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Gasification of waste biomass for the combined production of energy and adsorbents
International Workshop on Defining Issues in Biofuels R&D August 3-7, 2008 Cetraro (Calabria), Italy

Dr. Guillermo San Miguel Senior Research Fellow Departamento Ingeniera Qumica y Medio Ambiente, Universidad Politcnica de Madrid C/ Jos Gutirrez Abascal, 2, 28006 Madrid. g.sanmiguel@upm.es

INDEX
1. CONVENTIONAL BIOMASS GASIFICATION.
1.1 1.2 1.3 1.4 1.5 1.6 Introduction to biomass gasification. Biomass feedstock for gasification. Types of reactors for biomass gasification. Biomass gasification today. Gas cleaning and conditioning. Conclusions with conventional biomass gasification.

2. BIOMASS GASIFICATION FOR THE PRODUCTION OF ADSORBENTS.

2.1 2.2 2.3 Introduction to activated carbons. Feedstock for AC production. Development of porosity during gasification.

3. GASIFICATION FOR THE COMBINED PRODUCTION OF ENERGY AND ADSORBENTS: CONSIDERATIONS AND PROPOSED TECHNOLOGY. TECHNOLOGY
3.1 3.2 3.3 Previous research projects. Considerations for dual purpose. Project objectives.

4. CONCLUSIONS

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1. CONVENTIONAL BIOMASS GASIFICATION.

Laboratory scale gasifier.

Wood gasification plant at Gssing (Austria)

1.1

INTRODUCTION TO BIOMASS GASIFICATION.

BIOMASS

CONVERSION PROCESS

Direct extraction

Thermochemical processes

Biochemical processes

Combustion

Gasification

Pyrolysis

Alcoholic Fermentation

Anaerobic digestion

ENERGY PRODUCTS

Liquid fuels

Hot gases

Syngas

Char, Gases Pyro-oil

Ethanol

Methane

THERMOCHEMICAL PROCESSES: Incineration: in excess of oxygen energy. Pyrolysis: under inert conditions char, oils and gases. Gasification: under mildly oxidizing conditions syngas.
Mature technology. Experimental stage. Becoming commercial.

USE

Transport

Steam, heat, electricity

Heat, electricity. Chemical synthesis, H2

Steam, heat.

Transport

Heat, electricity

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PROCESS SCHEME OF BIOMASS GASIFICATION

Reception and conditioning Gasification Gas cleaning and conditioning Gas utilization
HEAT

H2
CH4 VOC

CO
N2 Tars CHEMICAL SYNTHESIS ENERGY

- Drying. - Milling. - Particle size selection selection. - Pelletisation.

- Drying. - Pyrolysis/carbonisation. - Partial combustion combustion. - Gasification. - Partial reforming and WGS.

- Condensation. - Separation of particulates. - Reforming of VOC. VOC - Cracking of tars. - WGS. - PSA.

HEAT and ENERGY - Boilers. - Internal combustion engines. -Gas turbines.

CHEMICAL SYNTHESIS - Methanol: MTBE and gasoline additives. - Fischer Tropsch: liquid fuels - H2 for fuel cells.

6 CHEMICAL REACTIONS IN GASIFICATION

Biomass combustion with oxygen: C + O2 CO2 C + O2 CO H = - 393,8 kJ/mol H = - 123,1 kJ/mol (complete combustion) (incomplete combustion) (water gas reaction) (Boudouard reaction) (1) (2) (3) (4) (5) (methanation reaction) (CO methanation reaction) (water gas shift reaction) (6) (7) (8) (9) (10)

Biomass gasification with steam or CO2: C + H2O CO + H2 H = 118,5 kJ/mol H = 159,9 kJ/mol C + CO2 2CO Steam reforming of small hydrocarbons H = 159,9 kJ/mol CH4 + H2O CO + 3 H2 Methanation reactions: C + 2H2 CH4 CO + 3H2 CH4 + H2O Water gas shift reaction: CO + H2O CO2 + H2 Oxidation of syngas components: CO + O2 CO2 H2 + O2 H2O H = 210,5 kJ/mol

H = - 41,2 kJ/mol H = - 238,9 kJ/mol H = - 285,9 kJ/mol

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1.2

BIOMASS FEEDSTOCK FOR GASIFICATION

a b

- Plentiful and cheap. - High carbon content. - Low humidity content. - Low ash content. Biomass crops: wood chips from pine, eucalyptus, poplar (a). Agricultural and forest waste: pruning, clearing, straw. Industrial waste: oil, sugar, wine, paper, beer production. Nut shells and stones: almonds, olive stones (b). Legume and grain hulls: rice (c). (c) Cereal and sugar cane bagass (d), straw (e).

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9 1.3 TYPES OF REACTORS FOR BIOMASS GASIFICATION.

FIXED BED REACTORS:

Gas, alquitranes. agua

Gas, alquitranes. agua PIRLISIS REDUCCIN

PIRLISIS COMBUSTIN Aire REDUCCIN CENIZAS

COMBUSTIN Aire CENIZAS

(1) downdraft

(2) updraft

(3) double fired

(4) two-stage

Status: mature and commercial. Reactor configurations: updraft, downdraft, double fire, multi stage. Capacity: small to medium (10-1000 KW). Big market for developed and developing economies. Problem with tar removal (mainly updraft, only heat applications). Higher investment costs per unit power: 4-8 Mill /Mwel. Higher electricity production costs: > 200 /MWh. Companies: Downdraft: Bioneer (Finland). Updraft: Babcock & Wilcox Vlund A/S (Denmark), PMR Energy (USA). Two stage: Vinking TK (Denmark).

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FLUIDISED BED REACTORS:

Bubbling fluidised bed Circulating fluidised bed

Status: several plants with > 20.000 operating hours. Feedstock: Particle size between 1100 mm. Ash may fuse with fluidising sand. Capacity: CFB medium to large size (10 100 MW). BFB small to medium (1-25 MW) Lower investment costs per unit of power: 2 4 Mill / MW electric Lower electricity production costs: 100 140 /MWh. Companies: CFB: TPS (Sweden), Ahlstrom-Foster Wheeler (US), Battelle (US), Lurgi GmbH (Germany) BFB: Carbona Corporation (US).

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ENTRAINED FLOW REACTORS:
High temperatures (>1200 C) Low particle diameter. Pressurized operation simple. y Very low tar contents. Low methane content. Currently for large scale and especially for synthesis process (methanol, Fischer-Tropsch) and hydrogen. Much experience from coal gasification Companies: Future Energy GmbH (Freiberg) Elcogs (Spain)

1.4

BIOMASS GASIFICATION TODAY.

A few examples
various sources

Gasification is considered to be close to commercially available

Harbore Plant, Denmark Updraft gasifier Capacity: 1.000 kW electric Experience: more than 2x20.000 hours

Wiener Neustadt, Austria. Double fire gasifier Capacity: 550 kW electric Experience: about 5 000 h E i b t 5.000 hours

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Viking Gasifier, Denmark Two stage gasifier Capacity: 200 kW electric Experience: about 2.000 hours

Low-tech small scale gasifiers (China, India, etc). Usually downdraft or updraft Capacity: usually < 50-100 kW heat or electric Experience: several years

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Gasification Plant ENAMORA, Spain Bubbling fluidised bed. Fuel: Almond shells and bagasse. Electric Power: 550 - 5.000 kW. Experience: 15.000 hours

Kymijrvi Lahti Gasification, Finland Circulating Fluidised Bed Fuel: several different types of wastes Capacity: 60 MWfuel Experience: more than 40.000 hrs.

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Vrnamo IGCC, Sweden Integrated Gasification Combined Cycle (IGCC). Circulating Fluidised Bed Fuel: wood Power: 6 MWe electricity and 9 MWth heat Experience: 8.500 hours of operation.

ELCOGAS, Spain. Integrated Gasification Combined C l (IGCC) I t t d G ifi ti C bi d Cycle (IGCC). Entrained flow gasifier. Project for co-gasification of coal and 10 % biomass. Electrical Power: 300 MWe. Experience: 18.600 hours of operation.

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Summary of commercial gasification plants in Europe
Company Energa Natural de Mora S.L.(Spain) Waste Gasification, Grve-in-Chianti , Italia CHP-Plant Gssing, Austria CHP-Plant Harboore, Denmark Kymiarvi Power Station, Lahti, Finland CFB-Plant Rdersdorf, Germany SVZ, SVZ Schwarze Pumpe Germany Vrnamo Demonstration Plant, Sweeden Carbo-V-pilot (a)plant Germany Construction 1996 Cost () 1.100.000 Technology BFB motogenerator

(extracted from Hofbauer and Knoef, 2004)

Type of fuel Almond shell Residues 40% plastics + 60 % paper Lignocelulsic waste Lignocelulsic waste Organic waste mixtures (paper, wood, plastics) Biomass and organic residues Waste biomass cogasified with 20 % coal. Wood and lignocellulosic residues Lignocellulosic residues Lignocellulosic residues Application Total power: 3500 kW. Electric power: 750kW Total power: 30 MW. Electric power: 6.7 MW Extra gas for cement kiln Total power: 8 MW. Electric power: 2 MW Total power: 5 MW. Electric power: 1.4 MW Total power: 70 MW. Electric power: 20 MW Total power:100 MW, para alimentacin de cementera Methanol production Potencia total: 420 MW Total power: 18 MW. Electric power: 6 MW Total power: 1 MW. Electric power: 150 kW Total power: 70 kW. Electric power: 17 kW

1992

20.000.000

CFB

2001 2002

8.700.000 15.000.000

CFB Fixed bed up-draft motogenerator CFB

1998

12.000.000

1996

CFB

1996

335.000.000

Fixed bed and entrained flow. Integrated Gasification Combined Cycle (IGCC) Carbo-V three step gasification Two stage fiexed bed

2000

25.000.000

1998

2.500.000

The Viking Gasifier, 2002 DTU, Denmark BFB = bubbling fluidised bed CFB = circulating fluidised bed

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17 1.5 GAS CLEANING AND CONDITIONING.

OBJECTIVES: - Reduce concentration of unwanted species: tars, VOC, particulates, SH2. p , - Increase concentration of wanted species: calorific value, H2. a) Products depending on type of reactor and operating conditions:
GASIFYING AGENTS AND PRODUCTS BIOMASS C C C C C GASIFYING AGENTS O2 H2O CO2 2 H2 Air (21 % O2 + 78 % N2) PRODUCTS CO CO + H2 2 CO CH4 CO + N2

Reactor

Temperature (C) Reaction Exit 800 250 850

Tars

Particulates

Down-draft Up-draft Fluidised bed

1000 1000 850

Very low Very high Low

medium medium high

b) Requirements depending on intended application: Heat: low requirements regarding the presence of tars and other impurities. Power: combustion engines and gas turbines require low tar, particulate and sulphur levels. Chemical synthesis: very low content of impurities.

18 GAS CLEANING AND CONDITIONING (2).

1) Physical removal of particulates, tars and other unwanted species (sulphur). 2) Thermo-catalytic removal of VOC and tars reforming and cracking catalysts. 3) Water Gas Shift to increase hydrogen content and reduce CO concentration. ) 4) Preferential oxidation of CO to CO2. 5) Separation of unwanted gases from the mixture: CO2, N2.

Fuel/ biomass
Steam Air O2,

Air

A
Gasification reactor

H2 Ash collection

Gas treatment.
A: cyclone B: filter C: desulphuration

Reformer Cracker

WGS HTS.

WGS LTS.

PROX

N2, CO2 removal

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19 REMOVAL OF TARS by THERMAL AND CATALYTIC METHODS

Tars: large molecular weight volatile compounds generated during the gasification of biomass. They condense at lower temperatures, blocking and fouling process equipments (valves, engines, turbines).

J. Han, H. Kim (2008) The reduction and control technology of tar during biomass gasification/pyrolysis: An overview, Renewable and Sustainable Energy Reviews, 12 (2), Pages 397-416 L. Devi, K.J. Ptasinski, F. J. Janssen (2003) A review of the primary measures for tar elimination in biomass gasification processes, Biomass and Bioenergy, 24 (2), 125-140 D. Sutton, B. Kelleher, J. R. H. Ross (2001) Review of literature on catalysts for biomass gasification, Fuel Processing Technology, 73 (3), 155-173

20 REMOVAL OF TARS by THERMAL AND CATALYTIC METHODS (2)

CATALYTIC CONDITIONING OF HOT GASES

REFORMING CATALYSTS: Transition metals (mainly Ni) supported on alumina or other porous materials. Precious metals (Pt, Pd, Ru, Rh). CRACKING CATALYSTS: Acid solids: zeolites (ZSM-5, Y, Beta), mesostructured solids (Al-MCM-41, Al-SBA15), active alumina.

CATALYSTS INSIDE GASIFICATION REACTOR Calcium and magnesium carbonates (dolomite, magnesite, lime). Impregnation of biomass with alkaline metal salts (K2CO3, Na2CO3, NaCl, KCl, ZnCl2, AlCl3) Increased conversion values and reduced formation of tars. Limited catalytic activity compensated by low cost.

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21 1.6 CONCLUSSION WITH CONVENTIONAL BIOMASS GASIFICATION

Gasification is considered to be close to commercially available (Hofbauer and Knoef, 2005). At current biomass and capital cost levels, incentives are essential for a commercially viable biomass projects (Bridgewater, 2002). Things to be considered: Capital investment: Operating and maintenance costs: Feedstock costs and availability: Market value of products: Risk and technical reliability:

PURPOSEOF GASIFICATION HEAT ELECTRICITY

CHEMICALSANDH2

GASCLEANINGANDCONDITIONING CAPITAL INVESTMENT OPERATINGCOSTS Tarandparticulateremoval low Low Tar,particulateremoval Medium Tar,particulateremoval Reforming High WGS PSA PROX

MARKETPRICE OFPRODUCTS Low Medium

ECONOMIC VIABILITY Limited Limited

High

Limited

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2. BIOMASS GASIFICATION FOR THE PRODUCTION OF ADSORBENTS

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23 2.1 INTRODUCTION TO ACTIVATED CARBONS:

a type of carbon that has been processed in order to develop an extended porosity (250-1000 cm3/g), surface area (500-2000 m2/g) and adsorption capacity. - Demand in developed countries: 0 5-2 0 kg per person and year Growing at annual 3-4 % 0.5 2.0 year. 3 4 %.

- Average market price: bulk GAC: 0.75-2.0 per kg

APLICATIONS
liquid phase applications (79 %): potable water (37 %); industrial and municipal wastewater (21%); sugar decolourization (10 %); groundwater (8 %); household uses (6 %); food and beverage (5 %); mining (4 %); pharmaceuticals (3 %). gas phase applications (21 %): air purification (40 %); automotive emission control (21 %); solvent vapour recovery (12 %); cigarette filter medium (8 %); miscellaneous (19 %).

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PRODUCTION OF AC BY PHYSICAL ACTIVATION

Conditioning, classification and grinding g g
Pelletizing drying

Starting material

Carbonisation and Activation

Classification

Final AC

Precursor Wood Coke Lignite Peat NutShell Other

Use(%) 35 28 14 10 10 3

Carbonisation: 400-550C Inert conditions Activation: 900-1100C Steam or CO2.

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25 REACTORS FOR AC PRODUCTION

Moving bed reactors.

Multiple hearth furnace.

Rotary kiln.

26 2.2 FEEDSTOCK FOR AC PRODUCTION

Precursor Wood Anthracite Lignite Peat Nut Shell Other Use (%) 35 28 14 10 10 3

Abundant and cheap. Development of porosity during activation. High carbon content. Low ash content. Mechanical strength for GAC.

but almost any carbonaceous material may be used as AC precursor.

(Crini, 2006)

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(Ioannidou and Zabaniotou, 2007)

RawMaterial
Apricotstones Cherrystones Grapeseeds Nutshells Pistachionutshells Macadamianutshells Peanutehulls Almondshells Corncob Olivestones RiceStraw Ricehusks Sugarcanebagasse

SBET(m2/g)
1190 875 497 743 778 1718 420 998 960 1550 2410 480 452

Vo (cm3/g)
0.50 0.28 0.12 0.21 0.47 0.72 0.17 0.40 0.49 1.4 1.3

Yield(%)
18 11 26 18

30 18 29 65

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2.3 DEVELOPMENT OF POROSITY DURING GASIFICATION.

Typical AC yields: 15-30 wt%.

Carbon gasification in steam (SP 925) and CO2 (P 950 and P 1100) at different temperatures.

Development of porosity and surface area during gasification of carbon.

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3. GASIFICATION FOR THE COMBINED PRODUCTION OF ENERGY AND ADSORBENTS: CONSIDERATIONS AND PROPOSED TECHNOLOGY.

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3.1 PREVIOUS RESEARCH PROJECTS:

thermal treatment of wastes for energy or adsorbents

(1) Title: Low-cost adsorbents from tyre rubber and other waste materials. (2) Title: Thermal regeneration of field spent activated carbons. (3) Title: Catalytic effects of metals during the thermal regeneration of granular activated carbon. (4) Title: Adsorbent slow rate filters for the removal of colour and metals from upland potable waters. (5) Title: Improvement of textural properties of zeolitic materials for their application as catalysts in chemical reactions hindered by steric and difussional impediments. (6) Title: Application of PY-GC/MS for the investigation of thermal and catalytic cracking of plastic polymers. (7) Title: Development of thermal and catalytic processes for the recovery of plastic wastes. (8) Title: Gasification of sewage sludge from urban water treatment plants.
H2 CO
N2

SYNGAS BIOMASS
Partial gasification
CH4

ADSORBENTS

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31 3.2 CONSIDERATIONS FOR DUAL PURPOSE

- Partial gasification of some types of biomass may favour the economic viability of the process.
H2 CO
N2

SYNGAS BIOMASS
Partial gasification
CH4

ADSORBENTS

- REQUIREMENTS FOR ACTIVATED CARBON PRODUCTION: Reactor should allow for recuperation of partially gasified char char. Biomass should be able to produce high quality activated carbon. - REQUIREMENTS FOR HIGH QUALITY GAS PRODUCTION: Catalytic treatment of vapours required to ensure low tar contents.

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33 3.3 PROJECT OBJECTIVES

- To prove the gasification technology for the combined production of high quality syngas and activated carbon from biomass residues. SPECIFIC OBJETIVES - WP 1: Assessment of biomass wastes with potential for being used for the combined production of energy and adsorbents: production, location, current use, economic value. - WP 2: Chemical, physical and thermal characterization of these wastes. - WP 3: Conventional gasification of biomass for the production of energy. - WP 4: Gasification of biomass for the production of adsorbents. - WP 5: Gasification of biomass for combined production of syngas and adsorbents (pilot scale tests). - WP 6: Assessment of the economic viability, design of full scale plant.

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4.

CONCLUSIONS

- Partial gasification of biomass for the combined production of adsorbents and energy may be an advantageous approach to this technology. - In specific cases, activated carbon production may contribute to the economics of the gasification technology. - The gasification technology needs to be adapted for this dual purpose and so do the operating conditions of the process.

Concluding remarks: Low cost biomass is an appropriate feedstock for the production of energy by gasification. But the activated carbons generated by partial gasification could be too valuable to be used as a source of energy.

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KEY ARTICLES
G. San Miguel, G. D. Fowler, C. J. Sollars (2003) A study of the characteristics of activated carbons produced by steam and carbon dioxide activation of waste tyre rubber, Carbon, Volume 41, Issue 5, Pages 1009-1016 G. San Miguel, S.D. Lambert, N.J.D. Graham (2006) A practical review of the performance of organic and inorganic adsorbents for the treatment of contaminated waters J Chem Technol Biotechnol 81 1685 1696 waters, J. Chem. Technol. Biotechnol., 81, 1685-1696 J.M. Dias, M.C.M. Alvim-Ferraz, M.F. Almeida, J.R.Rivera-Utrilla, M. Snchez-Polo (2007) Waste materials for activated carbon preparation and its use in aqueous-phase treatment: A review, Journal of Environmental Management, 85(4):833-46. H. Hofbauer, H. Knoef (2005) "Success Stories on Biomass Gasification"; in: "Handbook biomass gasification", BTG, 115 161. G. Crini (2006) Non-conventional low-cost adsorbents for dye removal: A review, Bioresource Technology, Volume 97, Issue 9, Pages 1061-1085 O. Ioannidou, A. Zabaniotou (2007) Agricultural residues as precursors for activated carbon productionA review, Renewable and Sustainable Energy Reviews, Volume 11, Issue 9, Pages 1966-2005 T. Bridgewater (2002) The future for biomass pyrolysis and gasification: status, opportunities and policies for Europe, European Commission, Altener contract 4.1030/S/01-009/2001, http://ec.europa.eu/energy/res/publications/doc1/report_p536_v2.pdf K. Maniatis (2002) Progress in biomass gasification. European Commission, http://ec.europa.eu/energy/res/sectors/doc/bioenergy/km_tyrol_tony.pdf Manahan S. E., Enriquez-Poy M., Tan Molina L., Durn C. (2007) Energy and activated carbon production from crop biomass byproducts, in Towards a Cleaner Planet Energy for the Future, SpringerLink, ISBN 354071345X

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