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SIXTH FRAMEWORK PROGRAMME PRIORITY 6.1

Project no. 502587

Project acronym: CHRISGAS

Project title: Clean Hydrogen-rich Synthesis gas Instrument: IP Thematic Priority: Sustainable Energy Systems

Final Publishable Results of the Plan for Using and Disseminating Knowledge

Period covered: Date of preparation: 1st September 2085 - 28th February 20108 28th February 2010 Start date of project: 1st September 2004 Duration: 5 years Project Co-ordinator: Exploitation Manager: Dr Sune Bengtsson Dr Björn Zethraeus Linnæus University Linnæus University

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Publications

The following list contains some examples of papers published in peer review papers or high-quality conferences within the project. Abstracts, full texts, or information on how to obtain some of them, is available on the CHRISGAS website: http://www.chridgas.com.

NB: The back-reporting, due to the very nature of publications, the list on the website is not complete/fully updated. However, this will be updated as far as possible after the project end in March/April 2010. Several further papers are also available via direct contact with the participating partners.

Also attached as an Appendix to this Report are the draft abstracts of the papers that will be published by the International Journal: Biomass & Bioenergy in early 2011.

1. CHRISGAS project – Clean hydrogen-rich gas through biomass gasification and hot gas upgrading - Krister Ståhl, Lars Waldheim, Michael Morris, Sune Bengtsson - presented at the 14th European Biomass Conference October 2005

2. Biomass IGCC at Värnamo, Sweden - Past and future - Krister Ståhl, Lars Waldheim, Michael Morris, Ulf Johnsson, Lennart Gårdmark - Presented at the GCEP Energy Workshop, April 2004

3. The technical feasibility of biomass gasification for hydrogen production - S. Albertazzi, F. Basile, J. Brandin, J. Einvall, C. Hulteberg, G. Fornasari, V. Rosetti, M. Sanati, F. Trifirò, A. Vaccari, Catalysis Today, 106 (4), 297-300

4. Advanced biomass conversion for transportation fuels - Technology platform - a background - A. Segerborg-Fick, November 2004

5. The technical feasibility of biomass gasification for hydrogen production - S. Albertazzi, F. Basile, J. Brandin, J. Einvall, C. Hultberg, G. Fornasari, V.Rosetti, M. Sanati, F. Trifiro, A. Vaccari, Catalysis Today (2005), vol 106, pp 297-300

6. Numerical Simulation of the Autothermal Reformer in a Syngas Process with Respect to the Burner Design and Development - Lixin Tao, Nader Padban and Lars Waldheim - presented at INFUB 7, April 2006

7. Karakterisierung von Produktgas aus einem 100 KWth

Biomassen gefeuerten dampf/sauerstoff zirkulierenden Wiberschichvergaser - W. de Jong, K.V. van der Nat, E. Simeone und M. Siedlecki The Velen Conference, April 2006

8. Particle size characterization of particles present in the producer gas of a steam and oxygen blown biomass circulating fluidized ed gasifier - K.V. van der Nat, W. de Jong, N.Woudstra, H.Spliethoff - Presented at Biomass for Energy Industry and Climate Protection, Paris, October 2005

9. Hot biosyngas filtration and integrated catalytic tar cracking. - Simeone, E. and de Jong, W., In proceedings of the International Symposium on Catalysis Engineering, Delft, 14 June 2007. (poster)

10. Hot gas filtration and particles characterization during steam-oxygen blown gasification of biomass fuels. - Simeone, E. , Siedlecki, M., de Jong, W. and Jansens, P. J., Delft University of Technology, Leeghwaterstraat 44, 2628 CA, Delft, the Netherlands, Presented at the 15th European Biomass Conference and Exhibition, Berlin, May, 2007

11. Deactivation of SCR Catalysts by Exposure to Aerosol Particles of Potassium and Zinc Salts - Ann-Charlotte Larsson, Jessica Einvall, and Mehri Sanati, School of Technology and Design – Bioenergy, Växjö University, SE-351 95 Växjö, Sweden, Published in Aerosol Science and Technology

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12. Study of catalyst deactivation in three different industrial processes - Ann-Charlotte Larsson, Doctoral thesis, Växjö University, 2007

13. Evaluation of a high temperature water gas shift catalyst for upgrading of synthesis gas from biomass - Maroño, M., Sánchez, J.M., Ruiz, E., CIEMAT, EUROPACAT VIII, Turku, Finland, August 2007

14. Effects of H2S and fly-ash on a Ni based catalyst for the reforming of a product gas from biomass gasification - S. Albertazzi, F. Basile, J. Brandin, J. Einvall, G. Fornasari, C. Hulteberg, M. Sanati, F. Trifirò, A. Vaccari, University of Bologna, Catator, Växjö University, EUROPACAT VIII, Turku, Finland, August 2007

15. Study of the deactivation of a Ni based catalyst for the reforming of a product gas from biomass gasification - S. Albertazzi, F. Basile, J. Brandin, J. Einvall, G. Fornasari, C. Hulteberg, M. Sanati, F. Trifirò, A. Vaccari, University of Bologna, Catator, Växjö University, EUROPACAT VIII, Turku, Finland, August 2007

16. Effects of fly ashes on Pt-Rh/MgAl(O) catalyst for the upgrading of the product gas coming from biomass gasification - S. Albertazzi, F. Basile, J. Brandin, J. Einvall, G. Fornasari, C. Hulteberg, M. Sanati, F. Trifirò, A. Vaccari, University of Bologna, Catator, Växjö University, Presented at the 15th European Biomass Conference and Exhibition, Berlin, May, 2007

17. Defluidisation and Agglomeration in Fluidised Beds during Gasification of Biomass - Truls Liliedahl, Krister Sjöström; Frank Zintl, Department of Chemical Engineering and Technology, Chemical Technology, KTH, Submitted to Fuel

18. Measurement of Aerosol Particles from Steam and Oxygen Blown Gasification of Wood Pellets in a 20 kW Atmospheric Bubbling Fluidised Bed (ABFB) Gasifier - Eva Gustafsson, Michael Strand and Mehri Sanati, School of Technology and Design – Bioenergy, Växjö University, S-351 95 Växjö, Sweden, Presented at the 15th European Biomass Conference and Exhibition, Berlin, May, 2007

19. A new method for the analysis of heavy tar in raw producer gases from biomass gasifiers - Claes Brage, Qizhuang Yu and Krister Sjöström, Department of Chemical Engineering and Technology, Chemical Technology, KTH – Royal Institute of Technology, Stockholm, Sweden, Presented at the 15th European Biomass Conference and Exhibition, Berlin, May, 2007

20. Characterization of gaseous and condensable components in the product gas obtained during steam-oxygen gasification of biomass in a 100 kWth CFB gasifier - M. Siedlecki, E. Simeone, W. de Jong, A.H.M. Verkooijen, Process and Energy Department, Faculty of Mechanical, Maritime and Materials Engineering, Delft University of Technology, Presented at the 15th European Biomass Conference and Exhibition, Berlin, May, 2007

21. Physical and Chemical Characterization of Aerosol Particles Formed During the Thermochemical Conversion of Wood Pellets Using a Bubbling Fluidized Bed Gasifier - Eva Gustafsson, Michael Strand, Mehri Sanatia, School of Technology and Design – Bioenergy, Växjö University, SE-351 95 Växjö, Sweden, aDepartment of Design Sciences – Ergonomics and Aerosol Technology, Lund University, Box 118, SE-221 00 Lund, Sweden, Energy & Fuels (2007) vol 21, pp 3660-3667.

22. Shift catalysts in biomass generated synthesis gas - Kirm I, Brandin J, Sanati M (2007) - Topics in catalysis 45 (1-4): 31-37 Aug 2007

23. Investigation of reforming catalyst deactivation by exposure to fly ash from biomass gasification in laboratory scale - J. Einvall, S. Albertazzi, C. Hulteberg, A. Malik, F. Basile, A-C Larsson, J. Brandin, and M. Sanati, (2007) - Energy & Fuels, 21 (5), 2481-2488

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24. Effect of fly ash and H2S on a Ni-based catalyst for the upgrading of a biomass-generated gas - Albertazzi, S. ; Basile, F.; Brandin, J.; Einvall, J.; Fornasari, G.; Hulteberg, C.; Sanati, M.; Trifiro, F.; Vaccari, A - Biomass and Bioenergy, v 32, n 4, April, 2008, p 345-353

25. Biomass Gasification in Atmospheric Fluidised Bed: Iron catalyst for Tar Removal - V. Nemanova, T. Nordgreen; K. Sjöström, Royal Institute of Technology, Stockholm, Sweden, M. Brundu, University of Calgari, Italy

26. Chemical Hot Gas Cleaning in the CHRISGAS Project - M. Stemmler, M. Müller, in Proceedings of the 17th European Biomass Conference and Exhibition on Biomass for Energy, Industry and Climate Protection, Hamburg, Germany, 2009, OB5.2, pp. 855-861.

27. Pt/Rh/MgAl(O) catalyst for the upgrading of biomass-generated synthesis gases - S. Albertazzi, F. Basile, J. Brandin, J. Einvall, G. Fornasari, C. Hulteberg, M. Sanati, F. Trifirò and A Vaccari, Energy & Fuels 2009,23, 573-579.

28. Study of the behaviour of a catalytic ceramic candle filter in a lab-scale unit at high temperatures - Simeone, E., Hölsken, E., Nacken, M., Heidenreich, S. and De Jong, W. (2010), International Journal of Chemical Reactor Engineering, 8, paper A11.

29. Effect of Magnesite as bed material in a 100kWth steam-oxygen blown Circulating Fluidized Bed biomass gasifier on gas composition and tar formation - Siedlecki, M., Nieuwstraten, R., Simeone, E., de Jong, W. and Verkooijen, A.H.M. (2009) , Energy & Fuels, 23(11), pp. 5643-5654. DOI: 10.1021/ef900420c

30. Hydrogen-Rich Gas Production From Oxygen Pressurized Gasification Of Biomass Using A Fe-Cr Water Gas Shift Catalyst - M. Maroño*, J.M. Sánchez, E. Ruiz, International Journal of Hydrogen Energy, 35(2010), 37-45

31. Study of the suitability of a Pt based catalyst for the upgrading of a biomass gasification syngas stream via the WGS reaction - M. Maroño, J.M. Sánchez*, E. Ruiz, A. Cabanillas; Catalysis Letters 126 2008), 396-406

32. Permeability and selectivity to H2 of Pd membranes supported on porous stainless steel tubes - J.M. Sánchez, M.Maroño, M.M. Barreiro, Pres. at Euromembrane 2009, in the Book of Abstracts, The EMS Conference, pp. 385-386 Sept 2009

33. Separation of CO2 and H2 using palladium membranes (for integration in power generation with CO2 capture) - J.M. Sánchez, M. Maroño, M.M. Barreiro, Pres. at Euromembrane 2009, in the Book of Abstracts, The EMS Conference, pp. 450, Sept 2009

34. Preliminary Studies of Water Gas Shift catalysts and a Pd-based membrane for H2 and CO2 production & separation in a Catalytic Membrane Reactor - J.M. Sánchez, M. Maroño & M. Barreiro, Pres. at 9th International Conference on Catalysis in Membrane Reactors, Lyon, June 28th - July 2nd 2009, Book of Abstracts, p.175-176

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Further Papers, Posters and other Scientific Presentations: Further partner contributions include mainly scientific results from the project. The following papers and presentations are not available at the web site but those interested should contact the corresponding authors. The following list aims to demonstrate that the project does not only produce high-quality scientific papers but that the information about the project is spread also to the wider audience visiting more applied conferences. Again, more papers are available through direct contact with the work package leaders.

I. “Ny Energiteknik”, oral presentation, Sjöström, at the BFR conference in Sundsvall, October 2005.

II. Participation and oral presentation at the IEA Task 33 workshop in Dresden, June 2006, Waldheim L.2005.

III. “The technical feasibility of biomass gasification for hydrogen production”, Mehri Sanati, Jan Brandin Thermochemische Umwandlungvon Biomasse, Fachhochschule Flensburg March 16th 2006, Lecture M.

IV. Paper contribution from TUD to the 15th European Conference and Technology Exhibition on Biomass for Energy, Industry and Climate Protection’, 7-11 May, Berlin, Germany is expected (abstract submitted).

V. “Synthesis gas from gasified biomass for vehicle fuel production”, Jan Brandin, Mehri Sanati, Transport Research Arena 12-15/6 2006 Göteborg, Proceeding paper, Lecture JB.

VI. “Numerical simulation of the autothermal reformer in a syngas process with respect to the burer design and development”, Tao, Waldheim, Poster at the International Conference on furnaces and boilers, INFUB, 2006.

VII. ”Charakterisierung von Produktgas aus einem 100 kWth Biomassen gefeuerten Dampf/Sauerstoff zirkulierenden Wirbelschichtvergaser, ‘' de Jong, W., van der Nat, K. V., Simeone, E. and Siedlecki, M. (2006) in Energetische Nutzung von Biomassen (W. Adlhoch, ed.), (Kapstadtring 2, 22297 Hamburg), pp. 67-74, Deutsche Wissenschaftliche Gesellschaft für Erdöl, Erdgas und Kohle e. V., 24-26 April 2006, Velen, Germany (oral presentation).

VIII. “The first results of gas and solids characterization obtained during steam-oxygen gasification of biomass in a 100kWth CFB gasifier”, M. Siedlecki, K. van der Nat, E. Simeone, W. de Jong (2006) paper submitted for the World Renewable Energy conference, 19-25 August 2006, Florence, Italy. (Oral presentation.

IX. Impact of fly ash from biomass gasification on reforming catalysts”, Jessica Einvall, Simone Albertazzi, Christian Hulteberg, Francesco Basile, Ann-Charlotte Larsson, Eva Gustavsson, Jan Brandin, Ferruccio Trifiro, Mehri Sanati, Paper submitted to topics on Catalysis.

X. ”Particle size characterization of particles present in the producer gas of a steam and oxygen blown circulating fluidized bed gasifier”. Van der Nat, K., De Jong, W., Woudstra, N. and Verkooijen, A.H.M. (2005) In: Proceedings of the 14th European Conference and Technology Exhibition on Biomass for Energy, Industry and Climate Protection’, 17-21 October, Paris, France, pp. 642-645. (Poster presentation.

XI. “Shift Catalyst in biomass generated syntheis gas”, Ilham Kirm, Jan Brandin, Mehri Sanati, Paper submitted to topics on Catalysis 2006.

XII. “The technical feasibility for transport fuel production from biomass”, Mehri Sanati, Jan Brandin Christian Hulteberg, The European challenge in the fuel production from biomass 3/4 2006 Bologna, Lecture CH.

XIII. “Catalytic Technology In Syngas Production From Biomass”, Jan Brandin, Christian Hulteberg, Mehri Sanati, Jessica Einvall, Eva Gustavsson, Ferruccio Trifiro, Francesco Basile, Simone Albertazzi, World bioenergy pre-conference 29/6 2006 Växjö, Lecture JB.

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XIV. “Impact of fly ash from biomass gasification on reforming catalysts”, Jessica Einvall, Simone Albertazzi, Christian Hulteberg, Francesco Basile, Ann-Charlotte Larsson, Eva Gustavsson, Jan Brandin, Ferruccio Trifiro, Mehri Sanati, Poster, 12th Nordic symposium on Catalysis 29-31/5 2006 Trondheim.

XV. “Shift Catalyst in biomass generated syntheis gas”, Ilham Kirm, Jan Brandin, Mehri Sanati, Poster, 12th Nordic symposium on Catalysis 29-31/5 2006 Trondheim

XVI. Pressurized CFB gasification of biomass for syngas generation – The EU CHRISGAS project”, L. Waldheim, Conference on Chemical Pulping & Biorefinery, Stockholm Nov 2006 – Also presented at the European Biofuel Congress in Essen, October 200.

XVII. “Shift Catalyst in biomass generated synthesis gas”, Ilham Kirm, Jan Brandin, Mehri Sanati, Poster, 12th Nordic symposium on Catalysis 29-31/5 2006 Trondheim

XVIII. “Measurement of Aerosol Particles from Steam and Oxygen Blown Gasification of Wood Pellets in a 20 kW Atmospheric Bubbling Fluidised Bed (ABFB) Gasifier”, 15th European Biomass Conference and Exhibition, Berlin, Germany, October 7-11, 2007.

XIX. “Production of syngas by thermochemical conversion of lignocellulosic biomass.”, Science & Technology of biomasses: advances and challenges, 200

XX. “Method for sampling of particles in the product gas at high temperatures in a biomass gasifier”, Strand, M., 16th European Biomass Conference and Exhibition, Valencia, Spain, June 2-6, 2008.

XXI. “Further development and testing of a method for characterization of particles from biomass gasification using a laboratory scale gasifier”, Gustafsson E., Strand M., 16th European Biomass Conference and Exhibition, Valencia, Spain, June 2-6, 2008.

XXII. “Sampling of particles from biomass gasification – a method for testing the tar adsorption capacity of a bed of granular activated carbon”, Gustafsson, E., Lin, L., Strand, M, 4th International Bioenergy Conference, Jyväskyle, Finland, August 31-September 4, 2009.

XXIII. “Investigation of the oxidation kinetics of biomass char particles”, Gustafsson, E., Lin, L., Strand, M, 4th International Bioenergy Conference, Jyväskyle, Finland, August 31-September 4, 2009.

XXIV. “Advanced Biofuels in Sweden”, Klas Engvall, KTH, Chemical Technology Workshop: Biogas from Biomass, Gothenburg 20-21 January 2010.

XXV. “Method for High-Temperature Particle Sampling in Tar-Rich Gases from the Thermochemical Conversion of Biomass”, Gustafsson, E, Strand M, Accepted for publication in Energy & Fuels 2010.

Further dissemination activities: Not only printed material – but also dedicated project dissemination activities have been supplied from the project. Three major activities of that kind have been the workshops arranged aimed at politicians, planners and decision-makers, and aiming to raise the awareness of the technology in a broader scope. There are no written minutes from these workshops but the main result is instead the networking between the participants and the informal exchange of information. Also (restricted) material from the four summer-schools is available upon request from the organizers. Details about this can be found on the CHRISGAS web-site.

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Results summary The feasibility of the suggested process in a long-term, sustainability perspective has been clearly demonstrated by the project work and has been documented in scientific papers. This is one important aspect of the Project: to promote the technology as such in a wide context.

One important factor in this context is also the availability of the raw material. This has been treated in the deliverables/reports from WP5 and from WP16. These are available to the general public on the CHRISGAS website.

A large number of the published papers from the Project aim to improve the general and fundamental understanding of the sub-processes, such as gas properties, gas contaminants and gas reforming. Special emphasis is put on the importance of understanding catalyst behaviour and catalyst performance limitations in case of particle-laden producer gas from biomass gasification.

The results clearly illustrate that such catalytic processes that are commercial with “natural” gas or other fossil and comparatively clean fuels are not necessarily readily applicable in the same way when biofuels are the raw material. The recent biological origins of the biofuels constitute a new set of tracer elements to those in the fossilised fuels, a set of elements that may poison or otherwise disturb the catalyst performance. This is due not only to the chemical composition of the fuels but also to the behaviour of the components during the gasification process – when submicron particles are formed. Thus the characterization of the gas- and particle phases is of utmost importance for the success of the process.

Therefore, the most fundamental and most condensed publishable result is:

“Biomass resources are available – but they are not unlimited. Thus, the total system efficiency in the process as a whole and the process flexibility are of the utmost importance for suture sustainability. Biofuels are also a very complex group of substances to be used for process input, but they are still necessary for a sustainable future and the problems can be solved! Also, an extended use of biofuel will create long-term, sustainable jobs.”

This may sound like a very crude conclusion – but it is important to stress the special difficulties with biofuels – without giving up.

Hence, the conclusion is that it is difficult to produce a clean, hydrogen-rich synthesis gas from biofuels – but it is possible. The CHRISGAS project has identified one possible way to move forward.

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Appendix

Biomass & Bioenergy:

Lead Paper & Abstracts

NB: Draft Versions

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The CHRISGAS Project

Sune Bengtsson School of Engineering, Bioenergy Technology, Linnæus University,

SE-351 95 Växjö, Sweden. Tel: +46 470 7088823, Fax: +46 470 708756

E-mail: sune.bengtsson@lnu.se Abstract CHRISGAS is the acronym for Clean Hydrogen-rich Synthesis Gas), a 5½-year “Flagship” project funded within the EC’s 6th Framework Programme and by the Swedish Energy Agency. 20 partners representing industry and research from 7 EU member states have been involved in the project which commenced in September 2004 and ended in February 2010. Research on the whole value chain from biomass resources, drying, pressurised gasification and other thermo-chemical processing to final synthesis (syngas) gas, as well as plant cost studies including synthesis of vehicle fuels for three full scale production capacities has been covered in the integrated CHRISGAS project (http://www.chrisgas.com). From a hydrogen-rich synthesis gas renewable transportation fuels, such as DME, FT-diesel and hydrogen can be produced. At the project onset one of the primary aims was to demonstrate the manufacturing of a suitable syngas based on biomass gasification at the Värnamo large scale pilot plant. Unfortunately due to insufficient additional funding this aim could not be fulfilled within the timeframe of the project. This paper describes the history and the evolution of the project; it also presents the other papers included in this edition within the context of the work areas of the CHRISGAS project. Keywords: gasification, syngas, biomass, reformation

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Introduction and Background Gasification is generally regarded as one of the most interesting and potentially feasible technologies to produce large quantities of renewable transportation fuels in the future. The existing Värnamo IGCC Demonstration Plant (6 MWe/9 MWth) in Sweden, now owned by VVBGC AB (Växjö Värnamo Biomass Gasification Centre AB), is considered to be extremely suitable to develop this technology.

Aerial view of the Värnamo IGCC demonstration plant. It is the first of its kind in the world and was built by Sydkraft AB in 1991-1993 and operated during 1993-1999. This IGCC project has been regarded as an important step forward in developing highly efficient and environmentally acceptable technologies based on biomass. The plant aimed to demonstrate the complete integration of a gasification plant and a combined cycle plant, fuelled by biomass; the basic idea (then in the 1990) being to demonstrate the technology rather than to run a fully optimized plant or to use it as a production plant. Flexible and conservative solutions were chosen for the plant layout and design to ensure the fundamental success of the project and to make the plant suitable for RD&D activities. This Demonstration Program was concluded in 2000 and results have been reported earlier [1]. They are summarized with regard to relevance for the CHRISGAS project below. IGCC Demonstration Experiences A simplified process diagram of the IGCC biomass gasification plant is shown below.

Process diagram of the IGCC process at Värnamo.

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The experiences from the demonstration testing at Värnamo during 1996 to 1999 were generally very positive [1]. The difficulties initially encountered were overcome after 2-3 years of intense commissioning and testing. The Demonstration Program that started during 1996 was very successful and proved that pressurized biomass IGCC technology works. The best evidence of this is the achieved number of operating hours, with gasifier operation of more than 8 500 hours; and operation of the complete plant with the gas turbine operating solely on product gas for more than 3 600 hours. Extensive experience was gained and the most important results achieved, particularly with relevance for CHRISGAS, are summarized as follows:

• High-pressure gasification technology works. • Gas produced can be burnt in a gas turbine under stable conditions. • Hot gas filtration is efficient and reliable. • Technology is capable of gasifying “difficult fuels”.

After the demonstration testing of the IGCC technology was completed in 1999 the plant was mothballed and placed under a conservation program with further use of the plant to be investigated further. The CHRISGAS Project In the Directive of the European Parliament and of the Council 2003/30/EC on “The promotion of the biofuels for transport” the EC set a minimum percentage proposal of biofuels to replace diesel and gasoline for transport purpose in each Member State. This Directive opened up an excellent opportunity to formulate a response containing both research and the opportunity to conclude with demonstration at the Värnamo site using extensive parts of the existing plant and adding the new equipment items required to convert the raw gas to a syngas. (Being a comparatively large pilot plant, and thus having a pressurized CFB gasifier, the plant in Värnamo was deemed to suit the demonstration purpose.) Thus the CHRISGAS project was drafted by interested parties, and this consortium led by Linnæus University (formerly Växjö University), applied for EC funding within the 6th Framework Programme in 2003. The primary objective of the CHRISGAS project [2] at the onset of the project was to demonstrate in the rebuilt Värnamo plant the manufacture of a hydrogen-rich gas from a renewable feedstock, primarily woody biomass. In parallel with the preparation work for demonstration testing a comprehensive program of research and complementary product development, research-related networking, training and dissemination activities as well as socio-economic research of the non-technical obstacles for penetration into markets was launched. The bench-scale and pilot test work of the project consisted of a number of tasks for which the objectives were:

• Conversion of cellulose biofuels into a medium calorific value gas by gasification at elevated pressure using a steam and oxygen mixture.

• Cleaning of the generated gas from particulates in a high temperature filter. NB: hot gas cleaning is advantageous for the overall energy balance when a reformer is applied directly after the cleaning section as reforming requires a high inlet temperature.

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• Purification of the generated gas by catalytic autothermal steam reforming of not only tars, but of methane and other light hydrocarbons, to generate a raw synthesis gas consisting mainly of carbon monoxide and hydrogen as energy carriers.

The block diagram below shows the new CHRISGAS syngas process flow of dry or pre-dried material; the flow of raw gas from the fluid bed gasifier (steam/oxygen blown); the subsequent equipment for particulate cleaning (hot gas filter); and catalytic gas upgrading reactor, i.e steam reformer; and the water gas shift and hydrogenation generation to arrive at a raw synthesis gas for further processing by conventional processing to a vehicle fuel.

Block diagram of the CHRISGAS syngas process. The rebuild at Värnamo is illustrated below in flow scheme, and shows the original IGCC units and the planned syngas version of the process.

STEAM

SYNTHESIS GAS

BIOFUEL

GASIFIER

HOT GAS FILTER

STEAM + OXYGEN

REFORMER

GAS COOLER

WATER GAS SHIFT

STEAM + OXYGEN

CONDENSER

STEAM TURBINE

FLARE

HYDRO-GENATION

STACK

HEAT RECOVERY BOILER

BURNER

GAS TURBINE

BURNER

BY-PASSED PROCESSES

ASH

QUENCH DUCT

GAS COOLER

DISTRICT HEATING

G

GSTEAM

SYNTHESIS GAS

BIOFUEL

GASIFIER

HOT GAS FILTER

STEAM + OXYGEN

REFORMER

GAS COOLER

WATER GAS SHIFT

STEAM + OXYGEN

CONDENSER

STEAM TURBINE

FLARE

HYDRO-GENATION

STACK

HEAT RECOVERY BOILER

BURNER

GAS TURBINE

BURNER

BY-PASSED PROCESSES

ASH

QUENCH DUCT

GAS COOLER

DISTRICT HEATING

G

G

Flow chart of the VVBGC pressure CFB gasification plant as equipped for syngas generation.

The realisation of the demonstration part of CHRISGAS was largely dependant on separate funding of approximately 25 M€ to finance: (i) the rebuild after the required engineering work (to be carried out in 2006 and 2007); and (ii) the demonstration testing originally planned to occur during years four and five (2008 & 2009) of CHRISGAS.

New syngas

Existing IGCC

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Content and Evolution of CHRISGAS The content of the CHRISGAS project was comprehensive and covered the whole value chain from biomass resources, drying, pressurised gasification and other thermo-chemical processing to final syngas, as well as plant cost studies. In addition certain special activities related to the planned pilot plant rebuild and demonstration were included. The work areas can be summarised as follows: 2.2. Evolution of the Värnamo pilot plant modification and pilot testing The early work within CHRISGAS was related to plant status check-up to certify the condition of the plant after the conservation, certain engineering tasks associated with the Värnamo pilot plant modification and the training of staff Also conducted within the CHRISGAS project were a number of highly successful gasification test runs at the existing IGCC plant at VVBGC during 2006 & 2007. This certified that the existing plant had maintained good operational standards over the seven years in which it was mothballed. Further test activities and evaluation of results, after start-up and commissioning of the rebuilt pilot plant, were included in the project funding from both the EC and the Swedish Energy Agency. The latter had set aside a budget to cover almost 75 % of the required funds, However, it conditionally also required the additional remaining funding to come from “industry”; this to secure industrial engagement and eventual commercialisation of the results. These conditions had not been fulfilled by December 2007 at which time the Swedish Energy Agency took a decision to put on hold and only release limited funding. Intensive efforts are still being pursued to resolve the financing situation and thus enable the rebuild and demonstration activities to be fully carried out at the VVBGC plant 2.3. Off-site fuel supply and management Feedstock questions are of crucial importance: the various biomass fuel qualities, their availability, supply as well as costs for harvesting, transport etc. for various regions of Europe. The GIS (Geographical Information System) presentation methodology was used for southern Europe; and within CHRISGAS a tool BIORAISE (www.bioraise.ciemat.es/) was developed to assess availability and potential for different types of biomass, together with the associated harvesting and transport costs. For central and northern Europe statistical data was mainly used to assess the availability. 2.4. On and off-site fuel drying The feed material in a biomass gasifier should be < 20 % moisture content to make efficient use of the energy. For forestry biomass this can only be achieved by drying, whist agrofuels can achieve this in the field. Both desktop and experimental work to study energy efficient drying methods for forestry biomass were performed. On-site, i.e. at the site of the gasifier as well as off-site drying were considered. 2.5. Pressurised fuel feeding The Värnamo pilot plant is equipped with a high operating cost lock-hopper system for the feeding of biomass. A new piston feeding equipment with potential to achieve substantially lower operating costs was developed by one of the partners in the project. This piston feeding technology is now commercialised and is described in one of the papers in this publication. 2.6.Gasification Investigations into the heart of the project – gasification of biomass in a fluid bed reactor –

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were performed focusing on different areas. Steam/oxygen blown gasification with different bed materials; in-bed S-capture; ash related issues; etc. were investigated at the partners’ laboratory pilot units of 10 to 100 KWth capacity. Results show that agglomeration and sintering tendencies are absent or at a minimum with magnesite and olivine as bed material. Furthermore it was found that the attained hydrogen content of the product gas was influenced by the bed material. 2.7. Gas and aerosol particle characterization Characterisation of the gaseous tar and trace components as well as aerosol particles from biomass gasifiers were other essential tasks. Know-how essential for the definition of the gas cleaning requirements e.g., for downstream processing and for the understanding of the down-stream catalyst behaviour was developed. Aerosol measurements were made at the laboratory pilot units. Chemical equilibria for typical potential condensable species of alkali metal compounds were calculated and on-line analyses were made using advanced mass spectrometric equipment, with emphasis on inorganic compounds of concern (e.g. KCl, KOH) down to 10 ppb. 2.8. Hot gas filtration The particle removal from the raw gas – the hot gas filtration as chosen in the CHRISGAS project – at very high temperature (600 to 900 °C) is recognised as very challenging and has been subject to development and testing work. Since the gasification is performed at 800 to 900 ºC and the downstream reforming also requires at least this inlet temperature, it is essential to perform filtration at the highest possible temperature to reduce cool down and heat up of process gas. Thus, to achieve a very high overall energy conversion efficiency of the process the hot gas filtration should be performed at highest possible temperature, whilst taking into consideration potential material problems which set limits to temperature as well as to pressure. Within CHRISGAS a pilot ceramic candle filter was tested at one of the laboratory CFB gasifiers (100 kWth) and the results are reported in this publication. 2.9. Process catalyst studies, steam reforming and water-gas-shift (WGS) The reforming process is necessary to arrive at a hydrogen-rich syngas by converting tar and hydrocarbons (mainly methane) in a gasifier product gas to hydrogen and carbon monoxide. Autothermal steam reforming (ATR), using a catalyst at a few hundred degrees lower temperature than a conventional thermal reformer, would serve to optimise the energy efficiency of the process. However, the conventional nickel catalyst is very sensitive to sulphur. Thus, different studies were carried out to assess the catalyst sensitivity for sulphur and other critical species in the gas. The results indicate that ATR steam reforming should work satisfactorily given the low sulphur content of woody biomass. The further upgrading to high hydrogen content was also performed in a catalytic WGS reactor. Although not as critical as the reforming nickel catalyst, research in this area was also performed in the CHRISGAS project to confirm the process and the work and findings are reported in one of the papers below. 2.10. Ancillary and novel processes Innovative gas separation and gas cleaning related to the CHRISGAS process has been considered as having future potential to justify further research, even though it would not be possible to pilot it within to the timeframe of the CHRISGAS project. Results from bench-scale, proof of concept testing based on membrane separation are the subject of one of the papers in this publication.

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2.11. Process system studies and cost studies Modelling of the fluid bed gasifier and extension of an available mass & energy balance model was carried out to enable prediction of gasification system output streams. Resulting data has been used to conduct individual studies related to air separation units to produce the required oxygen for gasification, acid gas removal as well as the synthesis to a variety of potential automotive fuels. These results were used to produce cost studies for plant capacities in the range 20 to 80 tonnes/hr dry biomass. In this cost work the following potential BTL-products methanol, DME and hydrogen were subject to production cost analysis. In separate complementary work FT-diesel was also considered. 2.12. Socio-economic studies The socio-economic effects of a bio-DME production plant of 400 000 tons DME/hr in Växjö have been focused upon. The raw material considered only logging residues and stumps, this was so as not to compete with existing industries such as the pulp and paper and saw mills. Important factors considered for the implementation of such a bio-DME plant are the raw material availability situation and employment. 3. Conclusions The transport sector’s dependence on oil must be reduced. For heavy transports an obvious way of achieving this reduction is to increase the use of vehicle fuels produced from renewables. The primary objective of the CHRISGAS project was to create more know-how and background for thermo-chemical processing; in this case the pressurized CFB gasification, hot gas cleaning and upgrading process for the manufacture of a hydrogen-rich gas from biomass. Several important and significant results were achieved within CHRISGAS:

• A new piston feeder for biomass to a gasifier was developed and commercialized. This significantly reduces the consumption of inert gas.

• A modified hot gas filter with new features was successfully pilot tested. • Important knowledge on oxygen/steam-blown biomass CFB gasification, catalytic

reforming and WGS process was developed, as well as within other key areas of the thermo-chemical conversion process.

Thus the results of the CHRISGAS project will contribute to the reduction of greenhouse gases and pollutant emissions, increase the security of energy supplies and increase the use of renewable energy in the transport sector when the studied technologies are introduced commercilally. Furthermore intense negotiations are still ongoing to secure the additional funding required to ensure that the original demonstration part of the CHRISGAS project will be realized in the near future. References: 1. Ståhl K, Neergaard M, Nieminen J. Värnamo Demonstration Programme – Final Report.

1st World Conference and Exhibition on Biomass for Energy and Energy and Industry, Sevilla, Spain, 5-9 June 2000.

2. Bengtsson S, Ståhl K, Waldheim L, Gårdmark L. The CHRISGAS Project – Clean Hydrogen-Rich Gas through Gasification and Hot Gas Upgrading, Bioenergy in Wood Industry 2005, Jyväskylä, Finland,12-15 September 2005.

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Biomass Resources and Costs: Assessment in Different EU Countries

Luis S. Esteban, Juan E. Carrasco CEDER-CIEMAT. Autovía A-15, salida 55, 42290-Lubia (Soria), Spain.

Tel: +34 975 281013, Fax: +34 975 281056 E-mail: luis.esteban@ciemat.es

Abstract The objective of the CHRISGAS Project in the field of biomass resources was to make an assessment of the biomass resources and costs available for fuel procurement to future biomass CHRISGAS technology hydrogen plants in different EU countries, as well as to investigate possible locations for the erection of CHRISGAS plants. The assessment work included France, Italy, Portugal, Spain and Greece (southern EU countries); Austria, Germany and Poland (central EU countries); and Sweden, Finland, Norway and Denmark (northern EU countries). A specific assessment methodology was developed and applied. For this purpose a European land use database (Corine Land Cover) CLC was used as basis and other different data from the National Forest Inventories and EUROSTAT regional statistics were also integrated. The quantification of potential resources in the five Southern countries amount to some 176 Million odt/yr; being 140 Million odt/yr agricultural field, and 36 Million odt/yr forest resources. The available resources estimated after the application of restrictions reached 104 Million odt/yr. Available agricultural residues were estimated in 86 Million odt/yr and the available forest resources in 18 Million odt/yr. The countries with higher quantities of available resources are France with 57 Million odt/yr, Italy with 21 Million odt/yr and Spain with 17 Million odt/yr. In the considered central and northern countries, the total biomass resources have been calculated at 188 Million odt/yr, of which 125.5 are agricultural residues, and 62.5 are forest biomass. The highest biomass potential is in Germany, with 67 and 9.5 Million odt/yr agricultural and forest biomass, respectively; and the country with higher potential of forest biomass is Sweden, with 20.7 Million odt/yr. The agricultural biomass available for energy use has been estimated at 72 Million odt/yr, with Germany also being the country with most available agricultural residues (45 Million odt/yr) and the available forest resources of 31.6 Million odt/yr being Sweden, the country with highest resources (9.5 Million odt/yr). In the southern EU countries, the average biomass extraction costs (harvesting and forwarding) estimated for Spain have been 23.03 €/odt for agricultural residues and 49.7 €/odt for forest residues. The highest costs have been obtained in Italy (33.2 and 74.0 €/odt, respectively, for agricultural and forest residues collection) and the lowest ones in Portugal (21.4 and 27.4 €/odt). In north and central Europe, the collection cost in Sweden have been estimated as 30.24 €/odt agricultural residues and 22.3 €/odt forest residues. The highest costs have been calculated to be for Norway (37.6 and 27.8 €/odt) and the lowest ones for Poland (15.6 and 11.5 €/odt) for agricultural and forest residues collection respectively.

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Experimental Study of Low-Temperature Biomass Bed Drying

Peter Bengtssona*, Olle Wennbergb aSchool of Engineering, Linnæus University, SE-351 95 Växjö, Sweden. bS.E.P. Scandinavian Energy Project AB, SE-417 55 Gothenburg, Sweden.

*Tel: +46 470 708982, Fax: +46 470768540 *E-mail: peter.bengtsso@lnu.se

Abstract Bed drying of wooden biomass particles such as sawdust and wood chips has been experimentally studied at low drying temperatures (<100°C). One particular focus has been on the development of the drying zone, where the actual drying takes place. Drying experiments and continuous bed temperature measurements were performed in an experimental batch dryer. It has been shown that both the velocity and the width of the drying zone are influenced by biomass characteristic properties and drying process parameters. The experiments indicate that the drying zone velocity increases with increasing drying temperature and air velocity but is uninfluenced by its height position. The width of the drying zone increases with increasing air velocity and height position, but is uninfluenced by temperature. Cross-sectional variations of the front velocity as well as the drying zone width were observed which show an irregular progress of the drying zone through the biomass bed. Such information is important for a complete understanding of the bed drying process and order to optimize the process for various biomass materials and drying conditions. A first-step optimization method based on the measurements is presented and discussed.

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Development of a Piston Feeder for High Pressure Gasification

Peter Friehling, Thomas Koch TKE Energie A/S, Værftsvej 8, DK-4600 Køge, Denmark.

Tel: +45 46 189000, Fax: +45 46 189018 E-mail: pf@tke.dk

Abstract A piston feeder for low inert gas “consumption” has been developed by TK Energi AS as part of the CHRISGAS project. Two feeders were designed and tested for several hundreds of hours with a wide range of materials. A well functioning control system was developed. It is able to control the whole process including start up, shut down and changes in the feeding material without interference from the user. The experiments showed that it was possible to create a plug of material able to work as a pressure barrier for a pressure difference of at least 25 bar. A very limited leak flow was observed, this occurred through the slit between the plug and the wall of the feeder. The lifetime of the critical parts of the feeder was estimated based on the wear measured during long term testing. A proper choice of construction material and/or coatings will secure a reasonable lifetime for the feeder. Based on the test results, a full scale feeder has been dimensioned and the energy consumption has been estimated to approximately 1% of the heating value of the biomass being fed into the process.

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Biomass Gasification as the First Hot Step in Clean Syngas Production Process – Gas Quality Optimization and Primary Tar Reduction Measures

in a 100 kWth Steam-oxygen Blown CFB Gasifier

Marcin Siedlecki, Wiebren de Jong Section Energy Technology, Department of Process & Energy, Faculty 3mE,

Delft University of Technology, Leeghwaterstraat 44, 2628 CA Delft, The Netherlands. Telephone: +31 15 2789476, Fax: +31 15 2782460

E-mail: m.siedlecki@tudelft.nl Abstract Syngas production based on biomass gasification is an attractive, feasible alternative to fossil fuel feedstock for the production of transportation fuels. However, gasification product gas using biomass as feedstock must be cleaned and tailored to comply with strict syngas quality requirements, as it consists of a wide variety of major and minor components and impurities. The characterization of such species is important to determine downstream gas treatment steps, and to assess the efficiency of the gasification process. This paper gives an overview of the results obtained during experiments on steam-oxygen gasification of biomass using 100 kWth,max circulating fluidized bed gasifier (CFBG) that have been performed at Delft University of Technology during the CHRISGAS project. The unit is equipped with a high temperature ceramic gas filter and downstream reactors for upgrading of the gas. In the experiments both woody and agricultural fuels, namely miscanthus and straw, have been used. These represent clean wood, demolition wood, an energy crop species and a true residue, respectively. Moreover, different bed materials have been applied, such as sand, treated/untreated olivine and magnesite. During the experiments extensive measurements of gas composition have been carried out throughout the integrated test rig. The gas characterization includes the major gas components as well as certain minor gas components. The results show that, with the use of magnesite as bed material, remarkable increases of hydrogen yield were attained as compared to sand or olivine – until almost 40%vol. (dry, nitrogen free basis) – and that the H2/CO ratio was increased from values near or lower than 1 to 2.3-2.6. This is near values needed for e.g. Fischer-Tropsch diesel production, indicating a potential for simplification of the gas upgrading. Moreover, by using magnesite tar content of the raw gas was reduced to values near 2 g/mn

3. Finally, magnesite appeared to have a positive impact on agglomeration prevention for the agricultural fuels containing alkali and chlorine in the ash. Correlations were determined between the operational conditions such as process temperature, equivalence ratio, type of biomass and product gas composition.

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Characterisation and Effects of Suspended Particulates during Fluidized Bed Gasification of Biomass

Eva Gustafsson, Leteng Lin and Michael Strand

School of Engineering, Bioenergy Technology, Linnæus University, SE-351 95 Växjö, Sweden.

Tel: +46 470 708981, Fax: +46 470 708756 E-mail: michael.strand@lnu.se

Abstract Biomass may be converted to second generation of biofuels through thermochemical conversion. One of the more promising methods is through fluidised bed (FB) gasification and upgrading to synthesis gas. If synthesis gas of proper composition and purity can be produced, the gas may be converted to a variety of chemicals and fuels including Fischer-Tropsch diesel, methanol and DME. The process-chain of transforming the solid biomass into pure synthesis gas is characterised by stepwise development from a multiphase system dominated by suspended solids, into a pure gas. The particulate solids include bed material, fly ash and char present at high concentrations in the gasifier. They also include particles formed though gas to particle conversion such as alkalis, soot and condensed tars. Depending on physical and chemical properties as well as where they appear in the process chain, solids and condensed particulate matter have a critical effect on operation of the gasifier and downstream process steps. Despite this, few attempts have been made to characterise particulates in the hot gas. This is mainly due to the challenges associated with extracting representative samples at the severe conditions prevailing in the hot gas, as well as the specialised instruments used for particle measurements, especially for on-line characterisation. In this paper the presence and effects of particulates during FB gasification and upgrading to synthesis gas will be overviewed, as well as various methods that can be used for sampling and characterisation of particulates in the hot product gas. Results including particle size distribution in the range 10-10 000 nm, as well as size segregated chemical speciation analysis from three FB gasifiers representing different gasification schemes will be presented and discussed. These gasifiers include a 20 kW steam and oxygen-blown bubbling fluidised bed gasifier, a steam- and oxygen- blown 100 kW circulating fluidized bed gasifier and a steam- blown 1MW indirect gasifier.

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Reforming of Hydrocarbons from Gasified Wood and Herbaceous Biomasses

F. Basile a*, S. Albertazzi a, D. Barbera a, P. Benito a, J. Brandin b,

G. Fornasari a, F. Trifirò a, A. Vaccari a .

a Dipartimento di Chemica Industriale e dei Materiali, ALMA MATER STUDIORUM -Università di Bologna,Viale Risorgimento 4, 401 36 Bologna, Italy.

b School of Engineering, Bioenergy Technology, Linnæus University, SE-351 95 Växjö, Sweden.

*Tel: +39 051 2093663, Fax: +39 051 2093675 *E-mail: f.basile@unibo.it

Abstract Biomass and residues are converted by gasification into a gas stream containing CH4, C2-3 CO, CO2, H2 and tars together with some contaminants. The yield in syngas (CO + H2) can be increased by hot gas cleaning followed by catalytic hydrocarbon conversion as proposed in the CHRISGAS project. In particular, the main aim of the CHRISGAS was to reach a 50-60 % of syngas (H2+CO) on dry bases in the exit gas, which can be converted either into H2 or BTL. In order to convert the hydrocarbons present in the gasification stream, reforming processes can be used. Although these are well-known processes for the production of H2 and/or syngas, the feasibility of the processes depends on the activity and stability of the catalysts. In fact, the main problem of the reforming process after the hot gas filtration is the deactivation of the catalyst, especially due to sulphur poisoning and, at long term, due to alkalis, as observed in previous deactivation studies with a model gas. Since the concentration of the contaminants is biomass dependent, the research was extended to perform reforming tests in a biomass raw gas stream using different kinds of woody and herbaceous biomasses to analyze the activity and deactivation behaviour. The reforming of a biomass gasification product stream was performed in a pilot plant equipped with a 100 kWth steam/oxygen gasifier and a hot gas filtration system working at 800 °C. A bench-scale reformer was placed downstream the gasifier, after the hot gas filter. A Ni-MgAl2O4 commercial-like catalyst was tested using three different feedstocks: the gasification product gas from a clean wood consisting of sawdust (Wood A), a wood mainly produced from bark and branches (Wood B) and a third gasification feedstock based on an herbaceous biomass (miscanthus). The effect of the temperature in the hydrocarbon conversion was studied. Low (< 600 °C), medium (750-900 °C) and high temperature (900-1050 °C) tests were carried out in order to study, respectively, the tar cracking, the lowest operating reformer temperature for clean biomasses and the highest methane conversion achievable and catalyst modification in real like conditions. During tests at low temperature tar conversion depended on the biomass. A high conversion was obtained for Wood A (> 95 % at 550 °C). However, when the sulphur content in the stream increased (Wood A < Wood B < miscanthus) the conversion decreased. The methane conversion was low, in agreement with thermodynamics; even negative values were obtained due to the CH4 formation by tar decomposition. However, the stream was enriched in H2 and CO2 because of the contribution of the water gas shift reaction. When using a clean wood (Wood A) a middle temperature (750 °C) is enough to convert about 90 % of the CH4 and to

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obtain a high syngas yield (CO + H2 > 60 %). On the other hand, when woody residues with larger S content (Wood B) are used as fuel, a higher temperature (~ 1000 °C) is required to reach a similar CH4 conversion. Finally, using an herbaceous biomass (miscanthus), which produces a gasification stream with a H2S content well above 200 ppm, even when raising the temperature, the methane conversion was lower producing a gas with a (CO + H2) content of only 63 %. The results demonstrate the feasibility of producing an enriched syngas stream by the upgrading of the gasification stream of woody biomasses with low S content by steam reforming. However, for herbaceous biomass the development of catalysts with an enhanced resistance to poisoning will be the clue in the applicability of the process.

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Release and Fate of Inorganic Trace Elements during Gasification of Wood, Straw and Miscanthus

Dirk Porbatzki, Michael Stemmler and Michael Müller

Forschungszentrum Jülich, Institut für Energieforschung, IEF-2, Leo-Brandt-Str., D-52425 Jülich, Germany.

Tel: +49 2461 614504, Fax: +49 2461 613699 E-mail: mic.mueller@fz-juelich.de

Abstract In recent years the importance of alternative energy sources using renewable raw materials has increased. Biomass gasification is one of the most efficient technologies for biomass energy conversion. It offers the advantage of product flexibility, e.g. heat, power or synthesis gas for production of synthetic fuels. The CHRISGAS project aims at the development of an energy-efficient and cost-efficient gasification technique to produce hydrogen-rich gases from biomass which are suitable for upgrading to liquid fuels. Syngas derived from biomass treated in a pressurised fluidised-bed gasifier suffers from contaminants released during thermal conversion which can harm downstream equipment, e.g. by fouling, filter plugging and poisoning of catalysts. The most important detrimental inorganic contaminants are alkalies, with other contaminants including ammonia, HCl, particulates and sulphur compounds. To avoid the mentioned problems, nowadays, the product gas is quenched as soon as it leaves the gasifier. This induces, for example, condensation of alkali species. After streaming through a “warm” gas treatment, the product gas is heated up again for subsequent upgrading. In order to improve the efficiency of the CHRISGAS process, an integration of a hot gas cleaning at gasification conditions in the process is planned. A prerequisite for the development of such cleaning systems is a basic knowledge about the amount and fate of detrimental trace elements and the corresponding release mechanisms. Therefore, the release of alkali metals, chlorine, sulphur, phosphorus and heavy metals during gasification of four different types of biomass at temperatures between 800 and 1000°C was investigated. The samples were two types of wood (clean and waste wood), miscanthus, and straw. Experiments were conducted in two different setups; in a tube furnace which could be considered as batch experiments, and in an atmospheric lab scale fluidised bed reactor with continuous fuel feed. Molecular beam mass spectrometry was used for on-line analysis of the hot fuel gas. The experimental results reveal that the release of inorganic species is strongly dependent on other inorganic constituents in the samples. Furthermore, thermodynamic model calculations using SimuSage were performed to investigate the release and fate of trace elements within the CHRISGAS process. Thus, it was possible to identify several risks caused by the released trace elements and to define the demands for a chemical hot gas cleanup.

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Chemical Hot Gas Cleaning in the CHRISGAS Process

Michael Stemmler and Michael Müller Forschungszentrum Jülich, Institut für Energieforschung, IEF-2,

Leo-Brandt-Str., D-52425 Jülich, Germany. Tel: +49 2461 614504, Fax: +49 2461 61369

E-mail: m.stemmler@fz-juelich.de Abstract In recent years the importance of alternative energy sources using renewable raw materials has increased. Biomass gasification is one of the most efficient technologies for biomass energy conversion. It offers the advantage of product flexibility, e.g. heat, power or synthesis gas for production of synthetic fuels. The CHRISGAS project aims at the development of an energy-efficient and cost-efficient gasification technique to produce hydrogen-rich gases from biomass which are suitable for upgrading to liquid fuels. Syngas derived from biomass treated in a pressurised fluidised-bed gasifier suffers from contaminants released during thermal conversion which can harm downstream equipment, e.g. by fouling, filter plugging and poisoning of catalysts. The most important detrimental inorganic contaminants are alkalies, with other contaminants including ammonia, HCl, particulates and sulphur compounds. To avoid the mentioned problems, nowadays, the product gas is quenched as soon as it leaves the gasifier. This induces, for example, condensation of alkali species. After streaming through a “warm” gas treatment, the product gas is heated up again for subsequent upgrading. In order to improve the efficiency of the CHRISGAS process, an integration of a chemical hot gas cleaning at gasification conditions in the process is planned. Calculations on hot gas cleaning were done with a thermodynamic process model using SimuSage. The main focus was set on KCl and H2S removal. The calculations show that H2S can only be limited to 100ppmv by sorption on Cu at temperatures below 830°C. Additional calculations of KCl sorption on alumosilicates show that the alkali concentration in gasifier derived gases can be limited to values below 100ppbv depending on the type of biomass. Thus, the condensation temperature of KCl can be decreased down to 430°C, which is much below the melting point. To validate the results of the calculations, sorption experiments on selected sorbents have been performed in a lab-scale tube furnace with hot gas analysis via molecular beam mass spectrometry (MBMS). All selected alkali-sorbents are aluminosilicates; in detail: bauxite, kaolinite, bentonite, and natural occurring zeolite. Except for bentonite, all chosen sorbents were found to be suitable for cleaning KCl laden gases below 100ppbv. Characterizations by XRD show that KCl is sorbed by forming microcline (KAlSi3O8).

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High Temperature Gas Filtration during Steam-Oxygen Blown Gasification of Biomass

Eleonora Simeonea*, Manfred Nackenb, Steffen Heidenreichb, Wiebren de Jonga

aSection Energy Technology, Department of Process & Energy, Faculty 3mE, Delft University of Technology, Leeghwaterstraat 44, 2628 CA Delft, The Netherlands.

bPall Filtersystems GmbH, Werk Schumacher, Zur Flügelau, 70, D-74564 Crailsheim, Germany.

*Tel: +31 152 788254, Fax +31 152 78246 *E-mail: e.simeone@tudelft.nl

Abstract Syngas from biomass gasification is an economically and technologically feasible alternative to fossil fuel feedstock in the production of transport fuel. The produced syngas is upgraded in downstream (catalytic) units in order to obtain the right specifications according to the end use. Aerosol particles transported by the produced syngas to the downstream units can create problems such as deactivation of the catalysts, enhanced corrosion and fouling can also be extremely harmful for gas turbines in case these are used in polygeneration concepts. A high temperature filtration unit is therefore necessary in order to reduce the particulate matter content in the gas. The present work is being performed at the Laboratory of Process and Energy at Delft University of Technology (DUT) and is focused on gas filtration at high temperatures. It is part of the CHRISGAS project, which aims to study the production of synthesis gas with high hydrogen content from biomass gasification. The test-rig consists of a 100 kWth atmospheric circulating fluidized-bed gasifier (CFBG) and a high temperature filter unit which contains 3 rigid ceramic candles with an outer diameter of 60 mm, an internal diameter of 40 mm and a length of 1500 mm. The filter elements are periodically cleaned with nitrogen pulses. For this purpose a CPP (Coupled Pressure Pulse) regeneration system recently developed and patented by Pall Filtersystems Werk Schumacher has been used in order to improve the filter cake removal during the filtration process. This paper gives an overview of the filtration performance during steam-O2 biomass gasification. Various biomass fuels were utilized (A wood, B wood, miscanthus and straw) with different bed materials (sand, magnesite and olivine). Dia-Schumalith ceramic filter candles were tested. The filter unit was heated from 450°C to 800°C and its performance was studied through continuous observation of the increasing pressure drop during the build-up of the dust cake. The cleaning parameters are defined as the frequency of the back pulses, the pulse gas pressure and the opening time of the valves. Different set points were adopted in order to obtain an optimal cleaning strategy. Gas and particles analyses were performed upstream and downstream of the filter. Dry gas composition was measured semi-online with a micro-GC and with an off-line FTIR. Water content was measured gravimetrically. Tars concentrations were obtained with the SPA method. A stable baseline pressure drop could be obtained for some tests with high filtration efficiency. Studies on the permeability of the filter elements as well as an investigation of the used candles were carried out.

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Defluidisation and Bed Agglomeration in Fluidised Beds during Gasification of Biomass

Truls Liliedahl

School of Chemical Science and Engineering, Kungl Tekniska Högskolan, SE-100 44 Stockholm, Sweden.

Tel : +46 8 790 8777, Fax: +46 8 108579 E-mail: truls@ket.kth.se

Abstract Bed agglomeration and defluidisation during fluidised bed gasification is discussed. It is argued that, in principle, these processes closely resemble the processes that determine the behaviour of glass during glass processing. Crucial properties for working with a glass melt are, for example, the viscosity, stickiness and surface tension. Therefore it is (very) difficult to theoretically predict, for example, agglomeration and defluidisation. Models for predicting defluidisation must therefore probably be of an empirical nature. As a consequence of the above a number of fluidised bed gasification tests were reviewed with respect to this aspect. In total 129 tests were evaluated, of these 45 defluidised or exhibited some kind of bed disturbance. Seven biofuels and four bed material were analysed. The data was analysed thorough multivariate statistical analysis (PCA, PLS). The relative tendency for promoting agglomeration and defluidisation of the different fuels were in decreasing order: miscanthus (with high potassium) > olive trash > reed canary grass, lucerne > salix > birch. Parameters that seem to influence sintering the most are the temperature and the potassium, silicon and calcium contents in the ash. Potassium and silicon seem to enhance sintering, whilst calcium has the opposite effect. This is in line with earlier findings. Of the bed materials magnesite, in contrast to silver sand, increases the defluidisation temperature; this is especially with Salix as fuel. A pressure dependence was also observed, the higher the pressure the lower the defluidisation temperature. A 1 MPa increase in pressure lowers the agglomeration/defluidisation temperature with 20 - 30°C. The true nature of this pressure dependence is doubtful though. Based on the results an empirical regression equation for predicting the defluidisation temperature during fluidised bed gasification is suggested.

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Unit Operations for Production of Clean Hydrogen-Rich Synthesis Gas from Gasified Biomass

Jan Brandina*, Truls Liliedahlb

a School of Engineering, Bioenergy Technology, Linnæus University, SE-351 95 Växjö, Sweden.

b School of Chemical Science and Engineering, Kungl Tekniska Högskolan, SE-100 44 Stockholm, Sweden.

*Tel: +46 470 708829, Fax: +46 470 708756 *E-mail: jan.brandin@lnu.se

Abstract In the CHRISGAS project the plan was to convert the VVBGC’s Värnamo IGCC plant into a clean hydrogen-rich synthesis gas producing unit. The Värnamo plant is equipped with an 18 MWth CFB gasifier, able to operate pressurized up to 18 bars. In this paper the layout and required unit operations for production of clean hydrogen rich synthesis gas from gasified biomass is presented according to the plan of the project. The first step to improve gas quality is to change from air blown to oxygen blown operation mode. This eliminates the dilution of the producer gas with nitrogen and improves the combustion value of the gas. The producer gas from gasified biomass contains dust that will disturb the downstream upgrading process if not removed. In the project sintered metallic candle-filters are developed to enable dust cleaning at high temperature. The producer gas, cleaned from dust contains, except for the synthesis gas, also methane, C2-C3 hydrocarbons, tars and contaminants like H2S, NH3, COS etc. To upgrade the producer gas into synthesis gas, the hydrocarbon part including the tars, must be converted into synthesis gas and this is done in the reformer step. The reformer step could be either catalytic or thermal. A catalytic reforming step is considered to be an auto-thermal reformer, where a portion of the fuel is burnt directly above the catalyst bed with oxygen to heat the reactor. The reason for this is that the expected temperature needed for the reforming step is higher than, for instance, steam reforming due to the decrease of catalyst activity caused by the sulphur content of the gas. A thermal reforming step, Partial Oxidation, POX will work but decreases the content of chemically stored heat in the gas more that an ATR-step due to higher operation temperature. When the hydrocarbons are converted, it might be necessary to adjust the H2/CO-ratio of the synthesis gas, making it suitable for the subsequent synthesis steps, for instance methanol, DME, Fisher Tropsch etc. This is done in the Water Gas Shift step, equipped with an FeCr high temperature shift catalyst. This catalyst shows the best potential to operate in the sulphur containing synthesis gas.

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High Temperature Water Gas Shift Step in the Production of Clean Hydrogen-Rich Synthesis Gas from Gasified Biomass

Jan Brandina*, Jessica Einvalla, Charlotte Parslanda, Francesco Basileb

a School of Engineering, Bioenergy Technology, Linnæus University, SE-351 95 Växjö, Sweden.

b Dipartimento di Chemica Industriale e dei Materiali, Università di Bologna, Viale Risorgimento 4, 401 36 Bologna,Italy. *Tel: +46 470 708829, Fax: +46 470 708756

*E-mail: jan.brandin@lnu.se Abstract In the CHRISGAS project, the possibility of using Water Gas Shift (WGS) step for tuning the H2/CO-ratio in synthesis gas produced from gasified biomass has been investigated. The synthesis gas produced will contain contaminants like 50-200 ppm of H2S, NH3 and chloride components. As the most promising candidate, FeCr catalyst was chosen. This catalyst was prepared in the laboratory but other samples were obtained from a commercial supplier. One part of the work was conducted in a laboratory setup with simulated gases and another part in real gases in the 100 kW CFB gasifier at Delft University of Technology. Spent catalysts from both tests have been characterized at Bologna University. In the first part of the laboratory investigation an experimental rig was build and put to operation. The main gas mixture consisted of CO, CO2, H2, H2O and N2 with the possibility to add contaminants in low concentration (0-3000 ppm) like H2S, NH3 and HCl. The setup can be operated up to 20 bars pressure at 200-600 oC and run unattended for 100 h or more. For the second part of the work, in real gases at Delft, a catalytic probe was developed that allowed exposure of the catalyst by inserting the probe into the flowing gas. The results show that the catalytic poisons, H2S, NH3 and HCl, decreases the catalytic activity, but the activity stays stabile in the laboratory tests (50-100 h). Similar decrease in activity was observed in the samples exposed for the real gases. Reactor inlet temperature should be at least 350 oC. Decreases in specific surface of the catalyst are connected to the crystallization of the active phase (magnetite) of the catalyst; the higher crystallinity the lower the specific surface. It is most likely that the FeCr catalyst is suitable to be used in a HT-shift step for industrial production of synthesis gas from gasified biomass.

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Enrichment and Separation of Hydrogen from Synthesis Gas Using Selective Membranes and Membrane Catalytic Reactors

J.M. Sánchez, M.M Barreiro, M. Maroño

CIEMAT, Combustion and Gasification Division, Avenida Complutense, 22, 28040 Madrid, Spain.

Tel: +34 91 3466377, Fax: 34 91 3466269 E-mail: josemaria.sanchez@ciemat.es

Abstract One of the objectives within the CHRISGAS project was to study innovative gas separation and gas upgrading systems that have not been developed sufficiently yet to be tested at a demonstration scale within the time frame of the project, but which nevertheless show some attractive merits and features for further development. In this framework CIEMAT has studied, on a bench scale, hydrogen enrichment and separation from syngas by the use of membranes and membrane catalytic reactors (MCR). In this paper results about hydrogen separation from synthesis gas by means of selective membranes are presented. Studies dealt with the evaluation of permeation and selectivity to hydrogen of prepared and pre-commercial Pd-based membranes. Whereas prepared membranes turned out to be non-selective, due to discontinuities of the palladium layer, studies conducted with the pre-commercial membrane showed that by means of a membrane reactor it is possible to completely separate hydrogen from the other gas components and produce pure hydrogen as a permeate stream, even in the case of complex reaction system (H2/CO/CO2/H2O) under WGS conditions gas mixtures. The advantages of using a water gas shift membrane reactor (MR) over a traditional fixed bed reactor (TR) have also been studied. The experimental device included the pre-commercial Pd-based membrane and a commercial high temperature Fe-Cr-based, WGS catalyst, which was packed in the annulus between the membrane and the reactor outer shell. Results show that in the MR concept, removal of H2 from the reaction side has a positive effect on WGS reaction, reaching higher CO conversion than in a traditional packed bed reactor at a given temperature. On increasing pressure on the reaction side, permeation is enhanced, and hence carbon monoxide conversion increases.

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Cost Estimation of Biomass-to-Fuel Plants Producing Methanol, DME or Hydrogen

G H Huisman, H de Lathouder, R LCornelissen, G L M A van Rens

CCS Energiemanagement B.V., Welle 36, 7411 CC Deventer, The Netherlands Tel: +31 570 667000, Fax: +31 570 667001

E-mail: cornelissen@cocos.nl Abstract A desktop study has been performed to estimate the cost of biomass-to-fuel plants producing methanol, dimethyl ether (DME) or hydrogen. Two different cases are distinguished. One case based on the technology today and one case based on the technology of tomorrow. The investment costs of the near-future case are lower, but the yearly running costs of the near-future case are higher than the present-day case. The latter is because in the present-day case more power can be generated thereby reducing the net power demand and more district heat can be sold. The specific production costs (€ per kg, or € per GJ) fuel are lower for the near-future case because of the higher product yield. In this case production costs are 357, 533 and 1 817 euro per metric ton methanol, DME and hydrogen, respectively. This is not a competitive level, when no additional value is given to the sustainability of the fuel. Production costs are sensitive to uncertainties in biomass price and to a lesser extent capital costs. A 50% change in biomass price changes the specific production cost between 20 and 35%.

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Performance Analysis of Biomass-To-Fuel Plants Producing Methanol, DME or Hydrogen

G H Huisman, H de Lathouder, R LCornelissen, G L M A van Rens

CCS Energiemanagement B.V., Welle 36, 7411 CC Deventer, The Netherlands Tel: +31 570 667000, Fax: +31 570 667001

E-mail: cornelissen@cocos.nl Abstract A desktop study has been performed to analyse the performance of biomass-to-fuel plants producing methanol, dimethyl ether (DME) or hydrogen. Two different cases are distinguished: One case based on the technology today and one case based on the technology of tomorrow. Mass and energy balances are presented for both cases and all three fuels. Biomass-to-fuel conversion efficiency of the plants range between 44 and 50 percent for hydrogen and methanol production respectively in the present-day case, and between 54 and 63 percent for hydrogen and methanol production respectively for the near-future case. Biomass-to-fuel conversion efficiency to DME is only marginally smaller than biomass-to-fuel conversion efficiency of methanol. Expression of efficiency of the biomass-to-fuel plant in biomass-to-fuel conversion efficiency does not include electrical power consumption and district heat grade heat. Therefore process efficiency is also expressed in exergetic efficiency. Methanol production using the technology of tomorrow is most efficient from exergy point of view with 56%. Hydrogen production is less interesting with only 41% in the present-day case, because of the large purge stream in the present plant design.

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Demonstration Plant Activities

Sune Bengtsson School of Engineering, Bioenergy Technology, Linnæus University,

SE-351 95 Växjö, Sweden. Tel: +46 470 7088823, Fax: +46 470 708756

E-mail: sune.bengtsson@lnu.se Abstract The demonstration part of CHRISGAS was originally one of the cornerstones of the project. These biomass-to-syngas demonstration activities were planned to take place at the VVBGC 18 MWth demonstration plant at Värnamo, Sweden. This plant was originally built by the Swedish utility Sydkraft in the first part of the 1990s as an IGCC combined heat and power plant. The plant was acquired by VVBGC from Sydkraft AB in 2004 for the purpose of performing the test work and demonstration activities within the CHRISGAS project after rebuild to syngas version. The required funds for plant modifications to syngas version, as well as operation were not covered in the CHRISGAS project grants, but had to be applied for elsewhere. The company VVBGC AB (Växjö Värnamo Biomass Gasification Centre), now owned by the holding company of Linnæus University, was founded during the course of the project and new staff were recruited s to head the rebuild project and be responsible of the operation of the plant within the CHRISGAS demonstration program. After IGCC demonstration activities were completed at the Värnamo demonstration plant in 1999 the plant had been mothballed. The first activities within the CHRISGAS demonstration program were to make a thorough status review of the plant and any necessary repair work. Further work at Värnamo in 2007 consisted of three hot test campaigns of the existing IGCC version to accumulate and record further experiences of plant status and to provide the new staff adequate training in plant operation. The results of this testing is reported in this paper

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The Socio-economic Effects of a Bio-DME Plant in Växjö

Anders Baudin, Hans-Olof Nordvall

School of Technology and Design, Linnæus University, SE-351 95 Växjö, Sweden. Tel: +46 470 708986, Fax: +46 470 708756

*E-mail: anders.baudin@lnu.se

Abstract The socio-economic effects of a bio-DME plant at full scale (400 000 tons) in Växjö is the focus of this paper. However, such a study cannot be carried out without consideration of a number of factors important for the implementation of bio-DME, namely (i) the raw material situation; and (ii) employment. In the study the raw material discussion is restricted to include only logging residues and stumps. The area around Växjö is concentrated upon since the largest bulk of raw material must be available in this region. Based on two independent data sources it was found that the bio-DME plant in Växjö to a large (or even full) extent can be supplied in a radius of 150 km around Växjö. From the aspect of competition of raw material the picture is more complicated. Logging residues and stumps will, to an increasing degree, be used by the thermal heating/power plants in south Sweden and, in addition, there is potential competition of raw material from other regions. Despite these uncertainties, the work within this study concludes that the raw material situation is favorable for the DME-plant in Växjö. The employment effects of a bio-DME plant in Växjö are considerable. For a full-scale bio-DME plant the analysis indicates a positive net employment effect of 550 to 750 full-time jobs. The geographical localization of jobs will be in or near Växjö (for operation of the plant), and in other parts of Småland (for collection of raw material and for transports).