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Slide 1 © Fraunhofer UMSICHT

Options to reach Syngas Quality Requirements by Catalytic Reforming of Tars and Methane from FB-gasification of Biomass

6th International Freiberg Conference on IGCC & XtL Technologies

Christian Hamel – Fraunhofer UMSICHT


Introduction

Still high demand for gasification systems depending on a variety of factors

Material utilization is desired

Gas from allothermal steam gasification (e.g. FICFB Güssing) with good prerequisites for material utilization

Difficulties with catalytic gas cleaning / tar reforming

Lower process temperatures in comparison to other gasification systems result in low activities

Few scientific insights available for monolithic catalysts in complex gas matrixes

Background

Allothermal FICFB gasifier in Güssing (AT )


Introduction

Aim: Development of catalysts or catalytic process suitable for tar reforming / removal in sulfur-containing syngas at relatively low temperatures

First step: Benchmark tests of a broad variety of different catalysts

Bulk and monolith catalysts

Nickel and precious metal (PM) catalysts

Influence of different preparation routes

Without and with H2S as severe catalyst poison

Recent focus:

Tests about influences of different precious metal amounts and components

Tests with different catalyst type combinations

Current research project at Fraunhofer UMSICHT


Tests at Fraunhofer UMSICHT Overview


3,5%

7,0%

16,0%14,0%

25,9%

33,7%

1470 ppm

370 ppm

Ar

CH4

CO

CO2

H2

H2O

Benzol

Naphthalin

Tests at Fraunhofer UMSICHT Synthetic Syngas Composition

Gas composition typical for allothermal gasifiers

Benzene and naphthalene taken as model tar substances

H2S used to investigate possible catalyst poisoning

+150 ppm H2S


Tests at Fraunhofer UMSICHT Details about testing conditions

Parameter Value Unit

Reactor inner diameter (ID) 18 mm

Catalyst length-to-diameter ratio (L / D) 2 -

Volumetric flow rate at STP (Input) 2 𝐿

𝑚𝑖𝑛

Space velocity (GHSV) at STP 16,000 h-1

Steam-to-carbon ratio (S/C) 0.86 -


Results Influence of 150 ppm H2S

Conversions of a commercial nickel catalyst with and without 150 ppm H2S added

The catalyst was applied as 3x3 mm pellets

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Gas temperature before catalyst [°C]

Methane

Methane - H2S

Benzene

Benzene - H2S

Naphthalene

Napththalene - H2S


Precious metal catalyst Nickel catalyst

Relative changes in main gas composition

H2S free results are shaded, results with H2S present are filled and calculated equilibriums are shown with black unfilled bars

Both catalysts were applied as 3x3 mm pellets

Results

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CO

CO2

H2

CH4

H2O

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CO

CO2

H2

CH4

H2O

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Results Influence of different precious metal components

Cat. Mass ratio Molar ratio

PM1 PM2 PM1 PM2

A 3 0 1 0

B 2 1 0,67 0,18

C 1 2 0,33 0,35

D 0 3 0 0,53

Catalysts applied as monoliths

No sulfur present

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A Naphthalene

B Naphthalene

C Naphthalene

D Naphthalene0%

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A Benzene

B Benzene

C Benzene

D Benzene

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A MethaneB MethaneC MethaneD Methane

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A Methane

B Methane

C Methane

D Methane

A Benzene

B Benzene

C Benzene

D Benzene

A Naphthalene

B Naphthalene

C Naphthalene

D Naphthalene


Results Influence of different precious metal components

Catalysts applied as monoliths

150 ppm H2S added


PM1 PM2 PM1 PM2

A 3 0 1 0

B 2 1 0,67 0,18

C 1 2 0,33 0,35

D 0 3 0 0,53

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A NaphthaleneB NaphthaleneC NaphthaleneD Naphthalene

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A BenzeneB BenzeneC BenzeneD BenzeneA NaphthaleneB NaphthaleneC NaphthaleneD Naphthalene

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A MethaneB MethaneC MethaneD Methane

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A MethaneB MethaneC MethaneD MethaneA BenzeneB BenzeneC BenzeneD BenzeneA NaphthaleneB NaphthaleneC NaphthaleneD Naphthalene


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Methane Benzene Naphthalene

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A B C D

Results Influence of PM components – conversions at 800 °C

150 ppm H2S added


PM1 PM2 PM1 PM2

A 3 0 1 0

B 2 1 0,67 0,18

C 1 2 0,33 0,35

D 0 3 0 0,53


Summary & Outlook

Precious metal catalysts

Depending on the PM combination, aromatic components can be almost completely converted in H2S free syngas down to temperatures of about 750 °C

Even with H2S present and at very high GHSV, high conversions for Naphthalene can be reached down to 800 °C

The effects of different PM ratios can be clearly seen especially with H2S present

High absolute amount of PM atoms is not the most important factor for conversion

Nickel catalysts

Total removal of tars difficult even at high temperatures

Reduction of temperature has relatively less effect on the reforming activity

High impact of sulfur on the overall activity of the catalyst

Overview of the project results


Summary & Outlook

Tests

Continued experiments to assess the different mechanisms of reforming on PM catalysts

Chemisorption

Variation and gradual reduction of the test gas matrix

Conduction of long-term tests

Tests with combinations of different catalyst types

E.g. sequential combination of Ni and PM based catalysts

Preparation

Development of a novel preparation technique for monolithic catalysts

Study

Economic feasibility and relevance of catalytic tar reforming systems

Outlook for the project


FRAUNHOFER UMSICHT Chemical Energy Storage Department

Foto: photocase.de

Thank you!

Contact: Fraunhofer UMSICHT Osterfelder Straße 3 46047 Oberhausen Germany E-Mail: [email protected] Internet: http://www.umsicht.fraunhofer.de

Dipl.-Ing. (FH) Christian Hamel Telefone: +49 208 8598-1358 E-Mail: [email protected]

mailto:[email protected]

http://www.umsicht.fraunhofer.de/

mailto:[email protected]

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Options to reach Syngas Quality Requirements by …tu-freiberg.de/sites/default/files/media/professur-fuer...Options to reach Syngas Quality Requirements by Catalytic Reforming of