Advanced utilisation options for biomass gasification fly ash



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15 th European Biomass Conference & Exhibition May 7 11, 2007, Berlin, Austria Advanced utilisation options for biomass gasification fly ash ICC Berlin - International Congress Center, 10 May 2007 Berlin, Germany A. Gómez-Barea, C. Fernández-Pereira, L.F. Vilches, C. Leiva; M. Campoy; P. Ollero Chemical and Environmental Department University of Seville Spain

Content 1. Objective 2. Fly ash generation 3. Fly ash characterisation 4. Screening methods for fly-ash utilisation 5. Manufacturing of lightweight wallboards 6. Manufacturing of bricks 7. Conclusions

1. Introduction Fly ash (FA) quality may limit biomass gasification FA from the gasification of biomass differs considerable from conventional combustion ash unburned carbon is much higher, typically 10 60% w.w. Relatively high chlorine and heavy metals in case of waste gasification These make the management of gasification fly ash a challenging task (difficult recycling or utilisation) 1. Introduction

1. Introduction An increase in carbon conversion results in higher: Efficiency direct positive influence on power production efficiency Utilisation potential facilitate the development of sustainable economical methods for ash management BFB gasification needs to optimise operation to improve ash quality (reduce carbon content in ash) 1. Introduction

2. Fly ash generation Pilot pant 150 kw th BFB pilot plant at the University of Seville Fuel Orujillo: by-product from the olive oil industry: 3 Mt/yr HV of 18 MJ/kg) Bed material ofite (also trials with limestone) Location Fly ash (bottom ash simpler) 2. Fly ash generation

Test facility 2. Fly ash generation

Technical and operating data of pilot plant facility Inside bed diameter 0.15 m Bed height 1.7 m Inside freeboard diameter 0.25 m Freeboard height 2.5 m Fluidisation velocity 0.8 1.4 m/s Bed material Ofite, limestone Fuel Orujillo, MBM Fuel feed rate 6 35 kg/h Gasification agent Air Operating temperature 700 850ºC Operating pressure Atmospheric Fluidisation regime Bubbling Maximum thermal capacity 150 kw th 2. Fly ash generation

3. Ash characterisation 21 Basic ash characterisation Physical analysis: density and PSD Elemental and ultimate analysis % C in ashes 19 17 15 13 11 9 7 Cyclone 1 5 650 700 750 800 850 T (ºC) Test T bed (ºC) ER %C Overflow %C Cyclone 1 %C Cyclone 2 1 700 0.17 37.54 20.18 22.08 2 740 0.20 20.77 12.00 15.24 3 750 0.22 37.44 15.78 18.08 4 760 0.23 29.85 14.51 19.51 5 785 0.24 19.85 14.03 15.86 6 780 0.29 8.24 11.58 9.66 7 820 0.31 5.33 9.09 12.04 3. Ash characterisation

5. Ash characterisation Basic ash characterisation Physical analysis: density and PSD Elemental and ultimate analysis % C in ashes 21 19 17 15 13 Test T 11 bed (ºC) ER %C Overflow %C Cyclone 1 %C Cyclone 2 1 700 0.17 37.54 20.18 22.08 2 9740 0.20 20.77 12.00 15.24 3 750 0.22 37.44 15.78 18.08 7 4 760 0.23 29.85 14.51 19.51 5 5785 0.24 19.85 14.03 15.86 6 780 650 0.29 700 750 8.24 80011.58 850 9.66 7 820 0.31 5.33 9.09 12.04 T (ºC) 3. Ash characterisation Cyclone 1

Detailed characterisation of ashes Further characterisation (necessary for the screening of existing utilisation options ) Trace elements (ASTM D-3683) Ashes leachability DIN 38414 TCLP (USEPA 1311) Compliance batch leaching test EN 12457/1-4 Up-flow percolation test EN 14405 (Column test) Analysis of Eluates (metals) Thermal analysis (TGA, DSC, DTA) Other: PAH, and specific for a given route being tested 3. Ash characterisation

4. Screening methods for fly-ash utilisation 1. Use as fuel: co-firing in coal/biomass-fired power plants; firing in a dedicated boiler replacement fuel in smelters/incinerators firing in cement kiln 2. Use in construction: Fine applications: cement replacement in concrete Less stringent applications: soil stabilization road base structural fill (filler in asphalt, asphalt-like products) 3. Use in agriculture: directly as fertilizer or as soil improver. 4. Methods for fly-ash utilisation

Conclusions from preliminary screening 1. Cl, alkali metals (K) and carbon content limit ash utilisation 2. Pretreatment necessary (washing and oxidation) 3. Economic methods for management without pretreatment are more attractive fuel in cement kilns Advanced utilisation Stabilisation/Solidification (S/S) lightweight wall boards bricks with special properties 4. Methods for fly-ash utilisation

5. Manufacturing of lightweight wallboards Method of preparation: low-cost moulding and curing methods ash percentages up to 60%w/w gypsum and additives (vermiculite and fibre) 5. Lightweight wallboards

5. Manufacturing of lightweight wallboards Main Results: Acceptable mechanical and properties ρ (kg/m 3 ) ph A(%) Rc (MPa) S H (Shore C) 652 9.95 67.4 0.43 28 Good environmental behaviour (leaching) Further studies on optimisation of blends 5. Lightweight wallboards

Fire resistance test curves for various board 900 200 Tº exposed surface (ºC) 800 700 600 500 400 300 200 Text Commercial 2 Gasification board Commercial 1 180 160 140 120 100 80 60 40 Tº non-exposed surface (ºC) 100 20 0 0 0 5 10 15 20 25 30 35 Time (min) 5. Lightweight wallboards

Leaching tests results (DIN: (μg/l)) Component Limit Orujillo gasification ash Cd 100 <30 Cr(VI) 100 --- Cr total 500 <50 Ni 500 50 Cu 2000 55 Zn 2000 20 As 100 <1 Hg 20 <50 Pb 500 100 4. Lightweight wallboards

6. Manufacturing of bricks Preparation Three types of blends prepared by adding ash to the clays as organic material Ash content in bricks up to 20% Three clay bodies tested (representative to the used in facing bricks) Tests Mechanical tests (standard for bricks) Fire test (similar to the tunnel kiln firing) Leaching tests 6. Manufacturing of bricks

6- Manufacturing of bricks 6- Manufacturing of bricks

6. Manufacturing of bricks Results Mechanical tests showed that the three clay bodies tested are very near (slightly below using 20%) the requirements for facing bricks, i.e. HD clay masonry units Environmental tests (leaching) favorable Optimisation There are two routes for further testing: Reduction of ash quantity (from 20% to 15%) Bricks with special insulating thermal and acoustic properties (body strength need to be slightly improved to meet UNE-EN 771-1) 6. Manufacturing of bricks

7. Conclusions Existing (combustion) options for utilisation of fly ash are not valid for the ash derived from the FBG of orujillo (pretreatment is needed) Demonstration that fly ash from FBG of orujillo has potential as the main constituent in lightweight wallboards (60% ash) and bricks (20% ash) Optimisation of the blend composition for the lightweight plates and the bricks are under study 7. Conclusions

Acknowledgements The authors acknowledge the financial support for this research by the Commission of Science and Technology, European Commission and Junta de Andalucía. We also acknowledge Cerámicas Malpesa (Bailén, Spain) for its help in preparing the brick samples.

Thank you for your attention

15 th European Biomass Conference & Exhibition May 7 11, 2007, Berlin, Austria Advanced utilisation options for biomass gasification fly ash ICC Berlin - International Congress Center, 10 May 2007 Berlin, Germany A. Gómez-Barea, C. Fernández-Pereira, L.F. Vilches, C. Leiva, M. Campoy, P. Ollero Chemical and Environmental Department University of Seville Spain