Hydrothermal liquefaction and carbonization for fuels and materials

Content:

Hydrothermal conversion:- overview- carbonization- liquefaction

chemicals

Conclusion

Feedstock:

100 200 300 400 500 600 700

0

500

1000

100 200 300 400 500 600 7000

50

100

0 100 200 300 400 500 600 70010

15

20

25

g/l

Organic compoundsand gases are solved.

Salts are solved

/ °C

Pressure: 25 MPa 55 MPa

pkrit

:22,1 MPa

pKw

Properties of Water

Data: Steam tables

374 °C

Hydrothermal Conversions of Biomass

Hydrothermal Biomass GasificationA. Kruse, J. of Supercritical Fluids 47, 391-399, 2009.

100 200 300 400 500 600 700

0

5

10

15

20

25

30

35

H2

Oil,Tarr

Chemicals

H2CH

4

C

p /

MP

a

/ °C

Water - A magic solvent for biomass conversion.A. Kruse, N. Dahmen, The Journal of Supercritical Fluids 96, 36-45, 2015.

Cellulose

Glucose ⇄ Fructose

FurfuralesDifferent short

Intermediates

Phenols

Gases: H2, CO2, CH4, CO Char / Coke

O

Hydrothermal Biomass GasificationA. Kruse, J. of Supercritical Fluids 47, 391-399, 2009.

Biomass Cellulose

Solved Intermediates

Coke (Carbon particles)

Char (Carbon particles)

A B

Degradation

Polymerisation

Solid-solid-conversion

Char and coke formation as unwanted side reaction of the hydrothermal biomass gasificationT. Karayildirim, A. Sinag, A. Kruse; Chemical Engineering & Technology 31, 1561-1568, 2008

Hydrothermal Carbonization: Chemistry

Experimental comparison of hydrothermal and vapothermal carbonizationA. Funke, F. Reebs, A. Kruse; Fuel Processing Technology 115, 261-269, 2013.

Hydrothermal Carbonization: Particles

HTC-product from digestate, spheres

HTC-product from digestate, porous

Digestate

1/°C0,002

°C50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850

Experimental comparison of hydrothermal and vapothermal carbonizationA. Funke, F. Reebs, A. Kruse; Fuel Processing Technology 115, 261-269, 2013.

Hydrothermal Carbonization: Properties

0,0 0,2 0,4 0,6 0,80,0

0,2

0,4

0,6

0,8

1,0

Um

satz

be

rech

ne

t

Umsatz gemessen

T

K

b etf

128841766,019,34

0,0019 0,0020 0,0021 0,0022-12,0

-11,5

-11,0

-10,5

-10,0

CO2

H2O

10

00

* ln

(k/k

')

T -1/ K -1

Conversion measured

Con

vers

ion

calc

ulat

ed

Biomass

Coal 1

Coal 2

Residue

Hydrothermal Carbonization: Kinetics

A. Kruse, R. Grandl, Hydrothermale Karbonisierung: 3. Kinetisches ModellHydrothermal Carbonization: 3. Kinetic Model. Chemie Ingenieur Technik 87 (2015) 449-456A. Kruse, F. Badoux, R. Grandl, D. Wüst, Hydrothermal

carbonization: 2. Kinetics of draff conversion. Chemie-Ingenieur-Technik 84 (2012) 509-512.

Reactors for Hydrothermal Carbonization

Autoclaves A-0.01 and A-0.25 Pilot plant K3-335 Demonstration plant HTC-0

in collaboration with

&

Hydrothermal Carbonization for Phosphate Recovery

HTC -> Leaching -> Precipation (N,P)Nearly 80 % yield (phoshate) from sewage sludge!

Diploma Thesis Dominik Wüst, Master Thesis Gero Becker

Mg,NH4-PhosphateTime / h

60%

30%

Solved Phosphate

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) 68-74.**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) 59-67.

Hydrothermal Conversions of Biomass

Hydrothermal Biomass GasificationA. Kruse, J. of Supercritical Fluids 47, 391-399, 2009.

100 200 300 400 500 600 700

0

5

10

15

20

25

30

35

H2

Oil,Tarr

Chemicals

H2CH

4

C

p /

MP

a

/ °C

Water - A magic solvent for biomass conversion.A. Kruse, N. Dahmen, The Journal of Supercritical Fluids 96, 36-45, 2015.

Comparison

HTL FP Fossil

H2O (wt%) <0.2 15-30 0.1

Density (kg/m³) 820-845 1100-1300 940

Viscosity (Pa s) 0.75-1 0.02-0.1 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.

Temperature: 300-375 ºC

Pressure: 10-25 MPa

Microalgae

Gas

Bio-Oil

Solid residue

Organics dissolved in the aqueous

phase

Hydrothermal Liquefaction: Algae I

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) 256-265.

Temperature: 350 °CHolding time: 15 minBiomass in water: 10% dw

Macroalgae

Microalgae

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) 256-265.

Hydrothermal Liquefaction: Algae II

Chemicals: Hydroxymethylfurfural I

Pictures: AVA Biochem

Biomass

Chemicals: Hydroxymethylfurfural II

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) 15053-15063.

Modeling the lignin degradation kinetics in an ethanol/formic acid solvolysis approach. Part 1. Kinetic model developmentD.Forchheim, J.R. Gasson, U. Hornung, A. Kruse, T.Barth Industrial and Engineering Chemistry Research 51 (32), 10595-10606, 2012

Chemicals: Phenols II

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

100 200 300 400 500 600 700

0

5

10

15

20

25

30

35

H2

Oil,Tarr

Chemicals

H2CH

4

C

p /

MP

a / °C

Tailor-made hydrochar

Many Thanks!

HTC product characterization

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 220 °C; 1 h 220 °C; 10 h

Stelta et al., 2011 Crelling et al., 2006

Coalification of biomass

Inkohlungsdiagramm für Blumenkohl, Gras und Stroh

y = 0,8334x + 0,8802

R2 = 0,8665

y = 0,89x + 0,7296

R2 = 0,7253

y = 0,8784x + 0,7767

R2 = 0,9804

0,00

0,20

0,40

0,60

0,80

1,00

1,20

1,40

1,60

1,80

2,00

0,00 0,20 0,40 0,60 0,80 1,00

O/C

H/C

for cauliflower, grass and straw