thermocatalytic-reforming (tcr®) and tcr®-biochar …
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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
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
Sheet 2 © Fraunhofer UMSICHT
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
Sheet 3 © Fraunhofer UMSICHT
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
Sheet 4 © Fraunhofer UMSICHT
TCR®-Process Scheme
Catalytic Reforming
Carbonisation
Feedstock input
Biochar
Gas
Oil
Process water
Thermo-catalytic Reforming (TCR®) TCR® process
Sheet 5 © Fraunhofer UMSICHT
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 [%
]
Sheet 6 © Fraunhofer UMSICHT
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
Sheet 7 © Fraunhofer UMSICHT
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).
Sheet 8 © Fraunhofer UMSICHT
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
Sheet 9 © Fraunhofer UMSICHT
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
Sheet 10 © Fraunhofer UMSICHT
Source: www.intechopen.com
Digestate Wood
Sewage sludge
Brewers spent grain
Biochar TCR®-Biochar properties
Sheet 11 © Fraunhofer UMSICHT
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
Sheet 12 © Fraunhofer UMSICHT
Labscale experimantal setup for demineralisation
Modification examples Demineralisation and influence on BET surface
Thermostat
Water bath
Sample vials
Stirring plate Styrofoam
Sheet 13 © Fraunhofer UMSICHT
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
Sheet 14 © Fraunhofer UMSICHT
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
*
Sheet 15 © Fraunhofer UMSICHT
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
Sheet 16 © Fraunhofer UMSICHT
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]