Coating Resins on Biobased Raw Materials Reality or
Coating Resins on Bio-based Raw Materials Reality or Distant Future? Tosko Misev, Dirk Stanssens DSM Resins bv, DSM Innovation Center DSM Coating Resins 2007/presentations/external/NVVT
Introduction 1 • Since existence of human beings, people have always used paints to express themselves • Early paints based on natural products were of inferior quality • Non-natural products were introduced to improve properties • alkyds, acrylics, polyurethanes, polyesters, epoxies, amino resins • Now we see a reverse movement • • • Oil reserves are limited and have a long cycle time (100 mln years) Natural renewable resources are abundantly available with cycle time of 1 year White biotechnology is developing with increasing speed DSM Coating Resins 2007/presentations/external/NVVT
What is white (industrial) biotechnology? Industrial applications Market penetration Biofeedstock Replacement of fossil feedstock by sugar and biomass Pharma (red) biotech Ag (green) biotech Bioprocesses White Biotech Use of natures toolbox for industrial processes (e. g. , enzymes, bacteria) Bioproducts Current and new bio based products (e. g. , fuel, materials) Bioremediation Today Source: Mc. Kinsey DSM Coating Resins 2007/presentations/external/NVVT Time Use of biological processes for environ mental cleanup (e. g. , waste water, oil pests)
White (industrial) biotechnology 3 Biotechnology: The use of nature’s toolbox for industrial processes Feedstock Fermentable sugars Bioprocess (cells / enzymes) Products Specialties Materials Base chemicals Fuel DSM Coating Resins 2007/presentations/external/NVVT
4 Basic feedstock price developments Over the last 10 years oil and sugar prices have followed quite opposite trends 250% Price CAGR 9, 1% 200% Crude oil price 150% 100% Raw sugar price (*) 50% CAGR -3, 4% DSM Coating Resins 2007/presentations/external/NVVT 04 02 01 20 00 99 98 97 96 95 19 9 4 0% 03 Year Feedstock prices are expected to decrease further on with the conversion of wood and agricultural waste into fermentable sugar
Resin Raw Materials Existing raw materials of petrochemical origin DSM Coating Resins 2007/presentations/external/NVVT 5
6 Polycondensation Resins Mineral oil - Natural gas Reformate Propylene Iso-or –nbutyraldehyde o, m, p-xylene Methanol Formaldehyde Ethanol Propylene Acetaldehyde Allyl Chloride Epichlorohydrine Phthalic acids 500 k. T Neopentyl Glycol Trimethylol Propane Pentaerytritol 200 k. T 150 k. T Polyesters DSM Coating Resins 2007/presentations/external/NVVT Alkyds 1800 k. T Glycerol
7 Polymerization Resins Mineral oil - Natural gas Propylene Alcohols Acetone Benzene Acetone cyanhydrine Acrolein HCN Ethylene Ethylbenzene Acetic acid H 2 SO 4 Acrylic acid Methacrylic esters Acrylic esters Styrene Acrylics, Styrene/Acrylics and Vinyl Acetate Copolymers 3200 k. T DSM Coating Resins 2007/presentations/external/NVVT Methanol Vinyl acetate
8 Upcoming bio-based building blocks DSM Coating Resins 2007/presentations/external/NVVT
Building Blocks Through White Biotechnology Biological Feedstock 9 Sugar crops 20 billion $ Oil crops Pharma intermediates Biomass (straw, switchgrass) Amino acids, Vitamins Citric acid, Oleochemicals Biotechnological and/or Conventional Processes Industrial Products DSM Coating Resins 2007/presentations/external/NVVT Fermentation Bio-catalysis Flavors, fragrances Enzymes Bio-fuel 1 billion $ Biomaterials Polylactic acid Nutritional Ingredients Glycols Specialty Chemicals Ethylene Commodity Chemicals Acrylic acid
10 What can we count on ? Sugar crops Biological Feedstock Oil crops Sugars Basic raw materials Vegetable oils Polyols Biotechnological Polyacids and/or Monomers Conventional Processes Polyesters Alkyd Resins Polyurethanes Epoxy Resins Acrylic resins DSM Coating Resins 2007/presentations/external/NVVT Coating Resins Polyols Fatty Acids Polyurethanes Alkyd Resins Polyamides Epoxy Esters
What we already use 11 Vegetable oils: Glycerol: Renewable Non toxic Biodegradable Full environmental acceptance Use: Alkyd resins, Polyesters DSM Coating Resins 2007/presentations/external/NVVT
What is already available in the market Soyol™ “biobased” polyols: OH functionality: 2 – 3 Molecular weight: 1000 -2000 Uses: • Seating foam furniture • Foam insulation • Carpet backing • Shoe soles • Roof coatings. Effects: • Cost less than the petroleum polyols they replace. • Plant based, annually renewable resources. • Reduce demand dependence on limited petroleum reserves. DSM Coating Resins 2007/presentations/external/NVVT 12
13 What we can expect to come ? DSM Coating Resins 2007/presentations/external/NVVT
What we expect to come 14 O Succinic Acid: C 4 H 6 O 4 One of the top 12 chemicals from biomass OH HO O Potential use: • Diacid for polyesters • Diacid for alkyds • Intermediate for manufacturing of: • Maleic acid (polyesters) • Butanediol (polyesters) • Diaminobutane (polyamides) • Adipic acid (polyesters, polyamides) DSM Coating Resins 2007/presentations/external/NVVT
Interrelation between the most relevant 1, 4 -bifunctional C 4 building blocks. 15 The reactions from left to right require reduction (so the reverse require oxidation), whereas the ring-closures are dehydratation reactions. HOOC- CH=CH-COOH HOOC-CH 2 -CH 2 OH HOCH 2 -CH 2 OH Succinic acid 4 - Hydroxybutanoic acid 1, 4 - Butanediol Fumaric/Maleic acid Maleic anhydride O= O =O Succinic anhydride O= DSM Coating Resins 2007/presentations/external/NVVT O =O gamma- Butyrolactone O =O Tetrahydrofuran O
What we expect to come 16 Isosorbide: C 6 H 10 O 4 Itaconic Acid: C 5 H 6 O 4 Via dehydration of sorbitol Via fungal fermentation of glucose OH O O OH HO O CH 2 HO OH Difunctional polyol for: • Polyesters • Polycarbonates • Polyamides • Polyurethanes • Plasticizers Commercial quantities: 2008/2009 DSM Coating Resins 2007/presentations/external/NVVT O 3 -Hydroxy Propionic Acid: C 3 H 6 O 2 Potential use: • Polymerization monomer • (Meth)acrylic esters alternative • Hydrogels for superabsorption Commercial quantities: 2007 Feedstock for: • Acrylonitrile • Acrylic Acid • Acrylamide Technically feasible, but not yet cost effective
Summary of existing and potential opportunities Acids: Polyols: Monomers: Fatty acids Glycerol Itaconic acid & esters Succinic acid Sorbitol Acrylic acid & esters Maleic acid Isosorbide Acrylonitrile Fumaric acid Butane diol Acrylamide Adipic acid Polycondensation resins Alkyd resins Polyesters Polyurethanes DSM Coating Resins 2007/presentations/external/NVVT Polymerization resins Acrylic resins Alternatives to acrylic resins 17
Can the prices go even further down? Energy crops: Miscanthus -1 years growth without replanting! 20 tons/acre? (www. bical. net) 10 -30 tons/acre (www. aces. uiuc. edu/DSI/MASGC. pdf) DSM Coating Resins 2007/presentations/external/NVVT 18
19 Biomass Will Make a Difference …a member of OPEC? ! Turning South Dakota into… Today Tomorrow 44 Million Tons/acre 5 15 Gallons/ton 25 80 Thousand barrels/day 857 3, 429 Farm acres DSM Coating Resins Source: 2007/presentations/external/NVVT Ceres Company Presentation Thousand barrels/day Saudi Arabia Iran South Dakota Kuwait Venezuela UAE Nigeria Iraq Libya Algeria Indonesia Qatar 9, 400 3, 900 3, 429 2, 600 2, 500 2, 200 1, 700 1, 650 1, 380 925 800
20 Biomass Will Make a Difference The chemical industry is working hard to use ligno-cellulose as a feedstock • Ligno cellulose is much more available than e. g. crops. • A whole plant can be used. • Use of land not suitable for food or feed ( prairies-USA, pampas-Argentina) • No competition between making chemicals and supplying food. • Selection andor genetically modified plants that grow very fast. • Environmentally friendly cultivation; plants that do not need fertilizers The next step: bio-refinery Switch-grass cultivation Extraction of valuable products (proteins) Chemical building blocks Rest for Bio -fuel The biomass as a feedstock will further reduce the prices of the chemicals DSM Coating Resins 2007/presentations/external/NVVT
21 Conclusion Mineral Oil Sugars USD/barrel USD/kg Vegetable oils USD/kg • Oil reserves are limited, not renewable. Oil price still volatile and has tripled in the past five years • Sugars/vegetable oils: Costs decreased with a tendency to stabilize. • Further progress in white biotechnology offers solutions based on even cheaper biomass feedstock Coating Resins on Bio-based Raw Materials: Reality or Distant Future? Not yet but will be soon DSM Coating Resins 2007/presentations/external/NVVT
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