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Biomass Derived Heterogeneous and Homogeneous Catalysts

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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 (30 June 2020) | Viewed by 46068

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Prof. Dr. José María Encinar Martín

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Department of Chemical Engineering and Physical Chemistry, University of Extremadura, Avda. De Elvas s/n, 06006 Badajoz, Spain
Interests: biomass; biodiesel; biolubricants; oxidative stability; fatty acid methyl esters; catalyst; pyrolysis; gasification
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Dr. Sergio Nogales Delgado

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Dear Colleagues,

Renewable energy sources will play a decisive role in the future development of mankind. The increase in energy demand and the need of replacing fossil fuels make the development of new renewable raw materials mandatory, in order to generate sustainable fuels and chemical products.

For this reason, the production of biodiesel, bioethanol, biolubricants and the development of biorefineries are promising research fields, among other alternatives. Some of these products are currently a reality, but the large-scale economic development is still uncertain due to the competition with fossil fuels. A significant and essential issue to overcome that challenge is the research and use of new catalysts to carry out the synthesis processes of bioproducts more efficiently.

For this Special Issue, we invite papers dealing with the use of homogeneous and heterogeneous catalysts for the development of processes such as biodiesel, biolubricant or biofuel production.

More specifically, topics of interest for the Special Issue include (but are not limited to):

Biomass
Biofuels
Biorefinery
Bioproducts
Biochemicals
Biorenewables
Bioenergy–Biofuels by-products
Biodiesel
Biolubricants
Bioethanol
Biomethane

Dr. José María Encinar Martín
Dr. Sergio Nogales Delgado
Guest Editors

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Keywords

Bioproducts
Biodiesel
Bioethanol
Bioenergy
Biolubricants
Homogeneous and Heterogeneous Catalysts

Published Papers (12 papers)

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Editorial

Jump to: Research, Review

3 pages, 457 KiB

Open AccessEditorial

Editorial Catalysts: Special Issue on “Biomass Derived Heterogeneous and Homogeneous Catalysts”

by José María Encinar and Sergio Nogales-Delgado

Catalysts 2020, 10(12), 1433; https://doi.org/10.3390/catal10121433 - 8 Dec 2020

Viewed by 1144

Abstract

The replacement of petrol products for environmentally-friendly ones is a reality today, as many governments and international organizations are promoting the implementation of renewable energy sources and natural feedstocks in industrial activity [...] Full article

(This article belongs to the Special Issue Biomass Derived Heterogeneous and Homogeneous Catalysts)

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Research

Jump to: Editorial, Review

18 pages, 2166 KiB

Open AccessArticle

Response Surface Methodology for the Optimization of Keratinase Production in Culture Medium Containing Feathers by Bacillus sp. UPM-AAG1

by Aa’ishah Abdul Gafar, Mohd Ezuan Khayat, Siti Aqlima Ahmad, Nur Adeela Yasid and Mohd Yunus Shukor

Catalysts 2020, 10(8), 848; https://doi.org/10.3390/catal10080848 - 29 Jul 2020

Cited by 26 | Viewed by 3895

Abstract

Keratinase is a type of proteolytic enzyme with broad application in industry. The main objective of this work is the optimization of keratinase production from Bacillus sp. strain UPM-AAG1 using Plackett-Burman (PB) and central composite design (CCD) for parameters, such as pH, temperature, feather concentration, and inoculum size. The optimum points for temperature, pH, and inoculum and feather concentrations were 31.66 °C, 6.87, 5.01 (w/v), and 4.53 (w/v), respectively, with an optimum keratinase activity of 60.55 U/mL. The keratinase activity was further numerically optimized for commercial application. The best numerical solution recommended a pH of 5.84, temperature of 25 °C, inoculums’ size of 5.0 (v/v), feather concentration of 4.97 (w/v). Optimization resulted an activity of 56.218 U/mL with the desirability value of 0.968. Amino acid analysis profile revealed the presence of essential and non-essential amino acids. These properties make Bacillus sp. UPM-AAG1 a potential bacterium to be used locally for the production of keratinase from feather waste. Full article

(This article belongs to the Special Issue Biomass Derived Heterogeneous and Homogeneous Catalysts)

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14 pages, 3839 KiB

Open AccessArticle

Study of Curing Characteristics of Cellulose Nanofiber-Filled Epoxy Nanocomposites

by Mohan Turup Pandurangan and Krishnan Kanny

Catalysts 2020, 10(8), 831; https://doi.org/10.3390/catal10080831 - 24 Jul 2020

Cited by 23 | Viewed by 3033

Abstract

In recent years, much attention was focused on developing green materials and fillers for polymer composites. This work is about the development of such green nanofiller for reinforcement in epoxy polymer matrix. A cellulose nanofiber (CNF)-filled epoxy polymer nanocomposites was prepared in this work. The effect of CNF on curing, thermal, mechanical, and barrier properties of epoxy polymer is evaluated in this study. CNF were extracted from banana fiber using acid hydrolysis method and then filled in epoxy polymer at various concentration (0–5 wt.%) to form CNF-filled epoxy nanocomposites. The structure and morphology of the CNF-filled epoxy nanocomposites were examined by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analysis. Curing studies shows CNF particles acts as a catalytic curing agent with increased cross-link density. This catalytic effect of CNF particles has positively affected tensile, thermal (thermogravimetry analysis and dynamic mechanical analysis) and water barrier properties. Water uptake test of nanocomposites was studied to understand the barrier properties. Overall result also shows that the CNF can be a potential green nanofiller for thermoset epoxy polymer with promising applications ahead. Full article

(This article belongs to the Special Issue Biomass Derived Heterogeneous and Homogeneous Catalysts)

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20 pages, 3591 KiB

Open AccessArticle

Conversion of Xylose to Furfural over Lignin-Based Activated Carbon-Supported Iron Catalysts

by Annu Rusanen, Riikka Kupila, Katja Lappalainen, Johanna Kärkkäinen, Tao Hu and Ulla Lassi

Catalysts 2020, 10(8), 821; https://doi.org/10.3390/catal10080821 - 22 Jul 2020

Cited by 16 | Viewed by 4683

Abstract

In this study, conversion of xylose to furfural was studied using lignin-based activated carbon-supported iron catalysts. First, three activated carbon supports were prepared from hydrolysis lignin with different activation methods. The supports were modified with different metal precursors and metal concentrations into five iron catalysts. The prepared catalysts were studied in furfural production from xylose using different reaction temperatures and times. The best results were achieved with a 4 wt% iron-containing catalyst, 5Fe-ACs, which produced a 57% furfural yield, 92% xylose conversion and 65% reaction selectivity at 170 °C in 3 h. The amount of Fe in 5Fe-ACs was only 3.6 µmol and using this amount of homogeneous FeCl₃ as a catalyst, reduced the furfural yield, xylose conversion and selectivity. Good catalytic activity of 5Fe-ACs could be associated with iron oxide and hydroxyl groups on the catalyst surface. Based on the recycling experiments, the prepared catalyst needs some improvements to increase its stability but it is a feasible alternative to homogeneous FeCl₃. Full article

(This article belongs to the Special Issue Biomass Derived Heterogeneous and Homogeneous Catalysts)

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17 pages, 3126 KiB

Open AccessArticle

Enzymatic Hydrolysis of Softwood Derived Paper Sludge by an In Vitro Recombinant Cellulase Cocktail for the Production of Fermentable Sugars

by Samkelo Malgas, Shaunita H. Rose, Willem H. van Zyl and Brett I. Pletschke

Catalysts 2020, 10(7), 775; https://doi.org/10.3390/catal10070775 - 11 Jul 2020

Cited by 7 | Viewed by 2390

Abstract

Paper sludge is an attractive biomass feedstock for bioconversion to ethanol due to its low cost and the lack of pretreatment required for its bioprocessing. This study assessed the use of a recombinant cellulase cocktail (mono-components: S. cerevisiae-derived PcBGL1B (BGL), TeCel7A (CBHI), ClCel6A (CBHII) and TrCel5A (EGII) mono-component cellulase enzymes) for the efficient saccharification of softwood-derived paper sludge to produce fermentable sugars. The paper sludge mainly contained 74.3% moisture and 89.7% (per dry mass (DM)) glucan with a crystallinity index of 91.5%. The optimal protein ratio for paper sludge hydrolysis was observed at 9.4: 30.2: 30.2: 30.2% for BGL: CBHI: CBHII: EGII. At a protein loading of 7.5 mg/g DW paper sludge, the yield from hydrolysis was approximately 80%, based on glucan, with scanning electron microscopy micrographs indicating a significant alteration in the microfibril size (length reduced from ≥ 2 mm to 93 µm) of the paper sludge. The paper sludge hydrolysis potential of the Opt CelMix (formulated cellulase cocktail) was similar to the commercial Cellic CTec2^® and Celluclast^® 1.5 L cellulase preparations and better than Viscozyme^® L. Low enzyme loadings (15 mg/g paper sludge) of the Opt CelMix and solid loadings ranging between 1 to 10% (w/v) rendered over 80% glucan conversion. The high glucose yields attained on the paper sludge by the low enzyme loading of the Opt CelMix demonstrated the value of enzyme cocktail optimisation on specific substrates for efficient cellulose conversion to fermentable sugars. Full article

(This article belongs to the Special Issue Biomass Derived Heterogeneous and Homogeneous Catalysts)

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12 pages, 2558 KiB

Open AccessEditor’s ChoiceArticle

Biolubricants from Rapeseed and Castor Oil Transesterification by Using Titanium Isopropoxide as a Catalyst: Production and Characterization

by José María Encinar, Sergio Nogales-Delgado, Nuria Sánchez and Juan Félix González

Catalysts 2020, 10(4), 366; https://doi.org/10.3390/catal10040366 - 29 Mar 2020

Cited by 48 | Viewed by 4923

Abstract

The transesterification of rapeseed and castor oil methyl esters with different alcohols (2-ethyl-1-hexanol, 1-heptanol and 4-methyl-2-pentanol) and titanium isopropoxide as a catalyst, to produce biolubricants, was carried out. Parameters such as temperature, alcohol/methyl ester molar ratio, and catalyst concentration were studied to optimize the process. The reaction evolution was monitored with the decrease in FAME concentration by gas chromatography. In general, the reaction was almost complete in two hours, obtaining over 93% conversions. All the variables studied influenced on the reaction yields. Once the optimum conditions for the maximum conversion and minimum costs were selected, a characterization of the biolubricants obtained, along with the study of the influence of the kind of alcohol used, was carried out. The biolubricants had some properties that were better than mineral lubricants (flash points between 222 and 271 °C), needing the use of additives when they do not comply with the standards (low viscosity for rapeseed biolubricant, for instance). There was a clear influence of fatty acids of raw materials (oleic and ricinoleic acids as majority fatty acids in rapeseed and castor oil, respectively) and the structure of the alcohol used on the final features of the biolubricants. Full article

(This article belongs to the Special Issue Biomass Derived Heterogeneous and Homogeneous Catalysts)

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14 pages, 2374 KiB

Open AccessArticle

Catalytic Performance of Bulk and Al₂O₃-Supported Molybdenum Oxide for the Production of Biodiesel from Oil with High Free Fatty Acids Content

by Alberto Navajas, Inés Reyero, Elena Jiménez-Barrera, Francisca Romero-Sarria, Jordi Llorca and Luis M. Gandía

Catalysts 2020, 10(2), 158; https://doi.org/10.3390/catal10020158 - 1 Feb 2020

Cited by 18 | Viewed by 2939

Abstract

Non-edible vegetable oils are characterized by high contents of free fatty acids (FFAs) that prevent from using the conventional basic catalysts for the production of biodiesel. In this work, solid acid catalysts are used for the simultaneous esterification and transesterification with methanol of the FFAs and triglycerides contained in sunflower oil acidified with oleic acid. Molybdenum oxide (MoO₃), which has been seldom considered as a catalyst for the production of biodiesel, was used in bulk and alumina-supported forms. Results showed that bulk MoO₃ is very active for both transesterification and esterification reactions, but it suffered from severe molybdenum leaching in the reaction medium. When supported on Al₂O₃, the MoO₃ performance improved in terms of active phase utilization and stability though molybdenum leaching remained significant. The improvement of catalytic performance was ascribed to the establishment of MoO₃-Al₂O₃ interactions that favored the anchorage of molybdenum to the support and the formation of new strong acidic centers, although this effect was offset by a decrease of specific surface area. It is concluded that the development of stable catalysts based on MoO₃ offers an attractive route for the valorization of oils with high FFAs content. Full article

(This article belongs to the Special Issue Biomass Derived Heterogeneous and Homogeneous Catalysts)

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17 pages, 6098 KiB

Open AccessArticle

Performance of a Ni-Cu-Co/Al₂O₃ Catalyst on in-situ Hydrodeoxygenation of Bio-derived Phenol

by Huiyuan Xue, Jingjing Xu, Xingxing Gong and Rongrong Hu

Catalysts 2019, 9(11), 952; https://doi.org/10.3390/catal9110952 - 14 Nov 2019

Cited by 10 | Viewed by 3357

Abstract

The in-situ hydrodeoxygenation of bio-derived phenol is an attractive routine for upgrading bio-oils. Herein, an active trimetallic Ni-Cu-Co/Al₂O₃ catalyst was prepared and applied in the in-situ hydrodeoxygenation of bio-derived phenol. Comparison with the monometallic Ni/Al₂O₃ catalyst and the bimetallic Ni-Co/Al₂O₃ and Ni-Cu/Al₂O₃ catalysts, the Ni-Cu-Co/Al₂O₃ catalyst exhibited the highest catalytic activity because of the formation of Ni-Cu-Co alloy on the catalyst characterized by using X-ray powder diffraction (XRD), temperature programmed reduction (TPR), N₂ physisorption, scanning electron microscope (SEM), and transmission electron microscope (TEM). The phenol conversion of 100% and the cyclohexane yield of 98.3% could be achieved in the in-situ hydrodeoxygenation of phenol at 240 °C and 4 MPa N₂ for 6 h. The synergistic effects of Ni with Cu and Co of the trimetallic Ni-Cu-Co/Al₂O₃ catalyst played a significant role in the in-situ hydrodeoxygenation process of phenol, which not only had a positive effect on the production of hydrogen but also owned an excellent hydrogenolysis activity to accelerate the conversion of cyclohexanol to cyclohexane. Furthermore, the catalyst also exhibited excellent recyclability and good potential for the upgrading of bio-oils. Full article

(This article belongs to the Special Issue Biomass Derived Heterogeneous and Homogeneous Catalysts)

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16 pages, 3685 KiB

Open AccessArticle

Irrigation Combined with Aeration Promoted Soil Respiration through Increasing Soil Microbes, Enzymes, and Crop Growth in Tomato Fields

by Hui Chen, Zihui Shang, Huanjie Cai and Yan Zhu

Catalysts 2019, 9(11), 945; https://doi.org/10.3390/catal9110945 - 11 Nov 2019

Cited by 17 | Viewed by 2543

Abstract

Soil respiration (Rs) is one of the major components controlling the carbon budget of terrestrial ecosystems. Aerated irrigation has been proven to increase Rs compared with the control, but the mechanisms of CO₂ release remain poorly understood. The objective of this study was (1) to test the effects of irrigation, aeration, and their interaction on Rs, soil physical and biotic properties (soil water-filled pore space, temperature, bacteria, fungi, actinomycetes, microbial biomass carbon, cellulose activity, dehydrogenase activity, root morphology, and dry biomass of tomato), and (2) to assess how soil physical and biotic variables control Rs. Therefore, three irrigation levels were included (60%, 80%, and 100% of full irrigation). Each irrigation level contained aeration and control. A total of six treatments were included. The results showed that aeration significantly increased total root length, dry biomass of leaf, stem, and fruit compared with the control (p < 0.05). The positive effect of irrigation on dry biomass of leaf, fruit, and root was significant (p < 0.05). With respect to the control, greater Rs under aeration (averaging 6.2% increase) was mainly driven by soil water-filled pore space, soil bacteria, and soil fungi. The results of this study are helpful for understanding the mechanisms of soil CO₂ release under aerated subsurface drip irrigation. Full article

(This article belongs to the Special Issue Biomass Derived Heterogeneous and Homogeneous Catalysts)

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16 pages, 1566 KiB

Open AccessFeature PaperArticle

Biodiesel Production from Castor oil by Two-Step Catalytic Transesterification: Optimization of the Process and Economic Assessment

by Nuria Sánchez, José María Encinar, Sergio Nogales and Juan Félix González

Catalysts 2019, 9(10), 864; https://doi.org/10.3390/catal9100864 - 17 Oct 2019

Cited by 25 | Viewed by 4166

Abstract

The use of biodiesel and the requirement of improving its production in a more efficient and sustainable way are becoming more and more important. In this research work, castor oil was demonstrated to be an alternative feedstock for obtaining biodiesel. The production of biodiesel was optimized by the use of a two-step process. In this process, methanol and KOH (as a catalyst) were added in each step, and the glycerol produced during the first stage was removed before the second reaction. The reaction conditions were optimized, considering catalyst concentration and methanol/oil molar ratio for both steps. A mathematical model was obtained to predict the final ester content of the biodiesel. Optimal conditions (0.08 mol·L⁻¹ and 0.01 mol·L⁻¹ as catalyst concentration, 5.25:1 and 3:1 as methanol/oil molar ratio for first and second step, respectively) were established, taking into account the biodiesel quality and an economic analysis. This type of process allowed cost saving, since the amounts of methanol and catalyst were significantly reduced. An estimation of the final manufacturing cost of biodiesel production was carried out. Full article

(This article belongs to the Special Issue Biomass Derived Heterogeneous and Homogeneous Catalysts)

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14 pages, 2706 KiB

Open AccessCommunication

One-Pot Solvent-Free Synthesis of N,N-Bis(2-Hydroxyethyl) Alkylamide from Triglycerides Using Zinc-Doped Calcium Oxide Nanospheroids as a Heterogeneous Catalyst

by Dinesh Kumar, Chan Hee Park and Cheol Sang Kim

Catalysts 2019, 9(9), 774; https://doi.org/10.3390/catal9090774 - 14 Sep 2019

Cited by 5 | Viewed by 4099

Abstract

N,N-Bis(2-hydroxyethyl) alkylamide or fatty acid diethanolamides (FADs) were prepared from a variety of triglycerides using diethanolamine in the presence of different transition metal-doped CaO nanocrystalline heterogeneous catalysts. The Zn-doped Cao nanospheroids were found to be the most efficient heterogeneous catalyst, with complete conversion of natural triglycerides to fatty acid diethanolamide in 30 min at 90 °C. The Zn/CaO nanoparticles were recyclable for up to six reaction cycles and showed complete conversion even at room temperature. The amidation reaction of natural triglycerides was found to follow the pseudo-first-order kinetic model, and the first-order rate constant was calculated as 0.171 min⁻¹ for jatropha oil aminolysis. The activation energy (Ea) and pre-exponential factor (A) for the same reaction were found to be 47.8 kJ mol⁻¹ and 4.75 × 10⁸ min⁻¹, respectively. Full article

(This article belongs to the Special Issue Biomass Derived Heterogeneous and Homogeneous Catalysts)

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Review

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26 pages, 4636 KiB

Open AccessReview

Recent Developments in Metal-Based Catalysts for the Catalytic Aerobic Oxidation of 5-Hydroxymethyl-Furfural to 2,5-Furandicarboxylic Acid

by Sohaib Hameed, Lu Lin, Aiqin Wang and Wenhao Luo

Catalysts 2020, 10(1), 120; https://doi.org/10.3390/catal10010120 - 15 Jan 2020

Cited by 46 | Viewed by 8090

Abstract

Biomass can be used as an alternative feedstock for the production of fuels and valuable chemicals, which can alleviate the current global dependence on fossil resources. One of the biomass-derived molecules, 2,5-furandicarboxylic acid (FDCA), has attracted great interest due to its broad applications in various fields. In particular, it is considered a potential substitute of petrochemical-derived terephthalic acid (PTA), and can be used for the preparation of valuable bio-based polyesters such as polyethylene furanoate (PEF). Therefore, significant attempts have been made for efficient production of FDCA and the catalytic chemical approach for FDCA production, typically from a biomass-derived platform molecule, 5-hydroxymethylfurfural (HMF), over metal catalysts is the focus of great research attention. In this review, we provide a systematic critical overview of recent progress in the use of different metal-based catalysts for the catalytic aerobic oxidation of HMF to FDCA. Catalytic performance and reaction mechanisms are described and discussed to understand the details of this reaction. Special emphasis is also placed on the base-free system, which is a more green process considering the environmental aspect. Finally, conclusions are given and perspectives related to further development of the catalysts are also provided, for the potential production of FDCA on a large scale in an economical and environmentally friendly manner. Full article

(This article belongs to the Special Issue Biomass Derived Heterogeneous and Homogeneous Catalysts)

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