GLYCEROL HYDROGENOLYSIS
1.3.2 Copper systems
The hydrogenolysis of solvent free glycerol to 1,2-PDO was studied by Huang et al. [33].
Several catalysts were screened and the most effective catalysts (Ni/Al2O3 and Cu/ZnO/Al2O3) were further tested for vapour phase hydrogenolysis in a fixed bed reactor. They found that Ni/Al2O3 is not an effective catalyst for the production of 1,2-PDO because of the high selectivity to CH4 and CO. Over the Cu/ZnO/Al2O3 catalyst, glycerol was mainly converted to 1,2-PDO and acetol (Table 1.8). This shows that Cu-based catalysts have poor activity towards C-C bond cleavage. High selectivities of 92 % to 1,2-PDO were achieved with high conversion of glycerol at 190 °C at 6.4 Bar H2 pressure. Higher pressures favoured 1,2-PDO formation and they found a stoichiometric relationship between 1,2-PDO and acetol.
Table 1.8: Vapour phase hydrogenolysis of glycerol over Ni/Al2O3 and Cu/ZnO/Al2O3
catalysts in a fixed bed reactor [33].
Selectivity to products (%) Catalyst Conversion
(%) 1,2-PDO EG Acetol 1-PO 2-PO Others*
Ni/Al2O3
a 92.3 43.6 18.6 13.4 3.2 1.5 19.7
Cu/ZnO/Al2O3
a 93.0 65.3 2.5 23.5 1.4 0.6 6.7
Cu/ZnO/Al2O3b
96.2 92.2 0.7 0.8 2.4 0.7 3.2
a) Reaction conditions: WHSV = 0.18h-1, 60 wt% glycerol solution, 190 oC, 1 Bar H2, H2/glycerol = 70:1 (molar ratio).
b) 6.4 Bar H2.
* Others = C1 gases (CO and CH4), ethanol, methanol and unknown products.
Supported Cu-containing bimetallic catalysts were prepared and the effect of different supports, metals, metal loading and impregnation sequences were studied [34]. A synergistic effect was observed between Cu and Ag when supported on γ-Al2O3. The addition of Ag resulted in an in situ reduction of CuO and also improved the dispersion of the Cu species on the support. This bimetallic catalyst system can be used directly without a reduction pre-treatment. A glycerol conversion of 27 % was obtained with 96 % selectivity to 1,2-PDO at 200 °C with 15 Bar H2
pressure in a batch reactor.
The vapour phase reaction of glycerol over copper metal catalysts at ambient hydrogen pressures was also investigated [35]. The 1,2-PDO yield was initially limited at 80 % due to the trade off between dehydration and hydrogenation. Dehydration needs relative high temperatures, whereas hydrogenation is favoured by low temperatures and high hydrogen concentration. A process was developed where glycerol was dehydrated to acetol at 200 °C followed by the subsequent hydrogenation to 1,2-PDO at 120 °C by controlling the thermodynamic equilibrium of the second hydrogenation step. Quantitative glycerol conversions were observed with 96 % selectivity to 1,2-PDO.
Different Cu-supported catalysts were synthesised and compared with a commercial copper chromite catalyst [36]. The Cu/Al2O3 showed a 35 % glycerol conversion with 94 % selectivity to 1,2-PDO whereas the commercial copper chromite showed a 13 % conversion with a 87 % selectivity to 1,2-PDO at 200 °C and 36 Bar H2. This result indicated that the support had a strong effect on the performance of the Cu-based catalysts.
A comparative study of the hydrogenolysis of glycerol to 1,2-PDO over a CuO/MgO catalyst, prepared by impregnation and co-precipitation, was published [37]. The CuO/MgO catalyst prepared by co-precipitation showed the best activity with a glycerol conversion of 72 % and a 1,2-PDO selectivity of 98 %. The glycerol conversion was further enhanced to 82 % with the addition of NaOH to the reaction mixture.
The effect that residual sodium has on the performance of the CuO/SiO2 catalysts in glycerol hydrogenolysis has also been studied [38]. Characterisation showed that residual sodium had a negative effect on the dispersion of the copper and the reducibility of the Cu2+ species, as well as the absorbance of the reactant molecules. As a consequence of this, the conversion and selectivity decreased with increasing sodium content. On the other hand, the leaching of sodium from the catalyst surface as a base could promote the activity of the catalyst and reduce the deactivation rate of the catalyst. The lowest glycerol conversion (15 %) was obtained with the highest amount of sodium with a 94 % selectivity to 1,2-PDO at 180 °C and 90 Bar H2.
The hydrogenolysis of glycerol was investigated over CuO/ZnO catalysts which were prepared by the oxalate gel method and co-precipitation [39]. The CuO/ZnO catalyst prepared by the oxalate gel method exhibited a much higher conversion than the catalyst prepared by the co- precipitation method (46 % compared to 17 %), but similar selectivities of 90 % were seen. The higher activity can be attributed to the higher surface area of the copper. In the presence of water, the copper crystallites of the CuO/ZnO catalyst increased significantly, leading to a decrease in active surface area and a loss of activity.
A method was investigated for the preparation of 1,2-PDO by reaction of 95 wt% glycerol solution under hydrogen pressures varying between 20-100 Bar and temperatures varying between 180-240 °C in an autoclave [40]. The catalyst used for this process comprises of CuO (20-60 wt%), ZnO (30-70 wt%) and MnO (1-10 wt%).
A further process for the preparation of 1,2-propanediol which permits the hydrogenation of the glycerol-containing streams with high selectivity was described by Henkelmann et al. [41]. This process is suitable for the further processing of glycerol streams obtained on industrial scale.
The hydrogenation catalyst used comprised at least 35 % by weight of copper, in oxide and/or elemental form, based on the total weight of the catalyst. Copper-containing catalysts of different compositions were tested: 100 % Cu (Raney-Cu) or CuO, ZnO, Al2O3 or CuO, Al2O3
or Cu, TiO2 or CuO, MnO3, Al2O3. Very high glycerol conversions of between 74 % and 99 % were obtained with selectivities of up to 96 % to 1,2-propanediol at high temperatures (100–
320 °C) and pressures (100–325 Bar).
1,2-Propanediol was prepared [42] by the catalytic hydrogenation of glycerol (20 wt% in water) at elevated temperatures (200–250 °C) and pressures (200–325 Bar H2). Catalyst systems used consisted of cobalt (CoO), copper (CuO), manganese (MnO2) and molybdenum (MoO3) with inorganic polyacids or heteropolyacids. The catalyst employed in this process generally contained no catalyst support. The hydrogenation gives selectivities of up to 95 % with 100 % conversions and other products that form are methanol, ethanol, iso-propanol and 1,3- propanediol.
A reactive-separation process was studied, which converts glycerol to propylene glycol through an acetol intermediate, by Suppes and Sutterlin [43]. The glycerol containing stream contained 5
% to 15 % water by weight and the conditions included a temperature range between 150 °C and 250 °C and pressures between 1 to 25 Bar. High glycerol conversions of up to 100 % were obtained with selectivities between 85 % and 95 % to propanediols. The hydrogenation catalyst comprises of 5 wt% to 95 wt% chromium (Cr2O3) and copper (expressed as CuO).
High surface area nanostructured Cu-Cr catalysts were prepared [44] and evaluated for the hydrogenolysis of glycerol. The reduced Cu-Cr catalysts showed significant catalytic activity and selectivity in glycerol hydrogenolysis. A 51 % glycerol conversion was obtained with a 96
% 1,2-propanediol selectivity under 41.5 Bar H2 at 210 °C. The Cu-Cr catalysts with low Cu/Cr molar ratio gave high glycerol conversion, which is different from the conventional copper- chromite catalysts.
Selective hydrogenolysis of glycerol to 1,2-PDO was also performed [45] using environmentally friendly hydrotalcite-derived mixed metal oxide catalysts. These mixed metal oxides are inexpensive and non-toxic and their acid-base properties can be tailored to improve the selectivity and conversion of the glycerol hydrogenolysis reaction. The Cu/Zn/Al mixed oxide was the most active catalyst at 48 % conversion with a selectivity of 94 % to 1,2-PDO at 200 °C, 7 Bar and glycerol dilution of 80 %.