Challenges of Ethanol Production from Lignocellulosic Biomass

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1 Challenges of Ethanol Production from Lignocellulosic Biomass Maha Dakar

2 Varieties of Carbohydrates Sugar Starch Cellulose/Hemicellulose

3 What All Plants Have in Common Cellulose Glucose Why is it difficult to hydrolyze lignocellulosic biomass into sugar to make ethanol?

4 Lignocellulosicc Biomass Biomass: biological material derived from living organisms. Biomass for energy related to plant Lignocellulosic biomass: cellulose, hemicellulose (complex carbohydrates) & lignin Cellulose: structural material in plants & most abundant biomass in earth Lignocellulose: strength, resistance to degradation Cellulose & hemicellulose: polyme ers of sugars, potential source of fermentable sugars Lignocellulosic biomass do not directly go into food

5 Lignocellulosic Biomass Feedstock Woody Biomass - Forest residues - Wood waste Non-Woody Biomass - Agricultural Residues: Straws (wheat, barley, ri ce) Bagasse (sugarcane, sweet sorghum) Stover (corn, milo) Organic Waste - Animal waste - Sewage sludge

6 What is Lignocellulosic Material? lignocellulose = lignin + cellulose + hemicellulose Cellulose Hemicellulose Lignin

7 Composition of Lignocellulose

8 1 st Generation vs. 2 nd Generation 2 nd 1 st 2 nd 1 st

9 How Do We Go From This To This? Switchgrass Bagasse

10 Plants Cell Walls Plants Cell Walls: - Middle lamella: pectin - Primary cell wall: cellulose, hemicellulose - Secondary cell wall: lignin Middle lamella Primary cell wall Secondary cell lwall Plasma membrane Optimizing i i plant biomass for efficient i processing requires understanding di of plant cell wall structure and function

11 Primary Cell Wall Cellulose microfibril Plasma membrane Hemicellulose

12 Cellulose, Hemicellulose, Lignin Composition (C-5, C-6, uronic acid, acetyl derivatives) (Phenolic monomers) Very high energy content

13 What We Know About Cellulose? Intrachain hydrog gen bond Interchain hydrogen bond Intersheet hydrogen bond

14 What We Know About Cellulose 1- Cellulose fibers 2- Macrofibril 3- Microfibril il 4- Chains of Cellulose molecules

15 What We Know About Cellulose Lignin Cellulose Amorphous regions Cellulose consists of: crystalline regions (blue) & amorphous/disordered regions (red) Crystalline regions 3 Blue : Red : 1 Hemicellulose

16 How An Engineer Can Visualize This? =

17 Starch vs. Cellulose Starch Monomer: glucose Linkage: α(1-4)(1-6) Dimer sugar: maltose Used for: storage Enzyme Hydrolysis: fast Branch: branched Chains: coiled/branched (bend) Result: granules Cellulose glucose β(1-4) cellobiose structural (support) very slow unbranched extended (rigid) long fibers

18 Ethanol Production Flowchart Lignocellulose Process Grain (starch) Process Cane (Sugar) Process Sugar Fermentation Distillation Starch Conversion (cook/hydrolysis) Lingocellulose Pretreatment Cellulose Conversion (hydrolysis)

19 BIOETH HANOL SUGAR STARC CH CELLULOSE

20 Steps of Biomass Processing Ethanol Grains Milling Cooking Liquefaction SSF Distillation Ethanol

21 1-Crushing Size reduction: milling or chipping Accessibility for pre-treatment step

22 Collection: Obstacles - Type/sequence of collection operations & equipment efficiency - Environmental restrictions ti (control erosion, soil productivity, it carbon level) l) Transportation: - Distance from plant & biomass amo ount - Bulky in nature - Increase density by chipping, grinding or shredding Storage: - Hauled to plant - Stored at production site

23 2- Pre-Treatment The main purpose for pretreatment: - Destroy lignin shell protecting cellulose and hemicellulose - Decrease crystallinity of cellulose - Increase porosity - Must break this shell for enzyme to access substrate (sugar) Amorphous region Pre-Treatment methods: - Chemical - Physical - Biological Crystalline region

24 Chemical Pre-Treatmet

25 Physical Pre-Treatment

26 Biological Pre-Treatment fungi

27 Obstacles Most expensive stage in 2nd generation bioethanol Inhibitors such as: - Phenolic from lignin degradation - Furfural from C-5 degradat tion - HMF from C-6 degradation Corrosion problems Acid recovery is expensive Material loss Better understanding of plant cell wall structure & function

28 3- Hydro olysis Polysaccharides break down into monomers followed by fermentation and distillation Cellulose can be hydrolyzed using: - Acid hydrolysis (Traditional method) - Enzymatic hydrolysis (The current state-of-art method) Acid hydrolysis advantages: - Faster acting reaction - Less residence time in reactor Enzymatic hydrolysis advantages: - Run at lower temperature - Higher conversion - Environmentally friendly

29 3- Hydrolysis Cellulase enzyme depolymerize cellulose into fermentable sugars Cellulase synthesized by fungi and bacteria work together to degrade cellulose Cellulosic enzyme system: 1- Endo-ß-glucanase 2- Exo-ß-glucanase 3- ß-glucosidase

30 From Cellulosee to Glucose Reaction Pathway: Optimum Parameters: ph: 4-5 Tempt: 40-50C Inhibitors: glucose, cellobiose, some minerals

31 Obstacles Problems for industrial application: 1- High production cost (~40% of total ) 2- Low yield Few microorganisms are capable of degrading cellulose Trichoderma produces endo-ß-glucanase, exo-ß-glucanase & low levels of ß-glucosidase Aspergillus produces endo-ß-glucanase, ß-glucosidase & low levels of exo-ß- glucanase Inhibitors formation Optimizing/understanding enzymes regulation and activity Understanding of plant cell wall structure & function

32 4- Fermentation Convert sugars (C-5 and or C-6) to ethanol using microbes S.cerevisie for ethanol from glucose (C-6) S.cerevisie not able to ferment (C-5) Some bacteria ferment C-5 & C-6 (E.coli & Z.mobilis)

33 Obstacles Inhibitors such as: - Phenolic from lignin degradation - Furfural from C-5 degradation - HMF from C-6 degradation R&D strategies: - Robust organism to fermenting C-5 & C-6 - Robust organism toward inhibitors/temperature Integrate hydrolysis and fermentation into a single microbe Low conversion rates for C-5 sugars Technology to remove inhibitors is expensive

34 After All Thesee Challenges In Cellulose Hydroly ysis, What About Hemicellulose?

35 Hemicelu ullose Polysaccharides that are more complex than sugar and less com mplex than cellulose The second abundant renewable biomass in earth after cellulose

36 Hemicellulose vs Cellulose Polysaccharides: Monomer: Hemicellulose hetro-polysacchar rides different sugar monomers (xylose, glucose, mannose, galactose, uronic acid) Acid Hydrolysis: fast Branch: branched DP: Structure: amorphous Cellulose homo-polysaccharides same monomer (glucose) slow unbranched crystalline

37 Bagasse Characteristics

38 Brazil Strategy Cane Extraction Bagasse Boiler Sugar Cane Steam Ethanol Ethanol Plant Steam Generator Electricity Electricity Grid

39 Bagasse Usage Bagasse Pulp and Paper Mill Bagasse Boiler NaOH Digester Electricity Steam Electricity Grid Suspended Pulp Liquor Pulp/paper

40 Bagasse Usage Bagasse Steam H 2 SO 4 Sludge Digester Furfural (Vapor) Boiler

41 Bagasse Usage Bagasse Water H 2 SO 4 Digester Separator C 5 Neutralization C 5 C 6, Lignin Fermentation CO 2 Boile er Ethanol

42 Bagasse Usage Bagasse Water Steam H 2 SO 4 Digester Separator C 5 Neutralization C 5 CO 2 Boiler Enzymes Lignin C 6, Lignin CO 2 Ferm mentation Extra Ethanol Fermentation Ethanol

43 Brazil Strategy H 2 SO 4 Cane Extraction Bagasse Digester Sugar Juice Ethanol Plant Neutralization C 5 Separator Water C 5 CO 2 C 6 Lignin Ethanol Extra Ethanol Fermentation Boiler

44 Where is KATZEN From This? KATZEN has worked with cellul lose feedstock for ethanol, pulp and paper & sulfite liquor over 50 years After this long history, we say C 6 will have contribution as ethanol feedstock but limited to special circumstances After this long history, we say YES for C 5

45

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