Catalytical Methods for the Production of Fine and Bulk Chemicals and Biomaterials from Biomass

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

Deadline for manuscript submissions: 31 August 2024 | Viewed by 14173

Special Issue Editors


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Department of Applied Chemistry, Faculty of Technology and Engineering, The Maharaja Sayajirao, University of Baroda, Vadodara 390 001, Gujarat, India
Interests: carbon dioxide absorption
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Special Issue Information

Dear Colleagues,

Biomass in the form of cellulose is the most abundant non-fossil-based carbon source on the surface of planet Earth. Catalytic methods to convert cellulose to bulk and fine chemicals and materials offers a smart route for the replacement of fossil-based resources, and this has been the key objective of this Special Issue. The US department of energy has proposed the following chemicals, namely, 1, 4 diacids (succinic, fumaric and malic), aspartic acid, glutamic acid, 2-5 furan dicarboxylic acid, 3-hydroxy propionic acid, glucaric acid, itaconic acid, levulinic acid, 3-hydroxy butyrolactone, glycerol, sorbitol and xylitol/arabinitol as top 12 value added chemicals that serve as economic drivers for the upcoming biorefinery. The key aspect of the afore mentioned chemicals is the presence of oxygen functionality that facilitates their easy product diversification and it is more so in levulinic acid, a key platform chemical. Multifunctionality, namely, the presence of carbonyl and carboxylic acid groups in the structure of levulinic acid (CH3COCH2CH2COOH, C5H8O3), makes it highly reactive, with easy product diversification, via oxidation, hydrogenation, esterification, amination, dehydration followed by hydrodeoxygenation, condensation, and polymerization resulting in the formation of value added fine and bulk chemicals and biodegradable polymers. The global market size of levulinic acid is USD 20.3 million and is expected to reach USD 30.21 million by 2028. A Web of Science search with the keyword “levulinic acid” shows 8097 results as on 24th February 2022, which shows that the research in this vital field of biofuels, biochemical and biomaterials is indeed at its incipient stages and an explosive outburst and ground breaking inventions are expected in the catalytic conversion of biomass to levulinic acid and its subsequent product diversification to strategically significant fuels like C7-C10 hydrocarbons and unconventional aviation fuels like γ-valerolactone and other prominent class of fuels by name valeric fuels. Levulinic acid is designated by food and drug administration (FDA) as a generally recognized as safe (GRAS) material useful in food and drug industries as well, which is one of the reasons for the expected explosive growth in this field of research. Owing to these reasons, the objective of launching the current Special Issue titled “Production of fine and bulk chemicals and biomaterials from levulinic acid” is to make the existing and new knowledge in this field freely and widely accessible to industrial personnel and policy makers facilitating the development of biorefinery facility leading to the growth of economy, clean environment and increased job opportunities apart from meeting the global energy, chemical and material needs. The research fraternity working on “levulinic acid” is encouraged to enthusiastically contribute their results for publication in the Special Issue of the journal “Catalysts”. 

Dr. Indra Neel Pulidindi
Prof. Dr. Aharon Gedanken
Dr. Pankaj Sharma
Guest Editors

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Keywords

  • biomass
  • fine chemicals
  • bulk chemicals. levulinic acid
  • diversification
  • oxidation
  • hydrogenation
  • esterification
  • amination
  • dehydration
  • fine chemicals
  • bulk chemicals
  • biodegradable polymers

Published Papers (8 papers)

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Research

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12 pages, 1684 KiB  
Article
Reaction Mechanisms and Production of Hydrogen and Acetic Acid from Aqueous Ethanol Using a Rn-Sn/TiO2 Catalyst in a Continuous Flow Reactor
by Takashi Nomura, Yuanyuan Zhao, Eiji Minami and Haruo Kawamoto
Catalysts 2024, 14(4), 249; https://doi.org/10.3390/catal14040249 - 09 Apr 2024
Viewed by 319
Abstract
The catalytic reforming of bioethanol can produce green hydrogen (H2) and acetic acid (AcOH). In the present study, the conversion of aqueous ethanol (EtOH) over 4 wt%Ru-4 wt%Sn/TiO2 in a flow reactor was investigated at different temperatures at 0.1 MPa [...] Read more.
The catalytic reforming of bioethanol can produce green hydrogen (H2) and acetic acid (AcOH). In the present study, the conversion of aqueous ethanol (EtOH) over 4 wt%Ru-4 wt%Sn/TiO2 in a flow reactor was investigated at different temperatures at 0.1 MPa or at various pressures at 260 °C. The ethanol conversion was rather slow in liquid water, while the reactivity increased significantly when water was evaporated. Under gas-phase conditions at 0.1 MPa, the conversion rate increased with increasing reaction temperature, but the AcOH yield and H2 purity decreased due to by-production of CH4, CO, and CO2. The CH4 and CO generated by fragmentation of acetaldehyde (AA), an intermediate, were suppressed by increasing reaction pressure, although the formation of CH4 and CO2 generated from AcOH was pressure independent. Thus, the highest-pressure conditions in steam at a given reaction temperature are preferred for the production of pure H2. The initial step, EtOH → AA, was the rate-determining reaction, and the model experiments using AA as a substrate showed that the Cannizzaro reaction of two AA molecules to form EtOH and AcOH occurred preferentially. This oxidation system was confirmed to be effective at EtOH concentrations of up to 500 g/L in water. Full article
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16 pages, 9525 KiB  
Article
Selective Hydrogenolysis of Furfuryl Alcohol to Pentanediol over Pt Supported on MgO
by Yuhao Yang, Qiaoyun Liu and Zhongyi Liu
Catalysts 2024, 14(4), 223; https://doi.org/10.3390/catal14040223 - 27 Mar 2024
Viewed by 515
Abstract
The catalytic conversion of naturally rich and renewable biomass into high-value chemicals is of great significance for pursuing a sustainable future and a green economy. The preparation of pentanediol from furfuryl alcohol is an important means of high-value conversion of biomass. The Pt-based [...] Read more.
The catalytic conversion of naturally rich and renewable biomass into high-value chemicals is of great significance for pursuing a sustainable future and a green economy. The preparation of pentanediol from furfuryl alcohol is an important means of high-value conversion of biomass. The Pt-based catalyst supported on MgO was applied to the selective hydrogenation of biomass furfuryl alcohol to prepare pentanediol. By adjusting parameters such as catalyst loading, reduction temperature, reaction temperature, and pressure, a highly active catalyst was designed and the optimal catalytic hydrogenation conditions were determined. The hydrogenation experiment results showed that the selectivity of the 2Pt/MgO-200 catalyst for 1,2-pentanediol and 1,5-pentanediol reached 59.4% and 15.2%, respectively, under 160 °C and 1 MPa hydrogen pressure. The catalyst was characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectrometer (XPS), CO2-temperature programmed desorption (CO2-TPD), and other methods. The characterization results indicate that the reduction temperature has a significant impact on the metal Pt, and an appropriate reduction temperature is beneficial for the hydrogenation performance of the catalyst. In addition, the basic sites on the carrier are also another important factor affecting the activity of the catalyst. In addition, stability tests were conducted on the catalyst, and the reasons for catalyst deactivation were studied using methods such as thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FT-IR). The results showed that the activity of the catalyst decreased after five cycles, and the deactivation was due to the hydrolysis of the carrier, the increase in metal particle size, and the surface adsorption of organic matter. Full article
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12 pages, 1653 KiB  
Article
Catalytic Conversion of Cyclopentanone into Dimethyl Adipate over Solid Basic Catalysts with Dimethyl Carbonate
by Irene Martínez-Salazar, Ana Orozco-Saumell, Manuel López Granados and Rafael Mariscal
Catalysts 2024, 14(1), 86; https://doi.org/10.3390/catal14010086 - 20 Jan 2024
Viewed by 1080
Abstract
The synthesis of dimethyl adipate (DAP), a stable configuration of adipic acid, from biomass-derived cyclopentanone (CPO) and dimethyl carbonate (DMC) constitutes an attractive greener route than petroleum-based industrial processes. Solid basic catalysts such as MgO, Mg5(CO3)4(OH)2 [...] Read more.
The synthesis of dimethyl adipate (DAP), a stable configuration of adipic acid, from biomass-derived cyclopentanone (CPO) and dimethyl carbonate (DMC) constitutes an attractive greener route than petroleum-based industrial processes. Solid basic catalysts such as MgO, Mg5(CO3)4(OH)2·4H2O, KOCH3 and Ca(OCH3)2 have been used achieving a DAP yield up to 30% at 533 K. In addition to the type of catalyst, other operating conditions such as the substrate, reaction time, temperature and CPO concentration have been studied. The methylation of DAP and CPO and the self-aldol condensation of CPO to form dimers and oligomers are reactions that occur in parallel with the production of DAP. It has been established that the main challenge is the self-aldol condensation of CPO. It has been identified that at short reaction times, to prevent methylation, and at dilute concentrations, to avoid CPO self-condensation, the DAP formation rate is much higher than these other competitive reactions. Finally, it should be noted that a DAP productivity up to 3.45 g·gcat−1·h−1 has been achieved under mild conditions. Full article
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15 pages, 7192 KiB  
Article
Mechanistic Studies into the Selective Production of 2,5-furandicarboxylic Acid from 2,5-bis(hydroxymethyl)furan Using Au-Pd Bimetallic Catalyst Supported on Nitrated Carbon Material
by Yiran Liu, Yao Chen, Wen Guan, Yu Cao, Fang Wang and Yunlei Zhang
Catalysts 2023, 13(2), 435; https://doi.org/10.3390/catal13020435 - 17 Feb 2023
Cited by 4 | Viewed by 1461
Abstract
Aerobic oxidation of bio-sourced 2,5-bis(hydroxymethyl)furan (BHMF) to 2, 5-furandicarboxylic acid (FDCA), a renewable and green alternative to petroleum-derived terephthalic acid (TPA), is of great significance in green chemicals production. Herein, hierarchical porous bowl-like nitrogen-rich (nitrated) carbon-supported bimetallic Au-Pd nanocatalysts (AumPdn [...] Read more.
Aerobic oxidation of bio-sourced 2,5-bis(hydroxymethyl)furan (BHMF) to 2, 5-furandicarboxylic acid (FDCA), a renewable and green alternative to petroleum-derived terephthalic acid (TPA), is of great significance in green chemicals production. Herein, hierarchical porous bowl-like nitrogen-rich (nitrated) carbon-supported bimetallic Au-Pd nanocatalysts (AumPdn/ N-BNxC) with different nitrogen content and bimetal nanoparticle sizes were developed and employed for the highly efficient aerobic oxidation of BHMF to FDCA in sodium carbonate aqueous solution. The reaction pathway for catalytic oxidation of BHMF went through the steps of BHMF→HMF→HMFCA→FFCA→FDCA. Kinetics studies showed that the activation energies of BHMF, HMF, HMFCA, and FFCA were 58.1 kJ·moL−1, 39.1 kJ·moL−1, 129.2 kJ·moL−1, and 56.3 kJ·moL−1, respectively, indicating that the oxidation of intermediate HMFCA to FFCA was the rate-determining step. ESR tests proved that the active species was a superoxide radical. Owing to the synergy between the nitrogen-rich carbon support and bimetallic Au-Pd nanoparticles, the Au1Pd1/N-BN2C nanocatalysts exhibited BHMF conversion of 100% and FDCA yield of 95.8% under optimal reaction conditions. Furthermore, the nanocatalysts showed good stability and reusability. This work provides a versatile strategy for the design of heterogeneous catalysts for the highly efficient production of FDCA from BHMF. Full article
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14 pages, 3344 KiB  
Article
Enhancing the Catalytic Activity of Eggshell-Derived CaO Catalyst and Its Application in Biodiesel Production from Waste Chicken Fat
by Muhammad Saleem, Farrukh Jamil, Obaid Ali Qamar, Parveen Akhter, Murid Hussain, Muhammad Shahzad Khurram, Ala’a H. Al-Muhtaseb, Abrar Inayat and Noor Samad Shah
Catalysts 2022, 12(12), 1627; https://doi.org/10.3390/catal12121627 - 12 Dec 2022
Cited by 5 | Viewed by 2061
Abstract
The comparatively greater cost of producing biodiesel in comparison to petroleum diesel is one of the key drawbacks. Eggshells and leftover chicken fat are examples of poultry wastes that can be used to produce biodiesel at a low cost as catalysts and oil, [...] Read more.
The comparatively greater cost of producing biodiesel in comparison to petroleum diesel is one of the key drawbacks. Eggshells and leftover chicken fat are examples of poultry wastes that can be used to produce biodiesel at a low cost as catalysts and oil, respectively. In this study, eggshell-derived CaO and its doping with sodium methoxide catalyst for enhancing catalytic activity was synthesized for the transesterification of waste chicken fat and characterized by FT-IR and XRD analyses. XRD studies confirmed the crystalline structure of the developed catalyst and doping of sodium with eggshell-derived CaO. The transesterification reaction was performed at different reaction parameters such as the catalyst loading, the methanol to oil ratio, the reaction temperature, and the reaction time. The biodiesel produced at the maximum yield was evaluated by gas chromatography mass spectrometry analysis. A maximum yield of 96% biodiesel was obtained with catalyst loading of 2 wt% of oil, as well as a methanol to oil ratio of 13:1 at 60 °C in 1 h. The output demonstrates that eggshell waste is a potentially accessible source of biomass-derived nano catalyst for the synthesis of biodiesel using chicken fat as a feedstock. Full article
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14 pages, 3956 KiB  
Article
Effects of Ca-Compounds on the Gases Formation Behavior during Molten Salts Thermal Treatment of Bio-Waste
by Jing He, Chan Zou, Xuanzhi Zhou, Yuting Deng, Xi Li, Lu Dong and Hongyun Hu
Catalysts 2022, 12(11), 1465; https://doi.org/10.3390/catal12111465 - 18 Nov 2022
Viewed by 1331
Abstract
Bio-waste utilization is essential, and pyrolysis is a prominent way for its effective utilization. However, the gradual accumulation of ash compounds in the intermediate products probably affects the thermal conversion characteristics of bio-waste. In the present study, beech wood and disposable chopsticks were [...] Read more.
Bio-waste utilization is essential, and pyrolysis is a prominent way for its effective utilization. However, the gradual accumulation of ash compounds in the intermediate products probably affects the thermal conversion characteristics of bio-waste. In the present study, beech wood and disposable chopsticks were selected as bio-waste samples. The effects of typical ash components (Ca-compounds) on volatile formation behavior were investigated during the molten salts thermal treatment of bio-waste. Results demonstrated that about 80% mass of initial bio-waste was gasified into the volatiles at 300 °C. The introduction of Ca-compounds in the molten salts slightly decreased the total yield of gaseous products. More specifically, Ca2+ could improve the generation of CO2 and suppress the generation of other gases (CO, H2, and CH4), and this is accompanied by a reduction in the low heating value (LHV) of the gases. The possible reason is that Ca2+ might act on the -OH bonds, phenyl C-C bond, methoxy bond and carboxylic acid -COOH bonds of the bio-waste to promote CO2 release. In contrast, the introduction of CO32− and OH- tended to relieve the inhibition effect of Ca2+ on the generation of H-containing gases. Meanwhile, the introduction of Ca2+ can promote the conversion of bio-waste into liquid products as well as increase the saturation level of liquid products. Moreover, as a vital form of carbon storage, CO2 was found to be abundant in the pyrolysis gases from molten salts thermal treatment of bio-waste, and the concentration of CO2 was much higher than that of direct-combustion or co-combustion with coal. It’s a promising way for bio-waste energy conversion as well as synchronized CO2 capture by using molten salts thermal treatment, while the introduction of small amounts of Ca-compounds was found to have no significant effect on the change of CO2 concentration. Full article
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12 pages, 1960 KiB  
Article
Multivariable Analysis Reveals the Key Variables Related to Lignocellulosic Biomass Type and Pretreatment before Enzymolysis
by Xiujun Wang, Deliang Fan, Yutong Han and Jifei Xu
Catalysts 2022, 12(10), 1142; https://doi.org/10.3390/catal12101142 - 29 Sep 2022
Viewed by 1157
Abstract
In this study, partial least square (PLS), a multivariable analysis, was used to simultaneously quantitatively evaluate the effects of variables related to three pretreatments (alkaline, hot water and acid) and the biomass properties of poplar, salix and corncob. The results showed that biomass [...] Read more.
In this study, partial least square (PLS), a multivariable analysis, was used to simultaneously quantitatively evaluate the effects of variables related to three pretreatments (alkaline, hot water and acid) and the biomass properties of poplar, salix and corncob. The results showed that biomass type was the most important variable influencing enzymolysis reducing sugar yield (ERSY). The biomass compositions affected the ERSY more than the pretreatment conditions, among which hemicellulose and lignin played vital roles. The alkaline pretreatment had a more positive effect on the ERSY than the acid and hot water pretreatments, in which alkaline content had more influence than temperature. This work provides a deeper understanding of the material properties and the pretreatment conditions in different complex systems before enzymolysis, which might be a guidance to future study. Full article
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Review

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15 pages, 4030 KiB  
Review
Levulinic Acid Is a Key Strategic Chemical from Biomass
by Amudhavalli Victor, Pankaj Sharma, Indra Neel Pulidindi and Aharon Gedanken
Catalysts 2022, 12(8), 909; https://doi.org/10.3390/catal12080909 - 18 Aug 2022
Cited by 7 | Viewed by 4791
Abstract
Levulinic acid (LA) is one of the top twelve chemicals listed by the US Department of Energy that can be derived from biomass. It serves as a building block and platform chemical for producing a variety of chemicals, fuels and materials which are [...] Read more.
Levulinic acid (LA) is one of the top twelve chemicals listed by the US Department of Energy that can be derived from biomass. It serves as a building block and platform chemical for producing a variety of chemicals, fuels and materials which are currently produced in fossil based refineries. LA is a key strategic chemical, as fuel grade chemicals and plastic substitutes can be produced by its catalytic conversion. LA derivatisation to various product streams, such as alkyl levulinates via esterification, γ-valerolactone via hydrogenation and N-substituted pyrrolidones via reductive amination and many other transformations of commercial utility are possible owing to the two oxygen functionalities, namely, carbonyl and carboxyl groups, present within the same substrate. Various biomass feedstock, such as agricultural wastes, marine macroalgae, and fresh water microalgae were successfully converted to LA in high yields. Finding a substitute to mineral acid catalysts for the conversion of biomass to LA is a challenge. The use of an ultrasound technique facilitated the production of promising nano-solid acid catalysts including Ga salt of molybophosphoric acid and Ga deposited mordenite zeolite, with optimum amounts of Lewis and Bronsted acidities needed for the conversion of glucose to LA in high yields, being 56 and 59.9 wt.% respectively. Microwave irradiation technology was successfully utilized for the accelerated production of LA (53 wt.%) from glucose in a short duration of 6 min, making use of the unique synergistic catalytic activity of ZnBr2 and HCl. Full article
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