2. Content:
Hydrothermal conversion:
- overview
- carbonization
- liquefaction
chemicals
Conclusion
Feedstock:

3. Properties of Water 374 °C Data: Steam tables
Auch das Ionenprodukt des Wasser ist eine Funktion von Dichte und Temperatur. Da die Ionenbildung ein stark endothermer Prozess ist, ergibt sich aber ein etwas anderer Verlauf als bei der relativen Dielektrizitätskonstante. Das Ionenprodukt ist unterhalb der kritischen Temperatur und bei höheren Drücken auch oberhalb der kritischen Temperatur wesentlich höher als unter Normalbedingungen. Diese um Größenordnungen höhere Ionenkonzentration führt zur Katalyse von Reaktionen, die normalerweise den Zusatz von Säuren und Basen erfordern.
Data: Steam tables

4. Hydrothermal Conversions of Biomass
Hydrothermal Biomass Gasification A. Kruse, J. of Supercritical Fluids 47, , 2009.
Water - A magic solvent for biomass conversion.A. Kruse, N. Dahmen, The Journal of Supercritical Fluids 96, 36-45, 2015.

5. Furfurales Different short Intermediates
Cellulose
Glucose ⇄ Fructose
Furfurales
Different short
Intermediates
Phenols
Gases: H2, CO2, CH4, CO
Char / Coke
Using groups the chemistry of hydrothermal biomass conversion looks simple…
Hydrothermal Biomass Gasification A. Kruse, J. of Supercritical Fluids 47, , 2009.

6. Hydrothermal Carbonization: Chemistry
Char and coke formation as unwanted side reaction of the hydrothermal biomass gasification T. Karayildirim, A. Sinag, A. Kruse; Chemical Engineering & Technology 31, , 2008

7. Hydrothermal Carbonization: Particles
Experimental comparison of hydrothermal and vapothermal carbonization
A. Funke, F. Reebs, A. Kruse; Fuel Processing Technology 115, , 2013.

8. Hydrothermal Carbonization: Properties
HTC-product from digestate, spheres
0,002
1/°C
HTC-product from digestate, porous
Digestate 50
100
150
200
250
300
350
400
450
500
550
600
650
700
750
800
850 °C
Experimental comparison of hydrothermal and vapothermal carbonization
A. Funke, F. Reebs, A. Kruse; Fuel Processing Technology 115, , 2013.

9. Hydrothermal Carbonization: Kinetics
Biomass
Conversion calculated
Residue
Conversion measured
Coal 1
Coal 2
A. Kruse, R. Grandl, Hydrothermale Karbonisierung: 3. Kinetisches Modell
Hydrothermal Carbonization: 3. Kinetic Model. Chemie Ingenieur Technik 87 (2015)
A. Kruse, F. Badoux, R. Grandl, D. Wüst, Hydrothermal carbonization: 2. Kinetics of draff conversion. Chemie-Ingenieur-Technik 84 (2012)

10. Reactors for Hydrothermal Carbonization
in collaboration with
&
The carbon materials and process waters for physical, chemical and biological investigations are produced within this risk-benefit analysis as part of the project CarboSolum in which Mrs. Dr. Holweg, the LTZ Augustenberg Karlsruhe-Durlach, the Institute of Catalytic Research and –technology from Karlsruhe Institute of Technology as well as other scientific institutions and the company AVA-CO2 Research GmbH are involved.
At the Institute of Catalytic Research and Technology as well as at the University of Hoheneheim HTC-experiments at lab and technical scale are possible. By working together with the company AVA-CO2 the production of greater amounts of HTC-products for providing field experiments for example have been conducted in a pilot and demonstration plant.
Autoclaves A-0.01 and A-0.25
Pilot plant K3-335
Demonstration plant HTC-0

11. Diploma Thesis Dominik Wüst, Master Thesis Gero Becker
Hydrothermal Carbonization for Phosphate Recovery
Solved Phosphate
60%
30%
Time / h
Mg,NH4-Phosphate
HTC -> Leaching -> Precipation (N,P)
Nearly 80 % yield (phoshate) from sewage sludge!
Diploma Thesis Dominik Wüst, Master Thesis Gero Becker

12. Hydrothermal Carbonization – Applications
Energy Carrier
Soil improver (?) *
Activated Coal (?)
Catalyst support (?)
Super-capacitors (?)
Fuel Cells (?)
Carbon Black (?)
Material for immobilization of microorganism (?)**
* I. Bargmann, M.C. Rillig, A. Kruse, J.M. Greef, M. Kücke, Initial and subsequent effects of hydrochar amendment on germination and nitrogen uptake of spring barley. Journal of Plant Nutrition and Soil Science 177 (2014)
**I. Bargmann, R. Martens, M.C. Rillig, A. Kruse, M. Kücke, Hydrochar amendment promotes microbial immobilization of mineral nitrogen. Journal of Plant Nutrition and Soil Science 177 (2014)

13. Hydrothermal Conversions of Biomass
Hydrothermal Biomass Gasification A. Kruse, J. of Supercritical Fluids 47, , 2009.
Water - A magic solvent for biomass conversion.A. Kruse, N. Dahmen, The Journal of Supercritical Fluids 96, 36-45, 2015.

14. Comparison HTL FP Fossil H2O (wt%) <0.2 15-30 0.1 Density (kg/m³)
940
Viscosity (Pa s)
0.75-1
0.18
HHV (MJ/kg)
30-36
16-19 40
N. Dahmen, E. Henrich, A. Kruse, K. Raffelt, Biomass liquefaction and gasification, in:H.P. Blaschek, N. Qureshi, A. Vertes, H. Yukawa (Eds.), Biomass to Biofuels: strategies for global industries, 2010, p. 91.

15. Organics dissolved in the aqueous phase
Temperature: ºC Pressure: MPa
Hydrothermal Liquefaction: Algae I
Gas
Organics dissolved in the aqueous phase
Microalgae
Bio-Oil
Solid residue
Assessing microalgae biorefinery routes for the production of biofuels via hydrothermal liquefaction , D. Lòpez Barreiro, C. Samorí, G. Terranella, U. Hornung, A. Kruse, and W. Prins, Bioresource Technology, 174 (2014)

16. Hydrothermal Liquefaction: Algae II
Temperature: 350 °C Holding time: 15 min Biomass in water: 10% dw
Microalgae
Macroalgae
Assessing microalgae biorefinery routes for the production of biofuels via hydrothermal liquefaction , D. Lòpez Barreiro, C. Samorí, G. Terranella, U. Hornung, A. Kruse, and W. Prins, Bioresource Technology, 174 (2014)

17. Chemicals: Hydroxymethylfurfural I
Pictures: AVA Biochem

18. Chemicals: Hydroxymethylfurfural II
Biomass

19. Chemicals: Phenols
Modeling the lignin degradation kinetics in a ethanol/formic acid solvolysis approach. part 2. validation and transfer to variable conditions, D. Forchheim, J.R. Gasson, U. Hornung, A. Kruse, and T. Barth, , Industrial and Engineering Chemistry Research, 51 (2012)

20. Chemicals: Phenols II
Within our research centre, five institutes are involved in these activities.
The site, where the pilot plant is envisage to build up, is shown in green.
Partners from nearby universities are already integrated into our fundamental studies.
With our cooperation partners Lurgi and Future Energy we will build up the pilot plant and bring the process into market.
Modeling the lignin degradation kinetics in an ethanol/formic acid solvolysis approach. Part 1. Kinetic model development
D.Forchheim, J.R. Gasson, U. Hornung, A. Kruse, T.Barth
Industrial and Engineering Chemistry Research 51 (32), , 2012

21. Conclusion Suitable for wet biomass
Higher selectivity, lower temperature than dry processes, high pressure
Applications of HTC under research
Hydrothermal liquefaction for algae (waste water treatment)
Platform chemicals (HMF, Phenols) available

22. Tailor-made hydrochar
Many Thanks!
Tailor-made hydrochar

23. HTC product characterization
Stelta et al., Crelling et al., 2006
Parameter
HTC-coal
Torrefied wood
Lignite
Carbon content (%), daf
50-70
51-76
~70
HHV (MJ/kg), daf
25-30
20-22
~28
Volatile matter (%), daf
60-70 -
~60
BET (m²), N2
1-10
Wheat straw °C; 1 h °C; 10 h

24. Coalification of biomass
for cauliflower, grass and straw