Andrej Ševčík Alexander Kaszonyi Slovak University of Technology, Bratislava Faculty of Chemical and Food Technology Dep. of Organic Technology Joint Slovak-Hungarian Laboratory for Development of Catalyzed Chemical Processes 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” 17 th 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 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-Al 2 O 3, 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 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 CuCr 2 O 4 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.

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

Effect of different amount of metals loaded on  alumina 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

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