Liquid Phase Hydrogenolysis of Glycerol over Highly Active 50%Cu–Zn(8:2)/MgO Catalyst: Reaction Parameter Optimization by Using Response Surface Methodology

Abstract

In this study, a highly promising bimetallic 50%Cu–Zn(8:2)/MgO catalyst was developed for selective hydrogenolysis of glycerol to 1,2-propanediol (1,2-PDO). The catalytic activity was evaluated in a high pressure autoclave reactor. Results demonstrated that the incorporation of Zn into Cu/MgO catalysts enhanced the glycerol conversion and selectivity to 1,2-PDO due to the hydrogen spillover effect. Experimentally maximum glycerol conversion of 98.7% with 94.6% selectivity to 1,2-PDO was achieved at mild reaction conditions. Response surface methodology (RSM) was employed to study the interaction of the various reaction parameters and develop an empirical process model followed by the optimization of the reaction parameters. The high values for determination coefficients (>0.95) obtained by analysis of variance indicated that the quadratic regression models developed were highly satisfactory. The results of numerical optimization demonstrated that 97.8% glycerol conversion with 93.5% selectivity to 1,2-PDO can be achieved at 212 °C and at 4.5 MPa pressure.

Copper Zinc Aluminate Synthesized by Sol‐Gel Method with Polyacrylic Acid as Catalysts for Glycerol Hydrogenolysis

“…[2,[6][7][8] Different supports have been employed, including ZnO, [9][10][11][12][13] Al 2 O 3 , [13][14][15][16] CeO 2 , [17] TiO 2 , [13,14] SiO 2 [13,[18][19][20][21] and some aluminosilicates, [15] ZrO 2 , [13,[22][23][24] and MgO. [13,22,[25][26][27][28] There is a general consensus that bifunctional catalysts with metallic Cu sites as well as (Brønsted and/or Lewis) acidic sites favor the selective formation of propanediols. Thus, the support plays a crucial role in the catalytic performance.…”

Hydrogenolysis of Glycerol to Propylene Glycol: Energy, Tech-Economic, and Environmental Studies

“…Extensive research efforts have been devoted to develop active and selective solid catalyst materials with bifunctional natures for both H 2 generation and hydrogenolysis reactions. Pt-based ( Tike and Mahajani, 2006 ; Falcone et al, 2015 ; Feng et al, 2015 ; Von Held Soares et al, 2017 ; Zhang et al, 2020b ; Hu et al, 2020 ; Xia et al, 2020 ; Nie et al, 2021 ; Song et al, 2021 ), Cu-based ( Nie et al, 2021 ; Feng et al, 2015 ; Wang et al, 2015b ; Priya et al, 2016 ; Feng et al, 2011 ; Kant et al, 2017 ; Vasiliadou and Lemonidou, 2013 ; A et al, 2017 ), and Pd-based ( Tike and Mahajani, 2006 ; Feng et al, 2015 ; Mauriello et al, 2015 ; Sun et al, 2017 ; Shafaghat et al, 2019 ; Xia et al, 2020 ; Song et al, 2021 ) catalysts have been proposed and investigated with respect to structure-performance relations. Those studies have confirmed that CTH of glycerol can be achieved under milder temperatures (<200 o C) and pressures (inert <2 MPa), with remarkable atom efficiency for the synthesis of PG as the main product ( Wang et al, 2013 ; Feng et al, 2015 ).…”

Selective Hydrogenolysis of Glycerol to 1,2‐Propanediol over Co‐Al2O3 Catalysts in Batch and Continuous Reactors

“…In contrast, the inexpensive Cu-based catalysts are highly selective to 1,2-PDO because of their low efficiency toward C-C bond breaking and high selectivity for C-O bond hydro-dehydrogenation [24,25]. Therefore, a variety of supports including Al 2 O 3 , Cr 2 O 3 , MgO, ZnO, ZrO 2 , SiO 2 , C and zeolite have been used in the preparation of Cu-based catalysts and evaluated for glycerol hydrogenolysis [26][27][28]. However, because of their poor thermal stability and pyrophoric nature, the Cu-based catalysts are easily sintered under conditions of high temperature and high hydrogen pressure, which leads to their deactivation [29][30][31].…”