Editorial

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4 pages, 181 KiB

Open AccessEditorial

Sustainable Catalytic Conversion of Biomass for the Production of Biofuels and Bioproducts

by Gabriel Morales, Jose Iglesias and Juan A. Melero

Catalysts 2020, 10(5), 581; https://doi.org/10.3390/catal10050581 - 22 May 2020

Cited by 10 | Viewed by 2664

Abstract

Biomass, in its many forms—oils and fats, lignocellulose, algae, etc [...] Full article

(This article belongs to the Special Issue Sustainable Catalytic Conversion of Biomass for the Production of Biofuels and Bioproducts)

Research

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32 pages, 11223 KiB

Open AccessArticle

Promotional Effect of Cu, Fe and Pt on the Performance of Ni/Al₂O₃ in the Deoxygenation of Used Cooking Oil to Fuel-Like Hydrocarbons

by Gisele C. R. Silva, Dali Qian, Robert Pace, Olivier Heintz, Gilles Caboche, Eduardo Santillan-Jimenez and Mark Crocker

Catalysts 2020, 10(1), 91; https://doi.org/10.3390/catal10010091 - 07 Jan 2020

Cited by 21 | Viewed by 3552

Abstract

Inexpensive Ni-based catalysts can afford comparable performance to costly precious metal formulations in the conversion of fat, oil, or greases (FOG) to fuel-like hydrocarbons via decarboxylation/decarbonylation (deCO_x). While the addition of certain metals has been observed to promote Ni-based deCO_x [...] Read more.

Inexpensive Ni-based catalysts can afford comparable performance to costly precious metal formulations in the conversion of fat, oil, or greases (FOG) to fuel-like hydrocarbons via decarboxylation/decarbonylation (deCO_x). While the addition of certain metals has been observed to promote Ni-based deCO_x catalysts, the steady-state performance of bimetallic formulations must be ascertained using industrially relevant feeds and reaction conditions in order to make meaningful comparisons. In the present work, used cooking oil (UCO) was upgraded to renewable diesel via deCO_x over Ni/Al₂O₃ promoted with Cu, Fe, or Pt in a fixed-bed reactor at 375 °C using a weight hourly space velocity (WHSV) of 1 h⁻¹. Although all catalysts fully deoxygenated the feed to hydrocarbons throughout the entire 76 h duration of these experiments, the cracking activity (and the evolution thereof) was distinct for each formulation. Indeed, that of the Ni-Cu catalyst was low and relatively stable, that of the Ni-Fe formulation was initially high but progressively dropped to become negligible, and that of the Ni-Pt catalyst started as moderate, varied considerably, and finished high. Analysis of the spent catalysts suggests that the evolution of the cracking activity can be mainly ascribed to changes in the composition of the metal particles. Full article

(This article belongs to the Special Issue Sustainable Catalytic Conversion of Biomass for the Production of Biofuels and Bioproducts)

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16 pages, 3777 KiB

Open AccessArticle

Selective Conversion of Glucose to 5-Hydroxymethylfurfural by Using L-Type Zeolites with Different Morphologies

by María José Ginés-Molina, Nur Hidayahni Ahmad, Sandra Mérida-Morales, Cristina García-Sancho, Svetlana Mintova, Ng Eng-Poh and Pedro Maireles-Torres

Catalysts 2019, 9(12), 1073; https://doi.org/10.3390/catal9121073 - 16 Dec 2019

Cited by 15 | Viewed by 3059

Abstract

In the present work, the morphology of L-type zeolite (LTL topology) has been modified in order to evaluate the influence of several protonated-form LTL-zeolites with different morphologies on their stability and catalytic performance in the conversion of glucose into 5-hydroxymethylfurfural (5-HMF). Physico-chemical characterization [...] Read more.

In the present work, the morphology of L-type zeolite (LTL topology) has been modified in order to evaluate the influence of several protonated-form LTL-zeolites with different morphologies on their stability and catalytic performance in the conversion of glucose into 5-hydroxymethylfurfural (5-HMF). Physico-chemical characterization of the LTL-based catalysts has revealed that the three types of morphologies (needle, short rod and cylinder) are active, providing complete glucose conversion and high 5-HMF yield values. The addition of CaCl₂ had a positive influence on the catalytic performance. It was found that morphology influences the textural and acid properties of LTL-zeolites, and hence their catalytic performance. The best catalytic results have been obtained with the NEEDLE-LTL, showing nanoparticles with a length of 4.46 μm and a width of 0.63 μm, which attains a 5-HMF yield of 63%, at 175 °C after 90 min of reaction, and a glucose conversion of 88%. The reusability study has revealed a progressive decrease in 5-HMF yield after each catalytic cycle. Different regeneration methods have been essayed without recovering the initial catalytic activity. The presence of organic molecules in micropores has been demonstrated by TG analysis, which are difficult to remove even after a regeneration process at 550 °C. Full article

(This article belongs to the Special Issue Sustainable Catalytic Conversion of Biomass for the Production of Biofuels and Bioproducts)

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9 pages, 2524 KiB

Open AccessArticle

Biodiesel Production Using Bauxite in Low-Cost Solid Base Catalyst Precursors

by Yong-Ming Dai, Cheng-Hsuan Hsieh, Jia-Hao Lin, Fu-Hsuan Chen and Chiing-Chang Chen

Catalysts 2019, 9(12), 1064; https://doi.org/10.3390/catal9121064 - 13 Dec 2019

Cited by 16 | Viewed by 2473

Abstract

Investigation was conducted on bauxite mixed with Li₂CO₃ as alkali metal catalysts for biodiesel production. Bauxite contains a high percentage of Si and Al compounds among products. Because of the high expense of commercial materials (SiO₂, Al₂ [...] Read more.

Investigation was conducted on bauxite mixed with Li₂CO₃ as alkali metal catalysts for biodiesel production. Bauxite contains a high percentage of Si and Al compounds among products. Because of the high expense of commercial materials (SiO₂, Al₂O₃) that makes them not economical, the method was very recently improved by replacing commercial materials with Si and Al from bauxite. This is one of the easiest methods for preparing heterogeneous transesterification catalysts, through one-pot blending, grinding bauxite with Li₂CO₃, and heating at 800 °C for 4 h. The prepared solid-base alkali metal catalyst was characterized in terms of its physical and chemical properties using X-ray powder diffraction and field-emission scanning electron microscopy (FE-SEM). The optimal conditions for the transesterification procedure are to mix methanol oil by molar ratio 9:1, under 65 °C, with catalyst amount 3 wt.%. The procedure is suitable for transesterifying oil to fatty acid methyl ester in the 96% range. Full article

(This article belongs to the Special Issue Sustainable Catalytic Conversion of Biomass for the Production of Biofuels and Bioproducts)

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15 pages, 2636 KiB

Open AccessArticle

Cleanup and Conversion of Biomass Liquefaction Aqueous Phase to C₃–C₅ Olefins over Zn_xZr_yO_z Catalyst

by Stephen D. Davidson, Juan A. Lopez-Ruiz, Matthew Flake, Alan R. Cooper, Yaseen Elkasabi, Marco Tomasi Morgano, Vanessa Lebarbier Dagle, Karl O. Albrecht and Robert A. Dagle

Catalysts 2019, 9(11), 923; https://doi.org/10.3390/catal9110923 - 06 Nov 2019

Cited by 8 | Viewed by 3228

Abstract

The viability of using a Zn_xZr_yO_z mixed oxide catalyst for the direct production of C₄ olefins from the aqueous phase derived from three different bio-oils was explored. The aqueous phases derived from (i) hydrothermal liquefaction of corn [...] Read more.

The viability of using a Zn_xZr_yO_z mixed oxide catalyst for the direct production of C₄ olefins from the aqueous phase derived from three different bio-oils was explored. The aqueous phases derived from (i) hydrothermal liquefaction of corn stover, (ii) fluidized bed fast pyrolysis of horse litter, and (iii) screw pyrolysis of wood pellets were evaluated as feedstocks. While exact compositions vary, the primary constituents for each feedstock are acetic acid and propionic acid. Continuous processing, based on liquid–liquid extraction, for the cleanup of the inorganic contaminants contained in the aqueous phase was also demonstrated. Complete conversion of the carboxylic acids was achieved over Zn_xZr_yO_z catalyst for all the feedstocks investigated. The main reaction products from each of the feedstocks include isobutene (>30% selectivity) and CO₂ (>23% selectivity). Activity loss from coking was also observed, thereby rendering deactivation of the Zn_xZr_yO_z catalyst, however, complete recovery of catalyst activity was observed following regeneration. Finally, the presence of H₂ in the feed was found to facilitate hydrogenation of intermediate acetone, thereby increasing propene production and, consequently, decreasing isobutene production. Full article

(This article belongs to the Special Issue Sustainable Catalytic Conversion of Biomass for the Production of Biofuels and Bioproducts)

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13 pages, 1366 KiB

Open AccessArticle

Ga/HZSM-5 Catalysed Acetic Acid Ketonisation for Upgrading of Biomass Pyrolysis Vapours

by Hessam Jahangiri, Amin Osatiashtiani, Miloud Ouadi, Andreas Hornung, Adam F. Lee and Karen Wilson

Catalysts 2019, 9(10), 841; https://doi.org/10.3390/catal9100841 - 11 Oct 2019

Cited by 23 | Viewed by 3651

Abstract

Pyrolysis bio-oils contain significant amounts of carboxylic acids which limit their utility as biofuels. Ketonisation of carboxylic acids within biomass pyrolysis vapours is a potential route to upgrade the energy content and stability of the resulting bio-oil condensate, but requires active, selective and [...] Read more.

Pyrolysis bio-oils contain significant amounts of carboxylic acids which limit their utility as biofuels. Ketonisation of carboxylic acids within biomass pyrolysis vapours is a potential route to upgrade the energy content and stability of the resulting bio-oil condensate, but requires active, selective and coke-resistant solid acid catalysts. Here we explore the vapour phase ketonisation of acetic acid over Ga-doped HZSM-5. Weak Lewis acid sites were identified as the active species responsible for acetic acid ketonisation to acetone at 350 °C and 400 °C. Turnover frequencies were proportional to Ga loading, reaching ~6 min⁻¹ at 400 °C for 10Ga/HZSM-5. Selectivity to the desired acetone product correlated with the weak:strong acid site ratio, being favoured over weak Lewis acid sites and reaching 30% for 10Ga/HZSM-5. Strong Brønsted acidity promoted competing unselective reactions and carbon laydown. 10Ga/HZSM-5 exhibited good stability for over 5 h on-stream acetic acid ketonisation. Full article

(This article belongs to the Special Issue Sustainable Catalytic Conversion of Biomass for the Production of Biofuels and Bioproducts)

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12 pages, 2120 KiB

Open AccessArticle

Ru-Catalyzed Oxidative Cleavage of Guaiacyl Glycerol-β-Guaiacyl Ether-a Representative β-O-4 Lignin Model Compound

by Mayra Melián-Rodríguez, Shunmugavel Saravanamurugan, Sebastian Meier, Søren Kegnæs and Anders Riisager

Catalysts 2019, 9(10), 832; https://doi.org/10.3390/catal9100832 - 03 Oct 2019

Cited by 7 | Viewed by 2858

Abstract

The introduction of efficient and selective catalytic methods for aerobic oxidation of lignin and lignin model compounds to aromatics can extend the role of lignin applications in biorefineries. The current study focussed on the catalytic oxidative transformation of guaiacyl glycerol-β-guaiacyl ether (GGGE)–a β-O-4 [...] Read more.

The introduction of efficient and selective catalytic methods for aerobic oxidation of lignin and lignin model compounds to aromatics can extend the role of lignin applications in biorefineries. The current study focussed on the catalytic oxidative transformation of guaiacyl glycerol-β-guaiacyl ether (GGGE)–a β-O-4 lignin model compound to produce basic aromatic compounds (guaiacol, vanillin and vanillic acid) using metal-supported catalysts. Ru/Al₂O₃, prepared with ruthenium(IV) oxide hydrate, showed the highest yields of the desired products (~60%) in acetonitrile in a batch reactor at 160 °C and 5-bar of 20% oxygen in argon. Alternative catalysts containing other transition metals (Ag, Fe, Mn, Co and Cu) supported on alumina, and ruthenium catalysts based on alternative supports (silica, spinel, HY zeolite and zirconia) gave significantly lower activities compared to Ru/Al₂O₃ at identical reaction conditions. Moreover, the Ru/Al₂O₃ catalyst was successfully reused in five consecutive reaction runs with only a minor decrease in catalytic performance. Full article

(This article belongs to the Special Issue Sustainable Catalytic Conversion of Biomass for the Production of Biofuels and Bioproducts)

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19 pages, 3813 KiB

Open AccessFeature PaperArticle

Sulfonated Hydrothermal Carbons from Cellulose and Glucose as Catalysts for Glycerol Ketalization

by Pablo Fernández, José M. Fraile, Enrique García-Bordejé and Elísabet Pires

Catalysts 2019, 9(10), 804; https://doi.org/10.3390/catal9100804 - 25 Sep 2019

Cited by 15 | Viewed by 3051

Abstract

Solketal is one of the most used glycerol-derived solvents. Its production via heterogeneous catalysis is crucial for avoiding important product losses typically found in the aqueous work-up in homogeneous catalysis. In this work, we present a study of the catalytic synthesis of solketal [...] Read more.

Solketal is one of the most used glycerol-derived solvents. Its production via heterogeneous catalysis is crucial for avoiding important product losses typically found in the aqueous work-up in homogeneous catalysis. In this work, we present a study of the catalytic synthesis of solketal using sulfonated hydrothermal carbons (SHTC). They were prepared from glucose and cellulose resulting in different textural properties depending on the hydrothermal treatment conditions. The sulfonated hydrothermal carbons were also coated on a graphite microfiber felt (SHTC@GF). Thus, up to nine different solids were tested, and their activity was compared with commercial acidic resins. The solids presented very different catalytic activity, which did not correlate with their physical-chemical properties indicating that other aspects likely influence the transport of reactants and products to the catalytic surface. Additionally, the SHTC prepared from cellulose showed better reusability in batch reaction tests. This work also presents the first results for the production of solketal in a flow reactor, which opens the way to the use of SHTC@GF for this kind of reactions. Full article

(This article belongs to the Special Issue Sustainable Catalytic Conversion of Biomass for the Production of Biofuels and Bioproducts)

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22 pages, 5306 KiB

Open AccessFeature PaperArticle

C-O Bond Hydrogenolysis of Aqueous Mixtures of Sugar Polyols and Sugars over ReO_x-Rh/ZrO₂ Catalyst: Application to an Hemicelluloses Extracted Liquor

by Modibo Mounguengui-Diallo, Achraf Sadier, Eddi Noly, Denilson Da Silva Perez, Catherine Pinel, Noémie Perret and Michèle Besson

Catalysts 2019, 9(9), 740; https://doi.org/10.3390/catal9090740 - 31 Aug 2019

Cited by 7 | Viewed by 4245

Abstract

The recovery and upgrade of hemicelluloses, a family of heteropolysaccharides in wood, is a key step to making lignocellulosic biomass conversion a cost-effective sustainable process in biorefinery. The comparative selective catalytic C-O bond hydrogenolysis of C5-C6 polyols, sugars, and their mixtures for the [...] Read more.

The recovery and upgrade of hemicelluloses, a family of heteropolysaccharides in wood, is a key step to making lignocellulosic biomass conversion a cost-effective sustainable process in biorefinery. The comparative selective catalytic C-O bond hydrogenolysis of C5-C6 polyols, sugars, and their mixtures for the production of valuable C6 and C5 deoxygenated products was studied at 200 °C under 80 bar H₂ over ReO_x-Rh/ZrO₂ catalysts. The sugars were rapidly converted to the polyols or converted into their hydrogenolysis products. Regardless of the reactants, C-O bond cleavage occurred significantly via multiple consecutive deoxygenation steps and led to the formation of linear deoxygenated C6 or C5 polyols. The distribution of products depended on the nature of the substrate and C-C bond scission was more important from monosaccharides. In addition, we demonstrated effective hydrogenolysis of a hemicellulose-extracted liquor from delignified maritime pine containing monosaccharides and low MW oligomers. Compared with the sugar-derived polyols, the mono- and oligosaccharides in the liquor were more rapidly converted to hexanediols or pentanediols. C-O bond scission was significant, giving a yield of desired deoxygenated products as high as 65%, higher than in the reaction of the synthetic mixture of glucose/xylose of the same C6/C5 sugar ratio (yield of 30%). Full article

(This article belongs to the Special Issue Sustainable Catalytic Conversion of Biomass for the Production of Biofuels and Bioproducts)

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9 pages, 2735 KiB

Open AccessArticle

Waste Seashells as a Highly Active Catalyst for Cyclopentanone Self-Aldol Condensation

by Xueru Sheng, Qianqian Xu, Xing Wang, Na Li, Haiyuan Jia, Haiqiang Shi, Meihong Niu, Jian Zhang and Qingwei Ping

Catalysts 2019, 9(8), 661; https://doi.org/10.3390/catal9080661 - 01 Aug 2019

Cited by 14 | Viewed by 3673

Abstract

For the first time, waste-seashell-derived CaO catalysts were used as high-performance solid base catalysts for cyclopentanone self-condensation, which is an important reaction in bio-jet fuel or perfume precursor synthesis. Among the investigated seashell-derived catalysts, Scapharca Broughtonii-derived CaO catalyst (S-shell-750) exhibited the highest [...] Read more.

For the first time, waste-seashell-derived CaO catalysts were used as high-performance solid base catalysts for cyclopentanone self-condensation, which is an important reaction in bio-jet fuel or perfume precursor synthesis. Among the investigated seashell-derived catalysts, Scapharca Broughtonii-derived CaO catalyst (S-shell-750) exhibited the highest dimer yield (92.1%), which was comparable with commercial CaO (88.2%). The activity sequence of different catalysts was consistent with the CaO purity sequence and contact angle sequence. X-ray diffraction (XRD) results showed that CaCO₃ in waste shell were completely converted to CaO after calcination at 750 °C or above for 4 h. CO₂ temperature-programmed desorption (CO₂-TPD) results indicate that both the amount and strength of base sites increase significantly when the calcination temperature climbs to 750 °C. Therefore, we can attribute the excellent performance of S-shell-750/850/950 catalysts to the higher CaO content, relatively low hydrophilicity, and stronger acidity and basicity of this catalyst. This study developed a new route for waste shell utilization in bio-derived ketone aldol condensation. Full article

(This article belongs to the Special Issue Sustainable Catalytic Conversion of Biomass for the Production of Biofuels and Bioproducts)

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12 pages, 3154 KiB

Open AccessArticle

Evaluation on the Methane Production Potential of Wood Waste Pretreated with NaOH and Co-Digested with Pig Manure

by Renfei Li, Wenbing Tan, Xinyu Zhao, Qiuling Dang, Qidao Song, Beidou Xi and Xiaohui Zhang

Catalysts 2019, 9(6), 539; https://doi.org/10.3390/catal9060539 - 17 Jun 2019

Cited by 21 | Viewed by 4870

Abstract

Wood waste generated during the tree felling and processing is a rich, green, and renewable lignocellulosic biomass. However, an effective method to apply wood waste in anaerobic digestion is lacking. The high carbon to nitrogen (C/N) ratio and rich lignin content of wood [...] Read more.

Wood waste generated during the tree felling and processing is a rich, green, and renewable lignocellulosic biomass. However, an effective method to apply wood waste in anaerobic digestion is lacking. The high carbon to nitrogen (C/N) ratio and rich lignin content of wood waste are the major limiting factors for high biogas production. NaOH pre-treatment for lignocellulosic biomass is a promising approach to weaken the adverse effect of complex crystalline cellulosic structure on biogas production in anaerobic digestion, and the synergistic integration of lignocellulosic biomass with low C/N ratio biomass in anaerobic digestion is a logical option to balance the excessive C/N ratio. Here, we assessed the improvement of methane production of wood waste in anaerobic digestion by NaOH pretreatment, co-digestion technique, and their combination. The results showed that the methane yield of the single digestion of wood waste was increased by 38.5% after NaOH pretreatment compared with the untreated wood waste. The methane production of the co-digestion of wood waste and pig manure was higher than that of the single digestion of wood waste and had nonsignificant difference with the single-digestion of pig manure. The methane yield of the co-digestion of wood waste pretreated with NaOH and pig manure was increased by 75.8% than that of the untreated wood waste. The findings indicated that wood waste as a sustainable biomass source has considerable potential to achieve high biogas production in anaerobic digestion. Full article

(This article belongs to the Special Issue Sustainable Catalytic Conversion of Biomass for the Production of Biofuels and Bioproducts)

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13 pages, 1613 KiB

Open AccessArticle

Effect of Dilute Acid and Alkali Pretreatments on the Catalytic Performance of Bamboo-Derived Carbonaceous Magnetic Solid Acid

by Yikui Zhu, Jiawei Huang, Shaolong Sun, Aimin Wu and Huiling Li

Catalysts 2019, 9(3), 245; https://doi.org/10.3390/catal9030245 - 07 Mar 2019

Cited by 15 | Viewed by 3230

Abstract

Lignocellulose is a widely used renewable energy source on the Earth that is rich in carbon skeletons. The catalytic hydrolysis of lignocellulose over magnetic solid acid is an efficient pathway for the conversion of biomass into fuels and chemicals. In this study, a [...] Read more.

Lignocellulose is a widely used renewable energy source on the Earth that is rich in carbon skeletons. The catalytic hydrolysis of lignocellulose over magnetic solid acid is an efficient pathway for the conversion of biomass into fuels and chemicals. In this study, a bamboo-derived carbonaceous magnetic solid acid catalyst was synthesized by FeCl₃ impregnation, followed by carbonization and –SO₃H group functionalization. The prepared catalyst was further subjected as the solid acid catalyst for the catalytic conversion of corncob polysaccharides into reducing sugars. The results showed that the as-prepared magnetic solid acid contained –SO₃H, –COOH, and polycyclic aromatic, and presented good catalytic performance for the hydrolysis of corncob in the aqueous phase. The concentration of H⁺ was in the range of 0.6487 to 2.3204 mmol/g. Dilute acid and alkali pretreatments of raw material can greatly improve the catalytic activity of bamboo-derived carbonaceous magnetic solid acid. Using the catalyst prepared by 0.25% H₂SO₄-pretreated bamboo, 6417.5 mg/L of reducing sugars corresponding to 37.17% carbohydrates conversion could be obtained under the reaction conditions of 120 °C for 30 min. Full article

(This article belongs to the Special Issue Sustainable Catalytic Conversion of Biomass for the Production of Biofuels and Bioproducts)

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Review

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24 pages, 772 KiB

Open AccessReview

Catalytic Thermochemical Conversion of Algae and Upgrading of Algal Oil for the Production of High-Grade Liquid Fuel: A Review

by Yingdong Zhou and Changwei Hu

Catalysts 2020, 10(2), 145; https://doi.org/10.3390/catal10020145 - 21 Jan 2020

Cited by 32 | Viewed by 6694

Abstract

The depletion of fossil fuel has drawn growing attention towards the utilization of renewable biomass for sustainable energy production. Technologies for the production of algae derived biofuel has attracted wide attention in recent years. Direct thermochemical conversion of algae obtained biocrude oil with [...] Read more.

The depletion of fossil fuel has drawn growing attention towards the utilization of renewable biomass for sustainable energy production. Technologies for the production of algae derived biofuel has attracted wide attention in recent years. Direct thermochemical conversion of algae obtained biocrude oil with poor fuel quality due to the complex composition of algae. Thus, catalysts are required in such process to remove the heteroatoms such as oxygen, nitrogen, and sulfur. This article reviews the recent advances in catalytic systems for the direct catalytic conversion of algae, as well as catalytic upgrading of algae-derived oil or biocrude into liquid fuels with high quality. Heterogeneous catalysts with high activity in deoxygenation and denitrogenation are preferable for the conversion of algae oil to high-grade liquid fuel. The paper summarized the influence of reaction parameters and reaction routes for the catalytic conversion process of algae from critical literature. The development of new catalysts, conversion conditions, and efficiency indicators (yields and selectivity) from different literature are presented and compared. The future prospect and challenges in general utilization of algae are also proposed. Full article

(This article belongs to the Special Issue Sustainable Catalytic Conversion of Biomass for the Production of Biofuels and Bioproducts)

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