Presentation on theme: "Dr. Suresh S. Narine Director, Alberta Bioplastics Network Professor, University of Alberta Industrial Uses of Vegetable Oils."— Presentation transcript:
Dr. Suresh S. Narine Director, Alberta Bioplastics Network Professor, University of Alberta Industrial Uses of Vegetable Oils
Feedstock for the Chemical Industry renewable resources coal fossil oil, gas 18501900195020002050 year
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 Plants are a gigantic sun reactor. Of the daily energy from sun of 1.5 x 10 22 J, only 4 x 10 18 J (0.008%) are use to build up biomass.Only approx 7% of the biomass is used by mankind. 7% utilized 93% unutilized
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. Polymers from Plants 200 bill. t 300 mio. t 8 mio. t 180 mio. t 0 10 12 biomasspaperstarchplastics 10 10 8 10 6 10 4 10 2
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. *Sorona TM - stretch fibre made from corn - Dupont Woodstalk TM - wheat straw wood alternative - Dow BioProducts Ltd. NatureWorks TM - 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 sunrain CO 2
Annual Production of Lipids
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 – Lubes1 X / kg –Plant Oils 1 – 2 X / kg –Synthetic Base Stock – Lubes3 – 8 X / kg –Resins – Coatings:3 – 6 X / kg –BioBased Synthetic Esters2 – 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 Applications, Functionalities Markets Value Creation Physical Structure and Properties Chemical Structure and Composition
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
North American Plastics Production Strong Growth
Product Production Index Source: Federal Reserve Board
Sources of Plastics 99.5% of current plastics are made from fossil fuel derivatives PolyethylenePolystyrene 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.”
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 RenewabilitySustainability Environmental Concerns –Biodegradability –Recyclability Economic Continuity Product Performance Etc.
Markets 1997 Figures Projected for 2004 Revenue US $23 M US $187 M Mass 20 M lbs 167 M lbs Biodegradable Plastics: US + Japanese Mkts
Markets 1997 Figures Projected for 2004 Revenue US $16.32 M US $73.15 M Mass 2, 340 tonnes 24, 160 tonnes Biodegradable Plastics: European Mkts
N.A. Biodegradable Polymer Market Millions of lbs Packaging Compost Bags Agricultural Films, Hygiene-related products, paper Coatings, etc. (35 M lbs) (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 Canola Soil Agricultural Feedstock Processing Biopolymer Resins Package Converter Fast Food Packaging Restaurant Waste Composting Humus CO2 Tremendous Economic Development Activity
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.
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. CostPerformance 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 molecules are worth growing in plants.
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 AAFRDAEDAAFC
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.
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.
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 $2 B market. An estimated 0.5% of this is vegetable oil based. However, major growth is predicted in this area as the cost of petroleum goes up, and issues such as health (trans, saturates) and production results in an over supply of vegetable oils.
Modified Oils for Lubricants
University of Alberta Activities We are well-equipped to chemically convert, modify, and test lubricant applications of vegetable oil derivatives Due to our oilseed lipid focus, we are able to assess a variety of oilseed sourced by- products for their suitability as lubricants.
Vegetable Oils as a Source for Specialty Chemicals
Possible products of 1,3- propanediol applications... Co-monomers in PTT (= polytrimethyleneterephthalate) –base for carpets (Corterra ® ) –Special-textile fibers (Sorona ® ) Co-monomer in polyesters –binders, adhesives and sealants in industry and housebuilding, lacquers, casting resins
Two ways to 1,3-propanediol from Renewable Resources ? starch sugar 1,3-propanediol GE (genetic engineering) Clostridium butyricum glycerol from rapeseed
1,3-Propanediol-fermentation which microorganism? sensitive against oxygen- difficult handling but... low risk class (R1/L1) ~ 0.50 kg PD per kg Glycerol no oxygen problems - robust organism but... potential pathogen (R2/L2) ~ 0.40 kg PD per kg Glycerol Clostridium butyricumKlebsiella pneumoniae, Citrobacter freundii use of Clostridium butyricum is preferable!
Cost comparison for chemical and biotechnical processes ChemSystems, BIOTICA study March 99 data basis 1997 USA very low prices for raw material if glycerol water is used crude oil price for 1997 approx. 18 to 19 US$ per barrel (annual average) US$ for 1 mt of 1,3-PD Shell Degussa DuPont ? ethylene oxide acroleine glucose glycerol 60,000 mt/a 45,000 mt/a 25,000 mt/a 25,000 mt/a 0.51 Euro per kg chemical biotechnical 0.26 Euro per kg 0.13 Euro per kg 0.21 Euro per kg raw material (1997) energy costs direct fixed costs allocated fixed costs depreciation price for 20 % ROI University of Alberta process for producing PDO as a by-product
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.
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
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.