From Research To Commercialization: How To Do It Faster

Chemical and Environmental Technologies

Health and Life SciencesAdvanced Engineering

Systems

Life-Changing Research and Innovation

www.matricresearch.com

Dr. George KellerChief Engineer800-611-2296

George.keller@matricresearch.com

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Two Basic Types of Research

Phenomenological Research: Deals mostly with fundamental research. A desire to understand at a fundamental level. Output is knowledge, papers, talks and sometimes patents, leading to promotions and/or attainment of tenure or longevity.

Mission-Oriented Research: Deals mostly with research intimately accompanied with process engineering and economics, and directed toward a well defined goal of a new product, process or other engineering outcome.

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The Role of Process Engineering

Construct process flowsheets and models from speculative chemistry and engineering dataDetermine the economically critical points of the processes under consideration and• choose what seems to be the most

economical pathway and • focus lab work on the most critical issues

Use lab data to refine the economic model and modify experimental directions

matricresearch.com

The Role of Process Engineering

Design a pilot plant based on assessment of critical factors to be studiedContinuously update the process model based on pilot plant resultsWork with design engineering to provide a complete transfer of all relevant data and model resultsParticipate in the final design, construction and start-up stages

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Example 1: A New-Generation Biodiesel Plant

MATRIC began basic lab work in March 2006The full-scale 8MM gpy plant was started up in December 2007The full-scale plant has the following characteristics– Continuous process, reducing investment by ~ 40%.– Process can accept not only refined soy oil, but also crude

soy oil, crude corn oil, fats, renderings, etc.– Process nearly completely eliminates off-site pollutants

(aqueous and air-borne)– Process is designed and constructed to exacting Dow/Union

Carbide quality standards.– Process will be licensed by BEST Energies around the

world.

Example 2: An Isosorbide Process

Process research was carried out by a large laboratory. After four years and $5M, the project was unsuccessful in achieving its goal.The project was given to MATRIC, and after six weeks, the process was developed and ultra-pure product was produced.A pilot plant (450 kg/month) was built to supply product to potential customers.

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Role of Separations Discipline

Chemical separations is key the economics for the production of most materials– Will be increasingly important as feedstocks evolve toward

biomass– Will be increasingly important under new toxic substance

control regulations (e.g. REACH)Current processes that are economically limited by separations– Corn ethanol both in ethanol distillation and DDG drying– Cellulosic ethanol in pretreatment/fractionation, C5 and C6

separations (different fermentation enzymes), and distillation

– Sea-water desalination for safe water supplies world-wide

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Industrialization of Cellulosic Ethanol

Five factors control the ability for cellulosic ethanol to become economically viable:– Process rate—slow process step

kinetics requires larger capital equipment costs

– Conversion efficiency—poor utilization of feed materials drives higher operating costs

– Capital equipment costs—exotic MOC, high pressure or temperature materials drive adversely impact cost of goods produced

– Operating costs—high temperatures or pressures require significant amounts of energy

– Product quality/consistency—Inconsistency increases the cost of the overall process

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Cellulosic Ethanol Process

Pretreatment phase, to make the lignocellulosic material such as wood or straw amenable to hydrolysis Cellulose hydrolysis (cellulolysis), to break down the molecules into sugars Separation of the sugar solution from the residual materials, notably lignin Microbial fermentation of the sugar solution Distillation to produce 99.5% pure alcohol

Chart courtesy of the National Renewable Energy Lab and appears on the Renewable Fuels Association website.

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Key Processing Cost Elements

www.everythingbiomass.org

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General Pretreatment Technologies

Mosier et al., Bioresour. Technol. 2005

Pretreatment technologies are mostly used as precursor to enzymatic hydrolysis

– Acid Hydrolysis– Steam Explosion– Ammonia Fiber Expansion (AFEX)– Alkaline Wet Oxidation– Ozone Pretreatment (Ozonolysis)

Each method has advantages and disadvantages

– No one method is best for all types of feedstock

– Optimum reaction parameters of the various pretreatments, like temperature, pressure, and reaction time, are specific to each feedstock

High yield of sugars does not always result in high conversion to ethanol

– lignocellulosic components or chemicals used in pretreatment may form compounds that inhibit fermentation

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Acid Hydrolysis

Concentrated or dilute mineral acids penetrate biomass, breaking down hemicellulose into monomeric sugars, and removing part of the lignin– First cellulosic pretreatment

technology dating from Germany in 1898

– Reaction is carried out at elevated temperatures

– Sulfuric acid is most often used, because it is available at low cost

– Low moisture content is preferred, since less energy is needed to heat the biomass

http://www1.eere.energy.gov/biomass/images/photo_05208_sugar_platform.jpg

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Acid Hydrolysis

Advantages– good hemicellulose sugar

yields – high cellulose digestibility

• removal of hemicellulose and lignin exposes more cellulose for enzymes to attack

– can solubilize heavy metals that may contaminate the feedstock

Disadvantages– requires downstream

neutralization– some degradation of

hemicellulose sugars• lower yield of sugars• may form compounds such

as acetic acid and furfural which inhibit bacteria or yeasts during fermentation

– equipment costs are high• reactors must be corrosion–

resistant, suitable for high temperature and pressures

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Steam Explosion

Physico-chemical pretreatment in which biomass is subjected to high-pressure saturated steam, followed by rapid depressurizationExpansion of water vapor exerts force, causing mechanical breakdown of biomass – degrades hemicellulose and

lignin, thus increasing the potential of cellulose hydrolysis

– acids or bases may be incorporated into the steam to increase hydrolysis

www.biogasol.dk/2me2.htm

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Steam Explosion

Advantages– economical for hardwoods– effectively hydrolyzes

hemicellulose – promotes delignification

• enlarges pore size in plant cells which is beneficial for subsequent cellulose hydrolysis

Disadvantages– increases crystallinity of

amorphous regions of cellulose, which decreases cellulose digestibility

– high equipment costs • need for high temperature

and high pressure reactors

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Ammonia Fiber Expansion (AFEX)

Physico-chemical pretreatment in which prewetted lignocellulosic material is treated with liquid anhydrous ammonia at high temperature and pressure, then pressure is rapidly released – Created and patented by Michigan State University– In contrast to most pretreatments, AFEX does not

significantly solubilize hemicellulose– Pressures exceeding 12 atm are required for operation at

ambient temperature

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Ammonia Fiber Expansion (AFEX)

Advantages– Much less sugar degradation

than acid pretreatment• inhibitor formation is very

limited– Fast reaction time (~5min)– Improves hydrolysis rates of

hemicellulose and cellulose in herbaceous crops and grasses

– Ammonia can serve as a nitrogen source for organisms downstream

– Ammonia is all volatilized and can be recovered as gas

• neutralization is not necessary

Disadvantages– High energy utilization to

achieve very high pressures– Relatively new and

undeveloped process– Not proven effective on

hardwoods or softwoods– AFEX effectiveness decreases

with increasing lignin content

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Alkaline Wet Oxidation

Water, sodium carbonate, and oxygen at elevated temperature and pressure interact with biomass by breaking ester bonds – Mechanism believed to be saponification of intermolecular

ester bonds that crosslink hemicelluloses with other components

– Porosity of the material is increased due to the removal of the crosslinks, so enzymes can attack sugars more easily

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Alkaline Wet Oxidation

Advantages– Readily oxidizes lignin – Significant decrease in

cellulose crystallinity• more accessible to enzymes

– Low formation of furfural, a microbial inhibitor often produced by other pretreatment methods

Disadvantages– Degradation of lignin and

hemicellulose to produce carboxylic acids

• hemicellulose sugars largely decompose, thus cannot be converted to ethanol

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Ozone Pretreatment (Ozonolysis)

Ozone acts primarily by degrading lignin, via attack and cleavage of aromatic ring structuresIn one study using wheat straw, ozone pretreatment removed 60% of lignin, which increased enzymatic hydrolysis rates five-fold

Sugimoto et al., “Ozone Pretreatment for Ethanol Production Using Lignocellulose Materials,” Forestry and Forest Products Research Institute

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Ozone Pretreatment (Ozonolysis)

Advantages• Effective delignification • Ozone does not form any toxic

compounds that inhibit hydrolysis

• ozone can be easily decomposed to oxygen using a catalytic bed or high temperatures, thus extensive downstream processing is avoided

• Can be conducted at ambient temperature and pressure

Disadvantages• Requires large amounts of

ozone, which is expensive • Generation of carboxylic

acids from extensive lignin degradation

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Cellulosic Ethanol Pretreatment Summary

None of the current pretreatment technologies described in this presentation meet the criteria for economic viabilityEach of these technologies is currently being demonstrated at scaleMATRIC is currently developing a proprietary chemical pretreatment technology that has the potential to satisfy all of the requirements outlined herein– Low capital costs– High fractionation rate– High availability of segregated sugars

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Marks of the R&DE Organizations of the Future

World-class-talent people who can form teams, begin new projects, learn new technologies and learn business and marketing aspects of their projects, as well as the research and engineering aspects, quickly

Disciplined assessment of economics of chemical processes, such as cellulosic ethanol pretreament

Seamless integration from basic research to commercial demonstration

Multidisciplinary system approach to complex problem solving

State-of-the-art engineering and scientific equipment

Experience with conducting large and small R&D programs

Effective leveraging and networking with industry, academe and government labs

Summary

Industry strongly favors mission-oriented RD&E, and there is much to learn about it by most companiesThe type of agile, entrepreneurial RD&E organization described herein may be difficult to establish in highly organized, hierarchical companiesNew forms of RD&E organizations will grow up, and some will become major suppliers to industryOrganizations that create technology that support economically viable chemical processes will be greatly advantaged in the marketplace– Cellulosic pretreatment is one example of a field requiring

economical innovation

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