Special Topics in Organic Chemistry Special Topics in Organic - - PowerPoint PPT Presentation

Special Topics in Organic Chemistry Special Topics in Organic Chemistry Biorenewable Biorenewable Polymers Polymers 86996 86996

Arthur J. Ragauskas School of Chemistry and Biochemistry Institute of Paper Science and Technology Georgia Institute of Technology

The Chemistry of Biomass is Experiencing a Modern Renascence WHY NOW ?

Global Challenges Energy Needs

Public opposition can be fierce

Riot police face a crowd of demonstrators protesting plans to export Bolivian gas, Oct. 13, 2003

Global Challenges: Energy Needs

Global Challenges Environment

Obvious Need for Sustainable Solutions

Research Opportunities: Carbohydrate Economy

David Morris - early 1980s

• Coined the term "carbohydrate economy" I
• Envisaged that by shifting society's engine toward renewable, environmentally

benign materials, agro/forestry-based manufacturing enterprises would have several positive ramifications including these:

• Pollution is no longer generated from extracting and processing crude oil into

chemicals.

• End-of-life disposal is not an issue–the products are completely biodegradable.
• Manufacturers are no longer saddled with high hazardous waste disposal costs,

lengthy permit processes and compliance costs.

• Agricultural Risk Protection Act of 2000 (PL 106-224)

Title III: Biomass R&D Act of 2000, established the Biomass Research and Development Board.

Agrofiber/Trees – A Global Chemical Resource

• Earth receives 36,000 GJ solar energy
• 33% received during growing season
• 20% reaches leaves (2400 GJ)
• 20% reflection loss
• Plant stores 180 GJ
• 220 billion tons of dry biomass available
• 0.4% of all biomass is for food
• Biomass consists primarily of cellulose,

lignin and hemicellulose

Chemical Resources - Polysaccharides

O O HO OH O O HO OH OH OH O HO OH O O HO OH O OH OH O

n: 10,000 -1500

O O O OAc O O HO OAc O HO O O O AcO OH O-Xylan O O HO OAc O O AcO OAc O O HO HO O HO O HO HO OH HO O O HO OH O O O H3CO OH OH

OH

Cellulose is the most abundant organic chemical on earth, with an annual biosphere production of ≈90x109 metric

• tons. When measured in energy terms, the

amount of carbon synthesized by plants is equivalent to about ten times the global energy consumption DP: 100 – 200 Main Sugars: Xylan, Glucouronic acid, Arabinose, Galactose, Mannose

• Approx. Production rate of 2-5 x 106 tons per year

Chemical Resources – Starch/Lignin

OH OH R R'

Enzymatic Polymerization for SW

R,R' Alcohol Name Source H,H p-coumaryl Compression Wood, Grasses H, OCH3 coniferyl Softwood and Hardwood OCH3, OCH3 sinapyl Hardwoods

3 x 1011 tons in the biosphere Production rate of 2 x 106 tons per year

O HO OH OH O O HO OH OH O O HO OH OH O O-Amylase

n: 100 - 8000

Ligno-Cellulosic Availability

Global Forest Coverage % Built-Up Land % Crop Land Trees Paper/Lumber Agro-Fibers

Lignocellulosics the most readily available bioresource available for biofuels/chemicals on a global basis

Defining a Biobased Economy

An economy based on renewable raw materials to produce products and energy

Benefits of the Biobased Economy

Economic

– Reduce cost, better control of product properties – New product & market opportunities – Improved balance of trade & energy independence

Environmental

– Pollution prevention, reduced emissions of GHG and toxics – ‘Green’ fuels, chemicals & materials – Reusable & recyclable products

Social

– Rural economic diversification & growth – Developing countries can access the biobased economy – Improvements in human/environmental health & quality of life

Benefits of the Biobased Economy

Non-renewable feedstock Process Product(s) Waste Renewable bioresource Bioprocess Bioproduct(s) By-product(s) Conventional Biobased Fossil energy Biomass Recycle into bioresource Landfill or incineration

Threshold of a New Era: Biorefinery

Bioethanol From Starch & Biomass: Enzyme Market Growth

Source: Renewable Fuels Association; GCOR Estimates

Sugars From Cellulosic Biomass

• Cellulose is a rigid crystalline carbohydrate
• It is the main component of plant cells
• Cellulose contains sugar building blocks -- but it

remains a difficult material to depolymerize.

Cellulose

Fermentable sugars (renewable carbon) Fermentable sugars (renewable carbon)

Enzymes

The Future of Biorefineries

• Bulk Chemicals

– Ethylene – Ethanol – Acetic acid – Adipic acid

• Polymers

– Nylons – Polyesters – Plastic additives

• New Biomaterials
• Fine/Specialty Chemicals

– Flavors, fragrances – Pharmaceutical intermediates, Aromatics

Chemical Industry: Progress and Promise

• Biotech will be one of key

drivers over the next 10 years

• In 2010, about 20% of the

chemical market (~USD 280 billion) will be affected by biotech with a total value creation of ~USD 160 billion

• In polymers, biotechnology

will open up avenues for novel materials and lead to new value chains

S

• urce: McKinsey & Co.

BioEconomy Production BioEconomy Production Chain Chain

Production

– Trees – Grasses – Agricultural Crops – Agricultural Residues – Animal Wastes – Municipal Solid Waste

End-Uses

Products

– Plastics – Functional Monomers – Solvents – Chemical Intermediates – Phenolics – Adhesives – Hydraulic Fluids – Fatty acids – Carbon black – Paints – Dyes, Pigments, and Ink – Detergents – Paper – Horticultural products – Fiber boards – Solvents – Adhesives – Plastic filler – Abrasives

Fuel Power

Processing

• Acid/enzymatic

hydrolysis

• Fermentation
• Bioconversion
• Chemical Conversion
• Gasification
• Combustion
• Co-firing

Plant Science

– Genomics – Enzymes – Metabolism – Composition

A Vision of the BioEconomy A Vision of the BioEconomy Year 2020 Year 2020

Biorefinery: Cluster

• f biobased

industries producing chemicals, fuels, pow er, products, and materials

Source: NREL

HO OH O CH3 O O O O CH3 H3C CH3 O O O n CO2, CH4, H2O

Today’s Forest Products BioRefiner

Lignin Cellulose Hemicellulose

Paper

• Carbohydrates

Products

Thermal Energy

• Lignin
• Carbohydrates

45 25 30

Cellulose Lignin Hemicellulose

Cellulose Lignin Hemicellulose

Starting Materials

Today’s and Tomorrow’s BioRefiner

• 1. Paper
• 2. Thermal Energy
• 3. Biofuels/Biochemicals

OH O O

Levulinic Acid

O OH O O H2N HO OH O O OH O HO OH

Epoxy resin Cellulose High Volume Value Added Chemicals

Biomass

Main components Cellulose/Starch [C6(H2O)5]n Hemi-cellulose [C5(H2O)4]n Lignin [C10H12O3]n Other components Turpentine C10H16 Vegetable Oil C18H34O2 Inorganic comp. K, P, S, Se (recycle)N, Si, etc. CO2 + H2O + => biomass + O2

Carbohydrate to Hydrocarbon Elimination of all oxygen [O] as: CO, CO2, H2O C6H12O6 => 3 CO2 + [C3H12] Splits : 3 CH4 C6H12O6 => 6 H2O + 6 [C] “Charcoal” C6H12O6 => 6 CO + 6 H2

(endothermic reaction)

Conclusion: C1 fragments obtained

CO2 loss H2O loss

methane ethanol 1-butanol ethene/butene (HMF) Trihydroxy benzene benzoquinone charcoal di-acids keto acids hydroxy acids polyols Methyl furan Valero lactone

Short Linear Saturated Medium Linear Polar Medium Cyclic Aromatic Unsaturated A-polar

C6H12O6

CO2 loss H2O loss

ethanol + methane Ethene + methane propane charcoal (di-)acids hydroxy acids polyols 2,3 dihydro furan

Short Linear Saturated Medium Linear Polar Medium Cyclic Aromatic Unsaturated A-polar

C5H10O5

furfural Vinyl - acetylene

Biocracking/Refining of Hemicelluloses/Cellulose

Bio-Diesel Substitutes Polysaccharides Enzymatic Hydrolysis C6H12O6 and C5H10O5 Cracking Loss of CO2 Ethanol

Methanol ethylene

BioRefining

O CHO HO OH OH HO Therm

• dynam

ic Product Kinetic Product

O R R: CH

3, CH

O

O OH HO O O O O

Bio-Gasoline Substitutes Bio-Diesel Precursors

BioEsterification

• r

BioEtherification

Tomorrow’s Forest BioRefiner

1. Collect readily available biomass 2. Physical refining of biomass 3. Extract cellulose/select hemicellulose for paper 2. Utilize remaining biomass to for biofuels/chemicals 4. Process into Biofuels And Biochemicals Forest Biorefiner Advantages: Environmental Permitting, Human Capital, Capital Infrastructure Wood is available year round and renewable. Wood can be stored easily and does not degrade rapidly. Wood has a higher bulk density and is more efficient to ship. Wood is a relatively low cost, important resource for most of rural America.

Tomorrow’s Urban BioRefiner

O H HO H HO H H OH H R OH OH OCH

HO R'

R: H, CH2-OH R': H, OCH3

Polymers of

Lignocellulosic Waste Consists of

BioCracking & Biorefining

What Else

NanoCellulose/NanoXylan

Cotton Tunicin Silk fibroin wood pulp

Elevated temperature Harsh Acids Physical Agitation

SEM images of untreated cellulose fibers (left) and fibers with sorbed xylan (right)

NanoCellulosic Composites

Takashi Endo: nanocomposites from polysaccharides/polymer Promising Application as a Reinforcing Phase in a Wide Variety of Polymers * High aspect ratio, large interface area, and, significant mech. properties * Enhances strength properties * Induces crystallinty * Emussion stabilizer

• Polyoxyethylene
• Water borne Epoxy Additives
• Polyesters
• Polypropylene
• Polyvinyalcohol

Cellulose fibers with controlled surface morphology. Linder, A. P.; Gatenholm, P. 225th ACS National Meeting, New Orleans, LA, (2003) Nano reinforcements of bio-based polymers: The hope and the reality. Mohanty, A.K.; Drzal, Lawrence T.; Misra, M. Composite Materials and Structures Center, ACS National Meeting, New Orleans, LA (2003) Studies on preparation and characterization of nano-crystal cellulose II. Li, G.; Ding, E.; Li, X.; Jiang, Y. Xianweisu Kexue Yu Jishu (2002), 10(2), 12-19. A method of preparing spherical nano-crystal cellulose with mixed crystalline forms of cellulose I and II. Li, X.-F.; Ding, E.-Y.; Li, G.-K. Chinese J. of Polymer Science (2001), 19(3), 291-296. Animal Cellulose: Tunicate

Future of Forest Products Industry

Egon Glesinger, 1949

Forests can be made to produce fifty times their present volume of end products and still remain a permanently self-renewing source for raw materials….. Only forests - no other raw material resource - can yield such returns. The forest can, and so must, end the chronic scarcities of material goods that have harassed man’s experience since the beginning of history

The Tools, Vision, and Societal/Commercial Needs have Now Developed!

“Destiny is not a matter of chance, it is a matter of choice, it is not a thing to be waited for, it is a thing to be achieved” W.J. Bryan

arthur.ragauskas@chemistry.gatech.edu