1. Industrial Uses of Vegetable Oils
Dr. Suresh S. Narine
Director, Alberta Bioplastics Network
Professor, University of Alberta

2. Feedstock for the Chemical Industry
renewable
resources
coal
fossil oil, gas
1850
1900
1950
2000
2050
year

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 1012 biomass paper starch plastics 1010 108 106
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.
200 bill. t
300 mio. t
8 mio. t
180 mio. t
1012
biomass
paper
starch
plastics
1010
108
106
104
102

6. Crude oil vs. renewable resources
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
rain
sun CO 2

9. Annual Production of Lipids

10. 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.

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 PUFA’s, 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 – 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

18. Unsaturated Fatty Acids Present in Canada’s Oilseeds

19. Exotic Oils with Specialized Functionality on the Fatty Acids

20. Properties / Functionality / Value
Markets
Value Creation
Applications,
Functionalities
Chemical
Structure and
Composition
Physical
Structure and
Properties 8

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 world’s 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 1997 Figures
Projected for 2004
Revenue
US $23 M
US $187 M
Mass
20 M lbs
167 M lbs

29. 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

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
Processing
Biopolymer
Resins
Package
Converter
Fast Food
Packaging
Restaurant
Waste
Composting
Humus
CO2
Tremendous
Economic
Development
Activity
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 (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.

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.

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 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 world’s 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.

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 materials polyols
1,3-propanediol
2,3-butanediol
1,4-butanediol
glycerol 2

69. Possible products of 1,3-propanediol 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 3

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-fermentation which 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 butyricum is 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$ for 1 mt of 1,3-PD
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)
University of Alberta
process for producing
PDO as a by-product
0.21 Euro per kg
0.51 Euro per kg
0.26 Euro
per kg
0.13 Euro per kg
chemical
biotechnical
Shell Degussa DuPont ?
ethylene oxide acroleine glucose glycerol
60,000 mt/a 45,000 mt/a 25,000 mt/a ,000 mt/a
ChemSystems, BIOTICA study March 99 data 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 (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.

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.