Supplementary Material

Glycerol Hydrogenolysis overRuthenium Supported on LanthanumModified ZrO2Catalysts

Bo He, Chuang Li,Zihui Xiao, Baowei Wang, Changhai Liang

Laboratory of Advanced Materials and Catalytic Engineering, Dalian University of Technology, Panjin, Liaoning 124221, China

Fig. S1XRD patterns of the reduced 2Ru/x%La-ZrO2 catalysts with different La content (x=0, 0.5,1.0, 2.5, 3.7, 5.0,10.0); x% represents the mass fraction of lanthanum in the catalyst

Fig. S2N2 adsorption-desorption isotherm for 2Ru/2.5%La-ZrO2 catalyst whose support wascalcined at 900oC

Fig. S3 SEM images of catalysts: (a) 2Ru/ZrO2and (b) 2Ru/2.5%La-ZrO2

Fig.S4TEM images of the 2.5%La-ZrO2calcined at 900 oC and 2Ru/2.5%La-ZrO2 catalyst

3.3 Effect of reaction conditions

Based on the results mentioned above, the 2Ru/1.0%La-ZrO2 catalyst was chosen to examinethe influenceof the reaction parameters, such as glycerol concentration, reaction temperature and reaction time. The results were shownin Fig.S5.

The effect of glycerol concentration (from 5wt% to 20wt%) was shown in Fig. S5a. The concentration had great effect for the hydrogenolysis of glycerol, especially for the selectivity of the CH4 and glycerol conversion. The CH4 selectivity decreased from 93% to 10% and the glycerol conversion decreased from 85% to 22%. While, the selectivity of the 1,2-PD and EG had a trend of increase. When the glycerol concentration was 20%, EG selectivity reached the highest point 44.4%. The further carbon skeleton broken of the generated material may explain the lower selectivity of 1,2-PD and EG in low substrate concentration.

The results of temperature influence (in the range of 190-230oC) were presented in Fig.S5b. As the temperature increased from190 oC to 230 oC, glycerol conversion increased apparently and reached its maximal value (approximately 82%) at230 oC and the selectivity for CH4 also increased regardless of the slight downward point at 200 oC. It indicted that the ability of C-C broken over the 2Ru/1.0%La-ZrO2 was enhanced when increased the reaction temperature.

The reaction time’s influence on the reaction was shown in Fig. S5c. The reaction time also had the great effect on the glycerol conversion and the selectivity of the EG and CH4. It was ready accepted that the conversion increased over time. While for the change ofEG and CH4 selectivity may due to the fact that the EG is much easier hydrogenolysis than glycerol at the reaction environment. With the reaction going, the obtained EG was converted to CH4 subsequently.

Fig. S5 The effect of reaction conditions(glycerol concentration, Temperature, Reaction time) over 2Ru/1.0%La-ZrO2 for glycerol hydrogenolysis.

Reaction conditions: (a) 30 g glycerol aqueous solution, 190 oC, 8h, 6 MPa H2, 800rpm; (b) 3 g glycerol, 27 g water, 0.3 g catalyst, 8 h, 6.0 MPa H2 , 800 rpm; (c) 3 g glycerol, 27 g water, 0.3 g catalyst, 190 oC, 6.0 MPa H2 , 800 rpm

In order to prove that the obtained EG was further reactedwhen prolonged the reaction time or increased the reaction temperature in the reaction. The following (the Entry 1 and 2 in Table S1) two experiments using EG and 1,2-PDas substratewere performed over the 2Ru/1.0%La-ZrO2 catalyst. When compared with the experiment that use glycerol as substrate, the reaction in the entry 1 have a similar substrate conversion and a higher reaction rate(8.53﹥7.83mmol/h). It indicated that with the progress of the glycerol hydrogenolysis reaction, more and more EGparticipatesthe further reaction of hydrogenolysis, which was responsible for the decrease of EG selectivity.

Table S1The reaction results of different substrates and the catalytic results of glycerol at optimal conditions

Entry / Substrate / Con.% / Rc
mmol/gcat·h / Selectivity (%)
CH4 / EGa / 1,2-PDb / methanol / Propanol / i-propanol
1 / EGa / 42.4 / 8.53 / 75 / - / - / 14 / - / -
2 / 1,2-PDb / 29.5 / 4.83 / 40 / - / - / 16 / 8.2 / 28.4
3 / glycerol / 57.8 / 7.83 / 50.0 / 21.0 / 22.0 / 1.2 / 1.9 / -

Entry 1，2 conditions: 3 g substrate, 27 g water, 0.3 g catalyst, 190 oC, 8 h,6.0 MPa H2 , 800 rpm;

aEG = ethylene glycol; b 1,2-PD = 1,2-propanediol;“-”presented no detected value; c R is reaction rate

1