Glycerol hydrogenolysis into propanediols using in situ generated hydrogen - A critical review (original) (raw)
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Hydrogenolysis through catalytic transfer hydrogenation: Glycerol conversion to 1,2-propanediol
Catalysis Today, 2012
Important biorefinery processes imply hydrogenolysis reactions where high hydrogen pressures are required. As most of the nowadays available hydrogen gas is produced from fossil fuels there are great incentives to develop alternative technologies able to both substitute non-renewable reactants and operate at lower severity conditions. The use of hydrogen donor molecules from renewable origin can be a promising alternative to tackle simultaneously with both objectives. In the present study the use of methanol, 2-propanol and formic acid in the glycerol hydrogenolysis process to obtain 1,2-propanediol was investigated using a Ni-Cu/Al 2 O 3 catalyst, prepared by sol-gel method, and under N 2 atmosphere. A semi-continuous set-up was designed in which the donor solution was continuously fed into the autoclave reactor containing the glycerol aqueous phase. The best results in terms of glycerol conversion and 1,2-propanediol selectivity were obtained with formic acid.
Development of Catalyst for Hydrogenolysis of Glycerol to 1,3 - Propanediol
2012
Background of Study. 1 1.1.1 Biodiesel production and availability of glycerol 1 1.1.2 Hydrogenolysis of Glycerol to 1,3-propanediol 3 1.1.3 Catalyst 4 1.1 Problem Statement 4 1.2 Objective and Scope of Studies 5 CHAPTER 2: LITERATURE RE VIEW , 2.1 Introduction 2.2 Metal used as the catalyst 7 2.3 Reaction Solution 2.4 Reaction Condition 2.5 Presence of Second Metal 12 2.6 Effectof Catalyst Reduction Temperature 12 CHAPTER 3: METHODOLOGY 13 3.1 Preparation of supported metal catalysts 3.1.1 Catalyst preparation procedures 3.2 Catalyst Characterization 19 3.3 Catalytic Test and Analysis 21 CHAPTER 4: RESULTS AND DISCUSSION 23 4.1 Catalyst Characterization 23 4.1.1 Fourier Transformed Infrared (FTIR) 23 4.1.2 Temperature Program Reduction (TPR) 24 4.1.3 X-Ray Diffraction (XRD) 26 4.1.4 Field Emission Scanning ElectronMicroscope (FESEM) 27 vi 32 LIST OF APPENDICES
Catalysts for glycerol hydrogenolysis to 1,3-propanediol: A review of chemical routes and market
Catalysis Today, 2020
Catalysts for glycerol hydrogenolysis to 1,3-propanediol: a review of chemical routes and market Alisson Dias da Silva Ruy (Conceptualization) (Investigation) (Methodology) (Writing-original draft) (Visualization), Rita Maria de Brito Alves (Supervision) (Writing-review and editing), Thiago Lewis Reis Hewer (Investigation) (Methodology) (Writing-original draft), Danilo de Aguiar Pontes (Writing-original draft) (Writingreview and editing), Leonardo Sena Gomes Teixeira (Investigation) (Supervision), Luiz Antônio Magalhães Pontes (Conceptualization) (Methodology) (Writing-original draft) (Supervision) (Writingreview and editing)
Hydrogen production from glycerol: An update
Energy Conversion and Management, 2009
The production of alternative fuels such as biodiesel and ethanol has increased over the last few years. Such fuels are vital for the reduction of energy dependence on foreign countries and to protect the environmental damage associated with the use of fossil fuels. Due to the increased production of biodiesel, a glut of crude glycerol has resulted in the market and the price has plummeted over the past few years. Therefore, it is imperative to find alternative uses for glycerol. A variety of chemicals and fuels including hydrogen can be produced from glycerol. Hydrogen is produced by using several processes, such as steam reforming, autothermal reforming, aqueous-phase reforming and supercritical water reforming. This paper reviews different generation methods, catalysts and operating conditions used to produce hydrogen using glycerol as a substrate. Most of the studies were focused on hydrogen production via steam reforming process and still less work has been done on producing hydrogen from crude glycerol.
Journal of Catalysis, 2011
2-Propanol was studied as a hydrogen donor molecule in the transfer hydrogenation process to selectively convert glycerol into 1,2-propanediol under N 2 pressure and using Ni or/and Cu supported on Al 2 O 3 catalysts. The results were compared to those obtained under the same operating conditions but under H 2 pressure. The results of the activity tests and catalyst characterization techniques (N 2-physisorption, H 2-chemisorption, TPD of NH 3 , TPR, TPO and XPS) suggest that glycerol hydrogenolysis to yield 1,2-propanediol occurred through a different mechanism regarding the origin of the hydrogen species. When atomic hydrogen came from dissolved molecular hydrogen dissociation, glycerol was first dehydrated to acetol and then hydrogenated to 1,2-propanediol. On the other hand, when the hydrogen atoms were produced from 2-propanol dehydrogenation, glycerol was directly converted to 1,2-propanediol through intermediate alkoxide formation.
Hydrogen production from glycerol reforming: conventional and green production
The use of biomass to produce transportation and related fuels is of increasing interest. In the traditional approach of converting oils and fats to fuels, trans-esterification processes yield a very large coproduction of glycerol. Initially, this coproduct was largely ignored and then considered as a useful feedstock for conversion to various chemicals. However, because of the intrinsic large production, any chemical feedstock role would consume only a fraction of the glycerol produced, so other options had to be considered. The reforming of glycerol was examined for syngas production, but more recently the use of photocatalytic decomposition to hydrogen (H 2) is of major concern and several approaches have been proposed. The subject of this review is this greener photocatalytic route, especially involving the use of solar energy and visible light. Several different catalyst designs are considered, together with a very wide range of secured rates of H 2 production spanning several orders of magnitude, depending on the catalytic system and the process conditions employed. H 2 production is especially high when used in glycerol-water mixtures.
Membranes, 2017
Glycerol represents an emerging renewable bio-derived feedstock, which could be used as a source for producing hydrogen through steam reforming reaction. In this review, the state-of-the-art about glycerol production processes is reviewed, with particular focus on glycerol reforming reactions and on the main catalysts under development. Furthermore, the use of membrane catalytic reactors instead of conventional reactors for steam reforming is discussed. Finally, the review describes the utilization of the Pd-based membrane reactor technology, pointing out the ability of these alternative fuel processors to simultaneously extract high purity hydrogen and enhance the whole performances of the reaction system in terms of glycerol conversion and hydrogen yield.
Molecular Catalysis, 2020
This paper is a review of the main scientific progresses achieved by the authors in the field of bioglycerol upgrading. Our research focused on the development of efficient precious and/or transition metals based γ-Al 2 O 3 catalysts for the bioglycerol Aqueous Phase Reforming, Steam Reforming and Hydrogenolysis in order to selectively obtain high value-added H 2 and/or propanediols. For each of the three conversion processes, using state-of-the art synthesis methods, characterization techniques, and kinetic and mechanistic studies, we obtained a better understanding of the structure-activity relationships of the developed systems. Special emphasis was placed on the identification of the active species, the synergy between the different functionalities, and the main factors causing deactivation. This information allowed us improving the catalytic performance, in terms of activity, selective and long-term stability. Moreover, our results and conclusions are contrasted with current stateof-the art, and the perspectives for further developments are addressed.
Overview of glycerol reforming for hydrogen production
Renewable and Sustainable Energy Reviews, 2016
Hydrogen is used by the chemical industry in numerous processes, and today almost 95% is produced from raw materials based on fossil fuels, such as methane (CH 4). However, catalytic reforming technologies face a number of technical and scientific challenges involving the quality of raw materials, conversion efficiency, and safety issues in the integration of systems of H 2 production, purification and use, among others. Glycerol is a versatile raw material for H 2 production because it is the main byproduct of biodiesel production, which a few years ago was consolidated in the world energy matrix and whose production continues to grow in the main consumer markets. Moreover, it has the noteworthy characteristic of decentralized production, which is directly reflected in its easy use. This paper presents a literature review on the reforming technologies applied to glycerol, the advantages of each route, and the main problems involved.