Biomass gasification to fuels and

chemicals

HighBio-seminar, Nov. 9, 2010, Oulu

Matti Reinikainen, D. Sc. (Chem. Eng.)

Senior research scientist, VTT, Espoo

2

GASIFICATION AND SYNTHETIC FUELS AT VTT

14 M€/year

40% customer projects

Over 15 patent families, 6 international patents and several license and

IPR agreements and well-focused IPR portfolio on fluidized-bed

gasification and hot gas cleaning

45 researchers, of which 20% hold a doctor’s degree

Excellent test facilities from laboratory to pilot scale

The leading research group in Europe in gasification and in fast

pyrolysis concept development. Coordination of over 10 EU and IAE

projects

Customers such as Neste Oil, Stora Enso, Corenso,

Metso Power, Nordkalk, Lahti Energia

3 3

Matti Reinikainen D.Sc.(Chem. Eng.)

Since1987 at VTT

1989-1991 AIST-fellow at NCLI in Tsukuba, Japan (C1-Chemistry

program, FT-pilot plant)

1995 STA-fellow at TNIRI in Sendai, Japan

1995 Licentiate's thesis on Co-catalysts for vapor phase

hydroformylation

1998 Doctor's thesis on Co-Ru-catalysts for FT-sythesis

1996-1999 superintendent of the synthesis pilot-plant (special

chemicals) at VTT

2000 - industrial contract research projects on catalysis

2006 moved to Gasification team

4

GAS CLEANING

• TAR & METHANE

REFORMING

• FILTRATION

• DIRTY SHIFT

FT-DIESEL

ULTRA

CLEANUP

SNG

FUEL-FLEXIBLE

FLUIDISED-BED

GASIFICATION

• STEAM/OXYGEN

• PRESSURISED

FT-GASOLINE

METHANOL

HYDROGEN

NEW INNOVATIVE TECHNOLOGY EXISTING & EFFICIENT

BUT EXPENSIVE

TECHNOLOGY

HEAVIER

ALCOHOLS

ETHANOL

FORMALDEHYDE

ACETIC ACID

DME

MTG, MTO

FUEL

CATALYTIC PROCESSES

(Co, Fe, Cu, Zn, Ni, Rh, Ag…)

Synthesis gas route to fuels and chemicals

5

Biomass gasification to chemicals and fuelsPatents and open publications / year (y. = pat., g. = other publ.)

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BIOMASS GASIFICATION PROCESSES

General 3D-View of the Research Landscape

Source: HCAplus database; Publications 1990 - 2010. Visualization by STN AnaVist.

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BIOMASS GASIFICATION PROCESSES”Methanol” highlighted (non-patents; green, patents; yellow

Source: HCAplus database; Publications 1990 - 2010. Visualization by STN AnaVist.

8

OPERATION CONDITIONS FOR CATALYTIC GAS CLEANING

IN BIOMASS GASIFICATION

800 - 900 °C

N2, CO, CO2, CH4,

CxHy, H2, H2O

tar 500 - 15 000 ppm

NH3/HCN 300 - 10 000 ppm

H2S/COS 50 - 500 ppm

HCl

alkali metals

heavy metals

particulates 1 - 10 g/m3n

N2, CO, CO2, CH4,

CxHy, H2, H2O

tar ~0

NH3/HCN ~equilibrium

H2S/COS 50 - 500 ppm

HCl

alkali metals

heavy metals

particulates 1 - 10 g/m3n

9

Biomass as a raw material for synthesis gas

In principal, syngas reactions are not dependant on the raw material,

but relevant differences still exist:

There is less experience about biomass gasification:

Biomass gasification plants are principally at least one order

of magnitude smaller than coal or natural gas plants

For instance: Shell-Pearl GTL-plant 140 000 bpd; 400 MW

BTL-plant ca. 4000 bpd

Gasification and gas cleaning constitute a decisive part of

the investment cost

Different kind of impurities (esp. tars)

Variation in the H/C ratio

Product upgrading (best product in small scale?)

10

10

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Processes based on biomass gasification

Lähde, TUW

Company Country Product Output [t/a] Total investment Unit Type Status Start-up Year

Chemrec AB Sweden DME; 1 800 28 500 000 EUR pilot under construction 2010

Chemrec AB Sweden methanol; DME;132 000

(Methanol) 250 000 000 EUR demo planned 2013

CHOREN Fuel Freiberg GmbH & Co. KG Germany FT-liquids; 14 000 100 000 000 EUR commercial under construction 2009

CHOREN Industries GmbH Germany FT-liquids; 200 000 commercial planned

CTU - Conzepte Technik Umwelt AG Austria SNG; 576 demo operational 2008

Cutec Germany FT-liquids; 0,02 pilot operational 1990

ECN Netherlands SNG; 346 pilot under construction 2011

ECN Netherlands SNG; 28800 demo planned

Enerkem Canada ethanol; 375 pilot operational 2003

Enerkem Canada ethanol; 4 000 demo under commissioning 2009

Enerkem Canada ethanol; 30 000 70 000 000 CAD commercial announced

Flambeau River Biofuels LLC United States FT-liquids; 51 000 200 000 000 USD pilot planned 2012

Forschungszentrum Karlsruhe GmbH Germany diesel; gasoline type fuel; 608 pilot under construction

GTI Gas Technology Institute United States FT-liquids; 26 pilot under construction 2009

NSE Biofuels Oy, a Neste Oil and Stora Enso JV Finland FT-liquids; 656 demo under construction 2009

NSE Biofuels Oy, a Neste Oil and Stora Enso JV Finland FT-liquids; 100 000 commercial planned

Range Fuels, Inc. United States mixed alcohols; pilot operational 2008

Range Fuels, Inc. United States ethanol; methanol; 300 000 commercial under construction 2010

Research Triangle Institute United States FT-liquids; mixed alcohols; 22 3 000 000 USD pilot planned

Southern Research Institute United States FT-liquids; mixed alcohols; 40 000 000 USD pilot operational

Tembec Chemical Group Canada ethanol; 13 000 demo operational

Vienna University of Technology Austria FT-liquids; 0,20 pilot operational 2005

Alico

NewPage

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Thermochemical / biochemical hybridprocesses

Company Country Product Output [t/a] Total investment Unit Type Status Start-up Year

Coskata United States ethanol; 120 demo under construction 2009

Coskata United States ethanol; 300 000 400 000 000 USD commercial planned

Coskata United States ethanol; pilot operational

Iowa State University United Statesethanol; FT-liquids;

biodiesel; pyrolysis oils;200 18 000 000 USD pilot under commissioning 2009

ZeaChem United Statesethanol; mixed alcohols;

various chemicals;4 500 pilot announced 2010

Abengoa

ICM

Lähde: TUW

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Required gas purity levels

Source: NREL 2003

14

Chemicals from methanol

Several important commercial processes:

Formaldehyde

Acetic acid (Monsanto-process)

MTBE

DME

Methylhalides

Also possible to produce gasoline with MTG-process (New Zealand)

ZSM-5 zeolite-catalyst

CH3OH + Gasoline

hydrocarbons

15

MTG-process, TIGAS

Developed by Haldor Topsøe

Methanol/dimethylether synthesis and the

subsequent conversion into gasoline are

combined in a single synthesis loop

Flexible to the variation in H/C-ratio of the

syngas

Desired conversion attained at a fairly low

pressure level

16

MTG-processes, TIGAS

8.12.2009 Topsøe published their plan to construct a demo plant in

Des Plaines, USA.

Fuel 25 t of wood / d

Demonstartion for industrial scale of 1000 t wood / d.

Energy efficiency ca. 60%.

Partners UPM-Kymmene and Conoco-Phillips.

”This is the last step before the technology will be made

commercially available.”

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Alcohol mixtures

Preferably higher alcohols, e.h. butanol

Good as a gasoline component

Biochemical routes

Catalytic route from synthesis gas

Direct route (modified methanol catalyst, sulphided Mo-catalyst...)

Olefinic FT-product => (Heterogeneous) hydroformylation

Safol-23-process

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Selectivity of Co2(CO)8 based catalysts

Promoted Co2(CO)8/SiO2. T=523 K, P=2.1 MPa,

GHSV=2000 h-1, CO:H2:Ar=3:6:1. The loading of

the promoters was 25 mmol/100g with the

exception of 43 mmol/100g for Li and 200

mmol/100g for Sr.

none Mg Ca Sr Ba Li Na K Rb Cs0

5

10

15

20

25

30

0

5

10

15

20

25

Promoter

Selectivity, C-% CO conversion, %

Ethanol Acetic acid Acetaldehyde Other oxygenatesCO conversion

SiO2 SiO2-K Al2O3 TiO2 ZrO2 MgO ZnO La2O3 CeO2

0

2

4

6

8

10

12

14

0

5

10

15

20

Support

Selectivity, C-% CO conversion, %

Ethanol Acetic acid Acetaldehyde CO conversion

• The effect of support on the CO hydrogenation

activity of Co2(CO)8 based catalysts with metal

loading of 5 wt.-%. T=523 K (493 K for Al2O3 and

ZnO), P=2.1 MPa, GHSV=2000 h-1,

CO:H2:Ar=3:6:1.

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Moist

feedstockDryer Gasifier Reforming

Heat

Oxygen

Recycle gas

Oxygen

plant

HP

Steam

HT

Shift

LP

Steam

HP

Steam

CombustorHP Steam

Scrubber-

cooler

Regenerative

AbsorberFT synthesis

FT primary liquids (C5+)

LP Steam

FT reforming loop

FT off-gas (purge)

H2O

MP Steam

SeparatorCW

CW

Steam: 0.33 kg/ kg

of dry biomass

Exceptionally high recovery

of exotherm as steam

Process Scheme for Production of FT Liquids

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Challenges of the Fischer-Tropsch-reaction

The selectivity of the FT-reaction is intrinsically bad and only to the admen the reaction product is simply ”diesel”

The product is always a complex mixture and it is necessary to find good use to all of the components

The necessary catalysts (Co, Ru, Fe) are very sensitive to sulphur

The reaction is highly exothermic and one must utilise the reaction heat

Source: Shell

α=0.85, Co-catalyst,

neutral Al2O3-support

T=200°C

α=0.61, Co-catalyst,

acidic Al2O3-support

T=250°C

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Thoughts on a possible research subject

”Badly selective FT-reaction

Aimed at a light FT-products, e.g. (27 % C1-C4; 50 % C5-C12; 16 % C13-C18, 7 % > C18

Fe-catalyst which is not so sensitive to sulphur

Save in the cost of final cleaning of the gas

Once through process – no hydrocracking

Easier to control the reaction heat than in the manufacture of wax

Reforming of the gas is easier since it is not necessary to attain full methane conversion

Methane can possibly be used as SNG. Other light hydrocarbons and the heaviest fraction as energy

Olefins used possibly as chemical raw materials

22

VTT-UCG

Optimised

syngas R&D

& PDU-scale

development

Industrial demon-

stration: 10-50 MW- replacement of oil/gas

- start-up in 2009

Further R&D- process optimisation

- waste gasification

- hydrogen technologies

New applications- fuel cells, 2nd gen. IGCC

- hydrogen or methane

- renewable chemicals

R & D on hot filtration

and

catalytic gas cleaning

Biomass/waste

gasification for power

(Lahti, Corenso,

Värnamo, Kokemäki)

Peat

ammonia

plant

Oulu/Finland

Synthesis gas

R&D in Europe

and USA in 1980’s

First synfuel production plant- 200-250 MW feed capacity

- 105 000 tons/a diesel fuel

- 3 % Finnish transport fuel

- start-up in 2012-14

1995 2000 2005 2010 2015 20201985 2025 2030

Biorefineries at pulp and paper mills

and at large CHP plants - diesel production: 70 -150 000 tons/plant

- by-product heat for process steam or

district heating

- high overall efficiency

SYNTHESIS GAS FROM BIOMASSFROM R&D TO INDUSTRIAL SUCCESS

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Forest biomass

in future also

urban waste and straw

- Southern hemisphere

plantations

Biofuel production

Optional Biofuels:

(pellets)

bio crude

EtOH/MeOH

BioDiesel

Wood

residues

Pulp &

Paper Mill

Wood

handling

Bark

boiler

Power

Heat

Power

Steam

Refinery

Crude Oil

OPTIONS FOR FOREST INDUSTRY ? - benefit of raw material, biorefinery and large scale operation -

BioPower

< 500 MWf

< 400 MWf

Paper and

Market pulp

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BEFORE INTRODUCTION OF FT PLANTPower-Boiler Energy flows (LHV basis)

Bark, etc

Black liquor

Purchased biofuel

P&P products

151 MW

Wood for fibre,

purchased fibre

Co-Production of Syngas Derivatives at Pulp and Paper Mills

Power

boiler

Electricity

Primary heat

100 MW

31 MWe

25

Bark, etc

Black liquorP&P products

Purchased electricity FT primary liquids161 MW

25 MW

Wood for fibre,

purchased fibre

25 MWe

Power

boiler

FT

plant

Purchased biofuel 260 MW

Electricity

Primary heat

100 MW

21 MWe

285 MW

Co-Production of Syngas Derivatives

at Pulp and Paper Mills

AFTER INTRODUCTION OF FT PLANT (260 MWfeed)Integration of steam system in conjunction with power boiler rebuild

Secondary heat used for biomass drying

Energy flows (LHV basis)

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Bark, etc

Black liquor

Purchased biofuel

P&P products

Purchased electricity

FT primary liquids

+ 161 MW

+ 134 MW*

Wood for fibre,

purchased fibre

Integrated

Pulp and

Paper Mill

or

Stand-Alone

Paper Mill

+ 35 MWe**

Co-Production of Syngas Derivatives at

Pulp and Paper Mills

* 134 MW = (285 – 151) MW

** 35 MW = (31 – 21 + 25) MW

NET CHANGES WITH INTRODUCTION OF FT PLANT (260 MWfeed)Integration of steam system in conjunction with power boiler rebuild

Secondary heat used for biomass drying

Incremental energy flows (LHV basis)

Nominal overall efficiency = 100 x 161/(134 + 35/0.4) = 73 %

(purchased electricity generated from biomass at 40 % η)

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Estimated Overall EfficienciesEfficiency = 100 x [LHV-energy of main product + high-grade byproduct energy - {electricity / 0.4}]

/ [LHV-energy of as-received feedstock]

Notes: (1) Feedstock drying: from 50 % moisture to 30 % with secondary heat; from 30 % to 15 % with

by-product steam. (2) FT: Fischer-Tropsch primary liquids; reforming loop included.

-40

-20

0

20

40

60

80

100

FT CH3OH SNG H2

Overa

ll E

ffic

ien

cy, %

Primary

energy out

Main product

(Electricity in)

/ 0.4

Integration benefits: large for FT; significant for CH3OH; negligible for SNG; minor for H2

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Equivalent Biomass-to-Pump Costs: Biomass-FT < Biomass-SNG

(and most probably Biomass-FT << Biomass-H2-FC!)

0

20

40

60

80

100

FT SNG

Co

sts

, E

UR

/MW

h

Vehicle-related extra

costs

Distribution costs,

incl. pressurisation for

SNGUpgrading costs (FT)

Production costs

Estimated (Equivalent) Biomass-to-Pump Costs260 MWfeed; Feedstock at 10 EUR/MWh; Interest on capital 10 %, 20 a

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Finnish biodiesel projects

Background: National UCG-project: budget 4 MEUR, duration 2004 –

2007

Wide industrial consortium: Foster-Wheeler, Neste Oil, Andritz-Carbona,

Vapo, PVO, UPM, M-real, Metsä-Botnia and Stora-Enso

Three Finnish consortia have published their biodiesel projects based on

F-T-technology:

Neste Oil + Stora Enso → NSE Biofuels Ltd- joint venture

UPM + Andritz/Carbona (+GTI)

Vapo + Metsäliitto

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NSE Biofuels Demo 1 plant in Varkaus

From Neste Oil and Stora Enso

1. Commissioning as air blown lime

kiln gasifier

2. Testing period as O2/H2O gasifier,

gas cleaning, FT tests

3. Return to lime kiln gasifier

Lime

kiln

5 MW

Gas cleaning

and FT

BiomassSiloKuivuriDryer 12 MW

Gasifier

1. Commissioning as air blown lime

kiln gasifier

2. Testing period as O2/H2O gasifier,

gas cleaning, FT tests

3. Return to lime kiln gasifier

Lime

kiln

5 MW

Gas cleaning

and FT

BiomassSiloKuivuriDryer 12 MW

Gasifier

Lime

kiln

5 MW

Gas cleaning

and FT

BiomassSiloKuivuriDryer 12 MW

Gasifier

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Wood

sourcing

UPM’s 2G BTL Concept

Gasification

& purification

FT-synthesis

& up-grading

Water

treatment

CHP

plant

Pulp & paper mill

Synthetic

biodieselH2+CO

CnH2n+2

Biomass

drying

Pulp,

wood

Bark

Stumps

Residues

Paper mill units

Additional units

Material flow

Energy flow

Gas Technology Institute, Des Plaines, Illinois, US

from: UPM

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UCGFUNDA 2008 - 2011

Biomass gasification for synthesis applications

- fundamental studies supporting industrial development projects

VTT, TKK and Åbo Akademi, total budget 1.5 M€

Financing by Tekes Biorefine, VTT and private companies

(Carbona, Foster Wheeler, Metso Power, Neste Oil, Stora Enso, UPM &

Vapo)

Biomass characterisation for pressurised steam/oxygen-blown gasification:

ash behaviour and reactivity

Filter blinding and catalyst deactivation studies

Tar reactions in non-catalytic and catalytic processes

System studies on BTL-applications and hydrogen production

Development of measuring methods for tars and other gas contaminants

IEA groups: ”Biomass thermal gasification” and ”Biomass Hydrogen”

34

On-line analysis of tars, water and ammonia

35

'Rapid' on-line tar

analysis

Analysis time 15-20 min

Calibrated compounds:

Benzene

Toluene

Naphthalene

Phenanthrene

Anthracene

Fluoranthene

Pyrene

Gas phase samples on-line

The results have been in good

agreement with the results from

off-line analysis off the

corresponding samples.

Especially useful in transient

conditions where the gas

composition changes quickly.

0

200

400

600

800

1000

1200

1400

1600

1800

2000

2200

2400

2600

2800

3000

26.8.2008 20:24 26.8.2008 21:36 26.8.2008 22:48 27.8.2008 0:00 27.8.2008 1:12 27.8.2008 2:24 27.8.2008 3:36 27.8.2008 4:48 27.8.2008 6:00 27.8.2008 7:12

mg

/m3

Naftaleeni

Tolueeni

Bentseeni

Results from BiGPower tests:

air-blown CFB gasification

followed by tar reformer

36

Recent trends based on projects and literature

Fischer-Tropsch BTL-concepts are very similar in the synthesis

step. Product is only ’diesel’.

MTG-route (Methanol To Gasoline) is gaining more interest

Haldor Topsøe’s TIGAS-process is in demonstration step

Skive Fjernvarme (methanol- and methanol to gasoline-process

Chemrec’s black-liquor based process

GTI

Ethanol from synthesis gas is a popular theme in Japan

Thermochemical route to butanol and mixed alcohols wait for an

efficient catalyst

37

Summary

Biofuels are limited by the available raw material – they can not solve the

energy problem

Diesel is not the only possible end product

Total efficiency about 90 % if process thermally integrated, otherwise

below 60 % -> importance of integration

There are plenty of functional options -> complex task to optimize

Raw material, size of plant, integration to other processes, political

decisions

Synthesis gas must be clean and contain a suitable H2/CO ratio

Primary product is has to be upgraded

One must find economical use to all product fractions and reaction heat

Plenty of development needs in gasification, gas cleaning as well as

synthesis steps: solutions for small scale; heat removal from process;

catalyst activity, selectivity and stability; uprading of products…