Advanced opportunities for the utilization of forest biomass in the

future

Mel Koch and Ray Chrisman

December, 2013

Authors Dr. Mel V. Koch

– PhD Organic chemist with three decades of experience in process R&D and analytical chemistry with Dow Chemical (Midland and Milan);

– Global responsibility for Dow’s analytical sciences, following a 4 year assignment with Lepetit, Dow’s Pharmaceutical Division in Italy;

– Faculty at the University of Washington for 15 years, Principal Scientist for CPAC (the Center for Process Analysis and Control;

– Member of committees for the US FDA in Pharmaceutical Sciences, for US Department of Energy Labs, and IFPAC (the International Foundation for Process Analytical Technology).

Dr. Ray W. Chrisman– PhD Inorganic Chemistry, Purdue University– Director of new technology development; microscale flow

technology, catalysis and process development; Chemical Sciences Dow Chemical company, retired

– Invited speaker International Biochar conference– Affiliate professor University of Washington, Forest Resources

Dept. working with CPAC– Past chairman of Chemistry Department Advisory Committee

Purdue university– Scientific Director, Atochemis, Italian process development Co.– Consultant Iowa Corn Promotion Board

Center for Process Analysis and Control

Industry Academic Consortium

• 29 years of bringing industry and academia together

• Solving multidisciplinary challenges in process analysis through fundamental and applied academic research

• CPAC is focused on developing tools that enable process optimization, control and quality improvements for our multi-industrial (Refineries, Commodity chemicals, Food, Specialties Chemicals and Pharmaceuticals) and multi-university partners

UNIVERSITY OF WASHINGTON, SEATTLE

CPAC Activities• Biannual Sponsor Meetings• Research Projects for Graduate Student Education• Industry Driven Initiatives• Visiting Scientist Program• Technology Webinars• Rome Workshop (March)• Summer Institute (July)• IFPAC and IFPAC Europa• FACSS, AIChE, ISA• FDA (PAT, QbD)

Private Capital Sources Regional and

NationalGovernment Agencies

Industrial Partners and Trade Associations

Research Universities and Institutes

Title

Key Relationships

5

Vendors and Suppliers Engineering Partners

The best solutions are developed by working with groups from around the world

Key Research contacts

Private Capital Sources EU, Regional and

NationalGovernment Agencies

Industrial Partners and Trade Associations

Research Universities and Institutes

Title

Key Relationships – Italy based

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• University of Washington (CPAC)• Milan Politecnico• Padova University• CINSA• Purdue University• University of Lyon• VITO Belgium• Univeristy of Bergen• Nelson Mandela University

AFIFederchimicaASCHIMICAAssobiotecTecnofarmaci

Regione LombardiaAIFAJRC Joint Research Committee IspraEFSA Parma

MATRIC USAFondazione Cariplo

Vendors and SuppliersEngineering Partners

Key Research contacts

• Corning• Kaiser Optical• AMT

• MATRIC USA• Insubria Biopark

Private Capital Sources

EU, Regional and National

Government Agencies

Industrial Partners and Trade Associations

Research Universities and Institutes

Title

Key Relationships – Norway based

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Vendors and Suppliers Engineering Partners

Key Research contacts

SintefNofimaAsBergenTrondheim(Hedmark)

Research Council

Innovation Norway

Tel-Tek

Process Analytical for Reaction/Fermentation Monitoring

8

– Funded by the FDA to demonstrate the benefits of improved reactor design, effective sampling and online analytics to increase process understanding and control

– Demonstration of Quality by Design for continuous processing – QbD

• Partners: FDA, CPAC, Parker, Corning, Kaiser Optical

US FDA Sponsored Continuous Flow Reactor Project at CPAC

9Brian J. Marquardt CPAC APL UW

Reactor System

Development of a continuous flow reactor system with integrated monitoring and control NeSSI sampling

system with all digital analytics and spectroscopy on reagent and product stream

What is NeSSI™?

• Industry-driven effort to define and promote a new standardized alternative to sample conditioning systems for analyzers and sensors

GEN I - Standard fluidic interface for modular surface-mount components

ISA SP76

GEN II - Standard wiring and communications interfaces

GEN III - Standard platform formicro analytics

Continuous Flow ConversionMoffat Swern Oxidation of Alcohol Initial study shows

comparable yield in continuous flow at -20°C 50°C higher than in

batch Results indicates

better yields at higher temperatures are possible as well

Temp % YieldBatch -70 93.5

-30 2.0Continuous -20 91.6

-10 67.20 33.8

10 8.320 3.2

NeSSI on Bio-Reactor. Fast-loop Design

• Custom designed NeSSI interfaces for all process analyzers in Marquardt lab • Plug and play analytics for any flowing system (liquid, slurry or gas) 13

Raman of Fermentation 3D Plot

10001150

800

Raman Shift (cm-1)

Time

Inte

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ty (

Arb

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nits

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Ethanol

Glucose

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Pretreatment of biomass hydrolysate

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Baseline removed

unfiltered0.8um 1.2um 5um

Raw spectra

Lignin is highly fluorescent and has to be removed

Filters with pore size 5 um are sufficient (no need to have a smaller pore size)

Greatly improves Raman SNR

MRI to Study the Flow of Biomass Undergoing Enzymatic Hydrolysis

• Rheological measurements

• Liquefaction characterization

• Kinetic modeling

No one analytical technique can fully describe a complex feed

• While multivariate techniques such as spectroscopy or chromatography cover significant portions of the variable space,

but other variables can still be present and impact the results

• For example, some components are below detection limits and others are non-detectable in the technique

(such as metal ions or pH in NIR measurements)

Examples of where more information could be used to reduce process

variability

Qualifying raw materials particularly bio-based raw materialsOrganism growth mediaExcipientsWater soluble polymersSurfactantsFibers including dietary usesGlues, adhesives, and coatingsFlocculantsMedical scaffoldsFood extractsPolymer monomers and additives

Modification reactions for any of the above biomaterialsPolymerization reactions including pre-polymer formation

R. Chrisman, Atochemis

Multiple Analytics for Improved Understanding- improved data analysis needed to quickly capture the information

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1000 2000 3000 4000 5000 60000

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Variables

Sig

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Fused IR, Raman and LIBS Spectra

Fused Raw Spectra

IR

LIBS Raman

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0

2

4

6

-2

-1

0

1

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-1.5

-1

-0.5

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Scores on PC 1 (77.77%)

Samples/Scores Plot of Fused Data Matrix of IR, LIBS and Raman

Scores on PC 2 (9.63%)

Sco

res

on P

C 3

(4.

01%

)

ModG1xMediaSupp

NutrientBroth1x

XYT2

Liu1xSupp

LeightDoiSupp and NutrientBroth2x

Fused Data Classification of MediaLegend

InnoculatedNoninnoculated

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More data can be very valuable for better process control but the question becomes how to cost effectively gather more data that contain usable information

More locations for simple sensors

A broader range of simple sensor types

More traditional multivariate analyzers

A hybrid approach (some of each)

R. Chrisman, Atochemis

The use of “big data” concepts with chemometric analysis for raw materials and nutrient characterization, as well as

for process control will have a significant impact on the efficient use of

bio-materials

New sensor systems that employ these concepts could make it more cost effective to add PAT to

small volume processes

!

R. Chrisman, Atochemis

FOREST RESOURCES TOPICS

Ray Chrisman

Typical bulk composition of forest biomass

In addition to the bulk materials, forest biomass has the following components

• Extractables such as resins, starches, waxes, lipids, hydrocarbons and various phenolics which in total are only about 1-5% on a dry basis.

• Water• Ash which is the metal ions and silica. Ash is about

0.5% for most woods

Tree bark, leaves, and needles can have higher levels of extractables

Key traditional uses of forest biomass

Structural materials that take advantage of the physical properties of wood; from building materials to paper

Source of chemicals; Both commodities such as methanol and specialities such as pine oil

Energy source; from direct combustion to pyrolysis for charcoal

New technology offers the potential for new uses in each of these areas

New technology developments offer the potential for enhanced value capture from forest biomass

Evolving strategies for bulk biomass processing; plasma decomposition to slow pyrolysisNew catalysts/chemistries for conversion of biomass to valuable feedstocks; New monomers for enhanced wood compositesNew process analytical technology, PAT, to characterize forest biomass during processingNew micro-scale processing techniques for the synthesis of value added materials from biomass*Enhanced separation techniques for the isolation of valuable biomass components*

* Since these are new general approaches to processing, more background will be given on the next slides

Micro-scale flow technology provide better reaction control

Very controlled high heat transfer (no hot spots or temperature gradients) and high mass transfer (mixing) for faster, cleaner reactions (Faster)Plug flow for less back mixing and better residence time control (Cleaner)Short residence times; often minutes or less for reduced impurity formation (Cleaner)Higher mass transfer improves the use of membrane based reactors, electrochemical reactors, and packed bed catalysts (New Routes)Small channel sizes for more uniform photochemistry (New routes)

Neutralization reaction (HCl and NaOH) in a 5 cubic M vessel (stirring 500 rpm)

sigma-aldrich.com/chemicalsynthesis

There is much less control in this stirred tank reaction environment where the 10 degree temperature change means part of this system is reacting twice as fast

http://researchspace.csir.co.za/dspace/bitstream/10204/2680/1/Buddoo_P_2008.pdf, S R BUDDOO, N SIYAKATSHANA, AND B PONGOMA ,CSIR Biosciences

Comparison of batch versus microreactor production of biodiesel for small distributed plant

Note plant size as construction costs can be 80% of capital cost; Also smaller plant size means flexibility in location

The previously mentioned features mean continuous micro-scale processing can lower costs and improve efficiencies

• Lower labor costs versus batch process (commodity continuous process is 50%-75% lower)

• Lower capital costs• Higher quality means less waste to handle• Energy recovery is easier• Much safer to operate as less material in process

Enhanced separation techniques for the isolation of valuable biomass components

A potential key example of what could be done with extraction of forest biomass

Another separation technique, Chromatography

has several key attributes for process separations

• High selectivity 1 in 10,000• Versatile mechanisms of separation- adsorption, ion

exchange, size exclusion etc.• Compact volume compared to extraction• Lower solvent usage than extraction• Mild operating conditions- suitable for fragile

compounds.Linda Wang, SI meeting 2010

It can be fast and low cost when operated continuously in the simulated moving bed format (SMB)

Affinity based separations offer another method of isolating low level components in

complex mixtures

The most commonly known method is the use of antibodies which have very high selectivity but are expensive and are somewhat fragile to use. Manmade polymers can now be made to mimic the high selectivity of antibodies with higher stability and lower cost.

There are various product possibilities that could utilize these new technologies

Advanced opportunities for the utilization of forest biomass; Structural materials

A new class of non-isocyanate based monomers which can be easily made in microreactors offer a range of advanced coating, adhesives and binders. Unlike isocyanates these monomers react with the –OH groups in cellulose and hemicellulose to form strong bonds

The R’ group can be aliphatic which means much greater light stability

Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 46, 2445–2458 (2008)

Structural materials continued

Biochar can be used to make much more stable composites since biochar does not swell in water and is not attacked by organisms in the soil

Development of advanced uses for biochar that are based on the unique microstructure of the forest biomass

Additional uses for agricultural applications also seem possible based on the unique microstructure and surface chemistry.

An ideal approach is a bio-refinery where a bulk process is coupled with a range of smaller processes which use the

products from the bulk process as starting materials

Advanced opportunities for the utilization of forest biomass; Chemicals

The next few slides describe possible bulk and specialty chemicals

http://bio.albertainnovates.ca/stratthemes/bioecoadvance/bioe-initiative/background/

Advanced opportunities for the utilization of forest biomass; Bulk Chemicals

A range of new approaches to the use of biomass for the production of higher volume materials are under development globally

Various fuels from diesel to jet fuels based on thermal (gasification or plasma) decomposition followed by conversion of the syn-gas with catalysts similar to the historic Fischer-Tropsch process to fuels or chemicalsGycols from the hydrogenolysis of sugars from biomass has been described and several groups are working to commercialize this approach A new route to phenol based chemicals has been described which could utilize the lignin stream

A group in Italy has built a fermentation plant based on the use of sugars from biomass.Shell the world's largest formulator of ethanol fuels has just patented a method for converting biomass to sugars for fermentation though it is not commercial. Hydrogen or CO from the syn-gas of any of the thermal decomposition methods can also be used for various other reactions or the syn-gas can be converted to energy Lower temperature pyrolysis methods can make bio-oil, biochar or with more control a range of oxygenates.

Bulk Chemicals continued

Many bulk chemicals require very large plants for economies of scale which consume very large quantities of biomass. Transportation costs can be a problem if the

biomass must be shipped large distances

Advanced opportunities for the utilization of forest biomass; Specialty chemicals

In a micro-reactor a surfactant can be produced for use in facial creams and lotions, a slight change could produce an ideal emulsifier for natural gas development. Use

of another alcohol can produce a key component of polymeric materials.

Different types of alcohols can be used to make various classes of compounds

Glycosides are a good example of a family of materials that can be made from bulk starting materials. There are multiple similar examples

Advanced opportunities for the utilization of forest biomass; Specialty chemicals

Key products that are often overlooked are the valuable extractables that are in forest biomass, especially forest waste piles

http://www.sisweb.com/referenc/applnote/app-41.htm

Many of these can be cost effectively isolated with the new separation technologies

An simple example

Forest waste can be pyrolyzed to produce syn-gas for process energy and bio-char. The bio-char could be used to make composite building materials. It could also be coated with natural insecticides isolated from birch bark and used to protect agricultural products

and build soil quality

New technology can be used to make a broad range of new products based on

the use of forest biomass

Conclusion

In 2003, the United States imported more than600 tonnes of pine oil, mostly from China [12]. Anadditional 5,000 tonnes of pine oil was exported [12].Reliable retail prices for pine oil were not available, but theretail sale price for comparable oils from other conifersranged from $5 to $8.66 per 10 ml in 1999 [13]. Assumingthat the oils extracted from ponderosa pine in northernArizona are similar in composition and product potentialas those imported and exported, it would appear that themarket potential could be substantial. Further assuming awholesale discount rate of 60 percent [13] for retail prices of$5 per 10 ml, the unrealized market value of ponderosapine oil is approximately $300,000 per tonne. If a viablemarket existed for the more than 700 tonnes of pine oilextracted from northern Arizona slash and sawdust in2002, gross value would have been more than $200 million(US$) not including production costs.

V.M. Kelkar et al. / Biomass and Bioenergy 30 (2006) 316–320