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”
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Glycerol carbonatePro
pert
ies High boiling
pointLow toxicityBiodegradability
Use
s Cosmetics, medicines, polycarbonates and polyurethanesReplacement for hazardous and volatile organic solventsOther uses...
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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
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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
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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
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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
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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
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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.)
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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
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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%
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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%
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Aim of studies
Preparation of stable heterogenized catalyst
Catalyst characterization Rate of GC formation and decomposition
at different reaction conditions Purification of GC
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Thank you for your attention
This work was supported by the Slovak Research and Development Agency under the contract No. APVV-
0133-11