Challenges and Opportunities in Manufacturing Panel

Kim Nelson, PhD American Process Inc.

Cellulose Nanomaterials –A Path Towards Commercialization A Workshop Co‐Sponsored by USDA Forest Service National Nanotechnology Initiative Sugar is the New Crude® American Process Inc. • Currently installing a 1 ton per day (dry basis) nanocellulose pilot line at our existing AVAP Biorefinery in Thomaston, Georgia to produce cellulose nanocrystals (CNC), cellulose nanofibrils (CNF), and hydrophobic, lignin‐coated varieties directly from biomass

CNF Biomass lignin coated product SO2, ethanol, CNC water CNF + CNC Fractionation and Cellulose Separation / Mechanical Mix Bleaching Washing / Lignin Coating treatment L‐CNF Liquor (hemicelluloses , L‐CNC Chemical solvent, SO2, lignin) 1% 10% Regenerated Regeneration L‐CNF + L‐CNC ethanol/ SO2 Mix AVAP CNC

Hemicelluloses Hydrolysis Lignin for energy Hemicelluloses sugars to biofuels/biochemicals 1% 10%

AVAP L‐CNC 2 Manufacturing Opportunities

• Low Production Cost for CNC and CNF with estimates of <$1 lb (wet basis). • Low cost feedstock utilization with omnivorous processes. • Low tonnage “side line” production in existing pulp mills for coproduction with pulp, lignin, and biofuels or biochemicals • High tonnage “stand alone” production in repurposed pulp mills using existing infrastructure including wood delivery and handling, utilities, waste water treatment, bleach lines etc. • Large demand potential with a near term global market size estimate for nanocellulose of 34 million tons per year (recent USDA funded study)1.

1. Cowie, J., Bilek, E.M., Wegner, T.H., et al.(2014)

3 Possible Global Production Curve

500 Plastics Timeline USDA’s near

Nanocellulose Timeline term global 2002 market size 400 PLA estimate for nanocellulose tonnes of 34 million 300 tons per year. 1970

million PET

200

1957 PP

Production, 100

1907 1977 Bakelite Cellulose 0 nanofibrils gel 1900 1920 1940 1960 1980 2000 2020 2040 2060 2080 2100

4 Manufacturing Challenge: Drying

• Economical preservation of discrete nanocellulose particle morphology during drying for effective re‐dispersion in hydrophobic plastic resins Cellulose Nanocrystals1

Original Air ‐dried Freeze‐dried Spray ‐dried

Cellulose Nanofibrils2

Original Air ‐dried Freeze‐dried Supercritical ‐dried Spray ‐dried

1. Drying Cellulose Nanocrystal Suspensions, Peng et al. Production and Applications of Cellulose Nanomaterials, TAPPI Press. 2. Drying Cellulose Nanofibril Suspensions, Peng et al. Production and Applications of Cellulose Nanomaterials, TAPPI Press. 5 Manufacturing Challenge: Drying • Lesson learned from similar experience: Coating CNC with lignin appears to prevent hydrogen bonding during freeze‐ drying. Resulting powder can be uniformly re‐dispersed in silicone for a semi‐transparent, stronger composite. • Research Question: Is there a Freeze‐Dried low cost, hydrogen bonding “blocker” for freeze‐drying of conventional CNC that Bonded 3D network CNC Foam Lignin coated CNC Powder maintains color/transparency and is compatible with hydrophobic plastics?

0% L‐CNC 1% L‐CNC 2% L‐CNC

Lignin coated CNC/silicone composite 6 Manufacturing Challenge: Rapid Particle Size Characterization • Develop rapid size characterization of CNC and CNF for process and product quality control TODAY TOMORROW

• Cost: $$$$ • Cost: $ • Sample prep time: ~30 min per • Sample prep time: <5 minutes per sample sample • Characterization time: ~15‐25 min per • Characterization time: <5 min per test sample + manual image analysis • Staff requirements: process operators • Staff requirements: highly technical • Location: Operating floor or process experts quality test lab • Location: Specially designed individual room‐ sensitivity to ambient

conditions 7 EHS Priorities

Safety Regulatory • Occupational Safety • Lack of clarity on regulatory – Detection in environmental requirements for media nanomaterials – Airborne exposure methods • Product Safety • Variability of requirements – Demonstrating safety of by geography and functionalized nanocellulosic application materials • Lack of standards for – Human health testing – Environmental releases nanomaterials • International Safety • Lack of validated methods Standards for assessing safety

8 Thank You

PRESENTED BY Kim Nelson, PhD Director of Nanocellulose Technology Development American Process Inc. [email protected]

Alpena Biorefinery, Michigan AVAP Biorefinery, Georgia 9