Transcript Biodegradable Polymers from Canola and Flaxseed Oils

Industrial Uses of Vegetable Oils
Dr. Suresh S. Narine
Director, Alberta Bioplastics Network
Professor, University of Alberta
Feedstock for the Chemical Industry
fossil oil, gas
coal
renewable
resources
1850
1900
1950
year
2000
2050
Carbon-Carbon Bonds: The
heart of the matter.
It is important to realize that the commodities
produced from “petro-products” derive their
properties from Carbon-Carbon bonds:
– Nature provides these via photosynthesis
– Fossil Fuels are just reserves of photosynthetic
Material that have not been utilized.
– Why not find ways of making direct use of such
bonds, without having to wait the thousands of
years for them to become oil or coal?
World Biomass Production
93%
unutilized
7%
utilized
Plants are a gigantic sun reactor.
Of the daily energy from sun of 1.5 x 1022 J, only 4 x 1018 J (0.008%) are use to build up
biomass.Only approx 7% of the biomass is used by mankind.
Polymers from Plants
The build up biomass is about 1000 times bigger than the amount of plastics produced
world wide.
The amount of paper produced world wide is about twice as big as the produced
amount of plastics.
1012
200 bill. t
1010
300 mio. t
10
180 mio. t
8
8 mio. t
106
104
102
0
biomass
paper
starch
plastics
crude
oil
Crude oil vs. renewable
resources
products
Monomers
Cosmetics
lubricants
fumaric acid
itaconic acid
renewable
resources
aconitic acid
succinic acid
sugar
2,3-butanediol
starch
Vegetable Oils
1,3-propanediol
Bio-Based Materials Are Becoming
Increasingly Important
By the year 2010, Dupont will be sourcing 25% of its materials for
polymers and petrochemicals from renewable resources.
*SoronaTM - stretch fibre made from corn - Dupont
WoodstalkTM - wheat straw wood alternative - Dow BioProducts Ltd.
NatureWorksTM - carpets, shirts, bottles, cups, films, etc. - Cargill
Dow LLC
Milligan Diesel Fuel Conditioner - canola based - Milligan Bio-Tech
Inc.
Natural resins and Bio-Oils from wood wastes - Ensyn Technologies
Inc.
Archer RC* Non-volatile coalescing agent for latex paints - Archer
Daniels Midland Co.
The Chemical Factory Moves
into the Plant
CO2
rain
sun
Annual Production of Lipids
Average Annual Production of Oils
MM tonnes
200
150
Soybean
100
World Total
Palm
50
Canola/Sunflower
Other Veg. Oils
0
1976 - 1980
1996 -2000
Years
2116 -2120
Animal Fats
Canadian Production
Canola
– Canada produces 20% of the world’s edible oil production, mostly as
Canola Oil
– Saskatchewan produces 50% of Canada’s production
– Manitoba and Alberta produces equal amounts of the remaining 50%
– Due to Soybean Oil production pressures from China and Brazil, Canola
Acreage in Western Canada is significantly below historical norms.
– The industry can easily produce an additional 4 Million Metric Tonnes,
with Alberta alone being able to produce 1.87 Million Metric Tonnes,
based on historical production patterns within the last 10 years.
Canadian Production
Flaxseed is the first oilseed to be widely grown in
Western Canada
Only 20% of the area devoted to Canola is devoted to
flax in Western Canada, with Saskatchewan and
Manitoba being the major producers.
Most of the flax grown here is for oil usage as opposed
to the European varieties, in which most of the flax
grown is for fibre utility.
99% of the flax grown in Western Canada is for industrial
use, although Flax is a major source of PUFA’s, edible
use is limited, primarily due to the high reactivity of the
oil with oxygen.
Major Industrial Uses
As Feedstock for Polymers
Drying Oils in Paints and Varnishes
As lubricants
As Feedstock for Specialty Chemicals
As Biodiesel
As ingredients for cosmetics
Marketing Advantage
Average Relative Price (Range)
– Petroleum base stock – Lubes
– Plant Oils
– Synthetic Base Stock – Lubes
1 X / kg
1 – 2 X / kg
3 – 8 X / kg
– Resins – Coatings:
– BioBased Synthetic Esters
3 – 6 X / kg
2 – 5 X / kg
Source: Dharma Kodali,
Cargill Inc.
Source: Dharma Kodali,
Cargill Inc.
Molecular Structure Determines Use.
The applicability of vegetable oils to industrial
processes are dependent on the predominant
functional groups within the triacylglycerol
molecules of the oil.
These oils are composed of a glycerol
backbone, to which are esterified three fatty acid
molecules.
The chain lengths, degree of unsaturation, and
types of functional groups on the fatty acid
molecules determine the native properties and
chemical possibilities of the oil
Unsaturated Fatty Acids Present in
Canada’s Oilseeds
Exotic Oils with Specialized
Functionality on the Fatty Acids
Properties / Functionality / Value
Markets
Value Creation
Applications,
Functionalities
Chemical
Structure and
Composition
Physical
Structure and
Properties
Property / Functionality / Value
Molecular Property
–
–
–
–
–
–
–
–
–
–
–
–
–
Reactivity
Iodine Value
Chain Lengths
Conjugation
Saponification Value
Acidic Value
Peroxide Value
Polarity
Solvency
Hydrophobicity
Molecular Weight
Molecular Packing
Heterogeneity
Derived Functionality
–
–
–
–
–
–
–
–
–
Appearance / Colour
Viscosity (flow properties)
Volatility (VOC)
Low Temperature Behavior
Drying (film formation)
Adhesion
Tack / Rub off
Lubricity
Oxidative Stability / Shelf
Life
– Compatibility
– Biodegradability
Millions of LB
North American Plastics
Production Strong Growth
80000
70000
60000
50000
40000
30000
20000
10000
0
1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000
Polyethylene
Polypropylene
Other
Product Production Index
Production Index 92=100
150
Source: Federal Reserve Board
140
130
120
110
100
90
80
1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000
Plastic Products
Paper Products
Steel and Mill
Sources of Plastics
99.5% of current plastics are made from fossil
fuel derivatives
Polyethylene
Polystyrene
Majority of such “Petro-Plastics” are nonbiodegradable.
Some exceptions do exist, e.g. PolyCaprolactone
Petro-Plastics are produced at large energy
costs, due to the need for “cracking.”
Plastic Production
Approximately 180 Million tonnes of plastic produced
annually
It takes approximately 141 MJ/kg of energy to produce
Nylon, and 76 MJ/kg of energy to produce amorphous
PET
Therefore millions of tons of fossil fuel is required to first
make the plastics, and then additional reserves are
required to process them into useful items.
Plastics production consumes 4% of the world’s supply
of petroleum!
What are the Drivers Impacting
the Future Polymer Industry
Finite Fossil Fuel Sources
Environmental and health
concerns.
Consumer attitudes.
Cost of “cheap” feedstocks.
Carbon Credits
Greenhouse Gas Reduction
Criteria Air Contaminant
Reduction
A cluttered way forward
Renewability
Sustainability
Environmental
Concerns
– Biodegradability
– Recyclability
Economic Continuity
Product Performance
Etc.
Markets
Biodegradable Plastics: US + Japanese Mkts
1997
Figures
Projected
for 2004
Revenue
US $23 M
US $187 M
Mass
20 M lbs
167 M lbs
Markets
Biodegradable Plastics: European Mkts
1997
Figures
Projected
for 2004
Revenue
US $16.32
M
US $73.15
M
Mass
2, 340
tonnes
24, 160
tonnes
N.A. Biodegradable Polymer Market
25
Agricultural Films,
Hygiene-related
products, paper
Coatings, etc.
20
15
10
5
2005 Projection
0
(35 M lbs)
Packaging
Compost
Bags
2000 Figures
(25 M lbs)
Major Barriers for Biodegradable Polymers
Legislation
Landfill taxes
Development of infrastructure to collect and
process biodegradable polymers
Development of universal standards for
biodegradability and compostability
Consumer attitude towards absorbing the cost
Technological improvements to improve price
differentiation.
Drivers for Biodegradable Polymers
Consumers becoming more environmentally
conscious
Prices of biodegradable polymers have
decreased significantly
Technological advances which impact both price
and performance are continually being
implemented.
Exotic Oils with Specialized
Functionality on the Fatty Acids
Vegetable Oils
as Feedstock
for Polymers
Biopolymer leads “naturally” to
Biodegradable Plastics
CO2
Humus
Composting
Restaurant
Waste
Canola
Soil
Agricultural
Feedstock
Tremendous
Economic
Development
Activity
Fast Food
Packaging
Package
Converter
Processing
Biopolymer
Resins
The PetroChemical Industry can
only benefit from this trend
The Kyoto issue is one that is not going to
disappear, regardless of what guise it
takes here on forward.
By partnering with the value-added
agricultural industry, technological
solutions which provide greater
sustainability may be achieved.
Sources of Agricultural Feedstock
Agricultural Polyesters:
– Poly Hydroxy Alkanoates (bacterial, plant)
– Poly Lactic Acid (fermented carbohydrates)
Agricultural Fibres
– Composites with “petro-plastics”
– Crop and forestry fibres
Starch-based polymers
– Corn, barley opportunities, etc.
Protein-based plastics
– Corn, elastin, collagen, spider silk, soy proteins
Lignin-based plastics
Oilseed Plastics
Two Major Avenues for producing
Agricultural Feedstock
Chemical Modification of existing agricultural
commodities or waste:
Chemical Synthesis in the case of oilseeds
Fermentation in the case of Poly Lactic Acid
Bio-engineering of current or new crops to
harvest molecules directly from the plant:
Genetic modification of plants like Canola to produce PHA
Genetic modification of plants like Canola to produce
Ricinoleic Acid
Barriers to Bio-Engineering
Regulations
Cross-Contamination Issues – difficult to
imagine agricultural acreage being devoted to
this in the short term.
Science is long term (only 14% of PHA has been
engineered into Arabidopsis, and Monsanto
through its Biopol operations, dumped this
initiative).
Drivers for Bio-Engineering
Can produce homogenous feedstock
Can remove the need for excessive processing
steps
Can allow food crops to continue to deliver their
main food product, whilst allowing leaves and
other plant parts to deliver plastic molecules.
Barriers to Chemical
Synthesis
Carbon and energy balances of the life-cycle of
such products are difficult to calculate.
Cost
Performance
Solvent-dependent Processes
Drivers for Chemical
Synthesis
Can be achieved in the short-term
Can address issues of renewability in the
short term, and biodegradability in the long
term.
Does not depend on regulations or
agricultural acreage.
By careful use of materials science and
fractionation techniques, can deliver
homogenous feedstock
Provides a roadmap for bio-engineers – what
How can we connect the
plastics markets, through
research, with Canola
production?
Centered at the University of
Alberta is a Major Initiative to
provide synthetic solutions to
this problem
The Alberta Bioplastics Network
Multi-institutional initiative to build a BioPlastics
Industry in Alberta.
University of Alberta (UofA)
Alberta Agriculture, Food and Rural Development (AAFRD)
Alberta Research Council (ARC)
Environment Canada (EC)
Agriculture and Agrifood Canada (AAFC)
Alberta Economic Development (AED)
The Alberta Bioplastics Network
Activity is on four broad nodes:
Fundamental Science
Materials Science, Biotechnology
University of Alberta, Alberta Research Council,
Agriculture and Food Labs (AAFRD)
Scale Up Technologies
Centre for Agri-Industrial Technology (AAFRD)
Alberta Research Council
Marketing and Investment Analysis
AAFRD
AED
AAFC
The Objectives
To develop a bio-polymer industry within
Alberta based on canola and flaxseed oils.
Elements:
1. Develop synthesis reactions to render
canola and flaxseed oils into polymers
2. Investigate relationships between
processing conditions, polymer structure,
physical and chemical properties.
The Objectives (con’t)
3. Scale up processes that are economic and
technically feasible.
4. Investigate and develop investment
opportunities.
5. Evaluate comparative environmental and
energy costs.
6. Develop effective knowledge and technical
transfer processes.
Technology Update
We have produced plastics from Canola Oil
which:
– Are suitable for automobile panels, and moulded
automobile parts such as bumpers and dashboards.
– Are suitable for medical tubing, catheter bags, etc.
– Are suitable for insulation, rust-coatings, and
protective coatings.
– Are suitable for moulded food packaging as well as
packaging film.
– Etc.
– Etc.
Technology Update
We also produce a number of very valuable byproducts, such as 1,3 propanediol.
We are currently commissioning a pilot plant in
Alberta to produce large quantities of our
monomers, for large scale testing on automobile
components.
We expect to have a commercial plant in Alberta
within three years.
Vegetable Oils as Drying Oils
Drying Oils: Flaxseed and Tung
– Iodine Value greater than or equal to 150
– Applications are in paints, resins, coatings, inks.
Semi-Drying Oils: Soybean, Sunflower,
Canola
– Iodine Value between 110 and 150
– Applications in term of drying are limited, although with
the use of some cationic catalysts, soybean oil has been
used as a drying oil
Non-Drying Oils: Palm Oil, Coconut Oil,
Olive Oil
– Iodine Value less than or equal to 100
– Applications are as lubricants, heat transfer fluids, etc.,
i.e. application which absolutely must resist oxidative
reactions.
Drying
Process
=
Polymerization
Process
Rate of Oxidation of Fatty Acids
Found in Canadian Oilseeds
University of Alberta Activities
We have used catalysts to develop faster rates
of drying for Canola Oil.
This can lead to the use of Canola oil as a
source of biodegradable agricultural film.
This can also lead to the use of Canola oil as a
drying oil in paints and varnishes, much like the
way in which linseed oil is currently used.
Vegetable Oils as Lubricants
Advantages
– Excellent boundary lubrication
– Good viscosity and viscosity index
– High Flash Point
– Biodegradable, non-toxic
– Environmentally Friendly, Renewable
Disadvantages
– Poor Oxidative Stability
– Poor Low Temperature Properties
– Lack of a good dynamic viscosity range
– Limited additive technology
Bio-Lubricants
Interest in the use of bio-lubricants has developed in part
due to concerns about sustainability of mineral oils and
for other environmental-related issues.
Europe is at the forefront of development of the global
biolubricant market.
In 1999, the European market volume for biolubricants
was estimated at 102 000 tonnes or roughly 1.9 % of the
total European market for lubricants.
The market value of this was estimated to be $231 M
(U.S.) – source, Frost and Sullivan, 2000.
Sectors
By revenue, the hydraulic fluid market accounts for 2/3 of
the European market
Chainsaw oils are the second largest category by
revenue, at 14%
Short-term forecasts sugest continued growth in the
share of the hydraulic oil market with other products
remaining flat or showing a decline.
It is important to note that biolubricant markets in
Germany, Scandinavia and Alpine Europe resulted from
regulations stemming from environmental concerns of
persistent toxicity of mineral oil lubricants.
Sources
The sources of biolubricants are primarily from
canola and rapeseed, with some amount of flax
also being used.
Fuchs Petrolub in Mannheim, Germany, is the
world’s leader in biolubricants from Canola.
They employ a variety of chemical modification
methods to increase the performance of the
lubricants.
United States
Vegetable oil based lubricants are a very small
part of the U.S. lubricant market- less than one
percent.
Canola oil is the main feedstock, accounting for
85% of the market, with Soybean and Flax oils
making up the balance.
Driving the U.S. markets is an oversupply of
vegetable oils and a slightly higher price
advantage from edible markets.
U.S. Players
Mobil and Pennzoil both offer vegetable oil based
hydraulic fluids
The market is approximately 1 M gallons, approximately
0.4% of the total U.S. hydraulic market.
Crankcase oils in the U.S. are a $2 B market.
An estimated 0.5% of this is vegetable oil based.
However, major growth is predicted in this area as the
cost of petroleum goes up, and issues such as health
(trans, saturates) and production results in an over
supply of vegetable oils.
Modified Oils for Lubricants
Modified Oils for Lubricants
Modified Oils for Lubricants
Modified Oils for Lubricants
University of Alberta Activities
We are well-equipped to chemically
convert, modify, and test lubricant
applications of vegetable oil derivatives
Due to our oilseed lipid focus, we are able
to assess a variety of oilseed sourced byproducts for their suitability as lubricants.
Vegetable Oils as a Source for
Specialty Chemicals
Starting materials
polyols
1,3-propanediol
HO
OH
2,3-butanediol
1,4-butanediol
HO
HO
OH
HO
OH
OH glycerol
OH
Possible products of 1,3propanediol
applications...
Co-monomers in PTT (=
polytrimethyleneterephthalate)
– base for carpets (Corterra®)
– Special-textile fibers (Sorona®)
Co-monomer in polyesters
– binders, adhesives and sealants in industry
and housebuilding, lacquers, casting resins
Two ways to 1,3-propanediol
from Renewable Resources
glycerol from rapeseed
Clostridium
butyricum
sugar
1,3-propanediol
GE
(genetic engineering)
starch
1,3-Propanediol-fermentation
which microorganism?
Clostridium butyricum
Klebsiella pneumoniae,
Citrobacter freundii
 sensitive against oxygen-
 no oxygen problems -
difficult handling
but...
 low risk class (R1/L1)
 ~ 0.50 kg PD per kg Glycerol
robust organism
but...
 potential pathogen (R2/L2)
 ~ 0.40 kg PD per kg Glycerol
use of Clostridium butyricum
is preferable!
Cost comparison for chemical
and biotechnical processes
3000
US$ for
1 mt
of 1,3-PD
2000
raw
material
(1997)
Rohstoffe
(1997)
energy
costs
Energiekosten
direct
costs
direktefixed
Fixkosten
allocated
fixed
sonstige Fixkosten
costs
Abschreibung
depreciation
20 % ROI
price for 20 % ROI
 very low prices for raw
material if glycerol
water is used
 crude oil price for 1997
approx. 18 to 19 US$
per barrel (annual
average)
1000
0
chemical
Shell
Degussa
ethylene oxide acroleine
60,000 mt/a 45,000 mt/a
0.21 Euro
per kg
0.51 Euro 0.26 Euro 0.13 Euro
per kg
per kg
per kg
University of Alberta
process for producing
PDO as a by-product
biotechnical
DuPont
?
glucose
glycerol
25,000 mt/a
25,000 mt/a
ChemSystems, BIOTICA study March 99
data basis 1997 USA
Bio-Based Solvents
Bio-Based Solvents
 Pressure to eliminate widely used solvents such
as:
– Chlorinated Hydrocarbons
– Methyl Ethyl Hydrocarbons
– Methyl Ethyl Ketones
is immense, due to their deleterious effects on
the environment and health.
 This provides market entrance advantages to
bio-based, biodegradable solvents.
Potential U.S. Market for Biobased
Solvents
300
250
200
150
100
50
Biobased
Replacement
Market ($M/yr)
0
Aqueous
Cleaners
Semiaqueous
Cleaners
Alternative
Solvents
Total
Current Solvent
Market ($M/yr)
SOURCE: Technical Insights Alert, SEPTEMBER 06, 2002, Frost and Sullivan
Target Areas
The big markets which are most likely to be
replaced by bio-based solvents are:
– Industrial Cleaners
– Carrier solvents for adhesives and coatings
It is estimated (Industrial Bioprocessing, 2002)
that between 2005 and 2010, biobased solvents
will replace 50% of the solvents currently used in
these applications.
Current Players
Polystyrene foam is widely used in packaging,
containers, household wares, boats, water coolers, and
a variety of other uses.
Polystyrene does not readily degrade and generally
cannot be reused.
Researchers at the University of Missouri-Rolla have
developed a use for soy and vegetable oil fatty acid
methyl esters in dissolving polystyrene foam, so that it
can be more usable in other resins, and coatings such
as fiberglass.
Current Players
Ethyl lactate is currently produced in the
US by ADM and marketed by Vertec
BioSolvents Inc. Current bulk market price
is about $1/lb. It is sold as a cleaner for
industrial inks, a degreaser for motors and
other machinery, and a number of other
uses.
Current Players
D-Limonene is a well-established commercial
product. Current annual usage in the US is
about 50 million lb. It has been down as low as
$0.25/lb.
It is a nonpolar solvent and so it does not mix
with water. It has many uses, but the most
important has been in cleaning products, both
industrial and household/institutional
preparations. It can replace a wide variety of
organic solvents.
Current Players
Methyl soyate is the cheapest bio-based solvent, now
selling for about $0.40/lb in bulk. In addition to its
industrial uses, it has a big potential market as biodiesel
fuel. It is produced by transesterification of methanol and
soybean oil, using sodium hydroxide as a catalyst and
generating glycerol as a byproduct. Nine companies
manufacture it in the United States.
it is not miscible with water, although it can be formulated
into water-miscible cleaners not only with ethyl lactate
but with detergents. It is readily biodegradable and has
low toxicity and a high flash point. It generates lower
levels of volatile organic compounds (VOCs), which is a
plus for reducing air pollution.
Edible Solvents
As mounting pressures are brought to
bear on the edible oil industry in terms of
trans fatty acid content and saturate
content, biotechnology and innovative
processing will be required to play
increasing roles.
Edible solvents for fractionation and
chromatographic application will become
of maximum importance.
University of Alberta Activities
We are developing synthetic methods on canola, and
flax as well as tall oil to create solvents competitive with
methyl soyate.
In particular, we have been using the waste streams
from Canola, Flax processing as a source of cheaper
raw materials.
We are also experimenting with edible bio-based
solvents specifically for the solvent-fraction of edible oils.
We have developed considerable expertise around the
use of edible solvents for novel chromatographic
separations of edible oils.
Making Biodiesel is Simple
Biodiesel
This is a common
sign in Germany
Biodiesel is not only
readily available, it is
cheaper than
Petroleum Diesel
because of the high
taxes levied against
Petroleum Products.
Personal Care and Cosmetics
Global Sales of cosmetics and toiletries (C&T)
reached $100 Billion in 2000 and is projected to
increase to $120 Billion by 2005.
The U.S. dominates worldwide C&T markets at
$25 Billion, followed by Europe and Japan.
The U.S. market for specialty chemicals used in
finished C & T products was approximately $4
Billion in 2000, and is projected to grow at a rate
higher than finished product projections.
Top 10 U.S. Companies in household
and personal products Industry
25
Billions of Dollars
20
15
10
5
0
Proctor Colgate
Estee
and
Palmolive Lauder
Gamble
SC
Johnson
Avon
Johnson
Diversey
Clorox
Alberto
Culver
Ecolab
Limited
Brands
Opportunities
Natural, plant derived ingredients are most
popular with consumers, with innovations
in extraction, processing, and chemical
modifications expected to drive growth in
this area.
Of particular importance to the lipids
industry are fatty acids and derivatives,
alpha hydroxy acids, wax-replacements,
gel replacements, and glycerol-based
compounds
Current Entrants
ADM and Cargill are both very active in this
area, using SOY as a source:
–
–
–
–
Petrolatums and waxes
Vegetable hard fats for aromatherapy candles
Paraffin-replacements in the packaging industry
Waxes as replacements for beeswax and carnauba
wax in cosmetics
– Replacement of castor oil by modified soybean oil in
cosmetics.
University of Alberta Activities
We have developed both soy based and canola based
paraffin-replacement waxes.
We have developed a number of unique oil-sourced
chemicals ideal for emulsifiers in cosmetic applications
We have developed methods to modify canola and flax
oils to replace castor oil in cosmetic applications
Conclusions
The North American markets for edible oils is not
increasing sufficiently to allow for significant growth in
acreage of canola.
Canola acreage is significantly below historical norms in
Western Canada.
By taking advantage of technological advances, we can
access industrial markets, and by protecting our ability to
supply these markets, we can command a premium
price for canola and increase acreage.
The environmental benefits are obvious and imperative.
Acknowldegements
Ed Phillipchuk, Connie Phillips, AAFRD
Processing Division, CAIT
Donna Day, ARC
Ed Condrotte, AED
Narine Gurprasad, ENV. CAN.
Brenda McIntyre, AAFC
Peter Sporns, Phillip Choi, Xiahua Kong, Rysard
Nowak, Andrew Heberling, Marc Boodhoo, UofA
Dharma Kodali, Cargill
AVAC, NSERC, ACIDF, AARI, ACPC, Bunge
Foods, ADM, Canbra Foods.