The Biomass to Biofuels Pipeline. Nick Carpita Dept. Botany & Plant Pathology Purdue University. EFRI Hy-BI. Office of Science

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1 The Biomass to Biofuels Pipeline Nick Carpita Dept. Botany & Plant Pathology Purdue University EFRI Hy-BI Office of Science

2 Options for liquid transportation fuels Decrease demand more fuel-efficient vehicles promote conservation behaviors light vehicle electrification Increase supply Athabasca oil sands (Canada), oil shale (U.S.), super heavy oil (Venezuela) Coal or natural gas to liquid fuels (U.S., South Africa, China) Biofuels but land, water, fertilizer, and energy required to grow bioenergy feedstocks are limiting

3 The U.S. renewable fuel standard passed under the Energy Independence and Security Act of 2007 defines advanced biofuel as any renewable fuel that meets a 50 percent life-cycle GHG emissions reduction from the petroleum baseline, and is not derived from corn starch. By 2022, the standard calls for 21 billion gallons of advanced biofuels to be used in our nation s fuel supply. Advanced biofuels include: * Ethanol from biomass * Biodiesel (methyl esters) * Biobutanol * Green diesel (hydroprocessed) * Biopropanol * Pyrolysis oil * Fischer Tropsch bio-derived diesel * Bio-derived synthetic paraffinic kerosene (bio jet fuel) * Biomass-based dimethyl ether * Renewable diesel (thermal depolymerization) * Green gasoline Too many choices...? No clear technological winners around which to frame policy Some of these are drop-in they do not require any changes in transportation infrastructure.

4 Hydrogen Sugar Oil Plants and BioEnergy Lignocellulosics

5 First generation biofuels are derived from starch, sugar or oils filieres-classiques-de-production-des-biocarburants/ eng-gb/first-generation-biofuels.jpg

6 The genetic diversity of maize is estimated at nearly 1.9% Maize genetic diversity permits selection and enhancement of several desirable traits; focus on the grain has increased yields about 8- fold since the advent of hybrid corn

7 The Corn Belt

8 Will people go hungry because of biofuels? Macronutrients: 2000 cal & 50 gm protein/person/day Total U.S. human demand: 205 trillion cal & 5.1 trillion grams protein/yr Three major U.S. crops alone (corn, soy, wheat) produce 1300 trillion kcal & 51 trillion grams protein/yr Could meet U.S. human demand for protein & calories with 25 million acres of corn Most U. S. agricultural production (inc. exports) is fed to animals.. Their needs are: 1040 trillion kcal/yr ( 5 times human demand) 56.6 trillion gm protein/yr (10 times human demand) Can address perceived food vs. fuel conflict by providing animal feeds more efficiently, on less land No...but not desirable to be using grains when we could access sugars from biomass

9 Second generation biofuels..from lignocellulosic biomass Wilfred Vermerris

10 The Corn Belt

11 A fundamental impasse: No investor wants to build a $500M biorefinery where no feedstocks are grown No grower wants to invest in developing energy crops where no biorefinery exists

12 Feedstock Issues Why grow biomass in the absence of a secondgeneration biofuels industry? What price will be economical for farmers to produce biomass? How will sustainability issues be addressed to ensure a recurring annual supply? How will food and feed production be impacted?

13 Rail Shuttle Transfer Stations

14 Ethanol Plants

15 The 2012 drought had little impact on biomass yields of most sorghums Cumulative rainfall at Purdue ACRE

16 Primary cell walls are mostly made of polysaccharides 200 nm McCann, M.C., Wells, B. and Roberts, K. (1990) Direct visualisation of cross-links in the primary plant cell wall. J. Cell Sci. 96,

17 Lignified secondary walls surround some specialized cell types but contribute greatly to the biomass Cellulose, hemicellulose, lignin

18 Imaging and modeling of cellulose microfibrils Shi-Yu Ding, Mike Crowley: NREL

19 Xyloglucans, arabinoxylans and xylans are types of hemicellulose Xyloglucan is the major hemicellulose in dicot species Arabinoxylans are the major hemicelluloses in grass species Carpita, N.C. and McCann, M.C. (2000) Chapter 2: The cell wall. In: Biochemistry and Molecular Biology of Plants (Eds. B.B. Buchanan, W. Gruissem, R. Jones), American Society Plant Physiologists, Rockville, MD, pp

20 Lignin is 15-25% of biomass but contains ca. 40% of the energy β-o-4 coumarate guaiacyl pinoresinol (β β) feruloyl syringyl 4-O-5 phenylcoumaran (β-5) Plants require the phenylpropanoid pathway for: UV resistance structural support water transport

21 Biological conversion route for biomass to biofuel DOE-GTL Research Roadmap to Breaking the Biological Barriers to Cellulosic Ethanol 2005

22 Transport costs will limit where biomass feedstocks are grown we need to increase yield per acre and conversion efficiency (fuel obtained per unit of plant material)

23 Third-Generation Biofuels: how can they can be used in the bioeconomy Power generation torrefaction Composites processing Biomass catalytic conversion extraction Polymers Fuels + High-Value Organics

24 High-temperature treatments may produce a bio-crude oil for biorefinery fractionation

25 The public benefit gained through biological research can be seen through the eyes of a farmer whose higher- yield crops are turned into fuels, food and intermediate chemicals, and a small business owner whose innovative biobased products are breaking new ground in manufacturing

26 Advanced (drop-in) biofuels..from lignocellulosic biomass Center for direct catalytic conversion of biomass to biofuels

27 Petrochemical industry: A 20 th century success story Fuel The Magnificent Six ethylene propylene C4-olefins benzene toluene xylene Interesting Materials

28 Magnificent six the six chemicals used as starting materials in the petrochemical industry H 2 C CH 2 H 2 C CH CH 3 ethylene propylene HC CH HC CH HC CH benzene C4-olefins HC CH HC C CH 3 HC CH toluene H 3 C HC CH C C CH 3 HC CH xylene ( BTX)

29 Selective hydrolysis and conversion: Tandem Catalysis Maleic acid & 10 mol% ZnCl 2 + ~170 C, 10 min Biomass Lignin & Cellulose Xylose 80% yield filter Maleic acid & 10 mol% ZnCl 2 HO HO O OH OH ~200 C, 5-10 min H 2, 150 atm O O furfural 70% yield Professors Mahdi Abu-Omar and Nate Mosier

30 Lignin is 15-25% of biomass but contains ca. 40% of the energy β-o-4 coumarate guaiacyl pinoresinol (β β) feruloyl syringyl 4-O-5 phenylcoumaran (β-5) Plants require the phenylpropanoid pathway for: UV resistance structural support water transport

31 The lignin biosynthetic pathway (simplified) phenylalanine ring modification side chain modification wild type high S highest S Clint Chapple: Purdue guaiacyl lignin syringyl lignin Huntley SK et al. (2003) J Agric Food Chem, 51,

32 A Zn/Pd/C catalyst that cleaves the ether bond in a synthesized model dimer BHT OH O 1 mol% Zn/Pd/C 300 psi H, 150 C 2 THF, 2h O HO O pa OH O OH O OH time (s) Mahdi Abu-Omar, Shuo Liu: Purdue

33 High oxygen content and huge range of undesirable products make bio-oil an suitable fuel Property Bio-oil Heavy Fuel Oil Moisture content / wt % ph C / wt % H / wt % O / wt % HHV / MJ kg Viscosity / cp (at 50 C) Fabio Ribeiro, Nick Delgass, Rakesh Agrawal, Hilkka Kentamaa: Purdue

34 CHCl 3 and nitrogen inlet Mass spectrometer Cl - CHCl 3 N 2 Cl - Cl - Corona discharge needle Pyrolysis products Pyroprobe

35 Chloride attachment mass spectrum for fast pyrolysis of cellulose Relative Abundance Levoglucosan isomer (monomer) Dimer Primary products are small molecules! Trimer m/z

36 Bioprocessing requirements inform geneticists for how to optimize cell wall properties of a feedstock Natural variation is rooted in a plant s genome and epigenome 36

37 The same breeding strategy that gave us hybrid corn is being used to create new biomass crops tailored to optimize biofuel and bioproduct synthesis

38 Roadmap for selective deconstruction of lignocellulosic biomass to useful products no carbon left behind