Biofuel Production

Prof. Tony Bridgwater Bioenergy Research Group Aston University, Birmingham B4 7ET
AV Bridgwater 2008

Biomass

Carbohydrates e.g. corn, wheat Sugar from cane or beet Vegetable oil e.g. rape, palm, soy, jatropha Lignocellulosics (lignin, cellulose and hemicellulose) e.g. wood, grass, straw, residues Fertiliser and other inputs have a major impact on the sustainability of crops. Lignocellulosics generally have a lower requirement. There are many agronomical criteria for crop selection of which yield (dry t / ha.y) is important for maximising use of land

Biofuels
Oxygenates Methanol Ethanol Butanol Mixed alcohols Dimethyl ether Hydrocarbons Biodiesel Synthetic diesel Synthetic gasoline Methane (CSNG) Other Hydrogen Generation First generation (1G) 2G biofuels are from food such 1G & 2G as: 1G & 2G Ethanol from sugar, corn 2G Biodiesel from rape oil 2G Second generation (2G) biofuels are from whole 1G 2G crops such as wood and 2G grasses: 1G & 2G Synthetic diesel Methanol 1G & 2G Ethanol

Feeds, processes, products

Starch & sugars Residues 1G 2G Biological conversion Ethanol, Butanol, Chemicals Lignocellulose 2G Thermal conversion Synthetic H/C, Ethanol, Butanol Methanol, Chemicals Power, Heat Esterification Biodiesel (FAME,RME) Chemicals Oil plants Residues 1G

1st and 2nd generation biofuels

First generation biofuels are from foodstuffs such as: Ethanol from sugar, wheat or corn about 2 t/ha/y in Europe and USA, up to 6 t/ha/y from sugar cane in Brazil Biodiesel from vegetable oils about 1 t/ha/y These are important in introducing biofuels and increasing awareness. Second generation biofuels are from whole crops such as wood, energy crops, residues, such as: Synthetic diesel about 4 t/ha/y Methanol about 8 t/ha/y Ethanol about 5 t/ha/y Higher yields and absence of competition with food give these a longer term future

Feeds, processes, products

Starch & sugars Residues Biological conversion Ethanol, Butanol, Chemicals Lignocellulose Oil plants Residues

Thermal conversion Synthetic H/C, Ethanol, Butanol Methanol, Chemicals Power, Heat

Esterification Biodiesel (FAME,RME) Chemicals

Bioethanol

5% limit in gasoline in Europe for cars (E5). E85 (85% ethanol) is used in USA and E100 in Brazil Concerns: Logistical and market compatibility Vapour pressure Hygroscopicity and low temperature properties Materials compatibility Low energy density ~1/3 Fuel compatibility

Bioethanol technology
Biological processes Mature technology for 1G from sugar, grain and corn. Developing technology for 2G from lignocellulosics. Hydrolysis releases C6 & C5 sugars, separates lignin. C6 sugars fermentation is commercial. C5 sugars fermentation needs to be demonstrated Lignin needs to be utilised for energy efficiency In 1G technology, more energy is often input than is derived in the ethanol, and significant improvements are needed. Thermal processes Commercial but mixed product with other alcohols.

2 Generation bio-ethanol
Biomass Thermal Gasification Syngas Syngas Ethanol synthesis Hydrolysis Sugars Fermentation Byproducts Residues Wastes

Distillation Other alcohols Bioethanol

Feeds, processes, products

Starch & sugars Residues Biological conversion Ethanol, Butanol, Chemicals Lignocellulose Oil plants Residues

Thermal conversion Synthetic H/C, Ethanol, Butanol Methanol, Chemicals Power, Heat

Esterification Biodiesel (FAME,RME) Chemicals

Biodiesel

Methyl esters of vegetable oil e.g. rape, soy, palm, sunflower to reduce viscosity and improve other properties. The process is low temperature and catalytic: batch, semi-batch, semicontinuous, or continuous Byproduct glycerine needs to be used Concerns Different oil sources result in different quality products that is difficult to control Low temperature performance is variable and poor Limited to 5% in diesel for vehicles in Europe due to materials and compatibility concerns

Current status 1st generation

Bioethanol is attractive as the technology is available commercially Concerns over properties and energy density Biological 1G technology from corn has low efficiency Biological 2G has some development challenges Thermal 2G gives mixed alcohol product Biodiesel is attractive as a motor fuel as it can be readily blended with diesel The quality is variable Low temperature characteristics are variable and poor Low yields and crops have high energy inputs Competition of food vs fuel has led to high food price rises; There is also competition for land and sustainability issues

Feeds, processes, products

Starch & sugars Residues Biological conversion Ethanol, Butanol, Chemicals Lignocellulose Oil plants Residues

Thermal conversion Synthetic H/C,

Ethanol, Butanol Methanol, Chemicals Power, Heat

Esterification Biodiesel (FAME,RME) Chemicals

Synthetic hydrocarbons

Synthetic hydrocarbons include diesel, gasoline, kerosene They are entirely compatible with conventional fuels in all proportions, but are much cleaner. At least in the medium term, these are likely to be the biofuels of choice due to their ease of assimilation into markets, familiarity by the vehicle industry and consumers, energy density,

Routes to 2nd G hydrocarbons

1. Thermal gasification a) + Fischer Tropsch b) + Methanol synthesis + upgrading by MTG or MOGD 2. Pyrolysis + upgrading a) by hydro-processing b) by zeolites 3. Hydro-processing vegetable oil

1: Biofuels via thermal gasification

Biomass

Solid Biomass Gasification Syngas Methanol MTG MOGD Mt synfuel Refining Conventional synthetic gasoline and diesel Fischer Tropsch

Challenges

The process most commonly considered is thermal gasification to clean syngas and synthesis of hydrocarbons by Fischer-Tropsch (FT) Biomass is a widely dispersed resource that must be transported over large distances at significant cost. Biomass preparation for entrained flow gasification can be: Torrefaction to render biomass more friable for grinding Liquefaction by fast pyrolysis Gasification technology is unproven at large scale. Gas cleaning is a major challenge and unproven The minimum economic size of Fischer Tropsch is widely considered to be 20,000 bbl/day or nearly 1 million t/y biofuels requiring nearly 5 million t/y biomass.

Pretreatment by pyrolysis
Biomass Torrefaction 85% wt. solid Fast pyrolysis 75% wt. liquid Gasification Syngas Methanol MTG MOGD Mt synfuel Refining Conventional synthetic gasoline and diesel Fischer Tropsch

Pretreatment

Torrefaction is low temperature pyrolysis to dry and partially devolatilise biomass. The product yield is around 85% and can be more readily ground like coal for gasification. Fast pyrolysis produces a mobile liquid (bio-oil) with up to 10 times the energy density of biomass. The product yield is up to 75% Liquids are easier to handle, store and transport. Fast pyrolysis can be decentralised and located near the biomass resources Conversion of biomass to a liquid near source reduces transport costs, and reduces gasification costs. Pressurised oxygen gasification of liquids is easier and lower cost than solid biomass

Pyrolysis + Fischer Tropsch

Biomass Biomass

Biomass Biomass

F-T
Biomass

Gasn.

Capital costs
Capital cost, million
16000 14000 12000 10000 8000 6000 4000 2000 0

Small gasification + small FT

Small FT unproven

Pyrolysis + large FT

Small pyrolysis & large FT proven Large gasification unproven

Large gasification + FT
0 2 4 6 8 10 12

Biomass input million dry t/y

Solid vs liquid gasification

Capital cost increase of ~10% due to diseconomies of scale in small pyrolysis plants Capital cost reduction of ~15% due to lower feed handling costs Capital cost reduction of ~10% due to lower costs in feeding a liquid to a gasifier at pressure compared to solid biomass Cost reduction of ~10% from absence of alkali metals slagging and erosion Efficiency loss of ~5% due to additional processing step

Methanol based processes

Methanol well established technology from natural gas. MTG (Methanol To Gasoline) commercial technology proven in New Zealand from natural gas. High yield and high efficiency MOGD (Methanol to Olefins, Gasoline and Diesel) well researched technology. High yield and high efficiency Mt synfuel new process via propylene Methanol, MTG etc are more selective than FT and potentially give up to 30% higher yields (from ~50% to ~65% on an energy basis)

2: Upgrading bio-oil directly

Production of hydrocarbons requires rejection of the oxygen: Hydro-processing rejects oxygen as H2O C1H1.33O0.43 + 0.77 H2 CH2 + 0.43 H2O Separate process, requires hydrogen, high pressure Gives projected yield of around 25% naphtha-like product for refining, without H2 or 15% with H2 Zeolite cracking rejects oxygen as CO2 C1H1.33O0.43 + 0.13 O2 0.66 CH2 + 0.34 CO2 Close coupled process requiring constant catalyst regeneration. No hydrogen requirement, no pressure Gives projected yield of around 20% aromatics Feeding to conventional refinery provides quality control and economies of scale

Costs of upgraded bio-oil

Wood feed (daf) Pyrolysis oil output Diesel (EXCL H2) Diesel (INCL H2 from biomass) Gasoline FT diesel * # MTG gasoline * Crude oil at $100/bbl Yield, wt% 100 70 23 13 22 20 26 /t product 67 147 592 880 453 1362 560 HHV, GJ/t 20 19 44 44 44 42 43 43 /GJ /toe product 3 145 8 331 13 578 20 860 10 443 1395 15 560

Basis: 1000 t/d daf wood feed at 67 /dry t, 2006 except * # DENA report 2006

3: Hydro-processing vegetable oil

Bio-diesel (by esterification of crude vegetable oil) is currently limited to 5% of conventional diesel. Vegetable oil can be hydroprocessed to synthetic diesel and Neste have built a 100,000 t/y plant in Finland based on palm oil and other vegetable oils. Other plants are under construction Generation 1 as feed is a foodstuff and product is 2nd generation equivalent The hydrogen requirement is much less than fast pyrolysis liquid, but the vegetable oil productivity, sustainability and food competition issues remain.

Thermal process summary

Biomass

Liquid bio-oil
Gasification

Fast pyrolysis Zeolite cracking

Syngas
Fischer Tropsch synthesis MTG Methanol synthesis MOGD MtSynfuels Refining

Hydrotreating

Liquid bio-oil

Conventional gasoline and diesel

Challenges

Improve crop yields and characteristics Improve 1st and 2nd generation bioethanol technology Improve lignocellulosics pretreatment for 2nd generation Demonstrate C5 fermentation Demonstrate large scale thermal gasification Demonstrate large scale gas cleaning & conditioning Demonstrate small scale hydrocarbon synthesis Demonstrate fast pyrolysis liquids upgrading Develop integrated biorefineries Improve catalysts Match catalysts to biomass derived primary products Robustly compare alternative systems Reduce costs

Thank you