The potential and challenges of drop in biofuels OH OH H O H H OH H HO OH H OH - O 2 H H H H H O H H H C C C C H OH H H H H H HO OH Carbohydrate Hydrocarbon Petroleum-like biofuel H OH Sergios Karatzos, Jim McMillan and Jack Saddler International Energy Agency Bioenergy Task 39 (liquid biofuels) Forest Products Biotechnology/Bioenergy (FPB/B)
OVERVIEW Definition Commissioned Task 39 drop in biofuel report Role of Hydrogen in drop in biofuels Role of Hydrogen in petroleum industry TECHNOLOGIES
Definition of a drop-in biofuel Bioethanol: Biogenic ethyl alcohol Biodiesel: Fatty acid methyl esters (FAME) Drop in Biofuels: Liquid bio-hydrocarbons that are functionally equivalent to petroleum fuels and as such compatible with existing petroleum infrastructure. Examples: Hydrotreated Vegetable Oils (HVO) Hydrotreated Pyrolysis Oils (HPO) Fischer Tropsch Liquids (FT liquids) 3
Oxygen Challenge Oxygen is present in biomass in the form of hydroxyls, esters, and ethers Can oxidize fuel components, reactors and pipeline metallurgy to cause corrosion Oxygen content reduces energy density CH 3 Ethanol Biodiesel (fatty acid methyl ester) 4
The Hydrogen-Oxygen dilemma Drop-in biofuels is a loose term referring to liquid biofuels containing low or no oxygen content Deoxygenation requires hydrogen inputs or oxidizing/burning of feedstock carbon High H/C eff ratio feedstocks such as lipids are well suited for drop-in biofuel production 5
What will determine the success of drop in biofuels? Drop-in biofuel technologies complexity and hydrogen demand Commercialization challenges such as capital, yield and refinery insertion Crude oil is becoming increasingly hydrogen deficient ( heavier and sourer ) 6
Million barrels per day Crude oil quality declining 90 80 70 60 50 40 30 20 10 0 1990 2000 2010 2020 Purvin & Gertz forecast for world crude oil quality (Source: data from EIA) Heavy Sour Light Sour Light Sweet Sour = High Sulfur 7
Future competition for Hydrogen inputs Heavy oil processing e.g. Venezuela and Alberta Ammonia industry Drop-in biofuels? 8
Hydrotreating and Hydrocracking Hydrotreating (Removes sulfur impurities as H 2 S) Hydrocracking (breaks heavy oil to lighter molecules) Heavy crude molecule Gasoline range molecule Diesel range molecule 9
million barrels per day US Hydrotreating capacity 1990-2030 30 25 20 15 10 5 Rapid increase in H 2 consumption in US refineries 0 1990 1995 2000 2004 2010 2015 2020 2025 2030 10 Source EIA, Annual Energy Outlook 2006
Natural gas: Where H 2 comes from 90 % of commercial H 2 comes from steam reforming natural gas CO 2 Steam reforming CH 4 H 2 ENERGY INTENSIVE PROCESS!! 11
Role of H 2 in upgrading petroleum and drop-in biofuels Petroleum Increasing Sulfur content Increasing heavy oil needs cracking Drop-in Biofuels No Sulfur High Oxygen content of feedstock needs hydrogenation Both require Hydrogen for upgrading to finished fuels Hydrogen will likely come from Natural Gas 12
OVERVIEW Definition Commissioned Task 39 drop in biofuel report Role of Hydrogen in drop in biofuels Role of Hydrogen in petroleum industry TECHNOLOGIES
The commercialization potential of Drop in Biofuel platforms and their H 2 dependence Oleochemical (HVO, algae) Thermochemical (Pyrolysis - HPO, Gasification FT-liquids) Biochemical (Advanced Fermentation) Hybrid platforms (e.g. Virent, Zeachem, Lanzatech) 14
Technology pathways to drop-in sugar crop hydrolysis sugars fermentation Oleo Sun photons, water, CO 2 and nutrients Biomass fiber Thermo Bio Hydroprocessing CONVENTIONAL INTERMEDIATES Higher alcohols (e.g. Gevo) Isoprenoids (e.g. Amyris) gasification pyrolysis animal digestion oilseed crop syngas biooil lipids catalytic conversion upgrading FT liquids (e.g. CHOREN) HPO (e.g. ENSYN) Blending Autotrophic algae LEGEND materials processes drop-in fuel 15
Commercial drop-in biofuel companies All based on oleochemical Neste Oil facility, Rotterdam Neste Oil: 630,000,000 gallons diesel from palm oil Dynamic Fuels: 75,000,000 gallons diesel from animal fat 16
Many examples of commercial biofuel flights Virtually all based on oleochemical US Navy: Sept 2011 Solazyme algae oil and palm oil Continental Airlines: Nov 2011 Solazyme algae oil Alaska Airlines: Jan 2012 tallow and algae Lufthansa: July 2011 Jatropha, Camelina Finnair: July 2011 Used Cooking Oils Many more 17
Fischer Tropsch Hydrocracking Hydro treatment 1 Hydro treatment 2 Thermochemical drop-in biofuel platforms INTER- MEDIATES CATALYTIC UPGRADING Gases 500 C No O 2 Pyrolysis oil HPO Gasoline Biomass Jet 900 C some O 2 Gasification Syngas FT liquids Diesel Forest Products Biotechnology/Bioenergy (FPB/B) 18
Example of pyrolysis drop in facility: KiOR 13,000,000 gallons per year in Mississippi (in operation) H 2 19
Forest BtL Oy and Choren s Carbo-V 34,000,000 gallons per year of Gasification FT liquids by 2016 (Finland) CO 2 H 2 H 2 Pretreat. Gasification conditioning FT Hydrocracking Sundrop biofuels 50 MGPY 20
Fischer Tropsch Hydro treatment 1 Hydro treatment 2 Hydrocracking Drop in biofuels leveraging on Oil refineries OLEOCHEMICAL Lipids OIL REFINERY Gases THERMOCHEMICAL Pyrolysis oil HPO Gasoline Jet Biomass Gasification Syngas FT liquids Diesel over the fence H 2 Forest Products Biotechnology/Bioenergy (FPB/B) 21
Challenges of hydrocracking biofeed: The Haldor Topsoe experience Higher Hydrogen consumption requirements more than doubled when just 5% of feed was replaced with biofeed! Presence of oxygenated gases such as CO and H 2 O Heterogeneity of feedstock (Catalyst design challenges) Source: Haldor Topsoe, 2009 22
Major upscaling challenges for each platform Pyrolysis Hydrogen Hydrotreating catalyst Gasification Capital / scale Feedstock /yields HVO oleochemical Feedstock Refinery insertion challenges Sources: Jones et al. 2009; Swanson et al. 2010; Pearlson et al. 2011 23
Biochemical: Sugar fermentation to drop-in SUGAR FERMENTATION Modified algae, bacteria or yeast Target molecule Long alcohols Aliphatic chains Major advantages Pure and functionalized product streams suitable for value added markets Major challenges Volumetric productivity about 10x lower than ethanol Recovery challenges: e.g. recovery from fermentation broth and intracellular expression Sugar feedstock highly oxidized (H/C = 0) 24
Summary Oleochemical: commercial now and less H 2 -dependent with considerable potential for growth (feedstock challenges?) Thermochemical well suited for long term drop-in biofuels H 2 and catalyst challenges (Pyrolysis), Scale challenges (Gasification) Leveraging on oil refineries: more challenging than expected Biochemical drop-in products more valuable in rapidly growing chemicals markets Accessing cheap/renewable Hydrogen will be a key challenge for both drop-in biofuels and crude oil of decreasing quality 25
ACKNOWLEDGEMENTS International Energy Agency Bioenergy Task 39 colleagues www.task39.org Forest Products Biotechnology/Bioenergy (FPB/B)