Special Issue "Catalysis for the Production of Sustainable Fuels and Chemicals"

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Biomass Catalysis".

Deadline for manuscript submissions: 30 November 2019.

Special Issue Editors

Guest Editor
Prof. Flora T. T. Ng Website E-Mail
Department of Chemical Engineering, University of Waterloo, 200 University Avenue West, Waterloo, Ontario N2L 3G1, Canada
Interests: solid acid catalysis; clean fuels; chemicals from biomass; process intensification; esterification; transesterification; hydrogenolysis; desulfurization; hydrocracking
Guest Editor
Prof. Ajay K. Dalai Website E-Mail
Department of Chemical and Biological Engineering, University of Saskatchewan, Saskatoon, SK Canada S7N 5A9
Phone: +1306-9664771
Interests: hydro-deoxygenation; hydrogenolysis; hydrogenation; biomass; esterification and transesterification; pyrolysis; gasification; hydrothermal treatment; Fischer-Tropsch synthesis; hydroprocessing

Special Issue Information

Dear Colleagues,

Green-house gas emissions and environmental concerns have led to recent research in the use of renewable feedstocks derived from biomass, waste oils, and fats as a source of fuels and chemicals. However, these feedstocks contain a large amount of oxygen functional groups. Processing these feedstocks generally requires esterification and transesterification, deoxygenation, hydrogenation, hydrogenolysis, aldol condensation and cracking reactions. In addition, the bio-oils produced through pyrolysis and hydrothermal treatment are treated through catalytic processes for producing clean fuels. In addition, syngas produced through gasification of biomass is converted to liquid fuels. The main focus of this Special Issue is to solicit recent advances in the catalytic processing of these renewable feedstocks to produce sustainable fuels and chemicals.

Prof. Flora T. T. Ng
Prof. Ajay K. Dalai
Guest Editors

Manuscript Submission Information

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Keywords

  • Sustainable Fuels and Chemicals
  • Hydrogenolysis
  • Deoxygenation
  • Esterification and Transesterification
  • Hydroprocessing
  • Cracking
  • Pyrolysis
  • Gasification
  • Hydrothermal Treatment Biomass
  • Bio-oil and Fats
  • Catalysis

Published Papers (9 papers)

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Research

Open AccessArticle
Artificial Intelligence Modelling Approach for the Prediction of CO-Rich Hydrogen Production Rate from Methane Dry Reforming
Catalysts 2019, 9(9), 738; https://doi.org/10.3390/catal9090738 - 31 Aug 2019
Abstract
This study investigates the applicability of the Leven–Marquardt algorithm, Bayesian regularization, and a scaled conjugate gradient algorithm as training algorithms for an artificial neural network (ANN) predictively modeling the rate of CO and H2 production by methane dry reforming over a Co/Pr [...] Read more.
This study investigates the applicability of the Leven–Marquardt algorithm, Bayesian regularization, and a scaled conjugate gradient algorithm as training algorithms for an artificial neural network (ANN) predictively modeling the rate of CO and H2 production by methane dry reforming over a Co/Pr2O3 catalyst. The dataset employed for the ANN modeling was obtained using a central composite experimental design. The input parameters consisted of CH4 partial pressure, CO2 partial pressure, and reaction temperature, while the target parameters included the rate of CO and H2 production. A neural network architecture of 3 13 2, 3 15 2, and 3 15 2 representing the input layer, hidden neuron layer, and target (output) layer were employed for the Leven–Marquardt, Bayesian regularization, and scaled conjugate gradient training algorithms, respectively. The ANN training with each of the algorithms resulted in an accurate prediction of the rate of CO and H2 production. The best prediction was, however, obtained using the Bayesian regularization algorithm with the lowest standard error of estimates (SEE). The high values of coefficient of determination (R2 > 0.9) obtained from the parity plots are an indication that the predicted rates of CO and H2 production were strongly correlated with the observed values. Full article
(This article belongs to the Special Issue Catalysis for the Production of Sustainable Fuels and Chemicals)
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Open AccessArticle
The Effects of Catalyst Support and Temperature on the Hydrotreating of Waste Cooking Oil (WCO) over CoMo Sulfided Catalysts
Catalysts 2019, 9(8), 689; https://doi.org/10.3390/catal9080689 - 15 Aug 2019
Abstract
Waste cooking oil (WCO) hydrotreating to produce green diesel is good for both the environmental protection and energy recovery problems. The roles of catalyst support and reaction temperature on reactions during WCO hydrotreating process were evaluated over an unsupported and a commercial sulfided [...] Read more.
Waste cooking oil (WCO) hydrotreating to produce green diesel is good for both the environmental protection and energy recovery problems. The roles of catalyst support and reaction temperature on reactions during WCO hydrotreating process were evaluated over an unsupported and a commercial sulfided cobalt and molybdenum (CoMoS) catalyst supported by a mixture of Al2O3, TiO2, and SiO2. The presence of catalyst support helped to improve the dispersion and enlarge the surface area of CoMoS, and was found to be a key factor in reducing reaction temperature, in enhancing the hydrodeoxygenation (HDO) and hydrogenation capabilities, and in decreasing polymerization capability. The increase of reaction temperature strongly improved the deoxygenation, hydrogenation, and cracking reaction activities. Compared to the unsupported CoMoS, the supported one exhibited good deoxygenation and hydrogenation capabilities at 340 °C in WCO hydrotreating to produce diesel fraction; however, high temperature operation needs to be carefully controlled because it may cause overcracking and dehydrogenation. Full article
(This article belongs to the Special Issue Catalysis for the Production of Sustainable Fuels and Chemicals)
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Open AccessArticle
Application of Microwave in Hydrogen Production from Methane Dry Reforming: Comparison Between the Conventional and Microwave-Assisted Catalytic Reforming on Improving the Energy Efficiency
Catalysts 2019, 9(7), 618; https://doi.org/10.3390/catal9070618 - 20 Jul 2019
Abstract
The microwave-assisted dry reforming of methane over Ni and Ni–MgO catalysts supported on activated carbon (AC) was studied with respect to reducing reaction energy consumption. In order to optimize the reforming reaction using the microwave setup, an inclusive study was performed on the [...] Read more.
The microwave-assisted dry reforming of methane over Ni and Ni–MgO catalysts supported on activated carbon (AC) was studied with respect to reducing reaction energy consumption. In order to optimize the reforming reaction using the microwave setup, an inclusive study was performed on the effect of operating parameters, including the type of catalysts’ active metal and their concentration in the AC support, feed flow rate, and reaction temperature on the reaction conversion and H2/CO selectivity. The methane dry reforming was also carried out using conventional heating and the results were compared to those of microwave heating. The catalysts’ activity was increased under microwave heating and as a result, the feed conversion and hydrogen selectivity were enhanced in comparison to the conventional heating method. In addition, to improve the reactants’ conversion and products’ selectivity, the thermal analysis also clarified the crucial importance of microwave heating in enhancing the energy efficiency of the reaction compared to the conventional heating. Full article
(This article belongs to the Special Issue Catalysis for the Production of Sustainable Fuels and Chemicals)
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Open AccessCommunication
Enhancement of Light Olefins Selectivity Over N-Doped Fischer-Tropsch Synthesis Catalyst Supported on Activated Carbon Pretreated with KMnO4
Catalysts 2019, 9(6), 505; https://doi.org/10.3390/catal9060505 - 31 May 2019
Abstract
Ammonium iron citrate was used as an iron precursor in order to prepare N-doped catalysts supported on KMnO4 pretreated activated carbon (10MnK-AC). Iron nitride was synthesized in company with the formation of α-Fe2O3 on 10MnK-AC. The characterizations of the [...] Read more.
Ammonium iron citrate was used as an iron precursor in order to prepare N-doped catalysts supported on KMnO4 pretreated activated carbon (10MnK-AC). Iron nitride was synthesized in company with the formation of α-Fe2O3 on 10MnK-AC. The characterizations of the catalysts show that nitrogen atoms were doped into iron lattice rather than the networks of the carbon support. The performance of Fischer-Tropsch synthesis to light olefins (FTO) suggest an improvement in O/P ratio (olefins to paraffins molar ratio of C2–C4) over the iron catalysts supported on 10MnK-AC. The further promotion of light olefins selectivity (up to 44.7%) was obtained over FeN-10MnK-AC catalyst owing to the collaborative contribution of the electron donor effect of nitrogen and the suppression effect on the second hydrogenation over 10MnK-AC support. Full article
(This article belongs to the Special Issue Catalysis for the Production of Sustainable Fuels and Chemicals)
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Open AccessArticle
Influence of Chemical Surface Characteristics of Ammonium-Modified Chilean Zeolite on Oak Catalytic Pyrolysis
Catalysts 2019, 9(5), 465; https://doi.org/10.3390/catal9050465 - 21 May 2019
Abstract
The influence of chemical surface characteristics of Chilean natural and modified zeolites on Chilean Oak catalytic pyrolysis was investigated in this study. Chilean zeolite samples were characterised by nitrogen absorption at 77 K, X-ray powder diffraction (XRD), and X-ray fluorescence (XRF). The nature [...] Read more.
The influence of chemical surface characteristics of Chilean natural and modified zeolites on Chilean Oak catalytic pyrolysis was investigated in this study. Chilean zeolite samples were characterised by nitrogen absorption at 77 K, X-ray powder diffraction (XRD), and X-ray fluorescence (XRF). The nature and strength of zeolite acid sites were studied by diffuse reflectance infrared Fourier transform (DRIFT), using pyridine as a probe molecule. Experimental pyrolysis was conducted in a quartz cylindrical reactor and bio-oils were obtained by condensation of vapours in a closed container. Chemical species in bio-oil samples were identified by a gas chromatography/mass spectrophotometry (GC/MS) analytical procedure. Results indicate that after the ionic exchange treatment, an increase of the Brønsted acid site density and strength was observed in ammonium-modified zeolites. Brønsted acids sites were associated with an increment of the composition of ketones, aldehydes, and hydrocarbons and to a decrease in the composition of the following families (esters; ethers; and acids) in obtained bio-oil samples. The Brønsted acid sites on ammonium-modified zeolite samples are responsible for the upgraded bio-oil and value-added chemicals, obtained in this research. Bio-oil chemical composition was modified when the pyrolysis-derived compounds were upgraded over a 2NHZ zeolite sample, leading to a lower quantity of oxygenated compounds and a higher composition of value-added chemicals. Full article
(This article belongs to the Special Issue Catalysis for the Production of Sustainable Fuels and Chemicals)
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Open AccessArticle
The Promoting Effect of Ni on Glycerol Hydrogenolysis to 1,2-Propanediol with In Situ Hydrogen from Methanol Steam Reforming Using a Cu/ZnO/Al2O3 Catalyst
Catalysts 2019, 9(5), 412; https://doi.org/10.3390/catal9050412 - 01 May 2019
Cited by 1
Abstract
Production of green chemicals using a biomass derived feedstock is of current interest. Among the processes, the hydrogenolysis of glycerol to 1,2-propanediol (1,2-PD) using externally supplied molecular hydrogen has been studied quite extensively. The utilization of methanol present in crude glycerol from biodiesel [...] Read more.
Production of green chemicals using a biomass derived feedstock is of current interest. Among the processes, the hydrogenolysis of glycerol to 1,2-propanediol (1,2-PD) using externally supplied molecular hydrogen has been studied quite extensively. The utilization of methanol present in crude glycerol from biodiesel production can avoid the additional cost for molecular hydrogen storage and transportation, as well as reduce the safety risks due to the high hydrogen pressure operation. Recently the hydrogenolysis of glycerol with a Cu/ZnO/Al2O3 catalyst using in situ hydrogen generated from methanol steam reforming in a liquid phase reaction has been reported. This paper focusses on the effect of added Ni on the activity of a Cu/ZnO/Al2O3 catalyst prepared by an oxalate gel-co-precipitation method for the hydrogenolysis of glycerol using methanol as a hydrogen source. It is found that Ni reduces the conversion of glycerol but improves the selectivity to 1,2-PD, while a higher conversion of methanol is observed. The promoting effect of Ni on the selectivity to 1,2-PD is attributed to the slower dehydration of glycerol to acetol coupled with a higher availability of in situ hydrogen produced from methanol steam reforming and the higher hydrogenation activity of Ni towards the intermediate acetol to produce 1,2-PD. Full article
(This article belongs to the Special Issue Catalysis for the Production of Sustainable Fuels and Chemicals)
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Open AccessArticle
Hydrotreated Vegetable Oil as a Fuel from Waste Materials
Catalysts 2019, 9(4), 337; https://doi.org/10.3390/catal9040337 - 04 Apr 2019
Abstract
Biofuels have become an integral part of everyday life in modern society. Bioethanol and fatty acid methyl esters are a common part of both the production of gasoline and diesel fuels. Also, pressure on replacing fossil fuels with bio-components is constantly growing. Waste [...] Read more.
Biofuels have become an integral part of everyday life in modern society. Bioethanol and fatty acid methyl esters are a common part of both the production of gasoline and diesel fuels. Also, pressure on replacing fossil fuels with bio-components is constantly growing. Waste vegetable fats can replace biodiesel. Hydrotreated vegetable oil (HVO) seems to be a better alternative. This fuel has a higher oxidation stability for storage purposes, a lower temperature of loss of filterability for the winter time, a lower boiling point for cold starts, and more. Viscosity, density, cold filter plugging point of fuel blend, and flash point have been measured to confirm that a fuel from HVO is so close to a fuel standard that it is possible to use it in engines without modification. The objective of this article is to show the properties of different fuels with and without HVO admixtures and to prove the suitability of using HVO compared to FAME. HVO can also be prepared from waste materials, and no major modifications of existing refinery facilities are required. No technology in either investment or engine adaptation of fuel oils is needed in fuel processing. Full article
(This article belongs to the Special Issue Catalysis for the Production of Sustainable Fuels and Chemicals)
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Open AccessArticle
Hydrotreatment Followed by Oxidative Desulfurization and Denitrogenation to Attain Low Sulphur and Nitrogen Bitumen Derived Gas Oils
Catalysts 2018, 8(12), 645; https://doi.org/10.3390/catal8120645 - 10 Dec 2018
Abstract
To lower the sulphur content below 500 ppm and to increase the quality of bitumen derived heavy oil, a combination of hydrotreating followed by oxidative desulfurization (ODS) and oxidative denitrogenation (ODN) is proposed in this work. NiMo/γ-Al2O3 catalyst was synthesized [...] Read more.
To lower the sulphur content below 500 ppm and to increase the quality of bitumen derived heavy oil, a combination of hydrotreating followed by oxidative desulfurization (ODS) and oxidative denitrogenation (ODN) is proposed in this work. NiMo/γ-Al2O3 catalyst was synthesized and used to hydrotreat heavy gas oil (HGO) and light gas oil (LGO) at typical operating conditions of 370–390 °C, 9 MPa, 1–1.5 h−1 space velocity and 600:1 H2 to oil ratio. γ-Alumina and alumina-titania supported Mo, P, Mn and W catalysts were synthesized and characterized using X-ray diffractions, N2 adsorption-desorption using Brunauer–Emmett–Teller (BET) method, X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FT-IR). All catalysts were tested for the oxidation of sulphur and nitrogen aromatic compounds present in LGO and HGO using tert-butyl hydroperoxide (TBHP) as oxidant. The oxidized sulphur and nitrogen compounds were extracted using adsorption on activated carbon and liquid-liquid extraction using methanol. The determination of oxidation states of each metal using XPS confirmed the structure of metal oxides in the catalyst. Thus, the catalytic activity determined in terms of sulphur and nitrogen removal is related to their physico-chemical properties. In agreement with literature, a simplistic mechanism for the oxidative desulfurization is also presented. Mo was found to be more active in comparison to W. Presence of Ti in the support has shown 8–12% increase in ODS and ODN. The MnPMo/γ-Al2O3-TiO2 catalyst showed the best activity for sulphur and nitrogen removal. The role of Mn and P as promoters to molybdenum was also discussed. Further three-stage ODS and ODN was performed to achieve less than 500 ppm in HGO and LGO. The combination of hydrotreatment, ODS and ODN has resulted in removal of 98.8 wt.% sulphur and 94.7 wt.% nitrogen from HGO and removal of 98.5 wt.% sulphur and 97.8 wt.% nitrogen from LGO. Full article
(This article belongs to the Special Issue Catalysis for the Production of Sustainable Fuels and Chemicals)
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Open AccessArticle
Influence of Bio-Oil Phospholipid on the Hydrodeoxygenation Activity of NiMoS/Al2O3 Catalyst
Catalysts 2018, 8(10), 418; https://doi.org/10.3390/catal8100418 - 25 Sep 2018
Cited by 2
Abstract
Hydrodeoxygenation (HDO) activity of a typical hydrotreating catalyst, sulfided NiMo/γ-Al2O3 for deoxygenation of a fatty acid has been explored in a batch reactor at 54 bar and 320 °C in the presence of contaminants, like phospholipids, which are known to [...] Read more.
Hydrodeoxygenation (HDO) activity of a typical hydrotreating catalyst, sulfided NiMo/γ-Al2O3 for deoxygenation of a fatty acid has been explored in a batch reactor at 54 bar and 320 °C in the presence of contaminants, like phospholipids, which are known to be present in renewable feeds. Oleic acid was used for the investigation. Freshly sulfided catalyst showed a high degree of deoxygenation activity; products were predominantly composed of alkanes (C17 and C18). Experiments with a major phospholipid showed that activity for C17 was greatly reduced while activity to C18 was not altered significantly in the studied conditions. Characterization of the spent catalyst revealed the formation of aluminum phosphate (AlPO4), which affects the active phase dispersion, blocks the active sites, and causes pore blockage. In addition, choline, formed from the decomposition of phospholipid, partially contributes to the observed deactivation. Furthermore, a direct correlation was observed in the accumulation of coke on the catalyst and the amount of phospholipid introduced in the feed. We therefore propose that the reason for the increased deactivation is due to the dual effects of an irreversible change in phase to aluminum phosphate and the formation of choline. Full article
(This article belongs to the Special Issue Catalysis for the Production of Sustainable Fuels and Chemicals)
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