KIT – Universität des Landes Baden-Württemberg und

nationales Forschungszentrum in der Helmholtz-Gemeinschaft

Institute of Catalysis Research and Technology - Project bioliq

www.kit.edu

Thermochemische Verfahren zur energetischen und

stofflichen Nutzung von Biomasse

Nicolaos Boukis, Nicolaus Dahmen, Axel Funke, Andrea Kruse, Klaus

Raffelt, Jörg Sauer, Hamm, 22.07.2015

Jörg Sauer 2 22.07.2015

Outline

Motivation

Hydrothermal Processes, Hydrothermal Gasification

The bioliq Approach to BtL

Conclusion and Outlook

Jörg Sauer 3 22.07.2015

Outline

Motivation

Hydrothermal Processes: Hydrothermal Gasification

The bioliq Approach to BtL

Conclusion and Outlook

Jörg Sauer 4 22.07.2015

„Magic Triangles“ of the German Energiewende

Sustain-

ability

Cost

Effictiveness Security of

Supply

Triangle of

Energy

Policy1)

1) Zweiter Monitoring-Bericht „Energie der Zukunft“, Bundesministerium für Wirtschaft und Energie (BMWi), Berlin, März 2014

2) AGEB, Arbeitskreis Energiebilanzen, September 2014, www.ag-energiebilanzen.de/ entnommen am 21.09.2014

Liquid

Fuels

37%

Electricity

21% Naturals Gas

25%

Energy

Carriers2)

Renewables

Control /

Networks /

Storages

Energy

Efficiency

Tools of the

energy

transition

Jörg Sauer 5 22.07.2015

„Energiewende in Germany“ –

Biofuels and Electricity1)

1) AGEB, Arbeitskreis Energiebilanzen, September 2014, www.ag-energiebilanzen.de/ retrieved on 2014-09-21

Electricity from

Renewables

Biofuels

Energy Carriers from Renewables [PJ] E

ne

rgy C

on

ten

t o

f E

ne

rgy C

arr

iers

fro

m [

PJ

]

Jörg Sauer 6 22.07.2015

Erdöl - Zahlen

Erdöl Tagesproduktion: 83 Mio bbl per day

= 13,2 Mio m³/Tag

Zum Vergleich:

Speichervolumen des Brombachsee 164 Mio m³

o Zeit bis zum Auffüllen des Brombachsees mit weltweiter

Erdölproduktion: 12 Tage 10 Stunden

Source: IEA, Energy Technology Perspectives 2014

http://www.landeskraftwerke.de/brombachsee.htm, entnommen am 14.07. 2014

http://www.zv-brombachsee.de/, entnommen am 14.07. 2014

Jörg Sauer 7 22.07.2015

Noch mehr Zahlen

Investitionssumme für Pearl GTL 18,5 Mrd USD

Produktionsmenge 0,14 Mio bbl per day

Anteil an der Welt-Ölproduktion 0,17%

Investkosten pro bbl 130.000 USD/(bbl per day)

Mitarbeiter für Anlagenbau: ca. 50.000

Hochrechnung auf Weltöl-Produktion:

Kosten: 10,8 Billionen USD

Investbudget der Ölkonzerne (2012): 260 Mrd USD (x 41)

ExxonMobile (2013): 42,4 Mrd USD (x 254)

Hochgerechneter Personalbedarf ca. 30 Mio für 5 Jahre

Source: http://www.platts.com/

http://www.shell.com/

http://ir.exxonmobil.com/

http://energypolicy.columbia.edu/

entnommen am 13.07.2014

Jörg Sauer 8 22.07.2015

Contribution of the Negative Residual Load

Sources: Deutsche Energie-Agentur GmbH (dena), Integration der erneuerbaren Energien in den

deutschen/europäischen Strommarkt, 2012

AGEB, Arbeitskreis Energiebilanzen, September 2014,

www.ag-energiebilanzen.de/ entnommen am 21.09.2014

Negative residual load: 66TWh = 240 PJ

After conversion losses: 33TWh = 120 PJ

Liquids consumption Germany 2012: 1290TWh = 4640 PJ

Potential for Liquids from residual load 2,2 Mio to (2,6%)

Availability max. 3000h

Jörg Sauer 9 22.07.2015

Agriculture

Straw, hay, ….

Energy crops

Forestry

Residues (brash, tops, stumps)

Thinnings

Short rotation plantation

Marginal Farmland

Streets, railway tracks

Power transmission lines

Organic residues

Recovered waste wood

Organic waste fractions

Algae

Feedstocks for Future Bionenergy Applications

Jörg Sauer 10 22.07.2015

Outline

Motivation

Hydrothermal Processes: Hydrothermal Gasification

The bioliq Approach to BtL

Conclusion and Outlook

Jörg Sauer 11 22.07.2015

Regimes for Hydrothermal Conversion

100 200 300 400 500 600 700

0

5

10

15

20

25

30

35

Critical

Point

Hydrothermal conversion

to platform chemicals

Catalysed near-critical gasification

Supercritical Water

Gasification

Hydrothermal Liquefaction /

Hydrothermal Upgrading

Aqeous Phase Reforming

Hydrothermal CarbonizationPretreatment

H2

"Oil"

Chemicals

H2

CH4

C

p / M

Pa

/ °CKruse et al., 2013, modified

Jörg Sauer 12 22.07.2015

Gasification of Waste Biomass and Organic

Waste Fractions

Feed

(Sludges, not

dried)

H2, CH4 ,

CO2 , C2H6

Heat exchanger

Salt separation

Reactor

Process

Conditions: T 650 °C; p 280 bar

Salt concentrate

(K, P, Ca, Mg)

Waste water,

NH4+

Jörg Sauer 13 22.07.2015

Gasification Yield as Function of the

Residence Time and the Reaction Temperature

[Corn silage] = 5 wt%, p=250 bar

P. D´Jesus, N. Boukis, B. Kraushaar-Czarnetzki, E. Dinjus. Ind. Eng. Chem. Res. 2006, 45, 1622-1630

Working space

Jörg Sauer 14 22.07.2015

Properties of Water at High Temperatures and

Pressure (Tc=374 °C, pc=221 bar)

Salt precipitation

Liquefaction Gasification

Water; isobar 300 bar

0

200

400

600

800

1000

1200

0 100 200 300 400 500 600 700T (°C)

De

ns

ity

(k

g/m

^3

);

Vis

co

so

ty µ

Pa

.s

-25

-20

-15

-10

Ion

Pro

du

ct

D kg/m^3

Viscosity µPa-s

Ion Prod. 2xLog10(kW

Regime of operation

Direct heat exchange is possible => no drying

Jörg Sauer 15 22.07.2015

LENA – Test Rig, continuous flow, Tmax=700 °C, max. flow rate 2 l/h, VReactor=270 cm3

HP-Filter

Salt separation

Jörg Sauer 16 22.07.2015

Sewage Sludge from Oljen and Lelystad

Type wDM

Dry matter, wt.%

Ash content by 550 °C, wt.%

Lelystad 17,5 18,8

Oijen 27,4 20,40

Parameter wt. [%] wt. [%]

Oijen Lelystad

TC 41,6 43,5

TIC 0,1 0,1

TOC ( C ) 41,5 43,4

H 4,22 6,37

N 4,22 7,28

P 2,4 3,16

S 0,78 1,11

Ca 2,25 1,4

K 0,36 1,14

Mg 0,31 0,72

Na 0,088 0,105

Si 2,65 2,63

Al 1,22 0,56

As 0,02 0,02

Cd 0,01 0,01

Cu 0,56 0,018

Pb 0,011 0,02

Zn 0,086 0,032

Cr 0,0039 0,01

Fe 1,38 0,38

Mo 0,02 0,02

Ni 0,02 0,02

Feed analysis

Jörg Sauer 17 22.07.2015

Main results, steady state operation Total sewage sludge treated 2 – 3 kg per experiment

Type Time steady

state

Feed steady

state

Ctotal

steady

state

Plugging YGas YC TOC-

destruction TOC-

waste water

NH4+-

waste water

TNb- waste water

[-] [h] [g] [g] [after h] [%] [%] [%] [mg/l] [mg/l] [mg/l]

Lelystad 5 2115 109,18 No 67,95 80,67 97,8 1953 11724 9300

Oijen 3,93 1656,5 88,86 6,5 71,21 81,83 96,7 2141 8821 5580

Carbon balance during steady state operation is 80 % an indication of

accumulation of Carbon in the system (insoluble carbonates in the filter cakes)

Jörg Sauer 18 22.07.2015

Hydrothermal Gasification of Sewage Sludge

Type Lelystad Type Oijen

H2 21,81 vol %

CO 0,04 vol %

CH4 31,80 vol %

CO2 34,25 vol %

C2H4 0,38 vol % C2H6

11,27 vol %

C3H6 0,10 vol %

C3H8 0,36 vol %

Gas composition

H2 17,18 vol %

CO 0,22 vol %

CH4 35,08 vol %

CO2 33,36 vol %

C2H4 0,61 vol %

C2H6 12,90 vol

%

C3H6 0,17 vol %

C3H8 0,47 vol %

Gas composition

Sewage sludge TReaction Concentration mean res. time

type [°C] [wt. % DM] [min]

Lelystad 653 11,69 2,75

Oijen 649 12,71 2,76

Jörg Sauer 19 22.07.2015

The Carbon Balance

Type “Lelystad” Type “Oijen”

Aq. Phase; 16,02

Filter aq. Phase; 1,35

Salt concentrate incl. Filter;

8,30

Gas; 80,90

Balance; -6,58

Carbon distribution %

Aq. Phase; 13,58

Filter aq. Phase; 6,06

Salt concentrate incl. Filter;

6,28

Gas; 79,75

Balance; -5,67

Carbon distribution %

The carbon balance for the whole experiment is much better.

About 10 % of the Carbon forms carbonates

Jörg Sauer 20 22.07.2015

Type Oijen C, N, P Detailed Analysis

Jörg Sauer 21 22.07.2015

Scale-up to Pilot Scale (1)

Biomass Water

Storage

Colloidal

mill

HP-pump

Reactor

Pre-

heater

Heat

exchanger

Cooler

Phase

separation

CO2-

scrubber

Residual water

Gas tank 650°C

300 bar

VERENA pilot plant at KIT

Jörg Sauer 22 22.07.2015

Scale-up to Pilot Scale (2)

Reactor

35 L volume

0,11 m i.D., 3,7 m length

Inconel Ni-Alloy

External Heating

35 Mpa; 700 °C

Feeding

100 kg / h

5-20 % dmc

Jörg Sauer 23 22.07.2015

Conclusions for Hydrothermal Gasification

Stable operation with “difficult feedstock” sewage sludge is possible

Good carbon balance in lab scale (100 ± 10 %)

High gasification yield (80 %) and η (up to 0.9). Acceptable efficiency at

12 wt.% DM possible

Challenges

Salt separation is of utmost importance

Fouling/ scaling e.g. in heat exchangers

Corrosion

HTG of sewage sludge operates at the frontier of development modern

materials of construction

Suitable models for reaction kinetics and gasification reactor are

missing

Jörg Sauer 24 22.07.2015

Outline

Motivation

Hydrothermal Processes: Hydrothermal Gasification

The bioliq Approach to BtL

Conclusion and Outlook

Jörg Sauer 25 22.07.2015

Thermochemical BtL Value Chains

Pyrolysis

Gasification

(CO+H2)

Purification

Catalytic Fuel

Synthesis

Lignocellulosic

Biomass

Syngas-

Fermentation

Catalytic/Biotech.

Upgrading

Torrefaction Catalytic/hydro-

thermal liquefaction

Fuels and/or chemicals

Jörg Sauer 26 22.07.2015

Biomass

Chemistry and Technology – decentralized

500 °C

Char/Ash

20 Gew.%

Condensate

60 Gew.%

Gases

20 Gew.%

Flashpyrolysis Biosyncrude

Char

Ash Condensates

Pyrolysis -

gas

Sand

Heat Carrier

Biomass

Cellulose

Hemicellulose

Lignin

Jörg Sauer 27 22.07.2015

Hydrocarbons Methanol

Dimethylether

Biosyncrude Syngas

CO2, u.a.

Chemistry and Technology – centralized

C O

>1200 °C

80 bar

Entrained Flow Gasification Gas Cleaning Fuel Synthesis

Biosyncrude

Diesel

Kerosine

Ethylene

Propylene

Methane

Hydrogen

…

Synthetic

biofuels

Kat Kat

O 2 ( Steam )

Particle - filter

Slag

H 2 O/CO 2 - Separation

Gasoline - Synthesis

DME - Synthesis

Benzin

Product separation

Catalysis Sorption

Jörg Sauer 28 22.07.2015

bioliq®-Pilot Plant at KIT Fast Pyrolysis

Biosyncrude-Production

Gasification

Syngas-Production

Gas-Cleaning and

Fuel Synthesis

Improved insights in processes

Optimization and development

Diagnostics, modelling, simulation

New applications of products

Mass and energy balances

Scale-up

Stability and availability

Production costs

Technical Validation Platform for Research &

Jörg Sauer 29 22.07.2015

Contributions to the Analysis

on the System Level

CO2 reduction potential > 80 %

Potentials of sustainable supply Logistics simulation and production network

www.bioboost.eu

Mass Potential

of Straw

Production Costs

0,50 €

0,90 €

1,30 €

1,70 €

2,10 €

0 MW 1000 MW 2000 MW 3000 MW 4000 MW

Plants

Water and

Carbon Dioxide - O 2

Photosynthesis

Fuel-Production

Combustion

+ O 2

Jörg Sauer 30 22.07.2015

Next steps

Improve availability of pilot plants

Process optimization and further development

Development of business models

& market implementation plans

Creation of a consortium for the development

of high performance fuel components

Investition in die Zukunft

gefördert durch die Europäische

Union Europäischer Fonds für

regionale Entwicklung und das

Land Baden-Württemberg Units Chains Networks Systems

Jörg Sauer 31 22.07.2015

Outline

Motivation

Hydrothermal Processes: Hydrothermal Gasification

The bioliq Approach to BtL

Conclusion and Outlook

Jörg Sauer 32 22.07.2015

Syngas-

Fermentation Intermediates /

Biomaterials

The Future of Bioenergy Research at KIT (1)

„Integration into the Energy System“

bioliq®

Entrained

flow gasi-

fication

Gas

cleaning

Catalytic

synthesis

Flash

pyrolysis

Fuels, chemical

energy carriers Biomass

(eg. straw)

Algae Value Chain

Photobio-

reactor

Cultivation/

harvesting

Elektro-

poration

Product

Separation

Hydro-

thermal

liquification Intermediates /

biomaterials

Methanation

Fischer-Tropsch

Synthesis

EnergyLab

2.0

Fuels, chemical

energy carriers

Gasturbine

+ Generator Electricity

Jörg Sauer 33 22.07.2015

The Future of Bioenergy Research at KIT (2)

„Synthetic High Performance Fuel Components“

0

Pa

rtic

ula

te m

att

er

NOx

Conventional diesel fuel

Oxygenated diesel blend

Pure OME

1: Effect of fuel change

2: Engine modification for NOx control

1 2

Elements

Compatible to present fuels (drop-in)

Reduced emissions

Increased performance

Reduced fuel consumption

Reduced CO2-footprint

Part

ikel

Bsp.: Oxymethylenether (OME)

Jörg Sauer 34 22.07.2015

From Fundamentals to Applications and the

Integration into the Energy System

Elementary Steps

Catalysts

Process Steps

Processes & Plants

Energy System & Application

Jörg Sauer 35 22.07.2015

Sponsors and Funding Agencies

Partners from Industry and Academia

The teams from KIT

The audience for your kind attention

Acknowledgements