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

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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
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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
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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.

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Modified Oils for Lubricants
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Modified Oils for Lubricants
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Modified Oils for Lubricants
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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.