+ Et3N. 135ºC, 60 min. TEA/GC MR = 1.5. - 77% Glycerol carbonate conversion. - FTIR: No linear carbonate band (1750 cm-1). - Residue viscosity = 2.1-fold that ...
2nd Conference on CO2 as Feedstock for Chemistry and Polymers 7-9 October 2013, Essen, Germany
Glycerol Carbonate from Glycerol α-mono-Chlorohydrin and CO2 Dr. José R. Ochoa-Gómez
Biorefinery and CO2 Valorization Department
TECNALIA THE FIRST SPANISH PRIVATE R&D ENTITY 1400 employees Revenues: 110 Million €
-
BUSSINESS DIVISIONS Sustainable Construction Energy & Environment Industry & Transport Health Technological Services Software Institute
Bioerefinery & CO2 Valorization Department
WHY GLYCEROL CARBONATE? Sonnati et al., Green Chem., 2013, 15, 283
O
Reference period 1935-2012: 86% in last 22 yr, 69% in last 12 yr
- BIODEGRADABLE O
O
- NON TOXIC - LOW VOLATILITY (Vapor Pressure 8 mbar at 177ºC)
HO
- LOW FLAMMABILITY (Flash point 190ºC)
- REACTIVITY
APPLICATIONS
Solvents
Pharmaceuticals (as a Carrier)
Cosmetics (Wetting Agent)
O
O
POLYMERS
O
Hyperbranched polyethers
Intermediates
Polycarbonates
Non-isocyanate polyurethanes
HO
Surfactants Cement and Concrete (Curing Agent) Lithium and Lithium-ion Batteries (as Electrolytes Liquid Carrier) Ochoa-Gómez et al., Org. Process Res. Dev. 2012, 16, 389−399 Sonnati et al., Green Chem., 2013, 15, 283
THE DREAM SYNTHETIC ROUTE! The direct one! O
OH Catalyst
CO2
+
HO
O
OH
O
+ H2O
HO
BUT…. Yields ≤ 10% 180ºC, 5 MPa, 15 h, tetra(ethylene glycol) dimethyl ether, catalysts: n-Bu2SnO, n-Bu2Sn(OMe)2, CeO2/Nb2O5, CeO2/Al2O3
Aresta M., Dibenedetto, A. et al. J. Mol. Catal. A: Chem. 2006, 257, 149−153; J. Catal. 2010, 269, 44−52.; Catal. Today 2008, 137, 125−131, Catal. Today 2008, 137, 44−51.
THE DREAM SYNTHETIC ROUTE! HOWEVER… Yield = 32%! George, J. et al., J. Mol. Catal. A: Chem. 2009, 304, 1−7. O
OH n-Bu2SnO
CO2
+
HO
O
OH 80ºC, 3.5 MPa, 4 h, MeOH HO
ALTHOUGH… RESULTS NOT CONFIRMED
Dibenedetto, A. et al. Tetrahedron 2011, 67, 1308−1313
O
+ H2O
THE DREAM SYNTHETIC ROUTE! PROFITABLE with 32% YIELD if SELECTIVITY = 100% MIBK From Reaction GC + Glycerol
O
O
LLE
EVAP. HO
> 98% OH
To Reaction HO
OH
Ochoa-Gómez, José R. et al. Green Chem. 2012, 14, 3368–3376
O
INDUSTRIAL FEASIBILITY = INDIRECT SYNTHETIC APPROACHES
Ochoa-Gómez et al., Org. Process Res. Dev. 2012, 16, 389−399 Sonnati et al., Green Chem., 2013, 15, 283
OH HO
OH J.B. Conant and O.R. Quayle
HCl (g) Org. Acids (cat) 100ºC, 3 h 94% Conversion 98% Selectivity
Org. Synth. 2:33 (1922)
EPICEROL® SOLVAY PROCESS Industrial start-up 2011
E. Santacesaria et al. PCT Patent WO 132770 A1, 2008
OH Cl
OH
HCl
+
Base
Glycerol α-monochlorohydrin (HAL) Epichlorohydrin
CO2 O
O
HO
O
Dichloropropanol (1,3- and 2,3-isomers)
E. Santacesaria et al.. Ind. Eng. Chem. Process Des. Dev. 1979, 18, 424–427, and 18, 428-433 E. Santacesaria et al., Ind. Eng. Chem. Res. 2010, 49, 964–970.
Ochoa-Gómez et al., Chem. Eng. J. 2011, 175, 505−511
HOW ACTIVATING CO2?
OH HO
HCl/H+ OH
CO2 Fixation-Activation through TRIETHYLAMINE
O
T. Endo. Prepr. Pap.-Am. Chem. Soc., Div. Fuel Chem. 2004, 49 (1), 112-113 C. Villiers et al., Angewandte Chemie, 2010, 122, 3543–3546 E.R. Pérez et al., J. Org. Chem. 2004, 69, 8005-8011
O
HO
O
DOES TEA ACTIVATE CO2 FOR THE TARGET REACTION? OH
CO2
CO2
Cl
STEP 1 TEA
25 bar 80ºC 15 min
OH
STEP 2 20ºC
1.5 TEA/HAL MR 80ºC 60 min
O
O
O
HO
12% YIELD
Analysis: Column: T (injector): T (detector): Injection vol.: Split ratio: Oven: Run time: Internal Standard:
GC-FID, Varian 450-GC DB-WAX 30 m x 0.25 mm x 0.25 µm 225 ºC 250ºC 1 µL 1:10 80ºC (2min); 15ºC/min up to 260ºC (5min) 19 min Butylene glycol or ethylene glycol
Autoclave Engineers model MagneDrive III: 5 stainless steel vessels of 100 mL
TEA/HAL MOLAR RATIO INFLUENCE
PCO2 25 bar 60 min
[CO2] = 17.2 wt%
[CO2] = 24.2 wt%
TEMPERATURE INFLUENCE
PCO2 25 bar 60 min 1.5 TEA/HAL molar ratio
ABOVE 100ºC O
TEA/GC MR = 1.5 O
O
+ Et3N
- 77% Glycerol carbonate conversion - FTIR: No linear carbonate band (1750 cm-1) - Residue viscosity = 2.1-fold that of GC (25ºC)
135ºC, 60 min
HO
GC Base-catalyzed Ring Opening Polymerisation G. Rokicki et al, Green Chem. 2005, 7, 529–539. O
O
O
O
O
O-
O
:NEt3
O
OH
OH
CO2
n CO2
O
n
Et3NH+
O
O
O
O
O
OH
O
O
O
O
HO
O O
O-
OH
O
O-
n
POLYGLYCEROLS
CO2 PRESSURE INFLUENCE S = 87% S = 52% 80ºC 60 min 1.5 TEA/HAL molar ratio
REACTION TIME INFLUENCE S = 83% S = 63% PCO2 35 bar 100ºC 1.5 TEA/HAL molar ratio
WATER CONTENT INFLUENCE
PCO2 35 atm 80ºC 1.5 TEA/HAL molar ratio
PROPOSED SIMPLIFIED MECHANISM O Et3N:
O-
O + Et3N
+ Et3N
C
O-
1
O
O
O : N Et 3
Cl- + Et3N
b
HO H
HO
O
O
Cl
a
Glycerol-α-mono-Chlorohydrin
HO 2
Attack to carbon atom a
Et3N
Attack to carbon atom b
1.5 MR, 80ºC, 60 min
5% Yield Et3N: +
-
CO2 + Et3NH Cl +
HO
O
O
Glycidol
H2O
O
HO
OH HO
O
OH
Glycerol carbonate
+
Et3NH+Cl-
SIMPLIFIED PROCESS FLOW-SHEET
Research funded by Ministerio de Ciencia e Innovación Spanish Government Project CTQ2009-11376 (2010-2012) Sub-programme: PPQ-Chemical Products and Processes
Dipl. Chem. Eng. MS Chem. B. Maestro M. Fernández Dr. Chem. Eng. J. Nieto
Dr. Chem. Eng. O. Gómez
Technician L. Lorenzo
Dr. C. Ramírez
THANKS SO MUCH
