Advances in the Catalytic Behavior of Ion-Exchange Resins

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

Deadline for manuscript submissions: closed (31 December 2023) | Viewed by 9430

Special Issue Editors

Department of Chemical Engineering and Analytical Chemistry, University of Barcelona, Marti i Franqués 1-11, 08028 Barcelona, Spain
Interests: catalytic reaction engineering; acid solid catalysts; biofuels; oxygenates; biomass
Department of Chemical Engineering and Analytical Chemistry, University of Barcelona, Marti i Franqués 1-11, 08028 Barcelona, Spain
Interests: chemical reaction engineering; acid solid catalysts; biofuels; oxygenates; biomass
Department of Chemical Engineering and Analytical Chemistry, University of Barcelona, Marti i Franqués 1-11, 08028 Barcelona, Spain
Interests: chemical reaction engineering; heterogeneous catalysis; biomass transformation; fuel reformulation

Special Issue Information

Dear Colleagues,

Acidic ion-exchange resins have been recognized as interesting catalysts for organic reactions such as etherification, hydration, dehydration, esterification, and many more for at least 60 years. These organic materials, mostly but not exclusively copolymers of styrene-DVB, have limited thermal stability in temperatures up to 120–150 °C. However, this drawback has perhaps become a strength regarding their use in academia and the industry. Ion-exchange resins can selectively catalyze—and with recognizable activity—thermodynamically favorable reactions at low/mild temperatures where classical catalysts such as alumina or zeolites are barely active.

Their catalytic behavior is complex because it depends on a variable morphology, since interaction with reaction media causes a swelling phenomenon, resulting in some regions of the polymer becoming accessible to reactants. This is dependent on the acid capacity and acid strength, with the latter being challenging to comprehensively characterize. Nowadays, it is difficult to detect the differences in the strength of ion-exchange resins, which might explain the observed catalytic behavior.

Recently, some new ion-exchange resins with novel morphology and structure have been developed, namely thermostable and hypercrosslinked resins. Moreover, acidic resins have been tested in new reactions and found to be successful in the transformation of biomass derivatives in biocompounds, which may eventually result in their application toward reducing the use of oil resources, prompting the rise of environmentally friendly processes and, in this way, reducing the carbon footprint. Basic ion-exchange resins have also been tested in academia for use at very low temperatures. Last but not least, ion-exchange resins have been used as supports for enzymes or metals such as Pd, Ru, and others, being, in this way, a key component of bifunctional catalysts.

This Special Issue will focus on the use of ion-exchange resins in green and sustainable chemical processes. Particular importance will be placed on their application to improving biomass derivatives, green synthesis, and environmental remediation processes. Works devoted to their morphological, physical, and chemical characterization are especially welcome as this contributes to advancing our understanding of their catalytic performance.  

We cordially invite you to submit a manuscript for consideration and possible publication. We hope this topic is of interest and look forward to hearing from you.

Prof. Dr. Javier Tejero Salvador
Prof. Dr. Montserrat Iborra Urios 
Dr. Eliana Ramírez Rangel
Guest Editors

Manuscript Submission Information

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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

  • resin morphology
  • acid strength
  • catalyst preparation
  • bifunctional catalysts
  • acidic resins as supports
  • biomass transformation
  • platform chemical production
  • organic synthesis
  • catalysis by basic resins

Published Papers (6 papers)

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Research

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11 pages, 1353 KiB  
Article
Sulfonic Resins as Catalysts for the Oxidation of Alcohols with H2O2/KBr
by Vicente Dorado, Clara I. Herrerías and José M. Fraile
Catalysts 2024, 14(1), 74; https://doi.org/10.3390/catal14010074 - 17 Jan 2024
Viewed by 796
Abstract
Sulfonic resins can replace homogeneous sulfonic acids in the oxidation of alcohols with the H2O2/KBr system. The performance of different resins was tested with methyl 9(10)-hydroxystearate, a secondary fatty alcohol. The structural features of the resin were more important [...] Read more.
Sulfonic resins can replace homogeneous sulfonic acids in the oxidation of alcohols with the H2O2/KBr system. The performance of different resins was tested with methyl 9(10)-hydroxystearate, a secondary fatty alcohol. The structural features of the resin were more important than the acid strength for the catalytic performance of this reaction. The optimization of the reaction conditions allows the recovery of the resin, although regeneration is required due to the active role of KBr, and a significant loss of sulfonic groups can be detected after nine runs. In the case of primary fatty alcohols, the oxidation leads to carboxylic acids, which are esterified with the starting alcohol under the acidic conditions. For cyclic secondary alcohols, the steric hindrance around the hydroxyl group seems to be important for the efficiency of the oxidation to ketone. Full article
(This article belongs to the Special Issue Advances in the Catalytic Behavior of Ion-Exchange Resins)
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15 pages, 1742 KiB  
Article
Two-Stage Conversion of Used Cooking Oil to Biodiesel Using Ion Exchange Resins as Catalysts
by Sumaiya Zainal Abidin, Misbahu Ladan Mohammed and Basudeb Saha
Catalysts 2023, 13(8), 1209; https://doi.org/10.3390/catal13081209 - 14 Aug 2023
Cited by 1 | Viewed by 1052
Abstract
This study focuses on the development of a novel two-stage (esterification–transesterification) synthesis of biodiesel from used cooking oil (UCO) using ion exchange resins as catalysts. Esterification of the UCO has been conducted using various types of ion exchange resin catalysts. Purolite D5081, a [...] Read more.
This study focuses on the development of a novel two-stage (esterification–transesterification) synthesis of biodiesel from used cooking oil (UCO) using ion exchange resins as catalysts. Esterification of the UCO has been conducted using various types of ion exchange resin catalysts. Purolite D5081, a hyper cross-linked resin, showed the best catalytic performance among all the catalysts investigated, with 92% of free fatty acid (FFA) conversion. The transesterification of pre-treated used cooking oil (P-UCO) was carried out sequentially using several acidic and basic ion exchange resin catalysts. In the screening process, the Diaion PA306s catalyst showed the best catalytic performance and was selected for the optimisation study. A triglyceride conversion of ca. 75% was recorded at the optimum reaction conditions (9% (w/w) catalyst loading, 328 K reaction temperature, 18:1 methanol to P-UCO feed mole ratio, and 350 rpm stirring speed). Furthermore, the reusability study of the Diaion PA306s catalyst gave a similar triglyceride conversion after a couple of cycles without losing its catalytic activity. A dry purification technique was found to give the lowest percentage of glycerides and glycerine content and, therefore, was chosen as the best biodiesel purification route. Full article
(This article belongs to the Special Issue Advances in the Catalytic Behavior of Ion-Exchange Resins)
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13 pages, 1635 KiB  
Article
The Role of Ion Exchange Resins for Solving Biorefinery Catalytic Processes Challenges
by Yolanda Patiño, Laura Faba, Raquel Peláez, Jennifer Cueto, Pablo Marín, Eva Díaz and Salvador Ordóñez
Catalysts 2023, 13(6), 999; https://doi.org/10.3390/catal13060999 - 13 Jun 2023
Cited by 2 | Viewed by 1186
Abstract
Different possible applications of ion exchange resins in the framework of biorefinery catalytic applications are discussed in this article. Three case studies were selected for this approach, connected to three main routes for biomass upgrading: syngas upgrading to high-value chemicals, biomass hydrolysate upgrading, [...] Read more.
Different possible applications of ion exchange resins in the framework of biorefinery catalytic applications are discussed in this article. Three case studies were selected for this approach, connected to three main routes for biomass upgrading: syngas upgrading to high-value chemicals, biomass hydrolysate upgrading, and direct upgrading of oily fraction. The tailored acidic properties of these materials, as well as their stability in the presence of water, have made them promising catalysts for applications such as obtaining biodiesel from activated sludge wastes in batch reactors and obtaining polyoxymethylene methyl ether from syngas (via formaldehyde and methylal, and working in a continuous fixed bed reactor). However, the acidity of these materials may still be too low for acid-catalyzed aldol condensation reactions in the aqueous phase. Full article
(This article belongs to the Special Issue Advances in the Catalytic Behavior of Ion-Exchange Resins)
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19 pages, 2463 KiB  
Article
Revisiting Isothermal Effectiveness Factor Equations for Reversible Reactions
by William Q. Rios, Bruno Antunes, Alírio E. Rodrigues, Inês Portugal and Carlos M. Silva
Catalysts 2023, 13(5), 889; https://doi.org/10.3390/catal13050889 - 15 May 2023
Viewed by 1184
Abstract
Ion exchange resins have many industrial applications, namely as sorbents and catalysts. In solid-catalyzed reactions, intraparticle reaction-diffusion competition is generally described by effectiveness factors calculated numerically or analytically in the case of isothermal particles and simple rate laws. Although robust, numerical calculations can [...] Read more.
Ion exchange resins have many industrial applications, namely as sorbents and catalysts. In solid-catalyzed reactions, intraparticle reaction-diffusion competition is generally described by effectiveness factors calculated numerically or analytically in the case of isothermal particles and simple rate laws. Although robust, numerical calculations can be time-consuming, and convergence is not always guaranteed and lacks the flexibility of user-friendly equations. In this work, analytical equations for effectiveness factors of reversible reactions derived from the general scheme A+BC+D are developed and numerically validated. These effectiveness factors are analytically expressed in terms of an irreversible nth order Thiele modulus (specifically written for the  nth order forward reaction), the thermodynamic equilibrium constant, the ratios of effective diffusivities, and the ratios of surface concentrations. The application of such analytical equations is illustrated for two liquid phase reactions catalyzed by Amberlyst-15, specifically the synthesis of ethyl acetate and acetaldehyde dimethyl acetal. For both reactions, the prediction of the concentration profiles in isothermal batch reactors achieved errors between 1.13% and 3.38% for six distinct experimental conditions. Finally, the impact of non-ideal behavior upon the multicomponent effective diffusivities, subsequently conveyed to the effectiveness factors, is enlightened. Full article
(This article belongs to the Special Issue Advances in the Catalytic Behavior of Ion-Exchange Resins)
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14 pages, 2335 KiB  
Article
Synthesis of Vinyl–Trivinyl Acidic Resins for Application in Catalysis: Statistical Study and Site Accessibility Assessment
by William M. Godoy, Leandro G. Aguiar, Nuno A. B. S. Graça and Alírio E. Rodrigues
Catalysts 2023, 13(1), 181; https://doi.org/10.3390/catal13010181 - 12 Jan 2023
Viewed by 1037
Abstract
This study aimed to synthesize sulfonated polymer resins based on styrene and trimethylolpropane triacrylate (TMPTA) and evaluate their catalytic efficiency in glycerol acetylation. A factorial design was used, with two factors, three levels, and three replicates of the center point. The factors were [...] Read more.
This study aimed to synthesize sulfonated polymer resins based on styrene and trimethylolpropane triacrylate (TMPTA) and evaluate their catalytic efficiency in glycerol acetylation. A factorial design was used, with two factors, three levels, and three replicates of the center point. The factors were cross-linker percentage (YTMPTA) and cross-linker feed time (TTMPTA). Ion-exchange capacity, swelling index, and catalytic efficiency were analyzed to characterize each resin. Lower cross-linker percentages resulted in higher catalytic efficiencies, as expected. Resins synthesized with 2, 6, and 10% TMPTA had mean catalytic efficiencies of 215, 176, and 121, respectively. A linear correlation was observed between catalytic efficiency and cross-linker percentage, with R2 = 0.9971. Statistical and kinetic models were developed to represent the experimental results and support the development of strategies to improve resin formulation and synthesis conditions. TMPTA feed time at low and high levels positively influenced catalytic efficiency; the result is attributed to the micro- and macrostructure of resins. This finding was corroborated by the kinetic constants provided by the model. Full article
(This article belongs to the Special Issue Advances in the Catalytic Behavior of Ion-Exchange Resins)
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Review

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36 pages, 1914 KiB  
Review
Role of Ion-Exchange Resins in Hydrogenation Reactions
by Jordi H. Badia, Rodrigo Soto, Eliana Ramírez, Roger Bringué, Carles Fité, Montserrat Iborra and Javier Tejero
Catalysts 2023, 13(3), 624; https://doi.org/10.3390/catal13030624 - 20 Mar 2023
Cited by 2 | Viewed by 3453
Abstract
The role of ion-exchange resins (IERs) as catalysts or catalysts supports, in hydrogenation reactions is revised and their potential application is presented. Both gel-type and macroreticular, basic or acid, IERs have been used for manifold metal-catalyzed hydrogenation processes in gas and liquid phase, [...] Read more.
The role of ion-exchange resins (IERs) as catalysts or catalysts supports, in hydrogenation reactions is revised and their potential application is presented. Both gel-type and macroreticular, basic or acid, IERs have been used for manifold metal-catalyzed hydrogenation processes in gas and liquid phase, including hydrogenation of alkenes, alkynes, carbonyls, arenes, nitroaromatics, and more. When available, qualitative relationships between the morphology and structure of resins and their performance as solid supports for metal catalysts are observed. Noble metals, such as Pt, Au, and Pd, and non-noble metals, such as Fe and Cu, have been introduced into IERs polymeric backbones by simple ion-exchange of a metal salt precursor with the resin, or by a combination of ion-exchange and other protocols, to obtain mono- and bimetallic catalysts supported on IERs. High yields towards target product, as well as the recyclability of metal-doped IERs, have been reported in the literature, with low metal leaching, which makes them highly interesting solid catalysts for a wide array of industrial applications. Multistep reaction processes, involving hydrogenation and hydration/cyclization/aldol condensation/etc., constitute promising applications due to the one-pot synthesis approach and relatively low temperatures required, which adds environmental interest in terms of process integration and optimization. Full article
(This article belongs to the Special Issue Advances in the Catalytic Behavior of Ion-Exchange Resins)
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