Renewable Feedstocks

Christopher ONeill November 14, 2003

What is a renewable resource?

Material that is readily replaced in the environment over a reasonable time frame Renewable feedstocks are a new area

Why renewable?
Cheaper raw materials Low environmental impact Common petroleum based feeds are a depleting resource

Sustainablility
Derived from renewable resources Recycling capability Triggered Biodegradability Environmentally Acceptable Viable economics

Overview
Biomass

Feedstocks Biocatalysis and Enzymes Biocomposites and Biopolymers Current Renewable Processes Economic Viability

Biomass feedstock
Plant

material on land Major components

Cellulose,

starch, oils, protein, lignin, and terpenes

Common
Corn,

crops

soybeans, sugarcane, wheat, hay, alfalfa, rye, rice

Implementing Biomass
Biomass Organic

easiest to use in production of organics

is organic

Biomass

compounds typically derived from petroleum and fossil fuels (> 98%)

Feasibility of Biomass
Cheaper

raw materials Expensive processing units Crops being used as feedstocks instead of food products
Enough

biomass waste generated to supply all processes synthesized with biomass

Biocatalysis and Enzymes

Area

of greatest importance in renewable feedstocks Biocatalysts and enzymes used to transform renewable and non-renewable feedstocks into final products Reduce protection and deprotection steps Remove toxins and carcinogens Foundational Pillar of Green Chemistry

Biocatalysts and Enzymes

Stereo-

and regio-selective Pure isomers instead of racemic mixtures High selectivity

Reduces

energy costs (easier separation)

Problems with Biocatalysts

Industry

not implementing Economic Viability

Complete

overhaul of plants Energy Efficiency More research necessary

Recent Developments
D-glucose
Wide

use Derived from starch, hemicellulose, and cellulose

Improved

catalysts

Adipic Acid
Current

process

material benzene By-product nitrous oxide

Starting

New

process

material D-glucose No hazardous by-products

Starting

Adipic Acid

Quinic and Shikimic Acid

Intermediate
For

product

flu virus pharmaceuticals More recently for hydroquinone

Produced
E.

from D-glucose

coli catalyst

Ratio

of the two acids depends on the feed rate of glucose

Quinic and Shikimic Acid

Hydroquinone
Used

as photographic developer and intermediate in antioxidants Original synthesis

Benzene

feed, byproduct salts

feed, no salts, fewer synthesis steps

Hock

oxidation or Peroxide oxidation of phenol

Benzene

Hydroquinone
Is

benzene free synthesis possible? Woskresensky 1838

Synthesis

from quinic acid Limited supply (Cinchona bark) Now possible because of biocatalytic route to forming quinic acid
Quinic

acid is oxidized to hydroquinone

Hydroquinone

Vanillin
Flavoring

compound naturally found in the orchid Vanilla planifolia Natural vanillin does not meet demand Synthetically produced
starting material DMS methylating agent Guaiacol intermediate product
Phenol

Vanillin
Alternate

route from D-glucose D-glucose converted to vanillic acid by E. coli Aryl aldehyde dehydrogenase produces vanillin Environmentally benign and still natural vanillin

Vanillin

Thymidine
Already
Used

produced from a renewable resource

through new biocatalyst

for antiviral nucleosides

Improved

is hypoxanthine uric acid Pulls reversible reaction to product side

Co-product

Yield

of 68%

Conversion of 90%

Thymidine

Road Deicer

Common salt is NaCl

Contaminates soil and groundwater Corrodes cars and roadways

CMA/CMP
Biodegradable Corrosion comparable to tap water

Economics
2-stage fermentation of whey permeate Viable due to savings from road damage

Biocomposites and Biopolymers

Environmentally Composites
Plant-derived

benign materials

fibers plastics

Polymers
Crop-derived

Natural Fibers
Kenaf,

flax, jute, hemp Advantages

Cheaper Low

density, strong Easy to separate Biodegradable

Disadvantages
Lower

tensile strength

Biopolymers
Biodegradable
Origin Chemical

structure industry

Restricted

use
with petroleum based materials?

Packaging

Competition

Attractive Biopolymers

PLA
Polylactides Corn Replace PET Cargill-Dow

CAP
Cellulose acetate propionate Toothbrush handles

PHA
Polyhydroxy alkanoates Ferment sugars Grown in a plant

CAB
Cellulose acetate butyrate Screwdriver handles

Current Status
Acrylamide
Derived

from Rhodococcus Rhodochrous Mitsubishi Rayon 30,000 tons/yr

Fructose
Derived

from glucose 1,000,000 tons/yr

Are Biobased Products Economically Feasible?

Cheaper

raw materials Costly processing technologies

Still

developing More economical with time and research

Properties

of final product may be different from the material being replaced

How green are green processes?

Use

renewable feedstocks Limit use of fossil fuels Separations? Energy requirements? Do new technologies require the use of more depleting resources than before

Conclusion
Reduce

environmental impact Many alternate routes discovered New products with different properties Economically viable? How green? Consumer role

Questions??