PdZn catalysts for CO2 hydrogenation to methanol using chemical vapour impregnation (CVI)

The formation of PdZn bimetallic alloys on ZnO, TiO2 and Al2O3 supports was investigated, together with the effect of alloy formation on the CO2 hydrogenation reaction. The chemical vapour impregnation (CVI) method produced PdZn nanoparticles with diameters of 3–6 nm. X-ray photoelectron spectroscopy and X-ray diffraction revealed the changes in the structure of the PdZn alloy that help stabilise formate intermediates during methanol synthesis. PdZn supported on TiO2 exhibits high methanol productivity of 1730 mmol kgcat−1 h−1 that is associated with the high dispersion of the supported PdZn alloy

Statistical Optimisation using Taguchi Method for Transesterification of Reutealis Trisperma Oil to Biodiesel on CaO-ZnO Catalysts

Optimisation of biodiesel production from non-edible Reutealis Trisperma oil (RTO) was investigated using Taguchi method. Biodiesel was produced via consecutive esterification and transesterification reactions. Esterification of RTO was carried out using acid catalyst to decrease the amount of free fatty acid from 2.24% to 0.09%. Subsequent transesterification of the treated oil with methanol over a series of CaO-ZnO catalysts was optimized based on the L9 Taguchi orthogonal approach. The optimization parameters are Ca/Zn ratio (0.25, 0.5, and 1), methanol/oil ratio (10, 20, and 30) and reaction time (0.5, 1, and 2 h). CaO-ZnO catalysts at variation of Ca/Zn ratios were prepared using co-precipitation method and characterized using XRD, SEM, TEM, and FTIR analysis. The amount of methyl ester yield was used as the response parameter in the S/N ratio analysis and Analysis of Variance (ANOVA). The optimum parameter for RTO transesterification to biodiesel was determined at Ca/Zn ratio of 1, methanol oil ratio of 30 and reaction time for 2 h. Transesterification under these optimized parameter generated 98% of biodiesel yield, inferring the validity of the statistical approach. Furthermore, ANOVA analysis also confirmed that all the parameters were significantly contributed at approximately equal percentage towards the amount of biodiesel. Copyright © 2021 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0)

CO2 hydrogenation to CH3OH over PdZn catalysts, with reduced CH4 production

Metallic Pd, under CO 2 hydrogenation conditions (> 175 °C, 20 bar in this work), promotes CO formation via the reverse water gas shift (RWGS) reaction. Pd‐based catalysts can show high selectivity to methanol when alloyed with Zn, and PdZn alloy catalysts are commonly reported as a stable alternative to Cu‐based catalysts for the CO 2 hydrogenation to methanol. The production of CH 4 is sometimes reported as a minor by‐product, but nevertheless this can be a major detriment for an industrial process, because methane builds up in the recycle loop, and hence would have to be purged periodically. Thus, it is extremely important to reduce methane production for future green methanol synthesis processes. In this work we have investigated TiO 2 as a support for such catalysts, with Pd, or PdZn deposited by chemical vapour impregnation (CVI). Although titania‐supported PdZn materials show excellent performance, with high selectivity to CH 3 OH + CO, they suffer from methane formation (> 0.01%). However, when ZnTiO 3 is used instead as a support medium for the PdZn alloy, methane production is greatly suppressed. The site for methane production appears to be the TiO 2 , which reduces methanol to methane at anion vacancy sites

Review on heterogeneous catalysts for the synthesis of perfumery chemicals via isomerization, acetalization and hydrogenation

Synthetic fragrance has dominated the perfumery industry in recent decades due to the ability to produce perfumery ingredients on a large scale at a low cost. Extensive research in the field of synthetic perfumery chemical involved the utilization of catalysts to improve the productivity. This review will discuss recent advances of heterogeneous catalysts for the synthesis of perfumery chemicals as fragrance ingredients. Transition from homogeneous to heterogeneous catalysts will be included in order to provide insight into the benefits of heterogeneous catalysts to overcome the limitation of homogeneous reaction. Isomerization, acetalization and hydrogenation were identified as three main reactions for the synthesis of perfumery chemicals based on the number of reported work since 2000. This review will focus on α-pinene and α-pinene oxide as the main molecular substrates, however, different molecules, for example, linalool, citronellal and cinnamaldehyde will also be included. The synthesis, modification and possible mechanisms for the reactions involving zeolite, aluminosilicate, metal oxides, metal organic framework, monometallic and bimetallic nanoparticles as heterogeneous catalysts will be discussed. Discussion on isomerization and acetalization reactions will focus on the acidity and the porosity of the catalysts as the two main factors that determine the conversion and selectivity. For perfumery chemicals produced via hydrogenation reaction, the role of monometallic and bimetallic nanoparticles catalysts will be discussed in the chemoselective reduction of cinnamaldehyde and citronellal

Selective hierarchical aluminosilicates for acetalization reaction with propylene glycol

Hierarchical micro-mesoporous aluminosilicates nanoparticles were synthesized at different of Si/Al ratios and were directly used as a solid acid catalyst for acetalization reaction with propylene glycol. TEM and N2 adsorption analysis of the resulting aluminosilicates revealed the formation of the hierarchical structure occurs on the Si/Al ratio increases the formation of mesoporous within the structure of aluminosilicate. The aluminosilicates exhibit high selectivity towards acetalization reaction in comparison with the homogeneous PTSA. The presence of mesoporous structures is crucial for increased conversion and selectivity of the reaction which presumably due to the improved diffusion of substrate to reach acid sites

CO 2

Metallic Pd, under CO 2 hydrogenation conditions (> 175 °C, 20 bar in this work), promotes CO formation via the reverse water gas shift (RWGS) reaction. Pd‐based catalysts can show high selectivity to methanol when alloyed with Zn, and PdZn alloy catalysts are commonly reported as a stable alternative to Cu‐based catalysts for the CO 2 hydrogenation to methanol. The production of CH 4 is sometimes reported as a minor by‐product, but nevertheless this can be a major detriment for an industrial process, because methane builds up in the recycle loop, and hence would have to be purged periodically. Thus, it is extremely important to reduce methane production for future green methanol synthesis processes. In this work we have investigated TiO 2 as a support for such catalysts, with Pd, or PdZn deposited by chemical vapour impregnation (CVI). Although titania‐supported PdZn materials show excellent performance, with high selectivity to CH 3 OH + CO, they suffer from methane formation (> 0.01%). However, when ZnTiO 3 is used instead as a support medium for the PdZn alloy, methane production is greatly suppressed. The site for methane production appears to be the TiO 2 , which reduces methanol to methane at anion vacancy sites