MJ/kg

C 45.0 wt.-%

H 6.4 wt.-%

N 0.1 wt.-%

S 0.1 wt.-%

O* 47.8 wt.-%

Ash 0.6 wt.-%

LHV 17.8 MJ/kg

* difference


Source: www.intechopen.com

Digestate Wood

Sewage sludge

Brewers spent grain

Biochar TCR®-Biochar properties


Ris

ing

Refo

rme

r Te

mp

era

ture

Pore size distribution of digestate TCR®-biochar by various reforming temperatures

Water injection

Modification examples Pore size distribution


Labscale experimantal setup for demineralisation

Modification examples Demineralisation and influence on BET surface

Thermostat

Water bath

Sample vials

Stirring plate Styrofoam


0,00

5,00

10,00

15,00

20,00

25,00

30,00

35,00

40,00

45,00

50,00

start 0,1 mol/l 1 mol/l 5 mol/l

Ash

co

nte

nt

[wt-

%]

HCl concentration

Demineralisation of digestate TCR biochar with various HCl solutions

Modification examples Demineralisation and BET surface

start 0,1 M

HCl

1,0 M

HCl

5,0 M

HCl

Ash content

[wt.-%] 46,1 39,3 21,3 19,9

Reduction

[%] - 14,7 53,8 56,9

HCl concentrations:

0.1 M, 1 M and 5 M

Particle size:

0.71 < x < 1 mm

Ratio biochar : acid

solution = 1:10

500 rpm

60 °C

Treatment time: 1 h

1 mol/l is sufficient by

1 h treatment duration


Various acids with 1 mol/l:

HNO3, Citric Acid and HCl

Particle size:

0.71 < x < 2 mm

Ratio biochar : acid solution = 1:10

500 rpm

30 °C

Treatment times:

1 h, 2 h, 4 h and 24 h

Only citric acid has significant

lower ash reduction

50 – 60 % ash reduction increases

the N2-BET surface up to about 2.5

times

Modification examples Demineralisation and influence on BET surface

*N2 BET surface measured by KIT, Karlsruhe Institute for Technology

*


http://de.disney.wikia.com/wiki/Dagobert_Duck

The TCR® technology is flexible and can use a wide range of biogenic material

TCR®-Biochar has a high stability (H/C and O/C ratios are comparable with anthracite and hard coal)

No organic pollutants left

Ash, C and nutrient content mainly dependig on feedstock

Biochars can be tailor-made for various applications

Ash content/reduction

Pore size distribution

BET surface

Material use of biochar shows ecological and economical added value faster market entry

Still more data needed to validate and show the potential of biochars

Summary and Outlook


Thermo-catalytic Reforming (TCR®) and TCR®-biochar properties

Thank you very much!

Contact:

Fraunhofer UMSICHT

Institute Branch Sulzbach-Rosenberg

An der Maxhütte 1

92237 Sulzbach-Rosenberg, Germany

E-Mail: [email protected]

Internet: http://www.umsicht-suro.fraunhofer.de

Dipl.-Ing. Markus Heberlein

Phone: +49 (0)9661-908-439

E-Mail: [email protected]

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Thermocatalytic-Reforming (TCR®) and TCR®-biochar …