Routes to Higher Hydrocarbons BIO, Pacific Rim Summit Thomas D. Foust, Ph.D., P.E. Director, National Advanced Fuels Consortium NREL Bioenergy Center December 9, 2013 NREL is a national laboratory of the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, operated by the Alliance for Sustainable Energy, LLC.
Advanced Biofuel Conversion Routes Sugar Catalytic- Conversion Fermentation with engineered microbes Gasoline Diesel Jet Biomass Pyrolysis/ Liquefaction Hydrotreating & Upgrading Algae growth & oil harvest Syngas gasification Methanol Synthesis Fischer-Tropsch Synthesis Gasoline Diesel Jet Refinery 2
Gasification Technology fairly well developed Classes of gasifiers Air Blown Gasification (updraft or downdraft) low cost and thermally efficient, product gas not well suited for fuel synthesis high N 2 content Indirect Gasification good thermal efficiency, syngas not diluted with N 2 product gas relatively high in tars Direct Gasification Good product gas, lower in tars, - high cost of O 2,, lower thermal efficiency, syngas high in CO 2 Entrained Flow Gasification Excellent product gas, essentially no tars high cost of O 2, low thermal efficiency, higher capital cost because of increased complexity 3
4 Thermodynamics and kinetics of biomass conversion Intermediates Gasification is inherently a lower efficiency process based on thermodynamic analysis
5 Pros/Cons and challenges of gasification routes Pros Good experience base Only significant technical challenge is cost and complexity Capable of producing high quality diesel and jet fuels Chemistry works and is relatively proven Cons Cost is a significant challenge Previous attempts to reduce costs have met with limited success Challenges Reducing capital costs High process complexity
Sugar or Soluble Carbon Intermediate Pathway 6 Fermentative Cell Enzyme Production Diesel HC Fuels Pretreatment & Conditioning Enzymatic Hydrolysis ISOPRENE ANTI-MALARIAL DRUG Lignin Aqueous Phase Reforming Acid Condensation Condensation & HDO Gasoline Jet Fuel Value Add Heat and Power Dehydration & Oligomerization Diesel
7 Fermentation Pathway hydrolysate YEAST CELL Mevalonate Pathway -Farnesene Farnesene Synthase Diesel & Chemical Precursor [1] [2] [3] [4] [1] Cane juice [2] Fermentation broth [3] Separations [4] Purification
Biomass Fractionation and Pretreament 8 Catalytic Pathway Process Heat Lignin C 1 -C 4 Alkanes Aromatics, Alkanes Lignocellulosic Materials Hydrogenolysis C 2 -C 6 Oxygenates H 2 ZSM-5 Gasoline Soluble Sugars Starches Polysaccharides C 5 &C 6 Sugars Furans Phenolics Acids Aqueous Phase Reforming H 2 Base Catalyzed Condensation HDO Alkanes Kerosene Jet Fuel Hydrogenation Sugar Alcohols Dehydration Alkene Oligomerization Alkene Saturation Alkanes Diesel
9 Pros/Cons and challenges of sugar routes Pros Produces high quality components for diesel and jet both fermentative and catalytic routes Initial higher value applications Builds upon OBP cellulosic ethanol technologies so good building base Cons High capital cost approaches Overall yields and efficiencies lower than thermal routes Lignin component only used for heat and power at high capital cost Challenges Better organisms fermentative Better catalysts catalytic Lower costs Better utilization of lignin
Lipid (Autotrophic/Heterotrophic) Intermediate 10 Algae Yeast or Bacteria Fungi Enzyme Production Commodity Chemicals (Ethylene) Pretreatment & Conditioning Enzymatic Hydrolysis Fatty Acids TAGs Specialty Chemicals (Carotenoids) Reduction/Decarbonylation HC Fuels Algae Cyanobacteria n-alkanes Olefins Photosynthetic Bacteria TAGs
11 Algal routes to advanced biofuels Biology and Cultivation Energy efficient harvesting and dewatering systems Biomass extraction and fractionation Product purification A gasifier being used by a NAABB partner to convert algal biomass to fuels Biomass Harvesting and Recovery Algal Strains - Growth, productivity, stability, and resilience Cultivation system design Temperature control Invasion and fouling Input requirements CO 2, H 2 O sources, energy Nitrogen and phosphorous Siting and resources A nano-membrane filter being developed by a NAABB partner. Process optimization Thermochemical Biochemical Fuels characteristics Co-Products Conversion and End-use
12 Pros/Cons and challenges of algal routes Pros Capable of producing high quality fuels High yields Negates food versus fuel debate Does not need fresh water Cons Significant technical risk Cost barriers significant and numerous Challenges Cell biology Cultivation Harvesting and extracting Economic uses of cell mass
13 Bio-Oil Intermediate Initial Results (NABC data) Good Feasibility tests very positive Economics show the potential to be very attractive (< $2.00 gge for refinery integration case) Excellent leveraging of petroleum refining infrastructure Bad Products are almost exclusively aromatics (BTX) mostly in the gasoline range Chemistry is very complex and poorly understood making process design dubious
14 Catalytic Fast Pyrolysis (CFP) Hydropyrolysis (HYP) Based on Fluidized Catalytic Cracking (FCC) Technology Pervasive in Petroleum Refining
0.549 1.272 2.685 2.644 2.594 2.559 2.827 - Acetadehyde 2.643 3.250 3.762 - IPA 3.779 - IPA 4.034 4.572 4.561 4.648 4.853 4.904 4.959 5.229-2-Butanone 5.637 5.590 - Acetic acid + 5.891 7.252 - Benzene 7.052 7.424 7.273 - Benzene 7.738 7.581 7.621 7.814 7.873 7.980 7.900 8.225 8.416 10.521 - Toluene 8.727 8.771 9.184 9.051 9.316 9.250 9.569 9.481 9.858 9.938 13.240 13.462 - Ethylbenzene - p-xylene 14.071 - o-xylene 10.732 10.562 - Toluene 10.821 10.944 11.222 11.316 11.548 11.606 11.687 11.765 11.808-11.897 Furfural - Octane 12.087 12.293 12.205 12.384 12.496 12.662 12.850 12.696 12.761 13.013 12.936 - dimethlycyclohexane 13.154 13.087 13.283 13.308 - Ethylbenzene 16.863 - Decane 13.748 13.663 13.618 13.908 13.954 13.827 14.089 13.980 14.155 14.019 14.199 - o-xylene 14.303 14.487 14.558 14.658 14.766 14.860 14.937 15.039 15.106 15.212 15.378 15.318 15.276 - Furancarboxaldehyde 20.524 - Naphthalene 15.604 15.432 15.472 15.653 15.846 - Phenol 16.093 16.147 16.233 - C9H20O2 ether 16.301 16.517 16.376 16.600 16.705 16.741 16.860 16.814 - C10H22O2 16.910 ether - Decane 17.198 17.151 17.107 17.348 22.910 22.614 - dimethoxy - methyl-naphthalene Phenol 17.430 17.469 17.683 17.570 17.613 17.524 - Cresol isomer -1 17.891 17.938 17.829 17.781 18.028 - Cresol isomer -2 18.108 18.064 18.185 18.221 18.500 18.376 18.326 18.599 18.678 18.869 18.927 18.769 19.058 19.161 19.202 19.573 19.400 19.491 19.453 19.734 19.764 19.959 19.893 19.807 20.152 20.066 20.355 20.217 20.412 20.266 20.624 20.453 20.510 - methoxy-methyl Phenol 20.772 20.850 20.959 21.142 21.031 21.421 21.363 21.625 21.586 21.554 21.794 21.674 21.866 22.089 22.122 21.993 22.435 22.375 30.177 22.772 22.969-23.098 dimethoxy Phenol 23.219 23.285 23.479 23.436 23.737 23.661 23.940 23.885 24.073 24.148 24.396 24.223 24.288 15 CFP/HYP Catalyst Impact Standard Fast Pyrolysis pa 90 80 70 60 50 40 30 20 FID1 A, (PY_081010-24\NB3425221R108IPA_2-1.D) 3.417 3.470 - Acetone 4.327 4.385 6.515 6.683 - methyl-propanol Area: 20.5488 8.120 8.176 9.757 9.792 10.117 10.299 13.423 13.476 - p-xylene 15.952 16.012 22.535 22.653 - methyl-naphthalene 25.068 24.742 24.960 10 0 0 2.5 5 7.5 10 12.5 15 17.5 20 22.5 min Catalytic Fast Pyrolysis/Hydropyrolysis pa FID1 A, (PY_100410-32\NB3425253R134IPA_2-5.D) 90 80 70 60 50 40 30 20 10 0 0 5 10 15 20 25 30 min Quality Yields
16 Potential Co-Processing Points Refineries contain many potential insertion points for co-processing of a variety of biomass-derived feedstocks Hydroprocessing Units Typically designed to remove sulfur Potentially suitable to deoxygenate triglycerides or other bio-oils Conversion Units Designed to break down larger molecules into smaller ones Potentially suitable for upgrading of pyrolysis oils into fuels Source: Wikipedia
17 Conclusions Ethanol future still uncertain Café standards driving to higher compression engines Significant activity in commercialization Butanol also a possibility Future is advanced biofuels drop- in. Although preliminary results are promising many challenges remain: Biomass Yields and costs Lignin utilization Must integrate into future fuel mix need Algae Significant technical challenges Cell biology Cultivation Harvesting Cell mass utilization
Questions? Biomass for Advancing America 18