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Biodegradable Polymers from Canola and Flaxseed Oils

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Title: Biodegradable Polymers from Canola and Flaxseed Oils


1
Industrial Uses of Vegetable Oils
Dr. Suresh S. Narine Director, Alberta
Bioplastics Network Professor, University of
Alberta
2
Feedstock for the Chemical Industry
3
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?

4
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.
5
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.
6
Crude oil vs. renewable resources
crude oil
products Monomers Cosmetics lubricants fumaric
acid itaconic acid aconitic acid succinic
acid 2,3-butanediol 1,3-propanediol
costs?
renewable resources
sugar
costs?
starch
Vegetable Oils
7
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.

8
The Chemical Factory Moves into the Plant
sun
rain
CO
2
9
Annual Production of Lipids
10
Canadian Production
  • Canola
  • Canada produces 20 of the worlds edible oil
    production, mostly as Canola Oil
  • Saskatchewan produces 50 of Canadas 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.

11
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 PUFAs, edible use is limited, primarily due
    to the high reactivity of the oil with oxygen.

12
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

13
Marketing Advantage
  • Average Relative Price (Range)
  • Petroleum base stock Lubes 1 X / kg
  • Plant Oils 1 2 X / kg
  • Synthetic Base Stock Lubes 3 8 X / kg
  • Resins Coatings 3 6 X / kg
  • BioBased Synthetic Esters 2 5 X / kg

14
Source Dharma Kodali, Cargill Inc.
15
Source Dharma Kodali, Cargill Inc.
16
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

17
(No Transcript)
18
Unsaturated Fatty Acids Present in Canadas
Oilseeds
19
Exotic Oils with Specialized Functionality on the
Fatty Acids
20
Properties / Functionality / Value
Markets
Value Creation
Applications, Functionalities
Physical Structure and Properties
Chemical Structure and Composition
21
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

22
North American Plastics Production Strong Growth
23
Product Production Index
Source Federal Reserve Board
24
Sources of Plastics
  • 99.5 of current plastics are made from fossil
    fuel derivatives
  • Polyethylene
  • Polystyrene
  • Majority of such Petro-Plastics are
    non-biodegradable.
  • Some exceptions do exist, e.g. PolyCaprolactone
  • Petro-Plastics are produced at large energy
    costs, due to the need for cracking.

25
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 worlds
    supply of petroleum!

26
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

27
A cluttered way forward
  • Renewability
  • Sustainability
  • Environmental Concerns
  • Biodegradability
  • Recyclability
  • Economic Continuity
  • Product Performance
  • Etc.

28
Markets
Biodegradable Plastics US Japanese Mkts
29
Markets
Biodegradable Plastics European Mkts
30
N.A. Biodegradable Polymer Market
Agricultural Films, Hygiene-related products,
paper Coatings, etc.
Millions of lbs
(35 M lbs)
Packaging
Compost Bags
(25 M lbs)
31
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.

32
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.

33
Exotic Oils with Specialized Functionality on the
Fatty Acids
34
Vegetable Oils as Feedstock for Polymers
35
Biopolymer leads naturally to Biodegradable
Plastics
Canola Soil
Agricultural Feedstock
36
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.

37
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

38
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

39
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).

40
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.

41
Barriers to Chemical Synthesis
  • Carbon and energy balances of the life-cycle of
    such products are difficult to calculate.
  • Cost
  • Performance
  • Solvent-dependent Processes

42
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
    molecules are worth growing in plants.

43
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

44
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)

45
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

46
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.

47
The Objectives (cont)
  • 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.

48
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.

49
Technology Update
  • We also produce a number of very valuable
    by-products, 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.

50
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.

51
Drying Process Polymerization Process
52
Rate of Oxidation of Fatty Acids Found in
Canadian Oilseeds
53
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.

54
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

55
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.

56
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.

57
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
    worlds leader in biolubricants from Canola.
  • They employ a variety of chemical modification
    methods to increase the performance of the
    lubricants.

58
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.

59
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.

60
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61
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62
Modified Oils for Lubricants
63
Modified Oils for Lubricants
64
Modified Oils for Lubricants
65
Modified Oils for Lubricants
66
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 by-products
    for their suitability as lubricants.

67
Vegetable Oils as a Source for Specialty Chemicals
68
Starting materialspolyols
1,3-propanediol
2,3-butanediol
1,4-butanediol
glycerol
69
Possible products of 1,3-propanediolapplications.
..
  • Co-monomers in PTT ( polytrimethyleneterephthalat
    e)
  • base for carpets (Corterra)
  • Special-textile fibers (Sorona)
  • Co-monomer in polyesters
  • binders, adhesives and sealants in industry and
    housebuilding, lacquers, casting resins

70
Two ways to 1,3-propanediol from Renewable
Resources
glycerol from rapeseed
Clostridium butyricum
?
sugar
1,3-propanediol
GE (genetic engineering)
starch
71
1,3-Propanediol-fermentationwhich microorganism?
Clostridium butyricum
Klebsiella pneumoniae, Citrobacter freundii
  • sensitive against oxygen-difficult handling
  • but...
  • low risk class (R1/L1)
  • 0.50 kg PD per kg Glycerol
  • no oxygen problems - robust organism
  • but...
  • potential pathogen (R2/L2)
  • 0.40 kg PD per kg Glycerol

use of Clostridium butyricumis preferable!
72
Cost comparison for chemical and biotechnical
processes
raw material (1997) energy costs direct fixed
costs allocated fixed costs depreciation price
for 20 ROI
US for1 mtof 1,3-PD
  • very low prices for raw material if glycerol
    water is used
  • crude oil price for 1997approx. 18 to 19 US per
    barrel (annual average)

University of Alberta process for producing PDO
as a by-product
0.51 Europer kg
0.26 Euro per kg
0.13 Europer kg
0.21 Europer kg
chemical
biotechnical
Shell Degussa DuPont
?
ethylene oxide acroleine glucose
glycerol
60,000 mt/a 45,000 mt/a 25,000 mt/a
25,000 mt/a
ChemSystems, BIOTICA study March 99data basis
1997 USA
73
Bio-Based Solvents
74
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.

75
SOURCE Technical Insights Alert, SEPTEMBER 06,
2002, Frost and Sullivan
76
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.

77
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.

78
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.

79
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.

80
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.

81
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.

82
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.

83
Making Biodiesel is Simple
84
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.

85
Personal Care and Cosmetics
  • Global Sales of cosmetics and toiletries (CT)
    reached 100 Billion in 2000 and is projected to
    increase to 120 Billion by 2005.
  • The U.S. dominates worldwide CT 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.

86
Top 10 U.S. Companies in household and personal
products Industry
87
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

88
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.

89
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

90
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.

91
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.
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