Special Topics in Organic Chemistry Special Topics in Organic Chemistry Biorenewable Polymers Polymers Biorenewable 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
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 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 Cellulose is the most abundant organic chemical on earth, with an annual OH biosphere production of ≈ 90x10 9 metric OH O OH O OH O HO O HO O O HO O tons. When measured in energy terms, the HO OH O OH O OH OH amount of carbon synthesized by plants is n: 10,000 -1500 equivalent to about ten times the global energy consumption O OAc O OAc O O OH AcO O HO O AcO O-Xylan O HO O HO O OAc O O OAc O O O O O HO O HO O O DP: 100 – 200 OH OH HO O OH Main Sugars: Xylan, Glucouronic HO HO acid, Arabinose, Galactose, Mannose O HO O H 3 CO OH HO OH Approx. Production rate of 2-5 x 10 6 tons per year
Chemical Resources – Starch/Lignin OH O O OH HO OH O O OH HO OH O O HO OH n: 100 - 8000 O-Amylase OH R,R' Alcohol Name Source H,H p-coumaryl Compression Wood, Grasses H, OCH 3 coniferyl Softwood and Hardwood OCH 3 , OCH 3 sinapyl Hardwoods R R' 3 x 10 11 tons in the biosphere OH Production rate of 2 x 10 6 tons per year Enzymatic Polymerization for SW
Ligno-Cellulosic Availability Global Forest Coverage % Crop Land % Built-Up Land Agro-Fibers Trees Paper/Lumber 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 Conventional Fossil energy Landfill or Process Product(s) Non-renewable feedstock incineration Waste Biobased Biomass Bioproduct(s) Renewable bioresource Bioprocess By-product(s) Recycle into bioresource
Threshold of a New Era: Biorefinery
Bioethanol From Starch & Biomass: Enzyme Market Growth Source: Renewable Fuels Association; GCOR Estimates
Sugars From Cellulosic Biomass Fermentable Fermentable sugars sugars Enzymes (renewable (renewable carbon) carbon) Cellulose • 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.
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 ource: McKinsey & Co.
BioEconomy Production BioEconomy Production Chain Chain End-Uses Products – Plastics – Functional Monomers – Solvents – Chemical Intermediates – Phenolics – Adhesives – Hydraulic Fluids – Fatty acids Plant Processing Production – Carbon black – Paints Science – Trees - Acid/enzymatic – Dyes, Pigments, and Ink – Grasses hydrolysis – Genomics – Detergents – Agricultural - Fermentation – Enzymes – Paper Crops - Bioconversion – Metabolism – Horticultural products – Agricultural - Chemical Conversion – Fiber boards – Composition – Solvents Residues - Gasification – Adhesives – Animal Wastes - Combustion – Plastic filler - Co-firing – Municipal Solid – Abrasives Waste Fuel Power
A Vision of the BioEconomy A Vision of the BioEconomy Year 2020 Year 2020 Biorefinery: Cluster of biobased industries producing chemicals, fuels, pow er, products, and materials O O O H 3 C O O HO CO 2 , CH 4 , H 2 O Source: NREL O OH O n CH 3 CH 3 CH 3 O
Today’s Forest Products BioRefiner Starting Materials Products Lignin Thermal Energy -Lignin Cellulose - Carbohydrates Hemicellulose Paper - Carbohydrates Hemicellulose Cellulose Lignin Hemicellulose 30 45 25 Cellulose Lignin
Today’s and Tomorrow’s BioRefiner 1. Paper 2. Thermal Energy 3. Biofuels/Biochemicals High Volume Value Added Chemicals O OH HO OH HO Epoxy O resin OH O Levulinic Acid O Cellulose OH O O O H 2 N OH O
Biomass CO 2 + H 2 O + � => biomass + O 2 Main components Cellulose/Starch [C 6 (H 2 O) 5 ] n Hemi-cellulose [C 5 (H 2 O) 4 ] n Lignin [C 10 H 12 O 3 ] n Other components Turpentine C 10 H 16 Vegetable Oil C 18 H 34 O 2 Inorganic comp. K, P, S, Se (recycle)N, Si, etc.
Carbohydrate to Hydrocarbon Elimination of all oxygen [O] as: CO, CO 2 , H 2 O C 6 H 12 O 6 => 6 CO + 6 H 2 (endothermic reaction) C 6 H 12 O 6 => 3 CO 2 + [C 3 H 12 ] Splits : 3 CH 4 C 6 H 12 O 6 => 6 H 2 O + 6 [C] “ Charcoal ” Conclusion: C 1 fragments obtained
Medium Short Linear Linear CO 2 loss Polar Saturated C 6 H 12 O 6 ethanol methane di-acids 1-butanol keto acids ethene/butene hydroxy acids Valero lactone Unsaturated polyols H 2 O (HMF) Methyl furan A-polar Trihydroxy benzene loss benzoquinone charcoal Medium Cyclic Aromatic
Medium Short Linear Linear CO 2 loss Polar Saturated ethanol + methane (di-)acids Ethene + methane C 5 H 10 O 5 hydroxy acids propane Unsaturated polyols 2,3 dihydro furan A-polar H 2 O Vinyl - furfural acetylene loss charcoal Medium Cyclic Aromatic
Biocracking/Refining of Hemicelluloses/Cellulose Polysaccharides Enzymatic Hydrolysis C 6 H 12 O 6 and C 5 H 10 O 5 Cracking Loss of CO 2 Ethanol BioRefining Methanol ethylene Bio-Gasoline Substitutes OH O O O CHO R HO HO OH OH HO Therm odynam ic Product Kinetic Product R: CH 3 , CH O O BioEsterification O Bio-Diesel Bio-Diesel or BioEtherification O O Precursors Substitutes
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 Polymers of H R H O HO HO OH H OH BioCracking H H Lignocellulosic R: H, CH 2 -OH Waste & HO Biorefining Consists of R' OCH 3 OH R': H, OCH 3
What Else
NanoCellulose/NanoXylan Elevated temperature Cotton Harsh Acids Tunicin Silk fibroin wood pulp Physical Agitation SEM images of untreated cellulose fibers (left) and fibers with sorbed xylan (right)
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