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Zeolites and Zeolite-Based Catalysts in Industrial Catalysis
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Zeolites and Zeolite-Based Catalysts in Industrial Catalysis

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

Deadline for manuscript submissions: closed (30 November 2023) | Viewed by 10149

Special Issue Editor

Prof. Dr. Izabela Czekaj

E-Mail Website
Guest Editor
Faculty of Chemical Engineering and Technology, Cracow University of Technology, 31-155 Krakow, Poland
Interests: porous materials; zeolites design and modeling; catalysis; biomass valorization; odor elimination; deNOx; deN2O; theoretical modeling; industrial catalytic processes design; electrochemistry; biofuels
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

This Special Issue is devoted to the design and characterization of zeolites for industrial processes. The aim is to determine the current state of knowledge, indicate areas requiring further research, and show the direction of ongoing development work regarding zeolites’ design, also including theoretical modeling as support for industrial processes. The main attention will be focused on comprehensive studies of the synthesis, characterization, and evaluation of zeolite performance in industrial processes such as, but not limited to, biomass valorization, the selective catalytic reduction of nitrogen oxides, N2O decomposition, alkylation, refinery, petrochemistry, organic compounds adsorption, filtration, and odor elimination.

The scope also includes the investigation of zeolites under conditions close to industrial ones, comparisons of the studied catalytic zeolite-based systems with the currently operating commercial systems, and demonstrations of the validity of their application in a given industrial process.

Prof. Dr. Izabela Czekaj
Guest Editor

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Keywords

  • industrial organic processes with zeolites
  • zeolite industrial catalysts
  • zeolites’ characterization
  • zeolites’ synthesis
  • theoretical modeling and design of zeolites
  • zeolites’ deactivation
  • modeling and design of zeolites
  • natural and synthetic zeolites

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Published Papers (6 papers)

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Research

16 pages, 4880 KiB  
Article
Transformation of Light Alkanes into High-Value Aromatics
by Muhammad Naseem Akhtar
Catalysts 2024, 14(3), 196; https://doi.org/10.3390/catal14030196 - 16 Mar 2024
Cited by 1 | Viewed by 1232
Abstract
This research work is focused on the transformation of light alkane (propane) into high-value aromatics using gallo-alumino-silicate catalysts. Two sets of gallo-alumino-silicates were synthesized for this study. In the first set, the ratio of Ga/(Al+Ga) was modified, while the Si/(Al+Ga) ratio was held [...] Read more.
This research work is focused on the transformation of light alkane (propane) into high-value aromatics using gallo-alumino-silicate catalysts. Two sets of gallo-alumino-silicates were synthesized for this study. In the first set, the ratio of Ga/(Al+Ga) was modified, while the Si/(Al+Ga) ratio was held constant. In the subsequent set, the Si/(Al+Ga) ratio was adjusted, while maintaining a consistent Ga/(Al+Ga) ratio. This approach aimed to directly assess the impact of each ratio on catalyst performance. The comprehensive characterization of all catalysts was conducted using various instrumental techniques, i.e., BET surface area, XRD, NH3-TPD, 27Al, 71Ga and 29Si MAS NMR, and XPS. A gradual reduction in the percentage of crystallinity and rise in meso-surface area was noticed with a rise in Ga/(Al+Ga) ratio. The total acidity (NH3-TPD) demonstrated a decline as the Si/(Al+Ga) ratio increased, attributed to an overall decline in Al3+ or Ga3+ species. The XPS intensity of the Ga 2p3/2 peak rose in correlation with an elevated ratio of Ga/(Al+Ga), suggesting the formation of extra-framework Ga species. The propane conversion, aromatic yield, and aromatization/cracking ratio exhibited an increase with an increasing Ga/(Al+Ga) ratio, reaching an optimum value of 0.46 before declining. Conversely, an appreciable drop in the conversion of propane and yield of aromatics was detected with the rise in Si/(Al+Ga) ratio, attributing to the decline in acidity. The catalyst having a Ga/(Al+Ga) ration of 0.46 exhibited the highest propane conversion and aromatic yield of 83.0% and 55.0% respectively. Full article
(This article belongs to the Special Issue Zeolites and Zeolite-Based Catalysts in Industrial Catalysis)
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18 pages, 7370 KiB  
Article
Zeolitic Imidazolium Frameworks-Derived Ru-Based Composite Materials Enable the Catalytic Dehydrogenation of Alcohols to Carboxylic Acids
by Zhan Chen, Jing Hang, Song Zhang, Ye Yuan, Francis Verpoort and Cheng Chen
Catalysts 2023, 13(8), 1225; https://doi.org/10.3390/catal13081225 - 20 Aug 2023
Viewed by 1346
Abstract
The metal-catalyzed dehydrogenation of alcohols without any oxidant or additive has been demonstrated as an atom-economic and environmentally friendly strategy for carboxylic acid synthesis. Among the various catalysts applied to this transformation, Ru-based homogeneous ones have been the most extensively studied owing to [...] Read more.
The metal-catalyzed dehydrogenation of alcohols without any oxidant or additive has been demonstrated as an atom-economic and environmentally friendly strategy for carboxylic acid synthesis. Among the various catalysts applied to this transformation, Ru-based homogeneous ones have been the most extensively studied owing to their remarkable catalytic activity. However, these catalysts required multiple complicated synthesis steps. In addition, they were either difficult to recycle or their recovery processes were relatively tedious. Therefore, a series of Ru-containing heterogeneous catalysts with zeolitic imidazolium frameworks (ZIFs)-derived materials were designed and fabricated. A thorough screening of various parameters was conducted, and it was found that the material obtained by loading a Ru concentration of 0.05 mol/L into Co species embedded in porous N-doped carbon (Ru0.05@Co-NC) had the best catalytic performance in this transformation, affording a handful of carboxylic acid products from the corresponding aromatic or aliphatic alcohols in moderate to high yields. Additionally, the catalyst showed remarkable recyclability as it could be recycled eight times with stable activity fluctuation (45–52%). It is noteworthy that catalyst recycling was convenient and fast, which could be realized simply by an external magnet. Moreover, the stable morphology and structure of Ru0.05@Co-NC, along with its high specific surface area, hierarchical pore structure, high porosity, and other properties, jointly contributed to its high catalytic activity and good recyclability. Furthermore, the stability and activity of Ru0.05@Co-NC were further evaluated through acid etching experiments, which revealed that some Ru species could stably exist in concentrated acids and play a pivotal role in promoting this catalytic process. Full article
(This article belongs to the Special Issue Zeolites and Zeolite-Based Catalysts in Industrial Catalysis)
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14 pages, 2539 KiB  
Article
Catalytic Cracking of Fischer-Tropsch Wax on Different Zeolite Catalysts
by Chao Yang, Lingtao Liu, Genquan Zhu, Chaogang Xie, Xiance Zhang and Xiaoqiao Zhang
Catalysts 2023, 13(8), 1223; https://doi.org/10.3390/catal13081223 - 18 Aug 2023
Cited by 1 | Viewed by 2108
Abstract
Fisher-Tropsch synthesis (FTS) is a promising method to make alternative hydrocarbons from biomass or other resources. Upgrading the primary FTS products is of considerable interest. Cracking FT wax is economically attractive to produce light olefins. Herein, the effects of the zeolite type, Si/Al [...] Read more.
Fisher-Tropsch synthesis (FTS) is a promising method to make alternative hydrocarbons from biomass or other resources. Upgrading the primary FTS products is of considerable interest. Cracking FT wax is economically attractive to produce light olefins. Herein, the effects of the zeolite type, Si/Al ratio of ZSM-5, and reaction condition on the catalytic cracking of FT wax were investigated. It was found that the pore structure and acid properties of zeolites had a significant impact on the product selectivity. USY was beneficial for the production of gasoline and diesel, while β was suitable for the production of propylene and butenes, and ZSM-5 was conductive to producing ethylene and propylene. Increasing the Si/Al ratio of ZSM-5 can suppress the hydrogen transfer reaction and increase the selectivity of light olefins. When the Si/Al ratio of ZSM-5 was 140, the mass yields of ethylene, propylene, and butenes were 6.40%, 26.83%, and 20.10%, respectively. Full article
(This article belongs to the Special Issue Zeolites and Zeolite-Based Catalysts in Industrial Catalysis)
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21 pages, 9011 KiB  
Article
Comparison of the Mechanisms of deNOx and deN2O Processes on Bimetallic Cu–Zn and Monometallic Cu–Cu Dimers in Clinoptilolite Zeolite—A DFT Study Simulating Industrial Conditions
by Izabela Kurzydym, Weronika Magnuszewska and Izabela Czekaj
Catalysts 2023, 13(8), 1210; https://doi.org/10.3390/catal13081210 - 14 Aug 2023
Cited by 1 | Viewed by 1640
Abstract
This paper presents two mechanisms for the deNOx process and for the deN2O process (in two variants). The processes were carried out on a clinoptilolite zeolite catalyst with a deposited Cu–Cu monometallic dimer and Cu–Zn bimetallic dimer with bridged oxygen between [...] Read more.
This paper presents two mechanisms for the deNOx process and for the deN2O process (in two variants). The processes were carried out on a clinoptilolite zeolite catalyst with a deposited Cu–Cu monometallic dimer and Cu–Zn bimetallic dimer with bridged oxygen between the metal atoms. Analyses were performed for hydrated forms of the catalyst with a hydrated bridging oxygen on one of the metal atoms. Calculations were performed using DFT (density functional theory) based on an ab initio method. The analyses included calculations of the energies of individual reaction steps and analysis of charges, bond orders and bond lengths as well as HOMO, SOMO and LUMO orbitals of selected steps in the mechanism. Based on the results obtained, it was determined that the most efficient catalyst for both processes is a Cu–Zn bimetallic catalyst with a bridged hydroxyl group. It shows higher efficiency in the limiting step (formation of the -N2H intermediate product) than the previously studied FAU and MFI zeolites with a Cu–Zn bimetallic dimer. In addition, the possibility of using the catalytic system from the deNOx process in the deN2O process was presented, which can benefit SCR installations. In addition, it was proved that the order of adsorption of NO and N2O has significance for further steps of the deN2O process. In order to improve the comparison of FAU, MFI and CLI zeolite catalysts with a Cu–Zn dimer, further studies on the deN2O mechanism for the first two zeolites are needed. This study allows us to propose a bimetallic catalyst for the deNOx and deN2O processes. Full article
(This article belongs to the Special Issue Zeolites and Zeolite-Based Catalysts in Industrial Catalysis)
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18 pages, 4451 KiB  
Article
Organic Acids from Glucose—Heterogeneous Catalysis with the Participation of Natural Zeolite
by Natalia Sobuś, Igor Łabaj and Magdalena Król
Catalysts 2023, 13(8), 1202; https://doi.org/10.3390/catal13081202 - 11 Aug 2023
Cited by 1 | Viewed by 1501
Abstract
In this paper, we present the results of a one-pot process for converting, utilizing a modified clinoptilolite catalyst. Iron, cobalt, and copper were introduced into the zeolite structure as active centers. The modified clinoptilolite catalyst was characterized in terms of phase composition, structure, [...] Read more.
In this paper, we present the results of a one-pot process for converting, utilizing a modified clinoptilolite catalyst. Iron, cobalt, and copper were introduced into the zeolite structure as active centers. The modified clinoptilolite catalyst was characterized in terms of phase composition, structure, and microstructure (using XRD, BET, FT-IR, and DRS UV-VIS), as well as the speciation of introduced metals. The catalytic process was conducted at a temperature of 250 °C for 1–5 h. Depending on the catalyst used and the specific process conditions, the reaction mixture exhibited the formation of various organic acids, including lactic acid (100% yield after 1 h using CLI), levulinic acid (40.3% yield after 5 h using Fe-H-CLI), formic acid (15.8% yield after 3 h using Fe-H-CLI), and acrylic acid (11.9% yield after 5 h using Fe-CLI). Full article
(This article belongs to the Special Issue Zeolites and Zeolite-Based Catalysts in Industrial Catalysis)
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12 pages, 2902 KiB  
Article
Nano-Hollow Zeolite-Encapsulated Highly Dispersed Ultra-Fine Fe Nanoparticles as Fischer–Tropsch Catalyst for Syngas-to-Olefins
by Rui Hu, Tianye Wang, Yifan Wang, Yuan Zhu, Li Xie, Enhui Xing, Yu Wu and Zhijian Da
Catalysts 2023, 13(6), 948; https://doi.org/10.3390/catal13060948 - 30 May 2023
Cited by 4 | Viewed by 1623
Abstract
A nano-hollow zeolite-encapsulating ultra-fine Fe nanoparticle catalyst denoted as Fe@n-hS-HT was successfully synthesized through a simple water steam treatment of the Fe@n-hS catalyst prepared by the “dissolution–recrystallization” (D-R) method. The Fe@n-hS-HT catalyst had a hierarchical porous structure [...] Read more.
A nano-hollow zeolite-encapsulating ultra-fine Fe nanoparticle catalyst denoted as Fe@n-hS-HT was successfully synthesized through a simple water steam treatment of the Fe@n-hS catalyst prepared by the “dissolution–recrystallization” (D-R) method. The Fe@n-hS-HT catalyst had a hierarchical porous structure and a high dispersion of Fe2O3 particles with a size of 3.4 nm. Furthermore, the results of several characterization methods, such as XRD, HAADF-STEM, and H2-TPR, further demonstrated the transformation of the skeleton Fe in Fe@n-hS into Fe2O3, which was uniformly dispersed in the Fe@n-hS-HT catalyst. Meanwhile, Fe@n-hS-HT had significantly higher selectivity and yield of C2-C4= than the reference catalysts Fe/S and Fe@n-hS, which provided strong proof for the confined catalysis of the metal@zeolite catalyst. Full article
(This article belongs to the Special Issue Zeolites and Zeolite-Based Catalysts in Industrial Catalysis)
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