Syngas from biomass - gas clean-upprocess developmentSGC International Seminar on Gasification,GASIFICATION FOR BIO-SNG and BIO-FUELS,Göteborg 16.10.2013

P. Simell, , I. Hannula, S. Tuomi, M. Nieminen, E. Kurkela,N. Kaisalo, J. Kihlman

VTT Technical Research Centre of Finland

221/10/2013

Key steps in gasification based synfuels process

Forestry residues,mill residues,straw, energy crops,urban biowaste

Synthesis& upgrading

Gasification

steam &oxygen

oxygen

ReformingFiltration

321/10/2013

Forestry residues,mill residues,straw, energy crops,urban biowaste

Synthesis& upgrading

Gasification andgas treatment

Pulp andpaper mill

Biomasshandling

anddrying

powerplantProcess steam & power

Paperor pulp

Hydrocarbon fuels (FT)or methanol, DME, SNG, H2, etc.

Energyto drying

synthesis-gas

bark,forestryresidues,otherbiomass

fuel gas+ steam

steam & oxygen

Syngas Route to Biofuels – Integrated Concept

150-300 MW

75-160 MW

50-150 MW

421/10/2013

Aspen Plus modelling platform

521/10/2013

• Mature technology• No investment support• No CO2 credits• No tax assumptions

Gasoline@150$/bbl

Gasoline@100$/bbl

Before taxRef.margin=13$/bbl

1€=1.3$ (2010)

Levelised production cost estimates*300 MW biomass @ 17 €/MWh, 0.12 ann. factorElectricity 50 €/MWh, DH 30 €/MWh@5500 h/a

*Liquid transportation fuels via large-scale fluidised-bed gasification of lignocellulosic biomass, Hannula, Ilkka; & Kurkela, Esa 2013. VTT, Espoo. 114 p. + app. 3 p. VTT Technology: 91

621/10/2013

Hot gas filtration

Forestry residues,mill residues,straw, energy crops,urban biowaste

Synthesis& upgrading

Gasification

steam &oxygen

oxygen

ReformingFiltration

500 °C 600 1 000 °C

Filter @ 500 °C

721/10/2013

Fuel: SRF (RDF); ceramic fibre filters (3M FB-900);

cyclone temp 700-750oC; filtration temp 395oC)

0,0

10,0

20,0

30,0

40,0

50,0

60,0

70,0

80,0

90,0

100,0

Na K Cl Al Ca Hg Sn Sb As Cd Pb V Mn Co Ni Cu Zn Mo Cr Si Mg

%of

outp

ut

Bottom ash Cyclone dust Filter dust Gas

Hot gas filtration

Hg, not measured from the gas phase

821/10/2013

The effect of filtration temperature on costs

Work objective: to operate the filter at a higher temperatureImproved efficiencyDecreased production costs

921/10/2013

Hot gas filtration – simplified process by increased temperature

1021/10/2013

Pressurized hot gas filtration test rig ALMAPressures up to 5 bar(g), temperatures up to 850 °CThe effect of the following parameters on filter performance (filter blinding) is studied:

Filtration pressure and temperatureUse of additivesTar and fly ash load in the gas

CH4 O2 N2

DUST REMOVAL

TO GASANALYZER

TO GASINCINERATION

TARSAMPLING

Pd

T

COOLER

CARRIERGAS N2

FC

FC

AIR

N2

SIMULATEDGASIFICATION

GAS

H2O FCBOILER

FLY ASH FEED

FC

TAR FEED

T

PULSE TANK

Pd

TO GASANALYZER

TARSAMPLING

CO,CO2, H2,CH4,H2O, tar

H2OFC

FC FC

FCC2H4

1121/10/2013

Filter blinding @ 800 °C, 1 – 4 bar(a)with and without steam

high-tar load, noadditional dustfeeding

1221/10/2013

Gas reforming

Forestry residues,mill residues,straw, energy crops,urban biowaste

Synthesis& upgrading

Gasification

steam &oxygen

oxygen

ReformingFiltration

500 °C 600 1 000 °C

Tar + H2O CH4 + H2O CO + H2O

nCO + mH2CO + 3H2 CO2 + H2

Ni cat. @ 1 000 °C

1321/10/2013

The effect of methane reforming extent on costs

Work objective: to operate the reformer at optimum methaneconversion (=temperature/catalyst loading)

Improved efficiencyDecreased production costs

1421/10/2013

The development steps

1985 1990 1995 2000 2005 2010

SCREENING

APPLICATION TO PRACTICE

SCALE-UP

DEMONSTRATION

Air,Natural

gas

Air

Catalystreactor

1

Catalystreactor

2

First catalystblock

Second catalystblock

Third catalystblock

Flow straightener

Flow straightener

T

T

T

T cat 1

T cat 2(avg)

T cat(avg)

Varkaus BTL-demo plant

Skive CHP-plant

1521/10/2013

Challenges in catalytic reforming: coke formation

Whisker coke below ~570 oC

Pyrolytic coke above ~800 oC

OBJECTIVE OF THE PRESENT WORK:Find optimum parameters for carbon-free operation byinvestigating the effects of temperature, pressure, gascomposition (especially H2S, tar, ethene and water) andcatalyst

Catalyst bed front face clogging bydust and/or carbon has been aproblem in various phases of our R&Dwork

1621/10/2013

Challenges in catalytic reforming: coke formation

Coke formation during process disturbance test: Standard experiment at 850 oC (catalyst)followed by temperature drop to 500 oC, oxidation and a second standard experiment.

1721/10/2013

Reforming catalysts

Doped zirconiaPOX catalyst

Precious metalcatalyst

Nickel steamreformingcatalyst

Ref: WO 2011/107661 A1, WO 07116121 A1, WO 03000829 A1

oxygen

STAGED REFORMER

1821/10/2013

Reformer long-term performanceTests at VTT 0,5 MW gasification PDU-plant

1921/10/2013

From: Sami Kokki,Foster Wheeler

2021/10/2013

Conclusions

Efficient and versatile gas clean-up technology developed forvarous syngas applications

Gasification based technology for the BTL route is competitivewhen

Mature technology availableOil price > 100 USD/bbl

Liquid fuel production cost reduction in the range of 5 % can beachived by

Increasing hot gas filtration temperature by 200 °C (550 to 750 °C)Increasing methane conversion from 50 to 90 %

2121/10/2013

Conclusions: bio-olefins and chemicals via gasification

Forestry residues,mill residues,straw, energy crops,urban biowaste

FT-reaction withCatalystLow T,p

H2CO

Separationprocess

Fischer-Tropsch

C2-C12 -olefins *Paraffinsoxygenantswater

Oxygenates indilute aqueoussolution

Gasoline

HDPE and LLDPE

Synthetic lubricants forautomotive andindustrial applications

Drag reducing agentsfor oil industryLubricants and fueladditives for engines

Oil field chemicals

Oil recovery surfactants

Detergents and personalcare

Sizing agents (ASA) forPulp&paper industry

Aromatics

Plasticiser alcohols for PVC,cables, leather etc.

steam &oxygen

Filtration +

Reforming +

Shift

Gas upgradingGasification

2221/10/2013

VTT creates business from technology

2321/10/2013

Investment cost factorsBalance of Plant 30 %Indirect costs 22 %Contingency for standard components 20 %Contingency for less mature components 30 %Interest during construction, fraction of TPC 5 %Capital charges factor, (10%, 20a) 12 %O&M costs factor, fraction of TPC/a 4 %Public investment support, M€ 0

Indirect costsEngineering &head office costs 15 %,start-up costs 5 % androyalties & fees 2 %

O&MPersonnel costs 0.5 %Maintenance &insurances 2.5 %Catalysts &chemicals 1 %

BOPinstrumentation andcontrols, electricalconnections, piping,insulation, and sitepreparation

PricesElectricity, €/MWh 50District heat, €/MWh 30Biomass, €/MWh 16.9Refining margin - low-S diesel, $/gal 0.25Refining margin - reformulated gasoline, $/gal 0.32

2421/10/2013

FT designSynthesis

Shell Middle Distillate Synthesis(Bintulu, Pearl)Cobalt-based (Co/Zr/SiO2) LTFTVery paraffinic syncryde, less alkenes andoxygenates than in any other large-scaleindustrial FT technology.80 % per-pass conversion, ~ 0.90Multitubular fixed-bed reactor at 200 °C and30 bar.

Recovery & upgradeC5 recovered by condensation at 45 °C

and PsynthNo cryogenic separation of C1-C2Hydrocracker at 325 °C and 40 bar with noblemetal hydrocracking catalyst

Simplified layout of the FT synthesis, product recovery and refinery section, adaptedSMDS design. From: Arno de Klerk (2011) Fischer-Tropsch refining, Wiley-VCH,642pp, ISBN 9783527326051