The potential and challenges of “drop in” biofuels OH OH O H H OH H - O2 H HO OH H H H H H H C C C C H H H H H OH Hydrocarbon H H HO OH H OH Carbohydrate O H H OH “Petroleum-like” biofuel Sergios Karatzos, Jim McMillan and Jack Saddler International Energy Agency Bioenergy Task 39 (liquid biofuels) Forest Products Biotechnology/Bioenergy (FPB/B) Commissioned Task 39 ‘drop in’ biofuel report § OVERVIEW § Definition § Role of Hydrogen in drop in biofuels § Role of Hydrogen in petroleum industry § TECHNOLOGIES Forest Products Biotechnology/Bioenergy at UBC Definition of a “drop-in” biofuel § Bioethanol: Biogenic ethyl alcohol § Biodiesel: Fatty acid methyl esters (FAME) § Drop-in biofuels are liquid hydrocarbons that are functionally equivalent and as oxygen-free as petroleumderived transportation blendstocks (fuels) § Examples: § Hydrotreated Vegetable Oils (HVO) § Hydrotreated Pyrolysis Oils (HPO) § Fischer Tropsch Liquids (FT liquids) Forest Products Biotechnology/Bioenergy at UBC 3 Properties of transportation fuels Drop-in biofuels need to have similar properties to petroleum fuels: • Fit the carbon number range • Low to No oxygen 24 22 20 18 16 14 12 10 8 6 4 2 0 400 carbon number 350 boiling point B10 ? 300 250 200 Jet 150 100 50 E10 0 Ethanol Gasoline Jet A Diesel Biodiesel Unlike conventional biofuels, “drop-in” biofuels should be Forest Products Biotechnology/Bioenergy at UBC indistinguishable from petroleum fuels for end uses! 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 CH3 Ethanol Biodiesel (fatty acid methyl ester) Forest Products Biotechnology/Bioenergy at UBC 5 Oxygen content vs. energy density Energy density (MJ/L) Drop in biofuel 45 Crude oil (No O2) 40 Biodiesel(11% O2) 35 Butanol (21.5% O2) 30 25 Ethanol(35% O2) 20 15 R² = 0.99438 Biomass/ 10 Sugar (50% O2) 5 0 0 0.1 0.2 0.3 0.4 0.5 0.6 O/C molar ratio Increasing Oxygen content reduces fuel energy density Forest Products Biotechnology/Bioenergy at UBC 6 Deoxygenating biomass dilemma …add H2 or lose yield? -H2O Insert Hydrogen A Hydrocarbon e.g. Butane A Carbohydrate e.g. Glucose - O2 C6H12O6 High H/C ≈ 2 Oxidize Carbon “sacrificing” feedstock C4H10 -CO2 Objective is to deoxygenate and enrich H2 content of biomass Forest Products Biotechnology/Bioenergy at UBC 7 Effective hydrogen to carbon ratio (Heff/C) § A high Effective Hydrogen to Carbon ratio is desired for drop-in biofuels § Heff/C =𝑛(𝐻)−2𝑛(𝑂)/𝑛(𝐶) Heff/C = 0 Heff/C ≈ 2 OH O H H OH H H H HO OH H OH Carbohydrate Forest Products Biotechnology/Bioenergy at UBC H H H H C C C C H H H H H Hydrocarbon (e.g. Butane, Diesel) 8 The Effective H/C ratio staircase… ‘Drop-in’ biofuel Oleochemical Diesel 2.0 Lipids 1.8 1.6 1.4 1.2 1.0 0.8 Lignin 0.6 Ethanol 0.4 Wood Sugar 0 Thermochemical 0.2 Biochemical High O2 or low H/C feedstocks require more processing and H2 inputs Forest Products Biotechnology/Bioenergy at UBC 9 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 Heff/C ratio feedstocks such as lipids are well suited for drop-in biofuel production Forest Products Biotechnology/Bioenergy at UBC 10 What will determine the success of “drop in biofuels”? § Drop-in biofuel technologies complexity/ selectivity and hydrogen demand § Commercialization challenges such as capital, yield and refinery insertion § Crude oil is becoming increasingly hydrogen deficient (‘heavier’ and ‘sourer’) Forest Products Biotechnology/Bioenergy at UBC 11 Crude oil quality declining… 90 Million barrels per day 80 70 an ” y v “Hea ing s a e r inc l i o ur” o S “ d 60 50 Heavy Sour 40 Light Sour 30 Light Sweet 20 “Sour” = High Sulfur 10 0 1990 2000 2010 2020 Purvin & Gertz forecast for world crude oil quality (Source: data from EIA) Forest Products Biotechnology/Bioenergy at UBC 12 The H/C ratio staircase for petroleum… Diesel 2.0 Light crude 1.8 1.6 Heavy crude 1.4 Oil sands 1.2 1.0 0.8 0.6 Coal 0.4 Lower quality fossil feedstocks = lower H/C ratio = higher H2 inputs Forest Products Biotechnology/Bioenergy at UBC 13 Hydrotreating and Hydrocracking § Hydrotreating (Removes sulfur impurities as H2S) § Hydrocracking (breaks heavy oil to lighter molecules) Heavy crude molecule Gasoline range molecule Forest Products Biotechnology/Bioenergy at UBC Diesel range molecule 14 US Hydrotreating capacity 1990-2030 million barrels per day 30 25 20 15 10 5 Rapid increase in H2 consumption in US refineries 0 1990 1995 2000 2004 Forest Products Biotechnology/Bioenergy at UBC 2010 2015 2020 2025 2030 15 Source EIA, Annual Energy Outlook 2006 Natural gas: Where H2 comes from CO2 § 90 % of commercial H2 comes from steam reforming natural gas CH4 Steam reforming H2 ENERGY INTENSIVE PROCESS!! Forest Products Biotechnology/Bioenergy at UBC 16 Role of H2 in upgrading petroleum and drop-in biofuels Petroleum ! Increasing Drop-in Biofuels Sulfur content ! Increasing heavy oil needs cracking § No Sulfur § High Oxygen content of feedstock needs hydrogenation Both require Hydrogen for upgrading to finished fuels Hydrogen will likely come from Natural Gas Forest Products Biotechnology/Bioenergy at UBC 17 Commissioned Task 39 ‘drop in’ biofuel report § OVERVIEW § Definition § Role of Hydrogen in drop in biofuels § Role of Hydrogen in petroleum industry § TECHNOLOGIES Forest Products Biotechnology/Bioenergy at UBC The commercialization potential of Drop in Biofuel platforms and their H2 dependence § Oleochemical (HVO, algae) § Thermochemical (Pyrolysis - HPO, Gasification FT-liquids) § Biochemical (Advanced Fermentation) § Hybrid platforms (e.g. Virent, Zeachem, Lanzatech) Forest Products Biotechnology/Bioenergy at UBC 19 Biomass fiber hydrolysis sugars fermentation gasification syngas catalytic conversion pyrolysis biooil upgrading animal digestion oilseed crop lipids Autotrophic algae Oleo Sun photons, water, CO2 and nutrients sugar crop FT liquids (e.g. CHOREN) HPO (e.g. ENSYN) Blending LEGEND materials processes Forest Products Biotechnology/Bioenergy at UBC Isoprenoids (e.g. Amyris) Hydroprocessing Higher alcohols (e.g. Gevo) Thermo CONVENTIONAL INTERMEDIATES Bio Technology pathways to “drop-in” drop-in fuel 20 Oleochemical Platform Hydrotreated Vegetable Oils or HEFAs Fatty acid feedstock Challenges § Costly feedstock (approx. $500-1000/t) § Sustainability? Forest Products Biotechnology/Bioenergy at UBC Hydroprocessing Major advantages § “Simple” technology, low risk (processes already commercial) § Bio SPK ASTM certification § High Hydrogen to carbon ratio (low Oxygen) of Feedstock § Palm oil Gases § Tallow (rendered animal fat) Gasoline Jet Diesel 21 Commercial drop-in biofuel companies Neste Oil facility, Rotterdam § All based on oleochemical § Neste Oil: 2,400,000,000 L diesel from palm oil § Dynamic Fuels: 280,000,000 L diesel animal fat Forest Products Biotechnology/Bioenergy at UBC fr 22 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 Forest Products Biotechnology/Bioenergy at UBC 23 Thermochemical drop-in biofuel platforms Pyrolysis oil Gases HPO 900°C some O2 Gasification Syngas Fischer Tropsch Biomass Forest Products Biotechnology/Bioenergy (FPB/B) FT liquids Hydrocracking No O2 Hydro treatment 2 500°C CATALYTIC UPGRADING Hydro treatment 1 INTERMEDIATES Gasoline Jet Diesel 24 Example of pyrolysis drop in facility: KiOR § 50,000,000 L per year in Mississippi (in operation) H2 Forest Products Biotechnology/Bioenergy at UBC 25 Forest BtL Oy and Choren’s Carbo-V § 130,000,000 L per year of Gasification FT liquids by 2016 (Finland) Pretreat. Gasification conditioning Sundrop biofuels 190 MLPY Forest Products Biotechnology/Bioenergy at UBC H2 H2 CO2 FT Hydrocracking 26 USD/ Gallon Gasoiline Equivalent Feedstock and Capital cost of drop-in Biofuels 18 16 14 12 10 8 6 4 2 0 Feedstock cost Capital (installed capacity) Oleochemical HVO Pyrolysis Gasifica6on Feedstock intensive vs Capital intensive platforms Forest Products Biotechnology/Bioenergy at UBC Source: Kazi et al. 2010, Pearlson et al. 2011, Jones et al. 2009 USD/ Gallon Gasoiline Equivalent “Over the fence” Hydrogen inputs can reduce capital and feedstock costs 18 16 14 12 10 8 6 4 2 0 H2 3% H2 7% H2 Feedstock cost Capital (installed capacity) Oleochemical HVO Pyrolysis Gasifica6on Pyrolysis is highly dependent on access to cheap Hydrogen Forest Products Biotechnology/Bioenergy at UBC Source: Kazi et al. 2010, Pearlson et al. 2011, Jones et al. 2009 Drop in biofuels leveraging on Oil refineries OLEOCHEMICAL OIL REFINERY Lipids HPO Gasification Syngas Fischer Tropsch Biomass Forest Products Biotechnology/Bioenergy (FPB/B) FT liquids Hydrocracking Pyrolysis oil Hydro treatment 2 THERMOCHEMICAL Hydro treatment 1 Gases Gasoline Jet Diesel over the fence H2 29 Drop in biofuels leveraging on Oil refineries DISTILLATION (CATALYTIC) UPGRADING Lipids FT liquids HPO Light ends Reformer Hydrotreatment Fluid catalytic cracking Vacuum unit Coker Jet Diesel, Jet Diesel, Jet Gasoline Hydrocracker Heavy ends Gasoline Hydrotreatment Gasoline Diesel, Jet Product blending Distillation tower Crude oil BLENDING Coke 30 Challenges of hydroprocessing 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 H2O § Heterogeneity of feedstock (Catalyst design challenges) Forest Products Biotechnology/Bioenergy at UBC Source: Haldor Topsoe, 2009 31 Major scale up challenges for each platform § Pyrolysis § Hydrogen § Hydrotreating catalyst § Gasification § Capital / scale § Feedstock /yields § HVO oleochemical § Feedstock § Refinery insertion challenges Forest Products Biotechnology/Bioenergy at UBC Sources: Jones et al. 2009; Swanson et al. 2010; Pearlson et al. 2011 32 Biochemical: Sugar fermentation to drop-in SUGAR FERMENTATION Target molecule Modified algae, bacteria or yeast 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) Forest Products Biotechnology/Bioenergy at UBC 33 Fermentation pathways for deoxygenating Carbohydrates Glucose (C6) x • High requirement for reducing power (derived from NADPH or Hydrogen) Pyruvate (C3) PPP cycle Elongation cycles: 7 Repeat • Energy intensive CO2 Compared to ethanologenic yeast: Example: acid LanzatechFatty CO2 + H2 biosynthesis example Forest Products Biotechnology/Bioenergy at UBC Acetyl-ACP (C2) HCO3 Malonyl-ACP (C3) Acetoacetyl-ACP ACP + 2x NADPH HCO3 ButyrylACP (C4) ACP Palmitate (C18) 34 Climbing fewer steps on the Heff /C staircase … ‘Drop-in’ biofuels Diesel 2.0 Lipids 1.8 1.6 1.4 1.2 1.0 0.8 0.6 Value-added biorenewables 0.4 Wood Sugar 0 0.2 Biochemical feedstock Value Forest added chemicals have Products Biotechnology/Bioenergy at UBClower Heff /C ratios than fuels 35 Summary § Oleochemical: commercial now and less H2-dependent with considerable potential for growth (feedstock challenges?) § Thermochemical well suited for long term drop-in biofuels § H2 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 Forest Products Biotechnology/Bioenergy at UBC 36 ACKNOWLEDGEMENTS International Energy Agency Bioenergy Task 39 colleagues www.Task39.org Forest Products Biotechnology/Bioenergy (FPB/B) Future competition for Hydrogen inputs… § Heavy oil processing e.g. Venezuela and Alberta § Ammonia industry § Drop-in biofuels? Forest Products Biotechnology/Bioenergy at UBC 38
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