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Catalytic Conversion of Biomass to Chemicals

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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 (20 January 2025) | Viewed by 25164

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Dr. Xiaofeng Wang

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College of Environmental Science and Engineering, Dalian Maritime University, Dalian 116026, China
Interests: biomass conversion; nanostructured catalyst design; environmental catalysis; hydrogenation reaction; selective catalytic reduction
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Dear Colleagues,

In the last decade, the rapid depletion of fossil fuels has escalated the demand for renewable biomass as alternatives to chemicals and fuels. Lignocellulose, as the main component of biomass, consists of cellulose, hemicellulose and lignin. All these compounds can be catalytically converted to valuable chemicals and high-quality biofuel. Currently, considerable research efforts have been devoted to screening out efficient catalysts using specific model compounds as reaction substrates, which lay the foundation for the development of general catalysts for bio-oil upgrading. However, the complexity of bio-oil components and the repolymerization of phenolic compounds in thermal environments have augmented the difficulty of exploring efficient catalysts and related reaction mechanisms.

This Research Topic aims to highlight and collect the latest progress regarding novel nanostructured catalysts for the conversion of biomass and derivatives to valuable chemicals and biofuels. In this Special Issue, we welcome manuscripts related to the catalytic conversion of biomass and upgrading of bio-oil and model compounds. Topics of interest include but are not limited to the following:

Hydrogenation/hydrogenolysis/hydrodeoxygenation of biomass and derivatives to biofuels and valuable chemicals;
Catalytic oxidation of biomass and derivatives;
Catalytic pyrolysis of biomass to bio-oil.

Dr. Xiaofeng Wang
Guest Editor

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Keywords

biomass conversion
hydrogenation
nanostructured catalysts
biomass derivatives
oxidation

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Related Special Issue

Catalytic Conversion of Biomass to Chemicals, 2nd Edition in Catalysts

Published Papers (11 papers)

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Research

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22 pages, 5953 KiB

Open AccessArticle

Catalytic Conversion of Levulinic Acid over Sn-BTC and Sn-H₃-5-SIP Heterogeneous Acid Catalysts

by Juan Pablo Chávez-León, Denis A. Cabrera-Munguia, Aída Gutiérrez-Alejandre, Dora A. Solis-Casados, Marcela L. Espinoza-Almeraya and Horacio González

Catalysts 2024, 14(11), 754; https://doi.org/10.3390/catal14110754 - 26 Oct 2024

Cited by 1 | Viewed by 1207

Abstract

This work presents the synthesis and characterization of materials that contain Sn metal clusters formed by ligands of trimesic acid (Sn-BTC) or 5-sulfobenzene-1,3-dicarboxylic acid (Sn-H₃-5-SIP). These catalysts were used to convert levulinic acid with ethanol to produce ethyl levulinate under mild reaction conditions. The characterization results confirmed that Sn is mainly present in the cassiterite crystalline phase with a tetragonal rutile structure in octahedral and tetrahedral coordination in the materials. The assembly of trimesic acid (a hard base) with metal species (Sn) results in the formation of acid and thermally stable metal–organic frameworks. The use of 5-sulfobenzene-1,3-dicarboxylic acid instead of trimesic acid in the synthesis incorporates sulfonic groups in the material, enhancing the total acidity of the Sn-H₃-5-SIP catalyst compared to the Sn-BTC material. The Sn-H₃-5-SIP catalyst exhibited the highest catalytic activity when converting levulinic acid with ethanol, resulting in a turnover frequency (TOF) of 0.0495 s⁻¹, which is a 50% increase compared to the TOF of the Sn-BTC catalyst (0.0329 s⁻¹). This result can be attributed to its higher concentration of acid sites (2.23 ± 0.05 mmol H⁺/g_cat) and specific area (139 m²/g). Thus, materials containing tin metal clusters and sulfonic groups are promising materials that could be used as catalysts for synthesizing ethyl levulinate under mild reaction conditions. Full article

(This article belongs to the Special Issue Catalytic Conversion of Biomass to Chemicals)

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12 pages, 3233 KiB

Open AccessArticle

Development of Robust CuNi Bimetallic Catalysts for Selective Hydrogenation of Furfural to Furfuryl Alcohol under Mild Conditions

by Deqin He, Zheng Liang, Juwen Gu, Xuechun Sang, Yujia Liu and Songbai Qiu

Catalysts 2024, 14(10), 683; https://doi.org/10.3390/catal14100683 - 2 Oct 2024

Viewed by 1543

Abstract

Furfuryl alcohol represents a pivotal intermediate in the high-value utilization of renewable furfural, derived from agricultural residues. The industrial-scale hydrogenation of furfural to furfuryl alcohol typically employs Cu-based catalysts, but their limited catalytic activity necessitates high-temperature and high-pressure conditions. Here, we develop robust CuNi bimetallic catalysts through direct calcination of dried sol–gel precursors under H₂ atmosphere, enabling the complete conversion of furfural to furfuryl alcohol under mild conditions. By adjusting the calcination atmosphere and introducing small amounts of Ni, we achieve the formation of highly dispersed, ultrasmall Cu nanoparticles, resulting in a significant enhancement of the catalytic activity. The optimized 0.5%Ni-10%Cu/SiO₂-CA(H₂) catalyst demonstrates superior catalytic performance, achieving 99.4% of furfural conversion and 99.9% of furfuryl alcohol selectivity, respectively, at 55 °C under 2 MPa H₂, outperforming previously reported Cu-based catalysts. The excellent performance of CuNi bimetallic catalysts can be attributed to the highly dispersed Cu nanoparticles and the synergistic effect between Cu and Ni for H₂ activation. This research contributes to the rational design of Cu-based catalysts for the selective hydrogenation of furfural. Full article

(This article belongs to the Special Issue Catalytic Conversion of Biomass to Chemicals)

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14 pages, 2887 KiB

Open AccessFeature PaperEditor’s ChoiceArticle

Renewable Diesel Production over Mo-Ni Catalysts Supported on Silica

by John Zafeiropoulos, George Petropoulos, Eleana Kordouli, Labrini Sygellou, Alexis Lycourghiotis and Kyriakos Bourikas

Catalysts 2024, 14(10), 662; https://doi.org/10.3390/catal14100662 - 24 Sep 2024

Viewed by 1515

Abstract

Nickel catalysts promoted with Mo and supported on silica were studied for renewable diesel production from triglyceride biomass, through the selective deoxygenation process. The catalysts were prepared by wet co-impregnation of the SiO₂ with different Ni/(Ni + Mo) atomic ratios (0/0.84/0.91/0.95/0.98/1) and a total metal content equal to 50%. They were characterized by XRD, XPS, N₂ physisorption, H₂-TPR, and NH₃-TPD. Evaluation of the catalysts for the transformation of sunflower oil to renewable (green) diesel took place in a high-pressure semi-batch reactor, under solvent-free conditions. A very small addition of Mo, namely the synergistic Ni/(Ni + Mo) atomic ratio equal to 0.95, proved to be the optimum one for a significant enhancement of the catalytic performance of the metallic Ni/SiO₂ catalyst, achieving 98 wt.% renewable diesel production. This promoting action of Mo has been attributed to the significant increase of the metallic Ni active phase surface area, the suitable regulation of surface acidity, the acceleration of the hydro-deoxygenation pathway (HDO), the creation of surface oxygen vacancies, and the diminution of coke formation provoked by Mo addition. Full article

(This article belongs to the Special Issue Catalytic Conversion of Biomass to Chemicals)

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14 pages, 2231 KiB

Open AccessArticle

Biodiesel Synthesis from Date Seed Oil Using Camel Dung as a Novel Green Catalyst: An Experimental Investigation

by Raiedhah A. Alsaiari, Esraa M. Musa and Moustafa A. Rizk

Catalysts 2024, 14(9), 643; https://doi.org/10.3390/catal14090643 - 20 Sep 2024

Cited by 1 | Viewed by 1917

Abstract

Biodiesel is seen as more environmentally benign than petroleum-based fuels. It is also cheaper and capable of creating cleaner energy, which has a good impact on increasing the bioeconomy. An investigation was conducted on a novel heterogeneous catalyst system utilized in the synthesis of eco-friendly biodiesel from date seed oil, a non-edible feedstock obtained through the calcination of desiccated camel manure at varying temperatures. X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) analysis, and scanning electron microscopy (SEM) were utilized to characterize this catalyst. As a result of raising the calcination temperature, the results showed that the pore size of the catalyst decreased. The biodiesel production was optimized to be 86% by using the transesterification method. The optimal reaction parameters included a catalyst with 4% loading, a molar ratio of 1:8 between date seed oil and ethanol, and a temperature of 75 °C for a reaction period of three hours. The confirmation of FAME generation was achieved by gas chromatography–mass spectrometry (GC–MS). The fuel qualities of fatty acid ethyl ester are in accordance with ASTM, suggesting that it is a suitable alternative fuel option. Utilizing biodiesel derived from waste and untamed resources to establish and execute a more sustainable and ecologically conscious energy plan is praiseworthy. The adoption and integration of green energy practices could potentially yield positive environmental outcomes, thereby fostering enhanced societal and economic development for the biodiesel sector on a broader scale. Full article

(This article belongs to the Special Issue Catalytic Conversion of Biomass to Chemicals)

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15 pages, 2241 KiB

Open AccessArticle

One-Pot Synthesis of Acidic Mesoporous Activated Carbon Obtained from Yerba Mate Twigs as Suitable Catalyst for the Production of Levulinic Ester Biofuel Additives

by John J. Alvear-Daza, Alexis Sosa, Diego M. Ruiz, Gustavo A. Pasquale, Julián A. Rengifo-Herrera, Gustavo P. Romanelli and Luis R. Pizzio

Catalysts 2024, 14(8), 522; https://doi.org/10.3390/catal14080522 - 13 Aug 2024

Cited by 2 | Viewed by 1423

Abstract

A series of activated carbons (YMBC) obtained from yerba mate twig residue (YMT) were prepared by chemical (H₃PO₄) and thermal activation. Five materials were synthesized, varying the carbonization temperature (400–600 °C under N₂ atmosphere) and H₃PO₄:YMT ratio (60–80 wt%). They were physicochemically and texturally characterized by SEM-EDX, BET, FT-IR, and ³¹P MAS-NMR. Potentiometric titration with the n-butylamine technique was used to evaluate their acidic properties. The materials exhibited a high specific surface area (572 m² g⁻¹ < S_BET < 1031 m² g⁻¹) and mesoporosity (67% < S_meso/S_BET < 93%). The results showed that the acid strength and the number of acid sites increased with the H₃PO₄:YMT ratio and decreased with the calcination temperature increment. The FT-IR and ³¹P characterization revealed the presence of H_n+2P_nO_3n+1 species firmly (via P-O-C linkages) and loosely attached (by electrostatic interaction). The latter were successfully removed by refluxing the material in water or n-propanol. The optimal reaction conditions were applied to the synthesis of other levulinic acid esters using YMBC-500-70_NP as a catalyst. Furthermore, the effective separation of the product combined with the use of a recyclable catalyst resulted in a clean and environmentally friendly strategy for the synthesis of alkyl levulinates, bioproducts of relevance to the biorefinery industry, which can be applied as fragrances, flavoring agents, as well as fuel additives. Full article

(This article belongs to the Special Issue Catalytic Conversion of Biomass to Chemicals)

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15 pages, 5164 KiB

Open AccessArticle

VO Supported on Functionalized CNTs for Oxidative Conversion of Furfural to Maleic Anhydride

by Pedro Rodríguez, Carolina Parra, J. Noe Díaz de León, Alejandro Karelovic, Sebastian Riffo, Carla Herrera, Gina Pecchi and Catherine Sepúlveda

Catalysts 2024, 14(8), 510; https://doi.org/10.3390/catal14080510 - 7 Aug 2024

Viewed by 1172

Abstract

Commercial non-functionalized (CNTs) and functionalized carbon nanotubes (CNT-COOH and CNT-NH₂) were used as supports to synthesize vanadium-supported catalysts to be used in the gas phase partial oxidation of furfural towards maleic anhydride (MA). The CNTs and the VO₂-V₂O₅/CNTs, so-called VO/CNT catalysts, were characterized by AAS, TGA, XRD, N₂ adsorption isotherms at −196 °C, Raman, NH₃-TPD and XPS. The surface area values, TGA and XRD results indicate that the larger thermal stability and larger dispersion of vanadium species is reached for the VO/CNT-NH₂ catalyst. XPS indicates presence of surface VO₂ and V₂O₅ species for the non-functionalized (CNT) and functionalized (CNT-COOH and CNT-NH₂) catalysts, with a large interaction of the functional group with the surface vanadium species only for the VO/CNT-NH₂ catalyst. The catalytic activity, evaluated in the range 305 °C to 350 °C, indicates that CO, CO₂ and MA yield (%) and MA productivity are associated to the redox properties of the vanadium species, the oxygen exchange ability of the support and the vanadium–support interaction. For the reaction temperatures between 320 °C and 335 °C, the maximum MA yield (%) is found in the functionalized VO/CNT-COOH and VO/CNT-NH₂ catalysts. This behavior is attributed to a decreased oxidation capability of the CNT with the functionalization. In addition, VO/CNT-NH₂ is the more active and selective catalyst for MA productivity at 305 °C and 320 °C, which is related to the greater interaction of the surface vanadium species with the -NH₂ group, which enhances the redox properties and stabilization of the VO₂ and V₂O₅ surface active sites. Recycling at 350 °C resulted in 100% furfural conversion for all catalysts and a similar MA yield (%) compared to the fresh catalyst, indicating no loss of surface active sites. Full article

(This article belongs to the Special Issue Catalytic Conversion of Biomass to Chemicals)

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14 pages, 8441 KiB

Open AccessArticle

H-Beta Zeolite as Catalyst for the Conversion of Carbohydrates into 5-Hydroxymethylfurfural: The Role of Calcination Temperature

by Xinyi Xing, Wanni Liu, Siquan Xu and Jianxiu Hao

Catalysts 2024, 14(4), 248; https://doi.org/10.3390/catal14040248 - 8 Apr 2024

Cited by 3 | Viewed by 5240

Abstract

H-Beta zeolite is a solid acid catalyst commonly utilized in the catalytic conversion of biomass resources. In this study, H-Beta zeolite was calcined at different temperatures (350, 550, 750, and 1000 °C) to explore the effects of high temperature-induced dealumination on its physicochemical properties and its catalytic ability to convert glucose into 5-hydroxymethylfurfural (HMF). It was shown that as the calcination temperature increased, the Si-O-Al bond of H-Beta zeolite was broken and its dealumination effect was enhanced. Dealumination led to the collapse of the framework of H-Beta zeolite and a reduction in the number of acid sites, which in turn reduced its catalytic performance and the efficiency of HMF formation from glucose. Furthermore, H-Beta zeolite exhibited an extraordinary catalytic ability for the production of HMF from carbohydrates. Using glucose and cellulose as substrates, superior HMF yields of 91% and 46%, respectively, were achieved under optimal reaction conditions. Further, calcination removes carbon deposits in the recovered H-Beta zeolite, but it affects the cycling stability of the catalyst. Meanwhile, the by-products formed during the synthesis of HMF from glucose catalyzed by H-Beta zeolite catalyst were also clearly detected. Full article

(This article belongs to the Special Issue Catalytic Conversion of Biomass to Chemicals)

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22 pages, 5605 KiB

Open AccessFeature PaperArticle

A Kinetic Model of Furfural Hydrogenation to 2-Methylfuran on Nanoparticles of Nickel Supported on Sulfuric Acid-Modified Biochar Catalyst

by Ismaila Mudi, Abarasi Hart, Andrew Ingram and Joseph Wood

Catalysts 2024, 14(1), 54; https://doi.org/10.3390/catal14010054 - 11 Jan 2024

Cited by 3 | Viewed by 2822

Abstract

Lignocellulosic biomass can uptake CO₂ during growth, which can then be pyrolysed into three major products, biochar (BC), syngas, and bio-oil. Due to the presence of oxygenated organic compounds, the produced bio-oil is not suitable for direct use as a fuel and requires upgrading via hydrodeoxygenation (HDO) and hydrogenation. This is typically carried out over a supported metal catalyst. Regarding circular economy and sustainability, the BC from the pyrolysis step can potentially be activated and used as a novel catalyst support, as reported here. A 15 wt% Ni/BC catalyst was developed by chemically modifying BC with sulfuric acid to improve mesoporous structure and surface area. When compared to the pristine Ni/BC catalyst, sulfuric activated Ni/BC catalyst has excellent mesopores and a high surface area, which increases the dispersion of Ni nanoparticles and hence improves the adsorptive effect and thus catalytic performance. A liquid phase hydrogenation of furfural to 2-methylfuran was performed over the developed 15 wt% Ni/BC catalyst. Langmuir–Hinshelwood–Hougen–Watson (LHHW) kinetic type models for adsorption of dissociative H₂ were screened based on an R² value greater than 99%, demonstrating that the experimental data satisfactorily fit to three plausible models: competitive (Model I), competitive at only one type of adsorption site (Model II), and non-competitive with two types of adsorption sites (Model III). With a correlation coefficient greater than 99% between the experimental rates and the predicted rate, Model III, which is a dual-site adsorption mechanism involving furfural adsorption and hydrogen dissociative adsorption and surface reaction, is the best fit. The Ni/BC catalyst demonstrated comparative performance and significant cost savings over previous catalysts; a value of 24.39 kJ mol⁻¹ was estimated for activation energy, −11.43 kJ mol⁻¹ for the enthalpy of adsorption for H₂, and −5.86 kJ mol⁻¹ for furfural. The developed Ni/BC catalyst demonstrated excellent stability in terms of conversion of furfural (96%) and yield of 2-methylfuran (54%) at the fourth successive experiments. Based on furfural conversion and yield of products, it appears that pores are constructed slowly during sulfuric acid activation of the biochar. Full article

(This article belongs to the Special Issue Catalytic Conversion of Biomass to Chemicals)

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19 pages, 6203 KiB

Open AccessArticle

Structure and Catalytic Performance of Carbon-Based Solid Acids from Biomass Activated by ZnCl₂

by Yao Wu, Hao Zhang, Zhaozhou Wei, Deyuan Xiong, Songbai Bai, Menglong Tong and Pengcheng Ma

Catalysts 2023, 13(11), 1436; https://doi.org/10.3390/catal13111436 - 14 Nov 2023

Cited by 4 | Viewed by 2130

Abstract

In the current investigation, carbon-based solid acid catalysts were synthesized from peanut shells (PSs) and rice straw (RS) using ZnCl₂ activation and concentrated sulfuric acid sulfonation. These catalysts were then employed for the hydration of pinene to produce terpineol. The research findings suggest that the natural porous structure of RS is more amenable to ZnCl₂ activation compared to PSs. Furthermore, the catalysts prepared from fully activated RS by ZnCl₂ (RSA-C-S) had a higher S_BET and higher density of oxygen-containing groups (–COOH) in comparison with unactivated RS-based solid acids (RSC-S). The characterization outcomes revealed that RSA-C-S possesses a specific surface area of 527.0 m²/g, significantly outperforming RSC-S, which has a surface area of 420.9 m²/g. Additionally, RSA-C-S registered a higher –COOH density of 1.37 mmol/g, as opposed to RSC-S’s, with 1.07 mmol/g, attributable to the partial oxidation of internal –OH groups during activation. Experimental data from hydration tests confirmed that the catalyst’s superior performance is largely attributed to its elevated specific surface area and a high density of –COOH functional groups. Under optimal reaction parameters, RSA-C-S demonstrated unparalleled catalytic efficiency in the synthesis of α-terpineol via hydration of α-pinene, achieving conversion and selectivity rates of 87.15% and 54.19%, respectively. Full article

(This article belongs to the Special Issue Catalytic Conversion of Biomass to Chemicals)

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Review

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27 pages, 1438 KiB

Open AccessFeature PaperReview

Metal-Based Catalysts in Biomass Transformation: From Plant Feedstocks to Renewable Fuels and Chemicals

by Muhammad Saeed Akhtar, Muhammad Tahir Naseem, Sajid Ali and Wajid Zaman

Catalysts 2025, 15(1), 40; https://doi.org/10.3390/catal15010040 - 4 Jan 2025

Cited by 2 | Viewed by 2137

Abstract

The transformation of biomass into renewable fuels and chemicals has gained remarkable attention as a sustainable alternative to fossil-based resources. Metal-based catalysts, encompassing transition and noble metals, are crucial in these transformations as they drive critical reactions, such as hydrodeoxygenation, hydrogenation, and reforming. Transition metals, including nickel, cobalt, and iron, provide cost-effective solutions for large-scale processes, while noble metals, such as platinum and palladium, exhibit superior activity and selectivity for specific reactions. Catalytic advancements, including the development of hybrid and bimetallic systems, have further improved the efficiency, stability, and scalability of biomass transformation processes. This review highlights the catalytic upgrading of lignocellulosic, algal, and waste biomass into high-value platform chemicals, biofuels, and biopolymers, with a focus on processes, such as Fischer–Tropsch synthesis, aqueous-phase reforming, and catalytic cracking. Key challenges, including catalyst deactivation, economic feasibility, and environmental sustainability, are examined alongside emerging solutions, like AI-driven catalyst design and lifecycle analysis. By addressing these challenges and leveraging innovative technologies, metal-based catalysis can accelerate the transition to a circular bioeconomy, supporting global efforts to combat climate change and reduce fossil fuel dependence. Full article

(This article belongs to the Special Issue Catalytic Conversion of Biomass to Chemicals)

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18 pages, 3129 KiB

Open AccessReview

Application of Catalysts in the Conversion of Biomass and Its Derivatives

by Jixiang Cai, Lianghuan Wei, Jianguo Wang, Ning Lin, Youwen Li, Feixing Li, Xianghao Zha and Weizun Li

Catalysts 2024, 14(8), 499; https://doi.org/10.3390/catal14080499 - 1 Aug 2024

Cited by 7 | Viewed by 3132

Abstract

With the continuous depletion of fossil resources and the deterioration of the global climate, it is particularly urgent to find green and sustainable renewable resources to replace non-renewable resources. Renewable biomass, which converts and stores light energy into chemical energy through photosynthesis by green plants, has received widespread attention due to its simultaneous resource and energy properties. Therefore, this article focuses on lignocellulose, an important component of biomass, in the fields of chemical conversion and high-value-added chemical preparation. A detailed review was conducted on the application of catalysts in biomass bio-char, bio-oil, bio-gas, and high-value added chemicals and their derivatives, represented by 5-hydroxymethylfurfural (5-HMF) and levulinic acid (LA). At the same time, the difficulties and challenges encountered by catalysts in biomass conversion were analyzed, and new ideas were proposed for future development directions, so as to provide new development pathways for efficient and green conversion of biomass into biomass energy and high-value-added chemicals. Full article

(This article belongs to the Special Issue Catalytic Conversion of Biomass to Chemicals)

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