KIT – University of the State of Baden-Wuerttemberg and

National Research Center of the Helmholtz Association

Institute for Catalysis Research and Technology

www.kit.edu

The bioliq BTL process for synthetic biofuels and chemicals production

Eckhard Dinjus

IKFT

2 19.09.2012

Motivation

Use of biomass as the only renewable carbon source for production of

fuels and chemicals prior to heat and power generation

Large scale production of energy related products

0

500

1000

1500

1900 1920 1940 1960 1980 2000 2020 2040 2060

noch offen

Geo- / ozeanische

Energie

Solarenergie

Neue Biomasse

Windenergie

Kernkraft

Wasserkraft

Erdgas

Erdöl

Kohle

Trad. Biomasse

Source: Deutsche Shell AG

IKFT

3 19.09.2012

Chemical pathways to synthetic products

Biomass Syngas

Fischer-

Tropsch-

synthesis

Propylene

Ethylene

Gasoline

Acrylic acid

Oxygenates

…….

Gases

LPG

Naphta

Cerosene

Diesel

……….

Dimethyl-

ether DME

Refining

H2 + CO

CH3OH

„C6H9O4“

Direct use (Fuel cell, PME production, …

Hydrogen

Methane (SNG)

CH3-(CH2 )n-CH3

Methanol-

synthesis

IKFT

4 19.09.2012

BTL-projects in Europe

Process Type Capacity Pressure

KIT bioliq, D Fast pyrolysis + high pressure entrained flow

gasification + hot gas celaning + DME and

DtG gasoline synthesis

5 MWth

(2 MWth) 80 bar

Choren Carbo-V, D

(IP now owned by Linde)

CGT pressurized entrained flow gasification,

FT-synthesis, SunFuel, plant mothballed! 45 MWth 4 bar

TBM, D Allothermal fluidized bed, SNG 10 MWth atm.

Biodies, F Planned for Choren-gasification + Rectisol +

GTL.F1-Synthese 45 MWth 4 bar

BioTfueL , F Torrefaction + Uhde Prentflo-gasification, FT-

synthesis 15 MWth n.b.

Güssing, A Staged fluidized bed, electricity,

SNG (1 MW) and FT-synthesis 8 MWth atm.

BioDME, S Black liquor entrained flow gasification,

DME/methanol-synthesis 5 t/d DME 29 bar

Neste Oil, FI Circulated fluidzed bed, FT-Synthese 12 MWth atm.

Värmlands Methanol HTW-gasifier, methanol+heat 111 MWth n.b.

IKFT

5 19.09.2012

Potential feedstocks

Agriculture

Straw, hay, ….

Energy crops

Forestry

Residues (brash, tops, stumps)

Thinnings

Short rotation plantation

Trackside vegetation clearance

Streets, railway tracks

Power transmission lines

Organic residues

Recovered waste wood

Organic waste fractions

IKFT

6 19.09.2012

Decentral-centralized concept

Energy density: 2 GJ/m3 25 GJ/m3 36 GJ/m3

Energy densification of biomass in regional distributed

plants by bioliqSyncrude production

Economic conversion in large scale to syngas and

further refining into fuels & chemicals

IKFT

7 19.09.2012

bioliq® process scheme

bioSyncrude

bioSyncrude

Synfuel

Bio

mass

Syngas

De-central Centralized

Fuel

synthesis

DME

synthesis

Filter Sorption CO2 and water

separation Catalyst

O2 (Steam)

Gas cleaning and conditioning

High pressure

entrained flow

gasification

Slag

Fast pyrolysis

Pre-treatment

IKFT

8 19.09.2012

Bioliq pilot plant

Designed for 1000 h/a operation

500 kg/h biomass input

(50 L/h synfuel output)

Mass and energy balances

Cost estimates

Scale-up considerations

IKFT

9 19.09.2012

State of construction

Stage 1 Stage 2 Stage 3 Stage 4

Process

Fast pyrolysis +

BioSyncrude

production

HP Entrained flow

gasification

Gas cleaning

+ Synthesis I Synthesis II

Product BioSyncrude Synthesis gas DME Gasoline

Capacity 2 MW (500 kg/h) 5 MW (1 t/h) 150 kg/h 50 l/h

Realization 2008 2011 2011 2011

Partner Lurgi + MAT

Mischanlagentechnik Lurgi

MUT Advanced Heating

Chemieanlagenbau Chemnitz

IKFT

10 19.09.2012

Total View of the pilot plant

Mechanical completion: Nov. 2011

IKFT

11 19.09.2012

Fast pyrolysis pilot plant

Biomass preparation

Biosyncrude preparation Feed stock storage

Pyrolysis product recovery Fast pyrolysis

IKFT

12 19.09.2012

Fast pyrolysis

Abrasives

Straw (waf)

WaterAqueous

condensate

Pyrolysis gas

Tar condensate

Solids

Char for

internal

combustion

Ash

Twin screw mixer reactor

Heat carrier loop with sand

Reaction temperature 500 °C

Gas retention time ~3 sec

Gaseous, liquid and solid products

M

M

Cutting

Hot sand

Sand

Flare

Burner

Cycone Filter

Cyclone Quench

Char cooling

Tar condensate Aqueous

condensate

Co

nd

en

ser

I

Air Reactor

Air

Char

Biomass

Silo

Co

nd

en

ser

II

Char Condensate Biosyncrude

85-90% energy conservation!

IKFT

13 19.09.2012

Energy balance of fast pyrolysis

0.0

5.0

10.0

15.0

20.0

25.0

Hartholz (wf) Weichholz (wf) Weizenstroh (wf) Weizenkleie (wf)

En

erg

iein

ha

lt d

er

Pro

du

kte

[M

J/k

g]

19.4120.04

17.55

5.20 4.59 6.62 3.87

0.971.40

1.78

1.35

12.60 13.49 8.31 13.33

0.640.56

0.83

0.76

Ko

ks

Ko

nd

en

sat

Gas

Δh

R

19.31

Heating up to 500 °C and reaction enthalpy: 0,54 – 0,83 MJ/kg

approx. Energy content of pyrolysis gas

Fast pyrolysis PDU

(10 kg/h, 500 °C)

IKFT

15 19.09.2012

Char Condensate Gas Water Ash Beech wood

Wheat straw

Rice straw

Hay

Wheat clay

0 20 40 60 80 100 wt. %

Gas composition:

CO2 50 %, CO 30 – 40 %, CH4 2 – 5 %, C6 3–6 %

Pyrolysis product distribution

Bagasse

IKFT

16 19.09.2012

Char Org. cond. Aqueous.

Cond. Ash

Particle size

d90 (m) 150

Water (wt.%) 4,7 6,4 49,7 0,1

Ash (wt.%) 1,8 0 <0,05

Elemental analysis

C (%) 84,4 58,6 24,3 2,6

H (%) 2,7 6,2 3,8 0,2

O (%) 6 28,4 21,9

N (%) 0,4 0,3 0,3 0,3

S (%) 0,07 <0,05 <0,05 1,0

Product composition of pyrolysis oil and char

Complex mixture of

organic acids, aldehydes,

ketones, furfurales,

phenols, pyrolytic lignin…

COOHCOOH

COOH

O

OH

OH

OH OH

O

CHO

OH

CHO

OH

CHO

O

CHO

O

CH2OH

IKFT

17 19.09.2012

Use of pyrolysis products

Separation of valuable components

Produce BioSyncrude from pyrolysis oil and char

for gasification and synthesis gas generation

Use of char for mono- and co-combustion for

heat and electrical power production

Upgrade of pyrolysis oils for

Fuel production

Refinery crude

Stabilization

H2, catalyst

175-250 °C, 20

MPa, min.

Hydrodexoygenation

H2, catalyst

>250 °C, 20 MPa

min.-hour

Hydrocracking

H2, catalyst

>250 °C, 35 MPa

hour

Stable

fragments

soluble in

water

Non-polar

fragments

insoluble

in water

> 1.0 g cm-3

Non-polar

fragments

insoluble in

water

< 1.0 g cm-3

Pyrolysis

oil

CxHy CxHy

Methanation Methanation

Mild hydro-treating of pyrolysis oils

according to Venderbosch, Prins 2010

IKFT

18 19.09.2012

BioSyncrude preparation

Free flowing suspension

High particle content up to 40wt.%

Stable for storage and transport

Easy to produce by colloidal mixing

Heating value up to 25 MJ/kg

Particle diameter / m

Dis

trib

utio

n s

um

Original char

Colloidal mixed char

IKFT

19 19.09.2012

Effect of energy densification by fast pyrolysis

Transport distance / km

100

50

0

0 100 200 300 400 500

30 km

250 km

Tra

nsp

ort

co

sts

€/t

(w

af)

BioSyncrude

Rail

Truck

Straw

Rail

Tra

ctor

Truck

KIT: Leible et al.

IKFT

20 19.09.2012

Suitable for feeds rich of ash

Gasification with oxygen

Temp. >1200 °C, up to 80 bar

Proof at the 3-5 MWth gasifier of

Future Energy (today Siemens FGT)

Tar free synthesis gas

No syngas compression

High pressure entrained flow gasification

boiler

feedwater

water pipe

gasifier reaction

chamber

> 1500 °C

liquid slag

solid slag

Cooling screen detail refractory

ramming mix

IKFT

21 19.09.2012

High pressure entrained flow gasification

IKFT

22 19.09.2012

Pilot gasifier

IKFT

23 19.09.2012

0

10

20

30

40

50

60

70

80

5 10 15 20 25 30

Co

ld g

as

eff

icie

nc

y /

%

BioSyncrude heating value (MJ/kg)

Pilot gasifier in

Freiberg, Germany

Gasification test campaigns

Komponent Vol.%

H2 20 – 25

CO 25 – 37

CO2 12 - 18

CH4 0 - 1

H2O 25 - 30

O2 0

N2 4 – 15

Typical syngas composition

IKFT

24 19.09.2012

ATMO (1 bar) PAT (up to 20 bar) Spray at 16 bar

Burner development

Liq

uid

feed

Gas

Gas Two-fluid nozzle

T. Kolb, ITC

IKFT

25 19.09.2012

High pressure hot gas cleaning

Hot gas filter for particle removal

Dry sorption for separation of

sour gases and alkali salts

Catalytic decomposition of

organic and nitrogen containing

compounds

CO2-separation (optional)

1000 Nm3/h synthesis gas

(45 Bm³/h at 80 bar, 800 °C)

Successfully verified in bench scale

Energy savings up to 10 %

Potential for process integration

Catalytic

ceramic filter

Raw syngas Syngas

Entrained flow adsorbens

Ceramic

particle filter

Fixed bed

sorption

Catalytic

reactor

Raw syngas Syngas

IKFT

26 19.09.2012

DME and fuel synthesis

DME-synthesis

One step DME synthesis

Innovative isothermal reactor

Temp. of 250 °C, pressure 60 bar

Lower investment costs

Direct use of CO-rich syngas

DtG-synthesis

Zeolithe catalyzed Dehydratization, oligomerization and isomerization

Temp. 350 - 450 °C, pressure 25 bar

Recycling of unconverted gas

Gasoline stabilization

high selectivity towards one product

methanol route useful for oxygenates

Flare

Air

Gasoline

Heavy fractionSeparator

Gasoline reactor

DME-reactor

WGS-reactor

Syngas

Desorber

CO

2 -Ab

so

rbe

r

CO

2 -Ab

so

rbe

r

Process water

Cycle gas

Dis

tilla

tio

n

CO2

IKFT

27 19.09.2012

Synthesis pilot plant

IKFT

28 19.09.2012

Catalyst preparation

Catalyst characterization

Screening in lab scale

Process development unit MOSYS

Syngas MeOH DME Olefins Fuels

EtOH + higher alcohols

Syngas-To-DME (STD) DME-To-Gasoline (DTG)

Syngas-To-Alcohols (STA) Dimethylether-To-Olefins (DTO)

0 10 20 30 40 50 60 70 80 90 100

-50

-25

0

25

50

75

100

125

150

175

200

225

250

275

Ottokraftstoff (DIN EN 228)

MLV1-14

MKL01-11

Tem

pera

tur

/ °C

Verdampfte Menge / Gew.%

Simulated distillation

curves of products

without up-grading

compared to gasoline

R&D on syngas chemistry

IKFT

29 19.09.2012

Process efficiency

To produce 1 t of synthetic biofuel 7 to of air dried biomass are required

Around 45% of the energy initially contained in the biomass remain in

the fuel

Residual heat can be used for electrical power production

Both can be used to make the process nearly energy autarkic

Therefore, the process provides a high CO2 reduction potential

IKFT

30 19.09.2012

Process implementation

Operation of the pilot plant

reliable cost estimate, practical experience

Construction and operation of a demo plant

Complementary R&D in lab and bench scale

Optimisation, process alternatives, new applications

Verification of potential feed stock range and availability

Different types of biomass

Alternative use of biosyncrude for:

Co-combustion (Power plant)

Mono-combustion (CHP)

Upgrading to refinery compatible fuel

Development of new products, e.g. oxygenates

Oxygen is contained in biomass for free!

Biomass much better fits to chemicals than to fuels capacities

Business models in cooperation with industry and other partners

IKFT

31 19.09.2012

„Stone era did not end because a lack of stones, and the oil era will not end up because oil is running out “

Sheich Zaki Yamani, 1974

former minister from Saudi Arab