Novel Technology for Ligno-Cellulosic Biomass Fractionation Biomass economical ecological energy Conversion

BIO e CON founded in 2006 as an independent privately funded R&D network. Pioneer in biomass waste conversion: Catalytic Pyrolysis  Khosla Ventures / KiOR. In-situ conversion in inorganic Ionic Liquids (ZnCl2)  PETROBRAS. G2: Biomass fractionation technology Based on inorganic ionic liquid (ZnCl2). A Short History

Novel inorganic ionic liquid (ZnCl 2 ) technology. Mild conditions: minimum product degradation. No bad actors: Enzyme inhibitors, Cat poisons. Simple, robust and feedstock flexible process. Non-destructive unraveling of high value : Unique G2-Cellulose (& G2-lignin) formed. Cost competitive with specialty Cellulosic’s. Enables strong business case: Combination of Advanced biofuels and Advanced Materials. G2 Technology

Open up the biomass, deconstruct, fractionate. Conceptual Idea: “Accessible biomass”

Observations: Saccharides are converted much faster than Cellulose Products of cellulose decomposition are degraded > 200 o C. (2006) Products of cellulose decomposition are degraded > 100 o C. (2016) Importance of Acid [H + ]  degradation < 100 o C (2016) 250 o C; 15 min Cellulose decomposition  Very reactive species!

Two possible regimes: High Temperature (Pyrolysis): fast conversion to a stable bio-oil (± 10% wt. Oxygen). This can be achieved with catalysts making use of low temperature mechano-chemistry. Low Temperature: conversion of biomass in a special solvent (“Ionic Liquids”). In both cases intimate contact achieved between biomass and “catalyst” at mild conditions. BIO e CON’s Philosophy

Acid treatments H2SO4, Acetic, Formic, HCl (Bergius) Steam Explosion T> 100 o C High Energy Milling + “Special” organic Chemicals Production of Cellulosic Nano Fibers. Supercritical Liquids HTU (Super critical 350 o C  IL). Ionic Liquids (IL) Special organic chemicals. Pre-treatment options

Thomas Edison Spinning Cellulose (Cotton) with ZnCl2 (1879)

An Inorganic Ionic Liquid 70 o C Dissolution occurs at mild conditions Separated polymeric chains At higher T: cleavage glucosidic bonds

Initial Focus: G1: “In-situ” Conversion of Glucose 11 Glucose Sorbitol IsosorbideSorbitan Polarity strongly reduced Easier separation Solid ZnCl 2 hydrate Liquid Cellulose H2H2 - H 2 O Hydrogenation Dehydration - H 2 O Dehydration More stable Already interesting product but difficult to separate

Novel Route: G2: Efficient separation of sugars and/or polymers Glucose ZnCl 2 hydrate Cellulose Separation Glucose(aqueos) ZnCl 2 hydrate Cellulose Mono sugar route Polymers Cellulose Polymers (solid) Polymer route Separation

G2 Technology: No degradation of Cellulose (90 o C)

2 min 5 min 7 min 10 min 15 min ZnCl 2 70 HCl 36,5 HCl 30 ZnCl 2 70 HCl 36,5 HCl ZnCl2 + HCl G2 Technology: No degradation of Glucose 70 o C

G2 Technology: Unique Cellulose Polymers ( ~ NCF) formed

Unique Cellulose Polymers

Unique Cellulose Polymers: ± nm

Unique Cellulose Polymers

Liquid Crystalline solutions: precursor for highly oriented yarns Unique Cellulose Polymers: Liquid Crystalline Phase H. Boerstoel - WO (1995) and PhD Thesis (2006)

Hydrolyse (Acid) Liquid Crystalline Cellulose for preparing yarns H. Boerstoel - WO (1995) and PhD Thesis (2006)

Unique Cellulose Polymers Easy to shape – cellulose based yarn Dried after spinning-out precipitation Promising precursor for fibre industry

Cellulose-P-Fibers Cellulose-P-Fibers  CF (1400 o C)

PO 4 Liquid Crystalline Cellulose for preparing yarns H. Boerstoel - WO (1995) and PhD Thesis (2006)

An Inorganic Ionic Liquid

Unique Cellulose Polymers  New Markets?

A Future vision: Renewable Enhanced Composite Materialsia ls Biomass C Wood M L P1P1 Additives A AEM “Artificially Enhanced Materials” (R)AEM (A) M L a a a Unique Cellulose Unique Lignin

What about Conversion to Fuels & Chemicals?

Enzymatic Conversion? Reduction (±75%) of Enzymes required for conversion to Sugars!

Thermo-Catalytic Conversion: Reduction of “liquefaction” Temperature

Unique Cellulose Polymers

Thermo-Catalytic Conversion: Liquefaction at Lower Temperature & Faster Lignin Oligomers Wood chips ( Milled) G2 Oligomers 100  “Charring” Incomplete Conversion Higher Conversion + Reduced Coke + Reduced Oxygen in Oil

Widening of the “Hour Glass”: Bio-refinery concept: Fuels/Chemicals + Materials Waste Biomass Treated Biomass Sugars PRODUCTS Waste Biomass G2 Cellulose Sugars PRODUCTS G2 Lignin

Novel inorganic ionic liquid (ZnCl 2 ) technology. Mild conditions: minimum product degradation. No bad actors: Enzyme inhibitors, Cat poisons. Simple, robust and feedstock flexible process. Non-destructive unraveling of high value : Unique G2-Cellulose (& G2-lignin) formed. Cost competitive with specialty Cellulosic’s. Enables strong business case: Combination of Advanced biofuels and Advanced Materials. Summary