The future for biofuels Bioen NW Brussels 24

The future for biofuels Bioen. NW, Brussels, 24 September 2015 Tony Bridgwater Bioenergy Research Group European Bioenergy Research Institute Aston University, Birmingham B 4 7 ET, UK

Thermal conversion for hydrocarbons Primary conversion Fast pyrolysis to bio-oil Gasification to syngas Hydrothermal processing to bio-crude Secondary conversion Fermentation of syngas to ethanol Synthesis of alcohols (Me. OH, Et. OH etc) from syngas Catalytic cracking bio-oil for deoxygenation Hydrodeoxygenation bio-oil or HTU product Synthesis of hydrocarbons e. g. Fischer Tropsch et al. Tertiary conversion Alcohol dehydration and oligomerisation Refining to specified fuel standards The future for biofuels AV Bridgwater, EBRI, © 2015 2

Routes to biofuels Gasification routes Pyrolysis routes HTP routes Biomass Fast pyrolysis Gasification Syngas Ferment Synthesise -OH dehydration Zeolite cracking Biooil Hydrotreating Refining Hydrocarbons The future for biofuels AV Bridgwater, EBRI, © 2015 Hydrothermal processing Hydrotreating

Fast pyrolysis requires: High heating rates: Small particle sizes needed Dry biomass: <10 wt. % water: Carefully controlled temperature: ~500 C Rapid and effective char removal: Char is catalytic Short hot vapour residence time: to avoid product loss reduces liquid yield Atmospheric pressure to minimise char formation The liquid product bio-oil is obtained in yields of up to 75 wt. % on dry feed. It has high oxygen, around 25 wt. % water and is not miscible with hydrocarbons. Charcoal is consumed in the process. . The future for biofuels AV Bridgwater, EBRI, © 2015 4

Decentralised fast pyrolysis Bulk density Biomass density can be as low as 100 kg/m 3 Bio-oil density is 1200 kg/m 3 Bio-oil liquid storage, handling and transport Tanks and pumps are used No windblown refuse, vermin, or mechanical handling Provides optimum use of loading weight restrictions The future for biofuels AV Bridgwater, EBRI, © 2015 Central processor e. g. for biofuel 5

Hydrothermal processing Otherwise known as liquefaction, biomass is heated under pressure in a liquid environment at moderate temperatures up to 350 C The technology was demonstrated at Albany, Oregon around 1980 with wood in a 1 tph plant. The liquid phase was either water or recycled product oil. Shell subsequently developed their own process - HTU Others have also investigated the technology. The product has much lower oxygen than fast pyrolysis (~15% vs 40%), has high viscosity, and phase separates from the aqueous phase. It is particularly suitable for wet feedstocks. The future for biofuels AV Bridgwater, EBRI, © 2015 6

Bio-oil for biofuels Indirect production Gasification of bio-oil followed by hydrocarbon or alcohol synthesis. There are many technical and economic advantages of gasification of liquid bio-oil rather than solid biomass; but higher costs for bio-oil Direct production Via catalytic upgrading of liquid or vapour Catalyst can be added to biomass; incorporated into the fluid bed material; use of a close coupled reactor; use of a remote reactor Ex-situ or secondary reaction offers independent control over process conditions; Direct feeding bio-oil into a suitable refinery operation The future for biofuels AV Bridgwater, EBRI, © 2015 7

Bio-oil and HTP oil upgrading Zeolite cracking rejects oxygen as CO 2 Vapour processing in a close coupled process No hydrogen requirement, no pressure Extensive coking requires burn-off as in FCC Hydro-deoxygenation rejects oxygen as H 2 O Liquid processing with hydrogen and high pressure Extent of deoxygenation depends on severity of upgrading conditions – pressure, temperature, catalyst and residence time Complex from hydrogen recycling and multiple steps Completion of partial upgrading in conventional refineries is an attractive opportunity for access to economy of scale and expertise. The future for biofuels AV Bridgwater, EBRI, © 2015

Gasification methods Gasification is the conversion of organic material into a mixture of CO, H 2, CO 2, CH 4 and impurities of which tar is critical. Type Oxidative Air Gas HV ~5 MJ/Nm 3 Oxygen ~12 MJ/Nm 3 Indirect Pressure % Hi Comments Simple but N 2 precludes biofuels Mod High cost and high energy use ~17 MJ/Nm 3 Lo Air ~5 MJ/Nm 3 Oxygen ~10 MJ/Nm 3 The future for biofuels AV Bridgwater, EBRI, © 2015 More complex. Gas needs compression for biofuels Hi Higher cost, but Mod higher efficiency O 2 for biofuels 99

System requirements - large scale Minimum FT size considered to be viable is 25000 bb/day = 1 mt/y product requiring 5 mt/y biomass Mini-systems under development e. g. Velocys Entrained flow gasifier requires small feed size or liquids. Pretreatment is necessary Grinding biomass has high economic and energy cost Torrefaction gives a brittle feed = higher costs Fast pyrolysis gives a liquid = higher preparation costs Pressure = higher cost; but higher efficiency; Oxygen for nitrogen free gas = high cost + high energy Indirect gasifiers give nitrogen free gas but are not large scale and cannot be pressurised Large scale gives higher efficiency The future for biofuels AV Bridgwater, EBRI, © 2015 10

Criteria for evaluation The key criteria for technology and process evaluation are: Development costs including demonstration Biomass availability, cost, logistics, characteristics Product selection Scale of operation Process route complexity and maturity Efficiency of process of biomass to biofuels Capital cost Biofuel production cost Integration into established infrastructure Scaleability Technology risks and uncertainties Current status The future for biofuels AV Bridgwater, EBRI, © 2015 11

BTL energy self sufficiency Energy conversion Mass conversion Self sufficient in heat and power. This costs about 4% in mass yield and 10% in energy yield Process 0. 0% 20. 0% 40. 0% The future for biofuels AV Bridgwater, EBRI, © 2015 60. 0% 80. 0%

Capital cost The future for biofuels AV Bridgwater, EBRI, © 2015 13

Capital costs Capital cost, million € 2008 Small gasification + small FT Small FT unproven Pyrolysis + large FT Small pyrolysis & large FT proven Large gasification + FT Large gasification unproven Biomass input million dry t/y The future for biofuels AV Bridgwater, EBRI, © 2015 14

Costs of bio-hydrocarbons Yield, €/t HHV, €/GJ €/toe wt% product GJ/t product Wood feed (daf) 100 67 20 3 145 Pyrolysis oil output 70 147 19 8 331 Diesel (EXCL H 2) & 23 592 44 13 578 Diesel (INCL H 2 from biomass) & 13 880 44 20 860 Gasoline & 22 453 44 10 443 FT diesel # 20 1060 42 25 1030 MTG gasoline # 26 1320 43 31 1320 Crude oil at $100/bbl 560 43 15 560 & Basis: 1000 t/d daf wood feed at 67 €/dry t, 2006 # Basis: 1 mt/y product derived by gasification (DENA report ) 2006 The future for biofuels AV Bridgwater, EBRI, © 2015 15

Unit processes and scale Process Max size TRL Risks Primary conversion Fast pyrolysis to bio-oil 125 t/d 7 Scale up Gasification to syngas 50 t/d 7 Size; gas cleaning Hydrothermal 25 t/d 3 Pressure, Feeding Fermentation of syngas 1000 t/d 7 Contamination Cat cracking bio-oil 50 kg/d 5 Unproven HDO bio-oil and HTU oil 50 kg/d 2 Hydrogen; Unproven 1000 t/d 8 Minimal 200 kbbl/d 9 Minimal kg/d 3 Unproven 9 Minimal Secondary conversion Alcohol synthesis Hydrocarbon synthesis Tertiary conversion Alcohol dehydration Refining to standards 100 kbbl/d The Refining future for biofuels AV Bridgwater, EBRI, © 2015 16

Conclusions Fast pyrolysis provides a liquid as an energy carrier Gasification has many variants but oxygen and pressure needed for biofuels. Gas clean up is critical. HTU has been demonstrated a long time ago. Increased interest for wet feedstocks. Liquid has higher HV than biooil but lower yield. Less developed, more costly. Hydrocarbons via ethanol dehydration offers potentially high yields and a “controlled” product. Process optimisation is essential with integration into established infrastructure Downscaling potential for dispersed biomass but capex increases No current “best” method but criteria are well understood The future for biofuels AV Bridgwater, EBRI, © 2015 17