catalytic transformation of polyols to carbonates lászló seemann, alexander kaszonyi, 17 th...
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Catalytic transformation of polyols to carbonates
László Seemann, Alexander Kaszonyi, 17th October, 2012, Bratislava
Slovak University of Technology, BratislavaFaculty of Chemical and Food TechnologyDep. of Organic Technology
Joint Slovak-Hungarian Laboratory forDevelopment of Catalyzed ChemicalProcesses of Biomass Utilization*
*Founded by financial support of project No. HUSK/1101/1.2.1/0318 “Chemical Processes of Biomass Utilization in the Slovak-Hungarian Frontier Region”
Glycerol carbonatePro
pert
ies High boiling
pointLow toxicityBiodegradability
Use
s Cosmetics, medicines, polycarbonates and polyurethanesReplacement for hazardous and volatile organic solventsOther uses...
Preparation of glycerol carbonate TRANSESTERIFICATION OF EC WITH GLY
80°C, 90 min Catalyst: TBA-MCM41 (X = 94%,S = 84%)
H.J. Cho at al., J. of Indust. and Engineering Chem. 16, 2006, 679-683
40°C, 10-13 MPa, 90 min in SC-CO2
Cat.: Amberlist26 (Y = 4,7%), Purosiv (Y = 32%)
C. Vievelle at al., Catal. Letters 56, 1998, 245-247
O O
O
OH
OHOH OH
O O
O
+ + OH OH
Preparation of glycerol carbonate
TRANSESTERIFICATION OF DMC WITH GLY
O O
O
OH
OHOH OH+ +
O O
OCH3OH
75-90°C, 50~90 minDMC/GLY = 3,5 (mol/mol)KAT/GLY = 0,06-0,08 (mol/mol)Azeotropic agent: benzene (1,5×MeOH)Cat.: CaO, CaCO3 (ht, b; Y=~91%, X>91%) KOH, K2CO3 (hm, b; Y, X = 100%)
78°C, 50 minDMC/GLY 1 (mol/mol)KAT/GLY 4 (w/w)Cat.: KF/HAP, KF.2H2O (ht, b; Y, X >99%)
75°C, 90 minDMC/GLY = 1:5 (mol/mol)KAT/GLY = 0,1 (w/w)Cat.: MAZ-311 (Y, X ~95%)
J.R. Oucha-Gómez at al., App. Catal. A: Gen. 366, 2009, 315-324,J. Li at al., Chem. Engineering and Proc. 49, 2010, 530-535,F.S. Hubertson Simanjuntak at al., App. Cat. A: Gen. 401, 2011, 220-
225,R. Bai at al., J. of Indust. And Engineering Chem. 17, 2011, 777-781,M. Malyaadri at al., App. Catal. A: Gen. 401, 2011, 153-157
Preparation of glycerol carbonate
OXIDATIVE CARBONYLATION OF GLY
140°C, PCO = 2 MPa, PO2 = 1 MPa, 2 h, Pd(phen)/KI (X = 92%, S = 99%) GLY/Pd = 400 (mol/mol)
J. Hu at al., App. Catal. A: Gen. 386, 2010, 188-193
20°C, 0,1 MPa K2CO3 (5 eq.), GLY (5 eq.), Se (1 eq.), (Y =
84%), DMF solventT. Mizuno at al., Heteroatom Chem., 2010
O O
O
OH
OHOH OH + +CO+ 1/2 O2
OH2
DIRECT CARBOXYLATION OF GLY
180°C, 5 MPa, 6-15 h Sn based cat. (max X = 7%)
M. Aresta a kol., J. of Mol. Catal. A: Chem. 257, 2006, 149-153
without cat., 40°C,10 MPa, 3 h, in SC-CO2, Y = 0 of GC
C. Vievelle at al., Catal. Letters 56, 1998, 245-247
O O
O
OH
OHOH OH +CO2+ OH2
Preparation of glycerol carbonate
Preparation of glycerol carbonate GLYCEROLYSIS OF UREA
O O
O
OH
OHOH OH +
NH2 NH2
O
+ NH3
140°C, 20 Pa, 3 hGLY/U = 1 (mol/mol)KAT/U = 100% (w/w)Cat.: g-ZrP (X = 76%)
140°C, 3 kPa, 1 hGLY/U = 2 (mol/mol)KAT/GLY = 0,22% (w/w)Cat.: La2O3 (Y = 89%, X = 99%) P = atm., N2, 4 h (X = 60%, Y = 3%)
145°C, 4 kPa, 5 hGLY/U = 1 (mol/mol),KAT/GLY = 5% (w/w) Cat.: HTc-Zn (Y = 72, X = 82%)
M. Aresta at al., J. of Catal. 268, 2009, 106-114,L. Wang at al., Catal. Communications 12, 2011, 1458-1462,M.J. Climent at al., J. of Catal. 269, 2010, 140-149,J.L. Dubois at al., EP2174937A1, 2010,J.L. Dubois at al., WO2010/040786A2, 2010
Overview of our studies Different types of homogeneous
catalysts (ZnCl2, ZnO, Zn(NO3)2, MgCl2, MgO, Alumina, also reaction without catalyst)
Optimization of catalyst composition and reaction conditions(G/C, T, G/U)
Heterogenization of the best homogeneous catalysts (ZnO/Alumina, ZnCl2/Silica, etc.)
Overview of our studiesProduct analysis
700120017002200270032003700
KARBGLCGLYUREA
Wavenumber, cm-1
15001600170018001900
final product by GCcolumn: Optima-Wax 0.53 mmProgram: 100°C for 1 min
10°C/min to 220°C
FID: 250°CInj.: 220°C
Preliminary results
0 1 2 3 4 5 60
10
20
30
40
50
60
70
80
90
100
ZnCl2ZnONo cat.
Reaction time, h
Gly
cero
l carb
onate
, w
t%
0 1 2 3 4 5 60
10
20
30
40
50
60
70
80
90
100Glycerol carbonate in reaction
mixture, K1 repeated
K1aK1bK1c
Reaction tim, h
Gly
cero
l ca
rbonate
, w
t%
0 1 2 3 4 5 60
102030405060708090
100Glycerol carbonate in re-
action mixture, K2 re-peated
K2aK2bK2cK2d
Reaction time, h
Gly
cero
l ca
rbonate
, w
t%
0 1 2 3 4 5 60
102030405060708090
100 Glycerol carbonate in reaction mixture, K3 repeated
K3aK3b
Reaction time (h)Gly
cero
l ca
rbonate
, w
t%
Preliminary results
0 1 2 3 4 5 60
10
20
30
40
50
60
70
80
90
100
ZnCl2ZnONo cat.
Reaction time, h
Gly
cero
l carb
onate
, w
t%
0 1 2 3 4 5 60
10
20
30
40
50
60
70
80
90
100Glycerol carbonate in reaction
mixture, K1 repeated
K1aK1bK1c
Reaction tim, h
Gly
cero
l ca
rbonate
, w
t%
0 1 2 3 4 5 60
102030405060708090
100Glycerol carbonate in re-
action mixture, K2 re-peated
K2aK2bK2cK2d
Reaction time, h
Gly
cero
l ca
rbonate
, w
t%
0 1 2 3 4 5 60
102030405060708090
100 Glycerol carbonate in reaction mixture, K3 repeated
K3aK3b
Reaction time (h)Gly
cero
l ca
rbonate
, w
t%
0 1 2 3 4 5 60
10
20
30
40
50
60
70
80
90
100Glycerol carbonate in re-
action mixture, K2 re-peated
K2a
K2b
K2c
K2d
Reaction time, h
Gly
cero
l ca
rbonate
, w
t%
Aim of studies
Preparation of stable heterogenized catalyst
Catalyst characterization Rate of GC formation and decomposition
at different reaction conditions Purification of GC
Thank you for your attention
This work was supported by the Slovak Research and Development Agency under the contract No. APVV-
0133-11
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