Hydrogenolysis of glycerol with FeCo macrocyclic complex bonded to Raney Nickel support under mild reaction conditions

Abstract

The hydrogenolysis of dilute glycerol solution to 1,2-propanediol was studied in the presence of heterogeneous catalyst (FeCoL/Raney Nickel) having a heterodinuclear FeCo macrocyclic complex ionically bonded to Raney Nickel. Studies on the stability of the complex bonded to the support were carried out at different temperature as well as the effect of solvent to confirm that it was stable up to 600 • C and 100 h of refluxing. In the hydrogenolysis of glycerol, the temperature has been varied from 165 to 220 • C with an initial hydrogen pressure 0.35 MPa and the conversion increases from 1% to 36% with no gases evolving in this temperature range. The major product is 1,2-propanediol which is formed with 80% selectivity. The initial water content (20-60%) in the feed was also varied and it was found that the conversion and yield of 1,2-propanediol increases when the water content increases. Based on literature, a kinetic model was proposed and optimal rate constants determined using Genetic Algorithm (GA).On aétudié l'hydrogénolyse d'une solution diluée de glycérol solution en 1,2-propanediol, en présence d'un catalyseur hétérogène (FeCoL/nickel de Raney) ayant un complexe macrocyclique hétérodinucléaire de FeCo ioniquement lié au nickel de Raney. Desétudes sur la stabilité du complexe lié au soutien ontété effectuéesà différentes températures et on aétudié aussi l'effet du solvant pour confirmer qu'ilétait stable jusqu'à 600 • C et 100 h de reflux. Dans l'hydrogénolyse du glycérol, la température variait de 165à 220 • C avec une pression initiale d'hydrogène de 0,35 MPa et la conversion augmente de 1%à to 36% sansévolution des gaz dans cet intervalle de température. Le produit majeur est le 1,2-propanediol, lequel est formé avec une sélectivité de 80%. Le contenu d'eau initial (20%à 60%) dans l'alimentation variaitégalement et on a conclu que la conversion et le rendement de 1,2-propanediol augmentait avec les augmentations de contenu d'eau. En se basant sur la littérature, un modèle cinétique aété proposé et des constantes de taux optimal ontété déterminées en utilisant un algorithme génétique.

Recent Advances in Catalytic Conversion of Glycerol

“…For example, it was revealed that the presence of the metallic Ni in Cu-Cr catalyst helped to increase the selectivity to 1,2-propanediol (188). Recently, Anand et al (189) described the hydrogenolysis of dilute glycerol solution to 1,2-propanediol in the presence of a heterogeneous FeCo(CH 3 C 6 H 2 (CH) 2 O(CH 2 ) 3 N 2 ) 2 /Raney Ni catalyst in which the heterodinuclear FeCo macrocyclic complex and Raney Ni species were probably bound together through ionic bonding. The conversion of glycerol and the yield of 1,2-propanediol were increased when the water content in the glycerol solution increased (189).…”

“…Recently, Anand et al (189) described the hydrogenolysis of dilute glycerol solution to 1,2-propanediol in the presence of a heterogeneous FeCo(CH 3 C 6 H 2 (CH) 2 O(CH 2 ) 3 N 2 ) 2 /Raney Ni catalyst in which the heterodinuclear FeCo macrocyclic complex and Raney Ni species were probably bound together through ionic bonding. The conversion of glycerol and the yield of 1,2-propanediol were increased when the water content in the glycerol solution increased (189). Such results were in line with the findings that low glycerol concentration was important in reducing the probability of dehydration reaction and hydrocracking (190 …”

Thermodynamic analysis of hydrogen production from glycerol at energy self‐sufficient conditions

“…Two major approaches are: (i) purifying glycerol to synthetic glycerin for later applications in drug/pharmaceuticals industries (Bernesson et al, 2004; Wicke et al, 2008; Malca and Fausto, 2011). Moreover, synthetic glycerin from fossil sources is being gradually substituted by glycerol from natural sources in the market (Niederl‐Schmidinger and Narodoslawsky, 2008), and (ii) converting glycerol to high‐value chemicals via different reactions such as condensation to [1,3]dioxan‐5‐ols and [1,3]dioxolan‐4‐yl‐methanols (Deutsch et al, 2007), hydrogenolysis to propylene glycol (Dasari et al, 2005; Lechon et al, 2009; Anand et al, 2010), dehydration to acrolein (Yang et al, 2008), oxidation to glyceric acid, tartronic acid and, oxalic acid (Ketchie et al, 2007) and etherification to higher glycerol ethers used as oxygenate additives for fuels such as biodiesel and diesel petroleum (Klepacova et al, 2007; Kiatkittipong et al, 2011) or gasoline (Kiatkittipong et al, 2010). Sometimes, it is directly used as a fuel for heat generation (Soimakallio et al, 2009; Thamsiriroj and Murphy, 2010) or as animal feed in agricultural industry (Malca and Fausto, 2011).…”