CATALYTIC TRANSFORMATION OF BIO-GLYCEROL TO DIOLS

Andrej ŠevčíkAlexander Kaszonyi

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”

17th October, 2012, Bratislava

Diols

selective catalytic hydrogenolysis of glycerol represents a low cost and green route for 1,2-propanediol which is a major commodity chemical used in the production of antifreeze functional fluids, paints and polyester resins.

due to a presence of -OH functional groups, diols can be converted to aldehydes, esters, amines and carboxylic acids

Hydrogenolysis of glycerol to 1,2-PD

Supported catalysts- Batch reactor :

Yuan (2010) - 180°C, 3 MPa, cat. CuO/MgO, conv. of GLY - 72%, sel. to 1,2-PD - 97 %

Zhao (2010) - 200°C, 6 MPa, cat. Ni/Na-X, conv. of GLY - 86 %,sel. to 1,2-PD - 94 %

Xia (2012) - 180°C, 2 MPa, cat. Cu-Pd/solid base, conv. of GLY - 70%, sel. to 1,2-PD -

98%

- Down-flow reactor:

Zhou (2010) - 220°C, 4 MPa, cat. CuO-ZnO-Al2O3, conv. of GLY - 81%, sel. to 1,2-PD -

93%

Zheng (2010) - 250°C, 4 MPa, cat. Cu/SBA-15, conv. of GLY - 96%, sel. to 1,2-PD - 90

%

Hydrogenolysis of glycerol to 1,2-PD

Unsupported catalysts

- batch reactor:

Kim (2010) - 220°C, 8 MPa, Cu-Cr-O cat., different methods of catalyst

preparation (wet impregnation, co-precipitation), important is the formation

of CuCr2O4 structure

- different activity for the hydrogenolysis of glycerol is caused by various

forms of copper in the catalyst structure

Mane (2011) - 220°C, 7 MPa, effect of promoters (Al, Ba, Zn) to Cu-Cr-O cat.

0 Al Ba Zn0

20

40

60

80

100konv. GLY 1,2-PD

Promoters

con

vers

ion

, se

lect

ivit

y [%

]

Influence of different supports to activity and selectivity of catalysts

Reaction conditions:

5g catalyst, 150 °C, flow rate of GLY 1ml/h, inicial concentration of GLY 50 wt.%,

flow rate of hydrogen 30ml/min, 5h time on stream

unsupported alumina silica0

20

40

60

80

100

Cu-Cr 1:2 mol. ratio catalysts

conv. GLY 1,2-PD 1,2-ED

support

co

nv

ers

ion

, se

lec

tiv

ity

[%

]

0.5 1 1.5 2 2.5 3 3.5 4 4.5 50

10

20

30

40

50

unsupported alumina silica

time on stream [h]

se

lec

tiv

ity

to

1,2

-PD

Effect of different amount of metals loaded on -g alumina

150 160 170 180 1900

20

40

60

80

100 K 10-0 conv. GLY 1,2-PD 1,2-ED

temperature [°C]

con

vers

ion

, se

lect

ivit

y [%

]

150 160 170 180 1900

20

40

60

80

100

K 5-5 conv. GLY 1,2-PD 1,2-ED

temperature [°C]

con

vers

ion

, se

lect

ivit

y [%

]

Reaction conditions: 5g of catalyst (K10-0 is 10 wt.% of Cu and K5-5 is 5 wt.% of Cu and 5 wt.% of Cr), inicial concentration of GLY 50 wt.%, flow rate of GLY 1ml/h, flow rate of hydrogen 30ml/min, 5h time on stream

Hydrotalcite types of catalysts on hydrogenolysis of glycerol

Reaction conditions: 5g catalyst, flow rate of GLY 1ml/h, flow rate of hydrogen 30ml/min, 5h time on stream

Cu:Cr 1:0 Cu: Cr 1:2 Cu:Cr 1:10

20

40

60

80

100conv. GLY 1,2-ED 1,2-PD

catalyst

co

nv

ers

ion

, s

ele

cti

vit

y

[%]

130 150 170 1900

20

40

60

80

100

Cu:Cr 1:2 conv. GLY 1,2-ED 1,2-PD

temperature [°C]

co

nv

ers

ion

. se

lec

tiv

ity

[%

]

50 70 900

20

40

60

80

100

Cu:Cr 1:2

conv. GLY 1,2-ED

inicial concentration of GLY [wt.%]

co

nv

ers

ion

, se

lec

tiv

ity

[%

]

Aim of Work

Preparation of catalysts based on copper on different supports

Modification of these catalysts with other metals, especially with

chrome

Study of the influence of catalyst preparation method and reaction

conditions on the catalytic activity

Study of the influence of impurities in glycerol on properties of

catalytic systems

Chemical and physical characterization of prepared catalysts

Optimization of reaction conditions with regard to maximize the

yield of the diols

Thank you for your attention

This work was supported by the Slovak Research and Development

Agency under the contract No. APVV-0133-11