Presentation on theme: "Industrial Uses of Vegetable Oils"— Presentation transcript:
1 Industrial Uses of Vegetable Oils Dr. Suresh S. NarineDirector, Alberta Bioplastics NetworkProfessor, University of Alberta
2 Feedstock for the Chemical Industry renewableresourcescoalfossil oil, gas18501900195020002050year
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 photosynthesisFossil Fuels are just reserves of photosyntheticMaterial 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%unutilized7%utilizedPlants 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 upbiomass.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 producedworld wide.The amount of paper produced world wide is about twice as big as the producedamount of plastics.200 bill. t300 mio. t8 mio. t180 mio. t1012biomasspaperstarchplastics1010108106104102
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 - DupontWoodstalkTM - wheat straw wood alternative - Dow BioProducts Ltd.NatureWorksTM - carpets, shirts, bottles, cups, films, etc. - Cargill Dow LLCMilligan 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 PlantrainsunCO2
10 Canadian Production Canola Canada produces 20% of the world’s edible oil production, mostly as Canola OilSaskatchewan produces 50% of Canada’s productionManitoba 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 ProductionFlaxseed is the first oilseed to be widely grown in Western CanadaOnly 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 VarnishesAs lubricantsAs Feedstock for Specialty ChemicalsAs BiodieselAs ingredients for cosmetics
13 Marketing Advantage Average Relative Price (Range) Petroleum base stock – Lubes 1 X / kgPlant Oils – 2 X / kgSynthetic Base Stock – Lubes 3 – 8 X / kgResins – Coatings : 3 – 6 X / kgBioBased Synthetic Esters 2 – 5 X / kg
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
22 North American Plastics Production Strong Growth
23 Product Production Index Source: Federal Reserve Board
24 Sources of Plastics99.5% of current plastics are made from fossil fuel derivativesPolyethylenePolystyreneMajority of such “Petro-Plastics” are non-biodegradable.Some exceptions do exist, e.g. PolyCaprolactonePetro-Plastics are produced at large energy costs, due to the need for “cracking.”
25 Plastic ProductionApproximately 180 Million tonnes of plastic produced annuallyIt takes approximately 141 MJ/kg of energy to produce Nylon, and 76 MJ/kg of energy to produce amorphous PETTherefore 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 SourcesEnvironmental and health concerns.Consumer attitudes.Cost of “cheap” feedstocks.Carbon CreditsGreenhouse Gas ReductionCriteria Air Contaminant Reduction
27 A cluttered way forward RenewabilitySustainabilityEnvironmental ConcernsBiodegradabilityRecyclabilityEconomic ContinuityProduct PerformanceEtc.
28 Markets Biodegradable Plastics: US + Japanese Mkts 1997 Figures Projected for 2004RevenueUS $23 MUS $187 MMass20 M lbs167 M lbs
29 Markets Biodegradable Plastics: European Mkts 1997 Figures Projected for 2004RevenueUS $16.32 MUS $73.15 MMass2, 340tonnes24, 160
30 N.A. Biodegradable Polymer Market Agricultural Films,Hygiene-relatedproducts, paperCoatings, etc.Millions of lbs(35 M lbs)PackagingCompostBags(25 M lbs)
31 Major Barriers for Biodegradable Polymers LegislationLandfill taxesDevelopment of infrastructure to collect and process biodegradable polymersDevelopment of universal standards for biodegradability and compostabilityConsumer attitude towards absorbing the costTechnological improvements to improve price differentiation.
32 Drivers for Biodegradable Polymers Consumers becoming more environmentally consciousPrices of biodegradable polymers have decreased significantlyTechnological advances which impact both price and performance are continually being implemented.
33 Exotic Oils with Specialized Functionality on the Fatty Acids
35 Biopolymer leads “naturally” to Biodegradable Plastics ProcessingBiopolymerResinsPackageConverterFast FoodPackagingRestaurantWasteCompostingHumusCO2TremendousEconomicDevelopmentActivityCanolaSoilAgriculturalFeedstock
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.
38 Two Major Avenues for producing Agricultural Feedstock Chemical Modification of existing agricultural commodities or waste:Chemical Synthesis in the case of oilseedsFermentation in the case of Poly Lactic AcidBio-engineering of current or new crops to harvest molecules directly from the plant:Genetic modification of plants like Canola to produce PHAGenetic modification of plants like Canola to produce Ricinoleic Acid
39 Barriers to Bio-Engineering RegulationsCross-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 feedstockCan remove the need for excessive processing stepsCan 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.CostPerformanceSolvent-dependent Processes
42 Drivers for Chemical Synthesis Can be achieved in the short-termCan 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 feedstockProvides 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 ScienceMaterials Science, BiotechnologyUniversity of Alberta, Alberta Research Council, Agriculture and Food Labs (AAFRD)Scale Up TechnologiesCentre for Agri-Industrial Technology (AAFRD)Alberta Research CouncilMarketing and Investment AnalysisAAFRDAEDAAFC
46 The ObjectivesTo 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 polymers2. 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 UpdateWe 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 TungIodine Value greater than or equal to 150Applications are in paints, resins, coatings, inks.Semi-Drying Oils: Soybean, Sunflower, CanolaIodine Value between 110 and 150Applications in term of drying are limited, although with the use of some cationic catalysts, soybean oil has been used as a drying oilNon-Drying Oils: Palm Oil, Coconut Oil, Olive OilIodine Value less than or equal to 100Applications are as lubricants, heat transfer fluids, etc., i.e. application which absolutely must resist oxidative reactions.
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 AdvantagesExcellent boundary lubricationGood viscosity and viscosity indexHigh Flash PointBiodegradable, non-toxicEnvironmentally Friendly, RenewableDisadvantagesPoor Oxidative StabilityPoor Low Temperature PropertiesLack of a good dynamic viscosity rangeLimited additive technology
55 Bio-LubricantsInterest 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 SectorsBy revenue, the hydraulic fluid market accounts for 2/3 of the European marketChainsaw 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 SourcesThe 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 StatesVegetable 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. PlayersMobil and Pennzoil both offer vegetable oil based hydraulic fluidsThe market is approximately 1 M gallons, approximately 0.4% of the total U.S. hydraulic market.Crankcase oils in the U.S. are a $2 B market.An estimated 0.5% of this is vegetable oil based.However, major growth is predicted in this area as the cost of petroleum goes up, and issues such as health (trans, saturates) and production results in an over supply of vegetable oils.
66 University of Alberta Activities We are well-equipped to chemically convert, modify, and test lubricant applications of vegetable oil derivativesDue to our oilseed lipid focus, we are able to assess a variety of oilseed sourced by-products for their suitability as lubricants.
67 Vegetable Oils as a Source for Specialty Chemicals
69 Possible products of 1,3-propanediol applications... Co-monomers in PTT (= polytrimethyleneterephthalate)base for carpets (Corterra®)Special-textile fibers (Sorona®)Co-monomer in polyestersbinders, adhesives and sealants in industry and housebuilding, lacquers, casting resins3
70 Two ways to 1,3-propanediol from Renewable Resources glycerol from rapeseedClostridiumbutyricum?sugar1,3-propanediolGE(genetic engineering)starch
71 1,3-Propanediol-fermentation which microorganism? Clostridium butyricumKlebsiella pneumoniae,Citrobacter freundiisensitive against oxygen-difficult handlingbut...low risk class (R1/L1)~ 0.50 kg PD per kg Glycerolno oxygen problems - robust organismbut...potential pathogen (R2/L2)~ 0.40 kg PD per kg Glyceroluse of Clostridium butyricum is preferable!
72 Cost comparison for chemical and biotechnical processes raw material (1997)energy costsdirect fixed costsallocated fixed costsdepreciationprice for 20 % ROIUS$ for 1 mt of 1,3-PDvery low prices for raw material if glycerol water is usedcrude oil price for 1997 approx. 18 to 19 US$ per barrel (annual average)University of Albertaprocess for producingPDO as a by-product0.21 Euro per kg0.51 Euro per kg0.26 Europer kg0.13 Euro per kgchemicalbiotechnicalShell Degussa DuPont ?ethylene oxide acroleine glucose glycerol60,000 mt/a 45,000 mt/a 25,000 mt/a ,000 mt/aChemSystems, BIOTICA study March 99 data basis 1997 USA
74 Bio-Based Solvents Pressure to eliminate widely used solvents such as: Chlorinated HydrocarbonsMethyl Ethyl HydrocarbonsMethyl Ethyl Ketonesis 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 AreasThe big markets which are most likely to be replaced by bio-based solvents are:Industrial CleanersCarrier solvents for adhesives and coatingsIt 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 PlayersPolystyrene 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 PlayersEthyl 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 PlayersD-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 PlayersMethyl 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 SolventsAs 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.
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 OpportunitiesNatural, 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 EntrantsADM and Cargill are both very active in this area, using SOY as a source:Petrolatums and waxesVegetable hard fats for aromatherapy candlesParaffin-replacements in the packaging industryWaxes as replacements for beeswax and carnauba wax in cosmeticsReplacement 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 applicationsWe have developed methods to modify canola and flax oils to replace castor oil in cosmetic applications
90 ConclusionsThe 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.