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Biomass Derived Heterogeneous and Homogeneous Catalysts, 2nd Edition

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

Deadline for manuscript submissions: closed (31 March 2024) | Viewed by 14256

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Special Issue Editors

Prof. Dr. José María Encinar Martín

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Guest Editor

Department of Chemical Engineering and Physical Chemistry, University of Extremadura, Avda. De Elvas s/n, 06006 Badajoz, Spain
Interests: biomass; biodiesel; biolubricants; oxidative stability; fatty acid methyl esters; catalyst; pyrolysis; gasification
Special Issues, Collections and Topics in MDPI journals

Dr. Sergio Nogales Delgado

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Dear Colleagues,

Renewable energy sources will play a decisive role in the future development of mankind. Indeed, at the present time, on account of the current global energy crisis, renewable energy sources will become more and more important, especially in areas such as Europe, among others. The increase in energy demand and the need for replacing fossil fuels make the development of new renewable raw materials mandatory in order to generate sustainable fuels and chemical products.

For this reason, the production of biodiesel, bioethanol, and biolubricants as well as the development of biorefineries are promising research fields, among other alternatives. Some of these products are currently a reality, but their large-scale economic development is still uncertain due to the competition with fossil fuels. A significant and essential issue that must be contended with to overcome this challenge is research into and the use of new catalysts to carry out the synthesis processes of bioproducts more efficiently.

For this Special Issue (which is the second part of the successful Special Issue with the same title, https://0-www-mdpi-com.brum.beds.ac.uk/journal/catalysts/special_issues/biomass_hete_homo_cata), we invite papers dealing with the use of homogeneous and heterogeneous catalysts for the development of processes such as biodiesel, biolubricant, or biofuel production.

More specifically, topics of interest for the Special Issue include (but are not limited to):

Biomass;
Biofuels;
Biorefinery;
Bioproducts;
Biochemicals;
Biorenewables;
Bioenergy–biofuels byproducts;
Biodiesel;
Biolubricants;
Bioethanol;
Biomethane.

Prof. Dr. José María Encinar Martín
Dr. Sergio Nogales Delgado
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Catalysts is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

bioproducts
biodiesel
bioethanol
bioenergy
biolubricants
homogeneous and heterogeneous catalysts

Published Papers (10 papers)

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Research

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20 pages, 6003 KiB

Open AccessArticle

A Green Nanocatalyst for Fatty Acid Methyl Ester Conversion from Waste Cooking Oil

by Sadaf Khosa, Madeeha Rani, Muhammad Saeed, Syed Danish Ali, Aiyeshah Alhodaib and Amir Waseem

Catalysts 2024, 14(4), 244; https://0-doi-org.brum.beds.ac.uk/10.3390/catal14040244 - 06 Apr 2024

Viewed by 532

Abstract

This study used a novel combination of cellulose nanocrystals (CNCs) and calcium oxide (CaO) nanocomposite (CaO/CNCs) for the production of biodiesel from waste cooking oil. The filter paper was used as a raw cellulose source to produce the CNCs from the acid hydrolysis of cellulose with sulfuric acid. The as-synthesized CaO/CNC nanocomposite is recyclable and environmentally friendly and was characterized using Fourier transform infrared spectroscopy, energy dispersive X-ray, scanning electron microscopy, and X-ray diffraction. The optimum process parameters investigated are a 20:1 methanol-to-oil molar ratio, 3-weight percent catalyst concentration, 60 °C temperature, and 90 min of reaction time. Under the optimum conditions, a biodiesel yield of 84% was obtained. The CaO/CNC nanocomposite achieved five times reusability, indicating its effectiveness and reusability in the transesterification reaction. The synthesized biodiesel chemical composition was examined using FTIR, GCMS, ¹H-NMR, and ¹³C-NMR, and its properties, including specific gravity, color, flash point, cloud point, pour point, viscosity, sulfur content, sediments, water content, total acid number, cetane number, and corrosion test, were ascertained using ASTM standard practices. The outcomes were determined to fulfill global biodiesel standards (ASTM 951, 6751). Five successive transesterification processes were used to test the regeneration of the catalyst; the first three showed no distinct change, while the fifth cycle showed a reduction of up to 79%. The innovative composite CaO/CNC and used cooking oil are stable, affordable, and extremely successful for long-term biodiesel generation. Full article

(This article belongs to the Special Issue Biomass Derived Heterogeneous and Homogeneous Catalysts, 2nd Edition)

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12 pages, 2456 KiB

Open AccessArticle

Organically Functionalized Porous Aluminum Phosphonate for Efficient Synthesis of 5-Hydroxymethylfurfural from Carbohydrates

by Riddhi Mitra, Bhabani Malakar and Asim Bhaumik

Catalysts 2023, 13(11), 1449; https://0-doi-org.brum.beds.ac.uk/10.3390/catal13111449 - 19 Nov 2023

Viewed by 1027

Abstract

Naturally occurring fossil fuels are the major resource of energy in our everyday life, but with the huge technological development over the years and subsequent energy demand, the reserve of this energy resource is depleting at an alarming rate, which will challenge our net energy resources in the near future. Thus, an alternative sustainable energy resource involving biomass and bio-refinery has become the most emerging and demanding approach, where biofuels can be derived effectively from abundant biomass via valuable chemical intermediates like 5-hydroxymethylfurfural (5-HMF). 5-HMF is a valuable platform chemical for the synthesis of fuel and fine chemicals. Herein, we report the synthesis of the organically functionalized porous aluminum phosphonate materials: Ph-ALPO-1 in the absence of any template and Ph-ALPO-2 by using 1,3-diaminopropane-N,N,N′,N′-tetraacetic acid as a small organic molecule template and phenylphosphonic acid as a phosphate source. These hybrid phosphonates are used as acid catalysts for the synthesis of 5-HMF from carbohydrates derived from biomass resources. These Ph-ALPO-1 and Ph-ALPO-2 materials catalyzed the dehydration of fructose to 5-HMF with total yields of 74.6% and 90.7%, respectively, in the presence of microwave-assisted optimized reaction conditions. Full article

(This article belongs to the Special Issue Biomass Derived Heterogeneous and Homogeneous Catalysts, 2nd Edition)

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23 pages, 9202 KiB

Open AccessArticle

Acid-Catalyzed Etherification of Glycerol with Tert-Butanol: Reaction Monitoring through a Complete Identification of the Produced Alkyl Ethers

by Alfonso Cornejo, Inés Reyero, Idoia Campo, Gurutze Arzamendi and Luis M. Gandía

Catalysts 2023, 13(10), 1386; https://0-doi-org.brum.beds.ac.uk/10.3390/catal13101386 - 23 Oct 2023

Viewed by 1228

Abstract

Higher tert-Butyl glycerol ethers (tBGEs) are interesting glycerol derivatives that can be produced from tert-butyl alcohol (TBA) and glycerol using an acid catalyst. Glycerol tert-butylation is a complex reaction that leads to the formation of five tBGEs (two monoethers, two diethers, and one triether). In order to gain insight into the reaction progress, the present work reports on the monitoring of glycerol etherification with TBA and p-toluensulfonic acid (PTSA) as homogeneous catalysts. Two analytical techniques were used: gas chromatography (GC), which constitutes the benchmark method, and ¹H nuclear magnetic resonance (¹H NMR), whose use for this purpose has not been reported to date. A method for the quantitative analysis of tBGEs and glycerol based on ¹H NMR is presented that greatly reduced the analysis time and relative error compared with GC-based methods. The combined use of both techniques allowed for a complete quantitative and qualitative description of the glycerol tert-butylation progress. The set of experimental results collected showed the influence of the catalyst concentration and TBA/glycerol ratio on the etherification reaction and evidenced the intrinsic difficulties of this process to achieve high selectivities and yields to the triether. Full article

(This article belongs to the Special Issue Biomass Derived Heterogeneous and Homogeneous Catalysts, 2nd Edition)

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13 pages, 3080 KiB

Open AccessArticle

Pretreatment and Nanoparticles as Catalysts for Biogas Production Reactions in Pepper Waste and Pig Manure

by Ana Isabel Parralejo Alcobendas, Luis Royano Barroso, Juan Cabanillas Patilla and Jerónimo González Cortés

Catalysts 2023, 13(7), 1029; https://0-doi-org.brum.beds.ac.uk/10.3390/catal13071029 - 21 Jun 2023

Viewed by 781

Abstract

The circular economy is based on using waste generated from any process to obtain products with zero residues’ criteria. This research was focused on pepper waste from the polyphenolic extraction method. Pepper waste was evaluated in batch and semi-continuous regime anaerobic digestion, adding, as catalysts, absorbent nanoparticles and/or using pretreatment strategies. The best methane yields were obtained from SB1 (assay without pretreatment in pepper waste): 464 ± 25 NL kg VS⁻¹ for batch assays; and from period II (1.47 g VS L⁻¹ d⁻¹) of S2 (assay of pig manure and pepper waste with thermal pretreatment): 160 NL/kg VS⁻¹ for semi-continuous experiments. However, a kinetic study showed a methane production rate higher for SB2 (assay with nanoparticles as catalyst) than SB1 in batch assays. Full article

(This article belongs to the Special Issue Biomass Derived Heterogeneous and Homogeneous Catalysts, 2nd Edition)

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14 pages, 1892 KiB

Open AccessArticle

Nano-Magnetic CaO/Fe₂O₃/Feldspar Catalysts for the Production of Biodiesel from Waste Oils

by Maryam Hanif, Ijaz Ahmad Bhatti, Muhammad Asif Hanif, Umer Rashid, Bryan R. Moser, Asma Hanif and Fahad A. Alharthi

Catalysts 2023, 13(6), 998; https://0-doi-org.brum.beds.ac.uk/10.3390/catal13060998 - 13 Jun 2023

Cited by 2 | Viewed by 1315

Abstract

Production of biodiesel from edible vegetable oils using homogenous catalysts negatively impacts food availability and cost while generating significant amounts of caustic wastewater during purification. Thus, there is an urgent need to utilize low-cost, non-food feedstocks for the production of biodiesel using sustainable heterogeneous catalysis. The objective of this study was to synthesize a novel supported nano-magnetic catalyst (CaO/Fe₂O₃/feldspar) for the production of biodiesel (fatty acid methyl esters) from waste and low-cost plant seed oils, including Sinapis arvensis (wild mustard), Carthamus oxyacantha (wild safflower) and Pongamia pinnata (karanja). The structure, morphology, surface area, porosity, crystallinity, and magnetization of the nano-magnetic catalyst was confirmed using XRD, FESEM/EDX, BET, and VSM. The maximum biodiesel yield (93.6–99.9%) was achieved at 1.0 or 1.5 wt.% catalyst with methanol-to-oil molar ratios of 5:1 or 10:1 at 40 °C for 2 h. The CaO/Fe₂O₃/feldspar catalyst retained high activity for four consecutive cycles for conversion of karanja, wild mustard, and wild safflower oils. The effective separation of the catalyst from biodiesel was achieved using an external magnet. Various different physico-chemical parameters, such as pour point, density, cloud point, iodine value, acid value, and cetane number, were also determined for the optimized fuels and found to be within the ranges specified in ASTM D6751 and EN 14214, where applicable. Full article

(This article belongs to the Special Issue Biomass Derived Heterogeneous and Homogeneous Catalysts, 2nd Edition)

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14 pages, 3227 KiB

Open AccessFeature PaperArticle

Conversion of Glucose to 5-Hydroxymethylfurfural Using Consortium Catalyst in a Biphasic System and Mechanistic Insights

by Geraldo Ferreira David, Daniela Margarita Echeverri Delgadillo, Gabriel Abranches Dias Castro, Diana Catalina Cubides-Roman, Sergio Antonio Fernandes and Valdemar Lacerda Júnior

Catalysts 2023, 13(3), 574; https://0-doi-org.brum.beds.ac.uk/10.3390/catal13030574 - 12 Mar 2023

Viewed by 2252

Abstract

We found an effective catalytic consortium capable of converting glucose to 5-hydroxymethylfurfural (HMF) in high yields (50%). The reaction consists of a consortium of a Lewis acid (NbCl₅) and a Brønsted acid (p-sulfonic acid calix[4]arene (CX4SO₃H)), in a microwave-assisted reactor and in a biphasic system. The best result for the conversion of glucose to HMF (yield of 50%) was obtained with CX4SO₃H/NbCl₅ (5 wt%/7.5 wt%), using water/NaCl and MIBK (1:3), at 150 °C, for 17.5 min. The consortium catalyst recycling was tested, allowing its reuse for up to seven times, while maintaining the HMF yield constant. Additionally, it proposed a catalytic cycle by converting glucose to HMF, highlighting the following two key points: the isomerization of glucose into fructose, in the presence of Lewis acid (NbCl₅), and the conversion of fructose into HMF, in the presence of CX4SO₃H/NbCl₅. A mechanism for the conversion of glucose to HMF was proposed and validated. Full article

(This article belongs to the Special Issue Biomass Derived Heterogeneous and Homogeneous Catalysts, 2nd Edition)

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13 pages, 3946 KiB

Open AccessArticle

Optimizing Al and Fe Load during HTC of Water Hyacinth: Improvement of Induced HC Physicochemical Properties

by Mara Olivares-Marin, Silvia Román, Beatriz Ledesma and Alfredo Álvarez

Catalysts 2023, 13(3), 506; https://0-doi-org.brum.beds.ac.uk/10.3390/catal13030506 - 28 Feb 2023

Viewed by 997

Abstract

Nowadays, several alternatives have been proposed to increase the porosity and/or modify the surface groups of hydrochars from biomasses as well as to develop additional features on them. These alternatives can include specific modifications for the process, as previous steps or as postreatments, and the wide variety of forms in which they can be made can substantially affect the product distribution and properties. In this study, the hydrothermal carbonization process of an invasive floating plant (Water hyacinth) has been modified by introducing different amounts of iron (FeCl₃) and aluminium alloy (shaving scrap waste) during the hydrothermal reaction. The effects on process reactivity, phase distribution, and physicochemical properties of the samples obtained were studied by means of different characterization techniques such as thermogravimetry (TG-DTG), physical adsorption/desorption of N₂ at −196 °C, FT-IR spectroscopy, and scanning electron microscopy (SEM). In the case of iron-catalyzed reactions, the magnetite formation and magnetic behavior of the prepared hydrochars after a pyrolytic treatment was also estimated. The results obtained indicate that the porosity of the hydrochars was clearly improved to different extents by the addition of Al or Fe during direct synthesis. In addition, porous carbons with a moderate magnetic character were obtained. Full article

(This article belongs to the Special Issue Biomass Derived Heterogeneous and Homogeneous Catalysts, 2nd Edition)

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17 pages, 2417 KiB

Open AccessArticle

Biodiesel Production from Waste Plant Oil over a Novel Nano-Catalyst of Li-TiO₂/Feldspar

by Maryam Hanif, Ijaz Ahmad Bhatti, Khurram Shahzad and Muhammad Asif Hanif

Catalysts 2023, 13(2), 310; https://0-doi-org.brum.beds.ac.uk/10.3390/catal13020310 - 31 Jan 2023

Cited by 7 | Viewed by 1686

Abstract

A novel Li-impregnated TiO₂ catalyst loaded on feldspar mineral (Li-TiO₂/feldspar) was synthesized via a wet impregnation method and was characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infrared (FTIR) analysis. Using these techniques, it was possible to confirm the catalyst’s structural organization with a high crystallinity. This catalyst was used in the transesterification of five waste plant oils of Citrullus colocynthis (bitter apple), Pongamia pinnata (karanja), Sinapis arvensis (wild mustard), Ricinus communis (castor) and Carthamus oxyacantha (wild safflower). The catalytic tests were performed at temperatures ranging from 40 to 80 °C, employing a variable methanol/ester molar ratio (5:1, 10:1, 15:1, 20:1 and 25:1) and different catalyst concentrations (0.5%, 1%, 1.5%, 2% and 2.5%) relative to the total reactants mass. Conversion of 98.4% of fatty acid methyl esters (FAMEs) was achieved for Pongamia pinnata (karanja). The main fatty acids present in bitter apple, karanja, wild mustard, castor and wild safflower oils were linoleic acid (70.71%), oleic acid (51.92%), erucic acid (41.43%), ricinoleic acid (80.54%) and linoleic acid (75.17%), respectively. Li-TiO₂/feldspar produced more than 96% for all the feedstocks. Fuel properties such as iodine value (AV), cetane number (CN), cloud point (CP), iodine value (IV), pour point (PP) and density were within the ranges specified in ASTM D6751. Full article

(This article belongs to the Special Issue Biomass Derived Heterogeneous and Homogeneous Catalysts, 2nd Edition)

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Review

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39 pages, 6032 KiB

Open AccessFeature PaperReview

A Review on the Use of Catalysis for Biogas Steam Reforming

by Sergio Nogales-Delgado, Carmen María Álvez-Medina, Vicente Montes and Juan Félix González

Catalysts 2023, 13(12), 1482; https://0-doi-org.brum.beds.ac.uk/10.3390/catal13121482 - 29 Nov 2023

Viewed by 1314

Abstract

Hydrogen production from natural gas or biogas, at different purity levels, has emerged as an important technology with continuous development and improvement in order to stand for sustainable and clean energy. Regarding biogas, which can be obtained from multiple sources, hydrogen production through the steam reforming of methane is one of the most important methods for its energy use. In that sense, the role of catalysts to make the process more efficient is crucial, normally contributing to a higher hydrogen yield under milder reaction conditions in the final product. The aim of this review is to cover the main points related to these catalysts, as every aspect counts and has an influence on the use of these catalysts during this specific process (from the feedstocks used for biogas production or the biodigestion process to the purification of the hydrogen produced). Thus, a thorough review of hydrogen production through biogas steam reforming was carried out, with a special emphasis on the influence of different variables on its catalytic performance. Also, the most common catalysts used in this process, as well as the main deactivation mechanisms and their possible solutions are included, supported by the most recent studies about these subjects. Full article

(This article belongs to the Special Issue Biomass Derived Heterogeneous and Homogeneous Catalysts, 2nd Edition)

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39 pages, 7936 KiB

Open AccessFeature PaperReview

A Review on Biolubricants Based on Vegetable Oils through Transesterification and the Role of Catalysts: Current Status and Future Trends

by Sergio Nogales-Delgado, José María Encinar and Juan Félix González

Catalysts 2023, 13(9), 1299; https://doi.org/10.3390/catal13091299 - 16 Sep 2023

Cited by 1 | Viewed by 2269

Abstract

The use of biolubricants as an alternative to petroleum-based products has played an important role in the last decade. Due to the encouragement of global policies, which mainly support green chemistry and circular economy, there has been an increasing interest in bio-based products, including biolubricants, from scientific and industrial points of view. Their raw materials, production, and characteristics might vary, as biolubricants present different applications for a wide range of practical uses, making this field a continuously changing subject of study by researchers. The aim of this work was to study biolubricant production from vegetable oil crops from a bio-refinery perspective, paying attention to the main raw materials used, the corresponding production methods (with a special focus on double transesterification), the role of catalysts and some techno-economic studies. Thus, the main factors affecting quality parameters such as viscosity or oxidative stability have been covered, including catalyst addition, reaction temperature, or the use of raw materials, reagents, or additives were also analyzed. In conclusion, the search for suitable raw materials, the use of heterogeneous catalysts to improve the effectiveness and efficiency of the process, and the optimization of chemical conditions seem to be the most interesting research lines according to the literature. Full article

(This article belongs to the Special Issue Biomass Derived Heterogeneous and Homogeneous Catalysts, 2nd Edition)

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