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New Catalysts and Reactors for the Synthesis or Conversion of...
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New Catalysts and Reactors for the Synthesis or Conversion of Methanol

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

Deadline for manuscript submissions: closed (10 March 2023) | Viewed by 28331

Special Issue Editor

Prof. Dr. Jaime Soler

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Guest Editor
Catalysis, Molecular Separations and Reactor Engineering Group (CREG), Aragon Institute for Engineering Research (I3A), University of Zaragoza, 50009 Zaragoza, Spain
Interests: heterogeneous catalysis; fluidized bed reactors; membrane reactors; zeolites; fuel cells; energy production systems; process modelling; biofuels; biomass utilization
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

The scientific community widely considers global warming to be a major challenge to our society. The main cause of this critical issue is the increase of CO2 concentration in the atmosphere due to the massive use of fossil fuels, which has only grown in recent years. Methanol is a versatile matter used both for industrial purposes and for various day-to-day life activities, and as it exhibits high effectiveness as an energy carrier, renewable methanol has been proposed by the Nobel Prize winner G. Olah as a way to close the CO2 loop. Methanol can be environmentally synthesized from any feedstock, and its reforming reaction does not alter net CO2 emission to atmosphere.

One of the ways to address this problem is to use CO2 as a resource in the synthesis of valuable products, such as methanol, which can be obtained from CO2 and hydrogen provided from renewable energy (solar or wind power). In industry, methanol synthesis using the catalyst CuO/ZnO/Al2O3 occurs at a high pressure (50 bar). This is of course very costly, and hence, one of the main aims of researchers is to find the right modifications to the traditional catalyst in order to make it work at a lower pressure while maintaining its high selectivity.

Methanol to hydrocarbon (MTH) is a promising process because it supplies a wide range of compounds as important intermediates in petrochemical synthesis, such as light olefins and high-quality gasoline. The conversion of methanol to hydrocarbons can be catalyzed by various catalysts (HZSM-5 for methanol to gasolines, SAPO-34 for methanol to olefines, etc.). The role of both catalyst and reactor in these reactions is very important, and the kinetic modeling of coke formation is necessary to reveal the effect of coke content on the product distribution of the reaction, and to optimize the design and operation of the reactor.

In this Special Issue entitled “New Catalysts and Reactors for the Synthesis or Conversion of Methanol”, we welcome all kinds of works in the form of original research papers or short reviews that reflect the state-of-the-art of the research area dealing with methanol applications, based on new catalysts or reactors.

Prof. Dr. Jaime Soler
Guest Editor

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

  • Methanol synthesis
  • CO2 hydrogenation
  • MTG
  • MTO
  • Hydrogen
  • Supported catalysts
  • Zeolites
  • Chemical reactors

Related Special Issue

Published Papers (8 papers)

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Research

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29 pages, 4142 KiB  
Article
Development of an Improved Kinetic Model for CO2 Hydrogenation to Methanol
by Siphesihle Mbatha, Sébastien Thomas, Ksenia Parkhomenko, Anne-Cécile Roger, Benoit Louis, Xiaoti Cui, Ray Everson, Henrietta Langmi, Nicholas Musyoka and Jianwei Ren
Catalysts 2023, 13(10), 1349; https://0-doi-org.brum.beds.ac.uk/10.3390/catal13101349 - 06 Oct 2023
Cited by 1 | Viewed by 1508
Abstract
The kinetics of methanol synthesis remains debatable for various reasons, such as the lack of scientifically conclusive agreement about reaction mechanisms. The focus of this paper is on the evaluation of the intrinsic kinetics of the methanol synthesis reaction based on CO2 [...] Read more.
The kinetics of methanol synthesis remains debatable for various reasons, such as the lack of scientifically conclusive agreement about reaction mechanisms. The focus of this paper is on the evaluation of the intrinsic kinetics of the methanol synthesis reaction based on CO2 hydrogenation and the associated reverse water–gas shift as overall reactions. The industrial methanol synthesis catalyst, Cu/ZnO/Al2O3/MgO, was used for performing the kinetic studies. An optimal kinetic model was assessed for its ability to predict the experimental data from differential to integral conditions, contrary to the typical fitting of only the integral conditions’ data (common practice, as reported in the literature). The catalyst testing and kinetic evaluations were performed at various temperatures (210–260 °C) and pressures (40–77 bar), and for different stoichiometric numbers (0.9–1.9), H2/CO2 ratios (3.0–4.4) and carbon oxide ratios (0.9–1.0), in an isothermal fixed bed reactor, operated in a plug-flow mode. Experiments with CO in the feed were also generated and fitted. Different literature kinetic models with different assumptions on active sites, rate-determining steps, and hence, model formulations were fitted and compared. The original Seidel model appeared to fit the kinetic data very well, but it has twelve parameters. The modified model (MOD) we propose is derived from this Seidel model, but it has fewer (nine) parameters—it excludes CO hydrogenation, but it takes into consideration the morphological changes of active sites and CO adsorption. This MOD model, with three active sites, gave the best fit to all the data sets. Full article
(This article belongs to the Special Issue New Catalysts and Reactors for the Synthesis or Conversion of Methanol)
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17 pages, 4520 KiB  
Article
Selective Methanol Oxidation to Green Oxygenates—Catalyst Screening, Reaction Kinetics and Performance in Fixed-Bed and Membrane Reactors
by Jan P. Walter, Tanya Wolff and Christof Hamel
Catalysts 2023, 13(5), 787; https://0-doi-org.brum.beds.ac.uk/10.3390/catal13050787 - 22 Apr 2023
Viewed by 1289
Abstract
Experimental and simulation-based investigations are carried out for the selective oxidation of green methanol to the oxygenates dimethoxymethane (DMM) and methyl formate (MF), including an initial catalyst screening, the derivation of a reaction kinetic model, and a feasibility study of a fixed-bed and [...] Read more.
Experimental and simulation-based investigations are carried out for the selective oxidation of green methanol to the oxygenates dimethoxymethane (DMM) and methyl formate (MF), including an initial catalyst screening, the derivation of a reaction kinetic model, and a feasibility study of a fixed-bed and a membrane reactor with oxygen distribution. The catalyst screening of different supports and loading of vanadium revealed a 6.6 wt.-% VOx/TiO2 catalyst offering the highest potential to the formation for the target products. Kinetic experiments performed in a broad range of operation conditions, e.g., residence time, temperature, and oxygen concentration, are used for the postulation of a reaction network, providing the basis for mathematical modeling of the individual five reaction rates with a reduced mechanistic approach. A simulation study based on the derived reaction kinetics and parameters revealed the high potential of a distributed oxygen dosing at high residence times, outperforming the conventional fixed-bed reactor by up to 6% in the yield of DMM and up to 19% in the yield of MF. The formation of DMM is favored at low temperatures, whereas the formation of MF is supported by high temperatures. Full article
(This article belongs to the Special Issue New Catalysts and Reactors for the Synthesis or Conversion of Methanol)
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19 pages, 3928 KiB  
Article
Photocatalytic Hydrogen Generation from Aqueous Methanol Solution over n-Butylamine-Intercalated Layered Titanate H2La2Ti3O10: Activity and Stability of the Hybrid Photocatalyst
by Ivan A. Rodionov, Ekaterina O. Gruzdeva, Anton S. Mazur, Sergei A. Kurnosenko, Oleg I. Silyukov and Irina A. Zvereva
Catalysts 2022, 12(12), 1556; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12121556 - 01 Dec 2022
Cited by 6 | Viewed by 1256
Abstract
The stability of platinized n-butylamine-intercalated layered titanate H2La2Ti3O10 during the process of photocatalytic hydrogen production from aqueous methanol under UV irradiation has been thoroughly investigated by means of XRD, CHN, TG, 13C NMR, BET, [...] Read more.
The stability of platinized n-butylamine-intercalated layered titanate H2La2Ti3O10 during the process of photocatalytic hydrogen production from aqueous methanol under UV irradiation has been thoroughly investigated by means of XRD, CHN, TG, 13C NMR, BET, SEM and GC-MS analysis. It was revealed that n-butylamine completely abandons the interlayer space and transforms into n-butyraldehyde within 3 h of the reaction, while the particle morphology and specific surface area of the photocatalyst are preserved. The resulting solid phase contains carbon in at least two different oxidation states, which are attributed to the intermediate products of methanol oxidation bound to the perovskite matrix. The activity of the photocatalyst formed in this way is stable in time and strongly depends on the medium pH, which is not typical of either the parent H2La2Ti3O10 or TiO2. An approximate linear equation φ ≈ 29−2∙pH holds for the apparent quantum efficiency of hydrogen production in the 220–340 nm range at 1 mol. % methanol concentration. In the acidic medium, the photocatalyst under study outperforms the platinized H2La2Ti3O10 by more than one order of magnitude. The variation in methanol concentration allowed a maximum quantum efficiency of hydrogen production of 44% at 10 mol. % to be reached. Full article
(This article belongs to the Special Issue New Catalysts and Reactors for the Synthesis or Conversion of Methanol)
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17 pages, 4703 KiB  
Article
3D-Printed Raney-Cu POCS as Promising New Catalysts for Methanol Synthesis
by Maximilian J. Poller, Christina Renz, Torsten Wolf, Carolin Körner, Peter Wasserscheid and Jakob Albert
Catalysts 2022, 12(10), 1288; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12101288 - 21 Oct 2022
Cited by 1 | Viewed by 1443
Abstract
Simultaneous generation and activation of Raney-type periodic open cellular structures (POCS) is a highly promising approach for generating novel structured methanol synthesis catalysts. In detail, we produced stable and highly active POCS from a Cu50Al50 alloy by additive manufacturing via Powder Bed Fusion [...] Read more.
Simultaneous generation and activation of Raney-type periodic open cellular structures (POCS) is a highly promising approach for generating novel structured methanol synthesis catalysts. In detail, we produced stable and highly active POCS from a Cu50Al50 alloy by additive manufacturing via Powder Bed Fusion by Electron Beam (PBF-EB) and activated them via selective leaching of aluminum in a sodium hydroxide/sodium zincate solution. The Raney-type Cu structures possessed catalytic methanol productivities of up to 2.2 gMeOHgnp-Cu h−1 (PBF-EB sticks) and 1.9 gMeOHgnp-Cu h−1 (PBF-EB POCS), respectively. Moreover, it was found that besides the nanoporous layer thickness, an optimum Zn/Cu ratio of 0.3–0.4 can also by adjusted by the leaching conditions. Full article
(This article belongs to the Special Issue New Catalysts and Reactors for the Synthesis or Conversion of Methanol)
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11 pages, 1519 KiB  
Article
Methanol to Gasoline (MTG): Preparation, Characterization and Testing of HZSM-5 Zeolite-Based Catalysts to Be Used in a Fluidized Bed Reactor
by Andrés Sanz-Martínez, Javier Lasobras, Jaime Soler, Javier Herguido and Miguel Menéndez
Catalysts 2022, 12(2), 134; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12020134 - 22 Jan 2022
Cited by 9 | Viewed by 4455
Abstract
The preparation of catalysts suitable for MTG processes in a fluidized bed reactor has been studied with emphasis on improving the textural, physico-chemical, morphological, structural and mechanical properties. A mixture of HZSM-5 zeolite (active material), boehmite or bentonite (binder) and alumina (inert filler) [...] Read more.
The preparation of catalysts suitable for MTG processes in a fluidized bed reactor has been studied with emphasis on improving the textural, physico-chemical, morphological, structural and mechanical properties. A mixture of HZSM-5 zeolite (active material), boehmite or bentonite (binder) and alumina (inert filler) was used to prepare different catalysts. After preparation, characterization by physical adsorption of N2, XRF, XRD and SEM-EDX techniques was carried out. The screening of catalysts was performed in a fluidized bed reactor. The distribution of products was very similar in all cases, with the yield of light hydrocarbons always being higher than that of gasoline. Among the catalysts tested, the one containing boehmite as a binder (HZ_Boeh) was found as the most appropriate due to its high mechanical strength, high yield to aromatics and lower yield to durene. Full article
(This article belongs to the Special Issue New Catalysts and Reactors for the Synthesis or Conversion of Methanol)
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13 pages, 5753 KiB  
Article
Modifications in the Composition of CuO/ZnO/Al2O3 Catalyst for the Synthesis of Methanol by CO2 Hydrogenation
by Bianca Trifan, Javier Lasobras, Jaime Soler, Javier Herguido and Miguel Menéndez
Catalysts 2021, 11(7), 774; https://0-doi-org.brum.beds.ac.uk/10.3390/catal11070774 - 25 Jun 2021
Cited by 9 | Viewed by 3564
Abstract
Renewable methanol, obtained from CO2 and hydrogen provided from renewable energy, was proposed to close the CO2 loop. In industry, methanol synthesis using the catalyst CuO/ZnO/Al2O3 occurs at a high pressure. We intend to make certain modification on [...] Read more.
Renewable methanol, obtained from CO2 and hydrogen provided from renewable energy, was proposed to close the CO2 loop. In industry, methanol synthesis using the catalyst CuO/ZnO/Al2O3 occurs at a high pressure. We intend to make certain modification on the traditional catalyst to work at lower pressure, maintaining high selectivity. Therefore, three heterogeneous catalysts were synthesized by coprecipitation to improve the activity and the selectivity to methanol under mild conditions of temperature and pressure. Certain modifications on the traditional catalyst Cu/Zn/Al2O3 were employed such as the modification of the synthesis time and the addition of Pd as a dopant agent. The most efficient catalyst among those tested was a palladium-doped catalyst, 5% Pd/Cu/Zn/Al2O3. This had a selectivity of 64% at 210 °C and 5 bar. Full article
(This article belongs to the Special Issue New Catalysts and Reactors for the Synthesis or Conversion of Methanol)
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18 pages, 4585 KiB  
Article
Understanding Selectivity in CO2 Hydrogenation to Methanol for MoP Nanoparticle Catalysts Using In Situ Techniques
by Melis S. Duyar, Alessandro Gallo, Samuel K. Regli, Jonathan L. Snider, Joseph A. Singh, Eduardo Valle, Joshua McEnaney, Stacey F. Bent, Magnus Rønning and Thomas F. Jaramillo
Catalysts 2021, 11(1), 143; https://0-doi-org.brum.beds.ac.uk/10.3390/catal11010143 - 19 Jan 2021
Cited by 11 | Viewed by 5210
Abstract
Molybdenum phosphide (MoP) catalyzes the hydrogenation of CO, CO2, and their mixtures to methanol, and it is investigated as a high-activity catalyst that overcomes deactivation issues (e.g., formate poisoning) faced by conventional transition metal catalysts. MoP as a new catalyst for [...] Read more.
Molybdenum phosphide (MoP) catalyzes the hydrogenation of CO, CO2, and their mixtures to methanol, and it is investigated as a high-activity catalyst that overcomes deactivation issues (e.g., formate poisoning) faced by conventional transition metal catalysts. MoP as a new catalyst for hydrogenating CO2 to methanol is particularly appealing for the use of CO2 as chemical feedstock. Herein, we use a colloidal synthesis technique that connects the presence of MoP to the formation of methanol from CO2, regardless of the support being used. By conducting a systematic support study, we see that zirconia (ZrO2) has the striking ability to shift the selectivity towards methanol by increasing the rate of methanol conversion by two orders of magnitude compared to other supports, at a CO2 conversion of 1.4% and methanol selectivity of 55.4%. In situ X-ray Absorption Spectroscopy (XAS) and in situ X-ray Diffraction (XRD) indicate that under reaction conditions the catalyst is pure MoP in a partially crystalline phase. Results from Diffuse Reflectance Infrared Fourier Transform Spectroscopy coupled with Temperature Programmed Surface Reaction (DRIFTS-TPSR) point towards a highly reactive monodentate formate intermediate stabilized by the strong interaction of MoP and ZrO2. This study definitively shows that the presence of a MoP phase leads to methanol formation from CO2, regardless of support and that the formate intermediate on MoP governs methanol formation rate. Full article
(This article belongs to the Special Issue New Catalysts and Reactors for the Synthesis or Conversion of Methanol)
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Review

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21 pages, 6484 KiB  
Review
Conversion of Green Methanol to Methyl Formate
by Doreen Kaiser, Luise Beckmann, Jan Walter and Martin Bertau
Catalysts 2021, 11(7), 869; https://0-doi-org.brum.beds.ac.uk/10.3390/catal11070869 - 20 Jul 2021
Cited by 26 | Viewed by 8439
Abstract
Methyl formate is a key component for both defossilized industry and mobility. The current industrial production via carbonylation of methanol has various disadvantages such as high requirements on reactant purity and low methanol conversion rates. In addition, there is a great interest in [...] Read more.
Methyl formate is a key component for both defossilized industry and mobility. The current industrial production via carbonylation of methanol has various disadvantages such as high requirements on reactant purity and low methanol conversion rates. In addition, there is a great interest in replacing the conventional homogeneous catalyst with a heterogeneous one, among other things to improve the downstream processing. This is why new approaches for methyl formate are sought. This review summarizes promising approaches for methyl formate production using methanol as a reactant. Full article
(This article belongs to the Special Issue New Catalysts and Reactors for the Synthesis or Conversion of Methanol)
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