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