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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?
2
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: McKinsey
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%
0%
DSM Coating Resins
2007/presentations/external/NVVT
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 kT
Neopentyl
Glycol
Trimethylol
Propane
Pentaerytritol
200 kT
150 kT
Polyesters
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Alkyds
1800 kT
Glycerol
7
Polymerization Resins
Mineral oil - Natural gas
Propylene
Alcohols
Acetone
Benzene
Acetone
cyanhydrine
Acrolein
HCN
Ethylene
Ethylbenzene
Acetic acid
H2SO4
Acrylic acid
Methacrylic
esters
Acrylic esters
Styrene
Acrylics, Styrene/Acrylics and Vinyl Acetate Copolymers
3200 kT
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
Flavors, fragrances
Fermentation
Enzymes
Bio-catalysis
Conventional Processes
Industrial Products
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Bio-fuel
1 billion $
Biomaterials
Polylactic acid
Nutritional Ingredients
Glycols
Specialty Chemicals
Ethylene
Commodity Chemicals
Acrylic acid
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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
Renewable
Non toxic
Non toxic
Biodegradable
Biodegradable
Full environmental acceptance
Full environmental acceptance
Use: Alkyd resins
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 and dependence on limited petroleum reserves.
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2007/presentations/external/NVVT
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What we can expect to come ?
DSM Coating Resins
2007/presentations/external/NVVT
What we expect to come
14
O
Succinic Acid: C4H6O4
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 C4 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-CH2 -CH2 -COOH
HOOC-CH2 -CH2 -CH2 OH
HOCH2 -CH2 -CH2 -CH2 OH
Succinic acid
4- Hydroxybutanoicacid
1,4- Butanediol
Fumaric/Maleic acid
Maleic anhydride
Succinic anhydride
O
O=
O
=O
O=
DSM Coating Resins
2007/presentations/external/NVVT
gamma- Butyrolactone
O
=O
Tetrahydrofuran
O
=O
What we expect to come
16
Isosorbide: C6H10O4
Itaconic Acid: C5H6O4
Via dehydration of sorbitol
Via fungal fermentation of glucose
OH
3-Hydroxy Propionic
Acid: C3H6O2
O
O
OH
HO
OH
HO
O
CH2
O
OH
Difunctional polyol for:
• Polyesters
• Polycarbonates
• Polyamides
• Polyurethanes
• Plasticizers
Commercial quantities:
2008/2009
DSM Coating Resins
2007/presentations/external/NVVT
O
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
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Biomass Will Make a Difference
…a member of OPEC?!
Turning South Dakota into…
Today
Tomorrow
44 Million
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
2,500
2,200
1,700
1,650
1,380
925
800
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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 and\or 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
80
Vegetable oils
0.6
0.7
70
60
0.68
0.5
USD/barrel
50
0.4
40
0.3
USD/kg
0.64
0.62
30
0.6
0.2
20
USD/kg
0.66
0.58
0.1
10
0
2001 2002
2003 2004
2005
2006
0.56
0
0.54
2001 2002
2003 2004 2005
2006
2001 2002
2003 2004 2005
2006
• 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