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Recent Trends in Catalysis for Syngas Production and Conversion

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

Deadline for manuscript submissions: closed (31 January 2023) | Viewed by 17580

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Special Issue Editors

Dr. Fanhui Meng

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Guest Editor

State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan University of Technology, Taiyuan 030024, China
Interests: heterogeneous catalysis; metal oxides; zeolite synthesis; hydrogenation of CO and CO₂; carbon one chemistry

Dr. Wenlong Mo

E-Mail Website
Guest Editor

State Key Laboratory of Chemistry and Utilization of Carbon-Based Energy Resources, Xinjiang University, Urumqi 830046, China
Interests: heterogeneous catalysis; hydrogenation of CO and CO₂; carbon one chemistry; coal gasification

Special Issue Information

Dear Colleagues,

Synthesis gas (or syngas) is a mixture composed of CO and H₂, which can be produced from fossil fuel and biomass. Syngas is a crucial platform for the production of a variety of high-value compounds, such as synthetic hydrocarbons and oxygenated fuels. More syngas will be required in the near future in order to satisfy the industrial demands.

Catalytic processes for CO hydrogenation emphasize the selective production of light olefins (C₂-C₄⁼), methane, lower alcohols (C_nOH, n = 1 − 5), dimethyl ether (DME) and hydrocarbons (C₅₊ as liquid fuels). Recent advances in understanding and developing active phases, supports, promoters, operation conditions and reactor configurations to control the selectivity in syngas production and conversion are the most challenging subjects for scientific research.

This Special Issue compiles and reviews the latest trends in heterogeneous catalysis for syngas production including the production from natural gas, coal and biomass, and the research on the conversion of CO into value-added products. Submissions are welcome in the form of original research papers or short reviews that reflect the state-of-the-art of this research area.

Dr. Fanhui Meng
Dr. Wenlong Mo
Guest Editors

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Keywords

production of syngas
coal catalytic gasification
biomass catalytic gasification
syngas to light olefins
syngas to methane
syngas to methanol
syngas to lower alcohols
syngas to DME
heterogeneous catalysts
Fischer–Tropsch synthesis

Published Papers (11 papers)

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Editorial

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3 pages, 183 KiB

Open AccessEditorial

Recent Trends in Catalysis for Syngas Production and Conversion

by Fanhui Meng and Wenlong Mo

Catalysts 2023, 13(9), 1284; https://doi.org/10.3390/catal13091284 - 07 Sep 2023

Viewed by 797

Abstract

Synthesis gas (or syngas) is a mixture of CO and H₂ that can be produced from fossil fuels or biomass [...] Full article

(This article belongs to the Special Issue Recent Trends in Catalysis for Syngas Production and Conversion)

Research

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16 pages, 3233 KiB

Open AccessFeature PaperArticle

Effect of MnO₂ Crystal Type on the Oxidation of Furfural to Furoic Acid

by Xu Wu, Heqin Guo, Litao Jia, Yong Xiao, Bo Hou and Debao Li

Catalysts 2023, 13(4), 663; https://doi.org/10.3390/catal13040663 - 28 Mar 2023

Cited by 5 | Viewed by 1298

Abstract

The base-free oxidation of furfural by non-noble metal systems has been challenging. Although MnO₂ emerges as a potential catalyst application in base-free conditions, its catalytic efficiency still needs to be improved. The crystalline form of MnO₂ is an important factor affecting the oxidation ability of furfural. For this reason, four crystalline forms of MnO₂ (α, β, γ, and δ-MnO₂) were selected. Their oxidation performance and surface functional groups were analyzed and compared in detail. Only δ-MnO₂ exhibited excellent activity, achieving 99.04% furfural conversion and 100% Propo._FA (Only furoic acid was detected by HPLC in the product) under base-free conditions, while the furfural conversion of α, β, and γ-MnO₂ was below 10%. Characterization by XPS, IR, O₂-TPD and other means revealed that δ-MnO₂ has the most abundant active oxygen species and surface hydroxyl groups, which are responsible for the best performance of δ-MnO₂. This work achieves the green and efficient oxidation of furfural to furoic acid over non-noble metal catalysts. Full article

(This article belongs to the Special Issue Recent Trends in Catalysis for Syngas Production and Conversion)

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13 pages, 3676 KiB

Open AccessArticle

Catalytic Performance for CO Methanation over Ni/MCM-41 Catalyst in a Slurry-Bed Reactor

by Guoqiang Zhang, Jinyu Qin, Yuan Zhou, Huayan Zheng and Fanhui Meng

Catalysts 2023, 13(3), 598; https://doi.org/10.3390/catal13030598 - 16 Mar 2023

Cited by 2 | Viewed by 1363

Abstract

The Ni-based catalyst has been intensively studied for CO methanation. Here, MCM-41 is selected as support to prepare xNi/MCM-41 catalysts with various Ni contents and the catalytic performance for CO methanation in a slurry-bed reactor is investigated under different reaction conditions. The CO conversion gradually increases as the reaction temperature or pressure rises. As the Ni content increases, the specific surface area and pore volume of xNi/MCM-41 catalysts decrease, the crystallite sizes of metallic Ni increase, while the metal surface area and active Ni atom numbers firstly increase and then slightly decrease. The 20Ni/MCM-41 catalyst with the Ni content of 20 wt% exhibits the highest catalytic activity for CO methanation, and the initial CH₄ yield rate is well correlated to the active metallic Ni atom numbers. The characterization of the spent xNi/MCM-41 catalysts shows that the agglomeration of Ni metal is accountable for the catalyst deactivation. Full article

(This article belongs to the Special Issue Recent Trends in Catalysis for Syngas Production and Conversion)

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14 pages, 7156 KiB

Open AccessArticle

DFT Investigations of the Reaction Mechanism of Dimethyl Carbonate Synthesis from Methanol and CO on Various Cu Species in Y Zeolites

by Yuan Zhou, Guoqiang Zhang, Ya Song, Shirui Yu, Jingjing Zhao and Huayan Zheng

Catalysts 2023, 13(3), 477; https://doi.org/10.3390/catal13030477 - 26 Feb 2023

Cited by 2 | Viewed by 1412

Abstract

In this study, a density functional theory method is employed to investigate the reaction mechanisms of dimethyl carbonate (DMC) formation, through oxidative carbonylation of methanol, on four types of Y zeolites doped with Cu⁺, Cu²⁺, Cu₂O and CuO, respectively. A common chemical route is found for these zeolites and identified as, first, the adsorbed CH₃OH is oxidized to CH₃O species; subsequently, CO inserts into CH₃O to CH₃OCO, which reacts with CH₃O to form DMC rapidly; and finally, the adsorbed DMC is released into the gas phase. The rate-limiting step on Cu²⁺Y zeolite is identified as oxidation of CH₃OH to CH₃O with activation barrier of 66.73 kJ·mol⁻¹. While for Cu⁺Y, Cu₂O-Y and CuO-Y zeolites, the rate-limiting step is insertion of CO into CH₃O, and the corresponding activation barriers are 63.73, 60.01 and 104.64 kJ·mol⁻¹, respectively. For Cu⁺Y, Cu²⁺Y and Cu₂O-Y zeolites, adsorbed CH₃OH is oxidized to CH₃O with the presence of oxygen, whereas oxidation of CH₃OH on CuO-Y is caused by the lattice oxygen of CuO. The order of catalytic activities of these four types of zeolites with different Cu states follows Cu⁺Y ≈ Cu₂O-Y > Cu²⁺Y > CuO-Y zeolite. Therefore, CuY catalysts with Cu⁺ and Cu₂O as dominated Cu species are beneficial to the formation of DMC. Full article

(This article belongs to the Special Issue Recent Trends in Catalysis for Syngas Production and Conversion)

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13 pages, 3187 KiB

Open AccessArticle

Efficient Pyrolysis of Low-Density Polyethylene for Regulatable Oil and Gas Products by ZSM-5, HY and MCM-41 Catalysts

by Ting Liu, Yincui Li, Yifan Zhou, Shengnan Deng and Huawei Zhang

Catalysts 2023, 13(2), 382; https://doi.org/10.3390/catal13020382 - 09 Feb 2023

Cited by 3 | Viewed by 1992

Abstract

In this research, catalytic cracking of low-density polyethylene (LDPE) has been carried out in the presence of three kinds of typical molecular sieves, including ZSM-5, HY and MCM-41, respectively. The effects of different catalysts on the composition and quantity of pyrolysis products consisting of gas, oil and solid material were systematically investigated and summarized. Specially, the three kinds of catalysts were added into LDPE for pyrolysis to obtain regulatable oil and gas products (H₂, CH₄ and a mixture of C₂–C₄⁺ gaseous hydrocarbons). These catalysts were characterized with BET, NH₃-TPD, SEM and TEM. The results show that the addition of MCM-41 improved the oil yield, indicating that the secondary cracking of intermediate species in primary pyrolysis decreased with the case of the catalyst. The highest selectivity of MCM-41 to liquid oil (78.4% at 650 °C) may be attributed to its moderate total acidity and relatively high BET surface area. The ZSM-5 and HY were found to produce a great amount of gas products (61.4% and 67.1% at 650 °C). In particular, the aromatic yield of oil production reached the maximum (65.9% at 500 °C) when the ZSM-5 was used. Accordingly, with the three kinds of catalysts, a new environment-friendly and efficient recovery approach may be developed to obtain regulatable and valuable products by pyrolysis of LDPE-type plastic wastes. Full article

(This article belongs to the Special Issue Recent Trends in Catalysis for Syngas Production and Conversion)

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15 pages, 3656 KiB

Open AccessArticle

Study on the Formaldehyde Oxidation Reaction of Acid-Treated Manganese Dioxide Nanorod Catalysts

by Yanqiu Li, Yuan Su, Yunfeng Yang, Ping Liu, Kan Zhang and Keming Ji

Catalysts 2022, 12(12), 1667; https://doi.org/10.3390/catal12121667 - 18 Dec 2022

Cited by 2 | Viewed by 1420

Abstract

Formaldehyde is an important downstream chemical of syngas. Furniture and household products synthesized from formaldehyde will slowly decompose and release formaldehyde again during use, which seriously affects indoor air quality. In order to solve the indoor formaldehyde pollution problem, this paper took the catalytic oxidation of formaldehyde as the research object; prepared a series of low-cost, acid-treated manganese dioxide nanorod catalysts; and investigated the effect of the acid-treatment conditions on the catalysts’ activity. It was found that the MnNR-0.3ac-6h catalyst with 0.3 mol/L sulfuric acid for 6 h had the best activity. The conversion rate of formaldehyde reached 98% at 150 °C and 90% at 25 °C at room temperature. During the reaction time of 144 h, the conversion rate of formaldehyde was about 90%, and the catalyst maintained a high activity. It was found that acid treatment could increase the number of oxygen vacancies on the surface of the catalysts and promote the production of reactive oxygen species. The amount of surface reactive oxygen species of the MnNR-0.3ac-6h catalyst was about 13% higher than that of the catalyst without acid treatment. Full article

(This article belongs to the Special Issue Recent Trends in Catalysis for Syngas Production and Conversion)

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18 pages, 4529 KiB

Open AccessFeature PaperArticle

Characterization and Syngas Production at Low Temperature via Dry Reforming of Methane over Ni-M (M = Fe, Cr) Catalysts Tailored from LDH Structure

by Manel Hallassi, Rafik Benrabaa, Nawal Fodil Cherif, Djahida Lerari, Redouane Chebout, Khaldoun Bachari, Annick Rubbens, Pascal Roussel, Rose-Noëlle Vannier, Martine Trentesaux and Axel Löfberg

Catalysts 2022, 12(12), 1507; https://doi.org/10.3390/catal12121507 - 24 Nov 2022

Cited by 3 | Viewed by 1638

Abstract

Bimetallic layered double oxide (LDO) NiM (M = Cr, Fe) catalysts with nominal compositions of Ni/M = 2 or 3 were tailored from layered double hydroxides (LDH) using a coprecipitation method to investigate the effects of the trivalent metal (Cr or Fe) and the amount of Ni species on the structural, textural, reducibility, and catalytic properties for CH₄/CO₂ reforming. The solids before (LDH) and after (LDO) thermal treatment at 500 °C were characterized using TGA-TD-SM, HT-XRD, XRD, Raman, and IR-ATR spectroscopies; N₂ physical adsorption; XPS; and H₂-TPR. According to the XRD and Raman analysis, a hydrotalcite structure was present at room temperature and stable up to 250 °C. The interlayer space decreased when the temperature increased, with a lattice parameter and interlayer space of 3.018 Å and 7.017 Å, respectively. The solids fully decomposed into oxide after calcination at 500 °C. NiO and spinel phases (NiM₂O₄, M = Cr or Fe) were observed in the NiM (M = Cr, Fe) catalysts, and Cr₂O₃ was detected in the case of NiCr. The NiFe catalysts show low activity and selectivity for DRM in the temperature range explored. In contrast, the chromium compound demonstrated interesting CH₄ and CO₂ conversions and generally excellent H₂ selectivity at low reaction temperatures. CH₄ and CO₂ conversions of 18–20% with H₂/CO of approx. 0.7 could be reached at temperatures as low as 500 °C, but transient behavior and deactivation were observed at higher temperatures or long reaction times. The excellent activity observed during this transient sequence was attributed to the stabilization of the metallic Ni particles formed during the reduction of the NiO phase due to the presence of NiCr₂O₄, opening the path for the use of these materials in periodic or looping processes for methane reforming at low temperature. Full article

(This article belongs to the Special Issue Recent Trends in Catalysis for Syngas Production and Conversion)

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17 pages, 2617 KiB

Open AccessArticle

Catalytic Performance of Alumina-Supported Cobalt Carbide Catalysts for Low-Temperature Fischer–Tropsch Synthesis

by Zahra Gholami, Zdeněk Tišler, Eliška Svobodová, Ivana Hradecká, Nikita Sharkov and Fatemeh Gholami

Catalysts 2022, 12(10), 1222; https://doi.org/10.3390/catal12101222 - 12 Oct 2022

Cited by 3 | Viewed by 1714

Abstract

The determination of the catalyst’s active phase helps improve the catalytic performance of the Fischer–Tropsch (FT) synthesis. Different phases of cobalt, including cobalt oxide, carbide, and metal, exist during the reaction. The content of each phase can affect the catalytic performance and product distribution. In this study, a series of cobalt carbide catalysts were synthesized by exposure of Co/Al₂O₃ catalyst to CH₄ at different temperatures from 300 °C to 800 °C. The physicochemical properties of the carbide catalysts (CoC_x/Al₂O₃) were evaluated by different characterization methods. The catalytic performances of the catalysts were investigated in an autoclave reactor to determine the role of cobalt carbides on the CO conversion and product distribution during the reaction. XRD and XPS analysis confirmed the presence of Co₂C in the prepared catalysts. The higher carbidation temperature resulted in the decomposition of methane into hydrogen and carbon, and the presence of graphitic carbon was confirmed by XRD, XPS, SEM, and Raman analysis. The Co₂C also decomposed to metallic cobalt and carbon, and the content of cobalt carbide decreased at higher carbidation temperatures. Higher content of Co₂C resulted in a lower CO conversion and higher selectivity to light alkanes, mainly methane. The higher carbidation temperature resulted in the decomposition of Co₂C to metallic cobalt with higher activity in the FT reaction. The CO conversion increased by increasing the carbidation temperature from 300 °C to 800 °C, due to the higher content of metallic cobalt. In the presence of pure hydrogen, the Co₂C could be converted mainly into hexagonal, close-packed (hcp) Co with higher activity for dissociative adsorption of CO, which resulted in higher catalyst activity and selectivity to heavier hydrocarbons. Full article

(This article belongs to the Special Issue Recent Trends in Catalysis for Syngas Production and Conversion)

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12 pages, 3063 KiB

Open AccessArticle

A Dual-Bed Strategy for Direct Conversion of Syngas to Light Paraffins

by Lina Wang, Fanhui Meng, Baozhen Li, Jinghao Zhang and Zhong Li

Catalysts 2022, 12(9), 967; https://doi.org/10.3390/catal12090967 - 29 Aug 2022

Cited by 3 | Viewed by 1350

Abstract

The authors studied the direct conversion of syngas to light paraffins in a dual-bed fixed-bed reactor. A dual-bed catalyst composed of three catalysts, a physically mixed methanol synthesis catalyst (CZA), and a methanol dehydration to dimethyl ether (DME) catalyst (Al₂O₃(C)) were put in the upper bed for direct conversion of syngas to DME, while the SAPO-34 (SP34-C) zeolite was put in the lower bed for methanol and DME conversion. The effects of the mass ratio of CZA to Al₂O₃(C), the H₂/CO molar ratio, and the space velocity on catalytic performance of syngas to DME were studied in the upper bed. Moreover, a feed gas with a CO/CO₂/DME/N₂/H₂ molar ratio of 9/6/4/5 balanced with H₂ was simulated and studied in the lower bed over SP34-C; after optimizing the reaction conditions, the selectivity of light paraffins reached 90.8%, and the selectivity of propane was as high as 76.7%. For the direct conversion of syngas to light paraffins in a dual bed, 88.9% light paraffins selectivity in hydrocarbons was obtained at a CO conversion of 33.4%. This dual-bed strategy offers a potential route for the direct conversion of syngas to valuable chemicals. Full article

(This article belongs to the Special Issue Recent Trends in Catalysis for Syngas Production and Conversion)

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12 pages, 3488 KiB

Open AccessArticle

The Promoting Effect of Ti on the Catalytic Performance of V-Ti-HMS Catalysts in the Selective Oxidation of Methanol

by Ley Boon Sim, Kek Seong Kim, Jile Fu and Binghui Chen

Catalysts 2022, 12(8), 869; https://doi.org/10.3390/catal12080869 - 06 Aug 2022

Cited by 1 | Viewed by 1524

Abstract

The effects of Ti modification on the structural properties and catalytic performance of vanadia on hexagonal mesoporous silica (V-HMS) catalysts are studied for selective methanol-to-dimethoxymethane oxidation. Characterizations including N₂ adsorption–desorption (S_BET), X-ray diffraction (XRD), UV-Vis diffuse reflectance spectroscopy (DRS UV-Vis), Micro-Raman spectroscopy, FTIR spectroscopy, and H₂ temperature-programmed reduction (H₂-TPR) were carried out to investigate the property and structure of the catalysts. The results show that Ti can be successfully incorporated into the HMS framework in a wide range of Si/Ti ratios from 50 to 10. Ti modification can effectively improve the distribution of vanadium species and thus enhance the overall redox properties and catalytic performance of the catalysts. The catalytic activity of the V-Ti-HMS catalysts with the Si/Ti ratio of 30 is approximately two times higher than that of V-HMS catalysts with comparable selectivity. The enhanced activity exhibited by the V-Ti-HMS catalyst is attributed to the improved dispersion and reducibility of vanadium oxides. Full article

(This article belongs to the Special Issue Recent Trends in Catalysis for Syngas Production and Conversion)

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Review

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25 pages, 2705 KiB

Open AccessReview

Research Progress of Carbon Deposition on Ni-Based Catalyst for CO₂-CH₄ Reforming

by Yuan Ren, Ya-Ya Ma, Wen-Long Mo, Jing Guo, Qing Liu, Xing Fan and Shu-Pei Zhang

Catalysts 2023, 13(4), 647; https://doi.org/10.3390/catal13040647 - 23 Mar 2023

Cited by 5 | Viewed by 2290

Abstract

As we all know, the massive emission of carbon dioxide has become a huge ecological and environmental problem. The extensive exploration, exploitation, transportation, storage, and use of natural gas resources will result in the emittance of a large amount of the greenhouse gas CH₄. Therefore, the treatment and utilization of the main greenhouse gases, CO₂ and CH₄, are extremely urgent. The CH₄ + CO₂ reaction is usually called the dry methane reforming reaction (CRM/DRM), which can realize the direct conversion and utilization of CH₄ and CO₂, and it is of great significance for carbon emission reduction and the resource utilization of CO₂-rich natural gas. In order to improve the activity, selectivity, and stability of the CO₂-CH₄ reforming catalyst, the highly active and relatively cheap metal Ni is usually used as the active component of the catalyst. In the CO₂-CH₄ reforming process, the widely studied Ni-based catalysts are prone to inactivation due to carbon deposition, which limits their large-scale industrial application. Due to the limitation of thermodynamic equilibrium, the CRM reaction needs to obtain high conversion and selectivity at a high temperature. Therefore, how to improve the anti-carbon deposition ability of the Ni-based catalyst, how to improve its stability, and how to eliminate carbon deposition are the main difficulties faced at present. Full article

(This article belongs to the Special Issue Recent Trends in Catalysis for Syngas Production and Conversion)

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