Green Applications for Acetal Solvents - Chemspec Events
Green Applications for Acetal Solvents - Chemspec Events
Green Applications for Acetal Solvents - Chemspec Events
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FUTUREFUEL ®
Site History<br />
1976<br />
Nov 1, 2006<br />
1994
Site In<strong>for</strong>mation<br />
• Established 1976<br />
• Employees ~ 540<br />
• 2,200 - Acre Site<br />
• 3 rd Largest Employer in the Area<br />
• Operations 24/7 x 365 days<br />
• Non-union<br />
• SAP ERP System<br />
Product Segments<br />
• Custom Chemicals<br />
• Per<strong>for</strong>mance Chemicals<br />
• Biofuels
Revenues<br />
2006 $157 MM<br />
2007 $172 MM<br />
2008 $198 MM<br />
2009 $197 MM<br />
2010 $219 MM<br />
2011 $310 MM<br />
Per<strong>for</strong>mance Chemicals<br />
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<strong>Green</strong> considerations<br />
Discussion of Alkoxymethanes<br />
› Dimethoxymethane<br />
› Dibutoxymethane<br />
› Glycerol Formal<br />
› Diethoxymethane<br />
Summary
Chemical Industry - $4 Trillion USD<br />
<strong>Green</strong> Chemistry (Current) - $2 Billion USD<br />
<strong>Green</strong> Chemistry (2020) - $100 Billion USD<br />
Source: ACS GCI Nexus Newsletter March/April 2012
Replacement of a hazardous or toxic material<br />
› ODS refrigerants replaced with non-ODS<br />
materials<br />
› Ethylene glycol replaced with propylene glycol<br />
in anti-freeze<br />
Material is prepared from a natural material<br />
› Ethanol from fermentation of carbohydrates<br />
› Biopolymers from carbohydrates<br />
Material is recycled within the industry<br />
› Refractory sand in metal casting<br />
› Ionic Liquids in fine chemical manufacturing<br />
FUTUREFUEL ®
Methanol Economy<br />
› CO 2 + 3H 2 CH 3 OH + H 2 O<br />
• Carbon Sequestration; mimics photosynthesis<br />
› 2CH 4 + O 2 2CH 3 OH<br />
• Large abundance of inexpensive Shale gas in US<br />
• Methane captured from landfills<br />
Ethanol<br />
› Established industry producing from corn, sugar cane,<br />
or sugar beets<br />
› Potential <strong>for</strong> cellulosic ethanol
Butanol<br />
› Multiple companies working to commercialize<br />
› Feedstocks include fermentation sugars, biomass,<br />
and waste food sources<br />
› Technologies include GM microbes and pyrolysis<br />
Glycerin<br />
› Co-product from biodiesel production<br />
› Abundant and inexpensive
Dimethoxymethane (DMM;Methylal)<br />
Dibutoxymethane (DBM;Butylal)<br />
Glycerol <strong>for</strong>mal<br />
Diethoxymethane (DEM;Ethylal)<br />
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Dimethoxymethane<br />
CAS # 109-87-5<br />
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Replacement <strong>for</strong> Dichloromethane in paint<br />
cleaning applications<br />
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Dimethoxymethane<br />
CAS # 109-87-5<br />
DMM CH 2 Cl 2<br />
Boiling Point, °C 42.3 39.8<br />
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Dimethoxymethane<br />
CAS # 109-87-5<br />
DMM CH 2 Cl 2<br />
Boiling Point, °C 42.3 39.8<br />
Freezing Point, °C -104 -97<br />
FUTUREFUEL ®
Dimethoxymethane<br />
CAS # 109-87-5<br />
DMM CH 2 Cl 2<br />
Boiling Point, °C 42.3 39.8<br />
Freezing Point, °C -104 -97<br />
Specific Gravity 0.86 1.32<br />
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Dimethoxymethane<br />
CAS # 109-87-5<br />
DMM CH 2 Cl 2<br />
Boiling Point, °C 42.3 39.8<br />
Freezing Point, °C -104 -97<br />
Specific Gravity 0.86 1.32<br />
Viscosity, cps 0.371 0.329<br />
FUTUREFUEL ®
Dimethoxymethane<br />
CAS # 109-87-5<br />
DMM CH 2 Cl 2<br />
Boiling Point, °C 42.3 39.8<br />
Freezing Point, °C -104 -97<br />
Specific Gravity 0.86 1.32<br />
Viscosity, cps 0.371 0.329<br />
KB Value 164 136<br />
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Dimethoxymethane<br />
CAS # 109-87-5<br />
DMM CH 2 Cl 2<br />
Boiling Point, °C 42.3 39.8<br />
Freezing Point, °C -104 -97<br />
Specific Gravity 0.86 1.32<br />
Viscosity, cps 0.371 0.329<br />
KB Value 164 136<br />
Water Solubility,% 32 1.3<br />
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Dimethoxymethane<br />
CAS # 109-87-5<br />
DMM CH 2 Cl 2<br />
SARA 313 No Yes<br />
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Dimethoxymethane<br />
CAS # 109-87-5<br />
DMM CH 2 Cl 2<br />
SARA 313 No Yes<br />
HAP No Yes<br />
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Dimethoxymethane<br />
CAS # 109-87-5<br />
DMM CH 2 Cl 2<br />
SARA 313 No Yes<br />
HAP No Yes<br />
ODP 0 0.011<br />
FUTUREFUEL ®
Dimethoxymethane<br />
CAS # 109-87-5<br />
DMM CH 2 Cl 2<br />
SARA 313 No Yes<br />
HAP No Yes<br />
ODP 0 0.011<br />
GWP
Dimethoxymethane<br />
CAS # 109-87-5<br />
DMM CH 2 Cl 2<br />
SARA 313 No Yes<br />
HAP No Yes<br />
ODP 0 0.011<br />
GWP
Replacement <strong>for</strong> Dichloromethane in paint<br />
cleaning applications<br />
Replacement <strong>for</strong> CFCs as blowing agent <strong>for</strong><br />
polyurethane foams<br />
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Blowing Agent GWP (100-yr) ODP<br />
CFC-12 10,900 1<br />
HCFC-22 1,810 0.055<br />
HFC-152a 124 0<br />
N-Pentane
Replacement <strong>for</strong> Dichloromethane in paint<br />
cleaning applications<br />
Replacement <strong>for</strong> CFCs as blowing agent <strong>for</strong><br />
polyurethane foams<br />
Ingredient in hard surface cleaners<br />
FUTUREFUEL ®
Water, % 72.4<br />
DMM, Tech % 23.0<br />
Glycerol Formal, % 4.5<br />
Orange Tuff 90, % 0.1<br />
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Dibutoxymethane<br />
CAS # 2568-90-3<br />
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Replacement <strong>for</strong> PERC/Trichloroethylene<br />
› Cleaning solvent (WO2010149521)<br />
› Vapor degreasing<br />
› Auto parts cleaner<br />
› Metal degreasers<br />
Capture of carbon oxides<br />
Removes CO 2 from gas streams (WO2012052671)<br />
Cellulose-based cosmetic <strong>for</strong>mulations<br />
› Solvent in lipstick <strong>for</strong>mulation (FR2966359)<br />
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Non-flammable<br />
› Flashpoint >140F<br />
› Boiling Point – 180C<br />
Biodegradable<br />
Non-chlorinated<br />
Low toxicity<br />
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Dibutoxymethane<br />
CAS # 2568-90-3<br />
DBM TCE PERC<br />
Boiling Point, °C 180 87 121<br />
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Dibutoxymethane<br />
CAS # 2568-90-3<br />
DBM TCE PERC<br />
Boiling Point, °C 180 87 121<br />
Freezing Point, °C -58 -87 -23<br />
FUTUREFUEL ®
Dibutoxymethane<br />
CAS # 2568-90-3<br />
DBM TCE PERC<br />
Boiling Point, °C 180 87 121<br />
Freezing Point, °C -58 -87 -23<br />
Specific Gravity 0.83 1.456 1.619<br />
FUTUREFUEL ®
Dibutoxymethane<br />
CAS # 2568-90-3<br />
DBM TCE PERC<br />
Boiling Point, °C 180 87 121<br />
Freezing Point, °C -58 -87 -23<br />
Specific Gravity 0.83 1.456 1.619<br />
Viscosity 25 °C, cps 1.083 0.54 0.75<br />
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Dibutoxymethane<br />
CAS # 2568-90-3<br />
DBM TCE PERC<br />
Boiling Point, °C 180 87 121<br />
Freezing Point, °C -58 -87 -23<br />
Specific Gravity 0.83 1.456 1.619<br />
Viscosity 25 °C, cps 1.083 0.54 0.75<br />
KB Value 75 129 90<br />
FUTUREFUEL ®
Glycerol Formal<br />
CAS # 68442-91-1<br />
FUTUREFUEL ®
Glycerol Formal<br />
CAS # 68442-91-1<br />
Only known current use is a solvent in<br />
anti-parasitic injectible <strong>for</strong> swine and<br />
cattle (Ivomec®)<br />
FUTUREFUEL ®
Coolants/Anti-freeze<br />
De-icing fluid<br />
Thermal transfer fluid<br />
<strong>Solvents</strong> in paints/coating/inks<br />
› Alkyd resins<br />
› Latex paints<br />
Dust suppressant<br />
Component of hard surface cleaner<br />
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Coolants/Anti-freeze<br />
De-icing fluid<br />
Thermal transfer fluid<br />
<strong>Solvents</strong> in paints/coating/inks<br />
› Alkyd resins<br />
› Latex paints<br />
Dust suppressant<br />
Component of hard surface cleaner<br />
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GF EG PG 2-BuOEtOH<br />
Boiling Point, °C 193 197 188 171<br />
Specific Gravity 1.203 1.115 1.036 0.901<br />
Viscosity, cP @ 25C 11.7 16.9 40.4 2.9<br />
Flash Point,°C 98 116 99 65<br />
Solubility Parameter,<br />
(M/Pa)<br />
25.8 14.5 14.0 10.5<br />
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Ethoxylation <strong>for</strong> surfactant<br />
Acrylate ester <strong>for</strong> polymerization<br />
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Diethoxymethane<br />
CAS # 462-95-3<br />
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SAFETY<br />
› Low rate of peroxide <strong>for</strong>mation<br />
REGULATORY<br />
› Not a SARA 313 listed chemical<br />
› Not a HAP solvent<br />
PROCESS FRIENDLY<br />
› Low boiling azeotrope with water<br />
› Low water solubility<br />
› Does not readily absorb water from atmosphere<br />
› Stable over wide range of pH and temperatures<br />
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Parameter THF MeTHF Et 2<br />
O MEK DEM<br />
Density (20C)[g/ml] 0.89 0.85 0.71 0.81 0.83<br />
Vapor Specific Gravity (air = 1) 2.5 3.0 2.6 2.5 3.6<br />
Boiling point [C] 65 80 35 80 88<br />
Melting point [C] -109 -136 -116 -87 -67<br />
Viscosity (20C)[cP] 0.55 0.6 0.24 0.41 0.41<br />
Azeotrope point with water [C] 64 71 34.2 74.3 75.2<br />
Water in azeotrope [%] -- 10.6 -- 11.3 10.0<br />
Solubility in water [g/100g] ∞ 14 6.5 26.8 4.2<br />
Solubility of water in solvent [g/100g] ∞ 4.4 1.2 11.8 1.3<br />
Flash point [C] -14.5 -11 -45 -3 -7<br />
Explosion range [vol %] 1.84-11.8 1.5-8.9 1.85-48 1.8-10.1 2.1-20.0<br />
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Temperature<br />
40°C 60°C 80°C<br />
pH<br />
2.0 0.0 0.4 3.3<br />
4.0 0.0 0.1 0.1<br />
10.0 0.0 0.0 0.0<br />
Hydrolysis of DEM as indicated by % Ethanol<br />
Coleman, M.T. Chemistry Today, 2009, 27, 43-45<br />
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Boaz, N.W. ; Venepalli, B. Org. Proc. Res. Dev. 2001, 5, 127-131<br />
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Boaz, N.W. ; Venepalli, B. Org. Proc. Res. Dev. 2001, 5, 127-131<br />
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Achmatowicz, et.al. J. Org. Chem. 2009, 74, 795-809<br />
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Achmatowicz, et.al. J. Org. Chem. 2009, 74, 795-809<br />
Boaz, N.W. ; Venepalli, B. Org. Proc. Res. Dev. 2001, 5, 127-131<br />
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Cohen, et.al. Org. Proc. Res. Dev. 1999, 3, 260-265<br />
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Cohen, et.al. Org. Proc. Res. Dev. 1999, 3, 260-265<br />
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Berliner, M.A.; Belecki, K. J. Org. Chem. 2005, 70, 9618-9621<br />
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Berliner, M.A.; Belecki, K. J. Org. Chem. 2005, 70, 9618-9621<br />
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Temperature compatible to PTC temperature<br />
range<br />
Stable to aqueous strong base<br />
Limited solubility in water<br />
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entry Method R 1<br />
R 2<br />
R 3<br />
X Yield<br />
1 A H H Bn Cl 81<br />
2 A H H Bu Br 82<br />
3 A MeO H Allyl Cl 91<br />
4 B MeO H Bu Br 83<br />
5 A MeO H Bn Cl 85<br />
6 B t-Bu H Bu Br 81<br />
7 A t-Bu H Allyl Cl 65<br />
8 B H Ac Bu Br 86<br />
9 A MeO H Me OSO 3 Me 86<br />
10 A t-Bu H Me OSO 3 Me 85<br />
11 A H Ac Me OSO 3 Me 81<br />
Method A - 2.0 M in DEM; 1.5 Eq. 25% NaOH; 2.0 Eq. Electrophile;10 mole % TBAB; 4 h @ 55 °C<br />
Method B - 2.0 M in DEM; 25% Aq. NaCl; 1.5 Eq. 50% NaOH; 1.5 Eq. Alkyl Halide; 10 mole % TBAB; 2 h @ 90 °C<br />
Coleman, M.T.; LeBlanc, G. Org. Proc. Res. Dev. 2010, 14, 732-736. FUTUREFUEL ®
entry R 1<br />
R 2<br />
X yield<br />
1 benzyl benzyl Cl 81<br />
2 phenyl benzyl Cl 78<br />
3 cyclohexyl benzyl Cl 82<br />
4 benzyl butyl Br 82<br />
5 cyclohexyl butyl Br 73<br />
6 benzyl allyl Cl 30<br />
7 cyclohexyl allyl Cl 18<br />
8 C 7<br />
H 15<br />
benzyl Cl 89<br />
9 C 7<br />
H 15<br />
butyl Br 72<br />
Coleman, M.T. Syn. Comm. 2012, 43, 1911-1913. FUTUREFUEL ®
Replacement <strong>for</strong> 2-Butanone<br />
› Similar physical properties<br />
› Not on US RCRA list of hazardous waste<br />
Solvent in two-component coating composition<br />
› Extends pot-life vs. traditional solvents<br />
› Does not cause discoloration<br />
› Ref: PCT/WO 2012/044509 A1
DMM<br />
Replace<br />
Toxic/Haz<br />
√<br />
Natural<br />
Feedstock<br />
Recycle<br />
DEM √ √ √<br />
DBM √ √ √<br />
Glycerol<br />
Formal<br />
√<br />
√<br />
FUTUREFUEL ®
Wide range of boiling points <strong>for</strong> use across a<br />
wide range of applications<br />
Various degrees of water solubility <strong>for</strong> use<br />
across a wide range of applications<br />
Strong solvency with high KB values<br />
Stable above pH 4<br />
Low toxicity<br />
Biodegradable<br />
Good environmental profile<br />
Prepared from renewable or potentially<br />
renewable alcohols<br />
FUTUREFUEL ®
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