Special Issue "Catalytic Conversion of Biomass-Derived Molecules to Chemicals and Fuels"

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

Deadline for manuscript submissions: closed (31 December 2018).

Special Issue Editors

Guest Editor
Prof. Dr. Mark Crocker Website E-Mail
Center for Applied Energy Research, University of Kentucky, Lexington, KY 40506-0055, USA
Phone: 18592570295
Interests: biomass conversion; environmental catalysis; CO2 utilization using microalgae
Guest Editor
Prof. Dr. Adam F. Lee Website E-Mail
School of Science, RMIT University, Melbourne VIC 3001, Australia
Phone: +61 3 9925 2623
Interests: surface science; heterogeneous catalysis; green chemistry; synchrotron radiation; porous solids; nanoparticles; alloys; selective oxidation; biofuels
Guest Editor
Prof. Dr. Karen Wilson Website E-Mail
School of Science, RMIT University, Melbourne VIC 3001, Australia
Interests: heterogeneous catalysis, green chemistry; surface chemistry; heterogeneous catalysts for biorefining; nano-porous hierarchical catalysts; solid acids and bases; hydrophobic catalytic materials
Guest Editor
Prof. Dr. Conrad Zhang Website E-Mail
Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China

Special Issue Information

Dear Colleagues,

Climate change and energy and materials security represent global challenges facing humanity, arising from past reliance on fossil fuel resources. Overcoming such challenges necessitates the identification and new technologies to utilize sustainable, low carbon alternatives, notably biomass and associated bioenergy. To be truly sustainable, biomass feedstocks must derive from sources which do not compete with agricultural land use for food production, or compromise the environment via, e.g., deforestation. Potential feedstocks include cellulosic or oil based materials derived from plant or aquatic sources (algae), with the so-called ‘biorefinery concept’ offering the co-production of fuels, chemicals and energy to maximise biomass valorisation, analogous to current petroleum refineries which deliver high volume/low value (fuels and commodity chemicals) and low volume/high value (fine/speciality chemicals) products. Catalysis is a key enabling technology to exploit biomass conversion to desirable chemical and fuels, however the inherent high functionality of biomass derived molecules, and conditions under which catalysts are required to operate, present a barrier to the development of commercial processes.

This Special Issue will feature contributions from an associated symposium on “Catalytic conversion of biomass derived molecules to chemicals and fuels” held under the Division of Catalysis Science and Technology at the 255th ACS National Meeting in New Orleans but is also open to general contributions from the catalysis community. Articles will particularly emphasise the transformation of non-lignin biomass derivatives, and encompass: (i) synthesis and characterization of new metal oxides, carbides, or phosphides based catalysts; (ii) experimental measurements and kinetic modelling of reaction rates/activities/selectivities; (iii) fundamental investigation of active sites, their stability and tenability; (iv) reactions catalyzed by bifunctional and cooperative catalysts; and (v) the impact of solvents and co-reactants on reaction rate and mechanism.

Prof. Dr. Mark Crocker
Prof. Dr. Adam F. Lee
Prof. Dr. Karen Wilson
Prof. Dr. Conrad Zhang
Guest Editors

Manuscript Submission Information

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Published Papers (10 papers)

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Research

Open AccessArticle
Continuous Catalytic Deoxygenation of Waste Free Fatty Acid-Based Feeds to Fuel-Like Hydrocarbons Over a Supported Ni-Cu Catalyst
Catalysts 2019, 9(2), 123; https://doi.org/10.3390/catal9020123 - 30 Jan 2019
Cited by 1
Abstract
While commercial hydrodeoxygenation (HDO) processes convert fats, oils, and grease (FOG) to fuel-like hydrocarbons, alternative processes based on decarboxylation/decarbonylation (deCOx) continue to attract interest. In this contribution, the activity of 20% Ni-5% Cu/Al2O3 in the deCOx of [...] Read more.
While commercial hydrodeoxygenation (HDO) processes convert fats, oils, and grease (FOG) to fuel-like hydrocarbons, alternative processes based on decarboxylation/decarbonylation (deCOx) continue to attract interest. In this contribution, the activity of 20% Ni-5% Cu/Al2O3 in the deCOx of waste free fatty acid (FFA)-based feeds—including brown grease (BG) and an FFA feed obtained by steam stripping a biodiesel feedstock—was investigated, along with the structure-activity relationships responsible for Ni promotion by Cu and the structural evolution of catalysts during use and regeneration. In eight-hour experiments, near quantitative conversion of the aforementioned feeds to diesel-like hydrocarbons was achieved. Moreover, yields of diesel-like hydrocarbons in excess of 80% were obtained at all reaction times during a BG upgrading experiment lasting 100 h, after which the catalyst was successfully regenerated in situ and found to display improved performance during a second 100 h cycle. Insights into this improved performance were obtained through characterization of the fresh and spent catalyst, which indicated that metal particle sintering, alloying of Ni with Cu, and particle enrichment with Cu occur during reaction and/or catalyst regeneration. Full article
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Open AccessArticle
ZnO/Ionic Liquid Catalyzed Biodiesel Production from Renewable and Waste Lipids as Feedstocks
Catalysts 2019, 9(1), 71; https://doi.org/10.3390/catal9010071 - 10 Jan 2019
Abstract
A new protocol for biodiesel production is proposed, based on a binary ZnO/TBAI (TBAI = tetrabutylammonium iodide) catalytic system. Zinc oxide acts as a heterogeneous, bifunctional Lewis acid/base catalyst, while TBAI plays the role of phase transfer agent. Being composed by the bulk [...] Read more.
A new protocol for biodiesel production is proposed, based on a binary ZnO/TBAI (TBAI = tetrabutylammonium iodide) catalytic system. Zinc oxide acts as a heterogeneous, bifunctional Lewis acid/base catalyst, while TBAI plays the role of phase transfer agent. Being composed by the bulk form powders, the whole catalyst system proved to be easy to use, without requiring nano-structuration or tedious and costly preparation or pre-activation procedures. In addition, due to the amphoteric properties of ZnO, the catalyst can simultaneously promote transesterification and esterification processes, thus becoming applicable to common vegetable oils (e.g., soybean, jatropha, linseed, etc.) and animal fats (lard and fish oil), but also to waste lipids such as cooking oils (WCOs), highly acidic lipids from oil industry processing, and lipid fractions of municipal sewage sludge. Reusability of the catalyst system together with kinetic (Ea) and thermodynamic parameters of activation (ΔG and ΔH) are also studied for transesterification reaction. Full article
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Open AccessArticle
Deoxygenation of Stearic Acid over Cobalt-Based NaX Zeolite Catalysts
Catalysts 2019, 9(1), 42; https://doi.org/10.3390/catal9010042 - 04 Jan 2019
Abstract
For the production of sustainable biofuels from lipid biomass it is essential to develop non-noble metal catalysts with high conversion and selectivity under inert gas atmospheres. Herein, we report a novel cobalt-based catalyst supported on zeolite NaX via ion-exchange synthesis. The resultant bifunctional [...] Read more.
For the production of sustainable biofuels from lipid biomass it is essential to develop non-noble metal catalysts with high conversion and selectivity under inert gas atmospheres. Herein, we report a novel cobalt-based catalyst supported on zeolite NaX via ion-exchange synthesis. The resultant bifunctional cobalt-based NaX zeolite catalyst displayed high conversion of stearic acid to liquid fuels. In addition, the effect of reaction temperature and catalyst loading was studied to evaluate the order of reaction and activation energy. Decarboxylation and decarbonylation were the dominant deoxygenation pathways. Stearic acid was successfully deoxygenated in N2 atmospheres using Co/NaX catalysts with a conversion as high as 83.7% and a yield to heptadecane up to ~28%. Furthermore, we demonstrate that higher reaction temperatures resulted in competing pathways of decarboxylation and decarbonylation. Finally, the fresh and recycled catalysts were characterized showing modest recyclability with a ~12.5% loss in catalytic activity. Full article
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Open AccessFeature PaperArticle
Alkali-Free Zn–Al Layered Double Hydroxide Catalysts for Triglyceride Transesterification
Catalysts 2018, 8(12), 667; https://doi.org/10.3390/catal8120667 - 18 Dec 2018
Cited by 1
Abstract
Zn–Al layered double hydroxides (LDHs) of general formula [Zn2+(1−x)Al3+x(OH)2]x+(CO32)x/2·yH2O are promising solid base catalysts for the transesterification of lipids to biofuels. However, conventional synthetic routes [...] Read more.
Zn–Al layered double hydroxides (LDHs) of general formula [Zn2+(1−x)Al3+x(OH)2]x+(CO32)x/2·yH2O are promising solid base catalysts for the transesterification of lipids to biofuels. However, conventional synthetic routes employ alkali hydroxide/carbonate precipitants which may contaminate the final LDH catalyst and biofuel. The use of (NH3)2CO3 and NH3OH as precipitants affords alkali-free Zn–Al-LDHs spanning a wide composition range. The hydrothermal reconstruction of calcined Zn–Al-LDHs offers superior solid basicity and catalytic activity for the transesterification of C4–C18 triglycerides with methanol, compared with cold liquid phase or vapour phase reconstruction. Hydrothermally activated Zn3.3–Al-LDH was stable towards leaching during transesterification. Full article
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Open AccessCommunication
Acetic Acid/Propionic Acid Conversion on Metal Doped Molybdenum Carbide Catalyst Beads for Catalytic Hot Gas Filtration
Catalysts 2018, 8(12), 643; https://doi.org/10.3390/catal8120643 - 09 Dec 2018
Abstract
Catalytic hot gas filtration (CHGF) is used to precondition biomass derived fast pyrolysis (FP) vapors by physically removing reactive char and alkali particulates and chemically converting reactive oxygenates to species that are more easily upgraded during subsequent catalytic fast pyrolysis (CFP). Carboxylic acids, [...] Read more.
Catalytic hot gas filtration (CHGF) is used to precondition biomass derived fast pyrolysis (FP) vapors by physically removing reactive char and alkali particulates and chemically converting reactive oxygenates to species that are more easily upgraded during subsequent catalytic fast pyrolysis (CFP). Carboxylic acids, such as acetic acid and propionic acid, form during biomass fast pyrolysis and are recalcitrant to downstream catalytic vapor upgrading. This work developed and evaluated catalysts that can convert these acids to more upgradeable ketones at the laboratory scale. Selective catalytic conversion of these reactive oxygenates to more easily upgraded compounds can enhance bio-refinery processing economics through catalyst preservation by reduced coking from acid cracking, by preserving carbon efficiency, and through process intensification by coupling particulate removal with partial upgrading. Two metal-doped molybdenum carbide (Mo2C) supported catalyst beads were synthesized and evaluated and their performance compared with an undoped Mo2C control catalyst beads. For laboratory scale acetic acid conversion, calcium doped Mo2C supported catalyst beads produced the highest yield of acetone at ~96% at 450 °C among undoped and Ca or Ni doped catalysts. Full article
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Open AccessArticle
Support Effect on the Performance of Ni2P Catalysts in the Hydrodeoxygenation of Methyl Palmitate
Catalysts 2018, 8(11), 515; https://doi.org/10.3390/catal8110515 - 03 Nov 2018
Cited by 3
Abstract
The effect of support nature, SiO2 and γ-Al2O3, on physicochemical and catalytic properties of nickel phosphide catalysts in methyl palmitate hydrodeoxygenation (HDO) has been considered. Firstly, alumina-supported nickel phosphide catalysts prepared by temperature-programmed reduction method starting from different [...] Read more.
The effect of support nature, SiO2 and γ-Al2O3, on physicochemical and catalytic properties of nickel phosphide catalysts in methyl palmitate hydrodeoxygenation (HDO) has been considered. Firstly, alumina-supported nickel phosphide catalysts prepared by temperature-programmed reduction method starting from different precursors (phosphate–Ni(NO3)2 and (NH4)2HPO4 or phosphite–Ni(OH)2 and H3PO3) were compared using elemental analysis, N2 physisorption, H2-TPR, XRD, TEM, NH3-TPD, 27Al and 31P MAS NMR techniques and catalytic experiments. The mixture of nickel phosphide phases was produced from phosphate precursor on alumina while using of phosphite precursor provides Ni2P formation with the higher activity in methyl palmitate HDO. Besides, the comparative study of the performances of Ni2P/SiO2 and Ni2P/Al2O3 catalysts demonstrates the apparent superiority of alumina-supported Ni2P in the methyl palmitate hydrodeoxygenation. Considering the tentative scheme of methyl palmitate transformation, we proposed that cooperation of Ni2P and acid sites on the surface of alumina provides the enhanced activity of alumina-supported Ni2P through the acceleration of acid-catalysed hydrolysis. Full article
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Open AccessArticle
Selective Dehydration of Glucose into 5-Hydroxymethylfurfural by Ionic Liquid-ZrOCl2 in Isopropanol
Catalysts 2018, 8(10), 467; https://doi.org/10.3390/catal8100467 - 18 Oct 2018
Cited by 1
Abstract
In this work, a heterogeneous catalytic system consisting of [HO2CMMIm]Cl and ZrOCl2 in isopropanol is demonstrated to be effective for 5-hydroxymethylfurfural (HMF) synthesis with glucose as the feedstock. Various reaction conditions for HMF synthesis by glucose dehydration were investigated systematically. [...] Read more.
In this work, a heterogeneous catalytic system consisting of [HO2CMMIm]Cl and ZrOCl2 in isopropanol is demonstrated to be effective for 5-hydroxymethylfurfural (HMF) synthesis with glucose as the feedstock. Various reaction conditions for HMF synthesis by glucose dehydration were investigated systematically. Under optimized reaction conditions, as high as 43 mol% HMF yield could be achieved. Increasing the water content to a level below 3.17% led to the production of HMF with a higher yield, while a lower HMF yield was observed when the water content was increased above 3.17%. In addition, the data also showed that ZrOCl2 could not only effectively convert glucose into intermediate species (which were not fructose, in contrast to the literature) but also catalyze the intermediate species’ in situ dehydration into HMF. [HO2CMMIm]Cl was used to catalyze the intermediate species’ in situ conversion to HMF. The kinetics data showed that a temperature increase accelerated the intermediate species’ dehydration reaction rate. The reaction of glucose dehydration was a strong endothermal reaction. Full article
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Open AccessArticle
Magnetic Combined Cross-Linked Enzyme Aggregates of Ketoreductase and Alcohol Dehydrogenase: An Efficient and Stable Biocatalyst for Asymmetric Synthesis of (R)-3-Quinuclidinol with Regeneration of Coenzymes In Situ
Catalysts 2018, 8(8), 334; https://doi.org/10.3390/catal8080334 - 15 Aug 2018
Cited by 6
Abstract
Enzymes are biocatalysts. In this study, a novel biocatalyst consisting of magnetic combined cross-linked enzyme aggregates (combi-CLEAs) of 3-quinuclidinone reductase (QNR) and glucose dehydrogenase (GDH) for enantioselective synthesis of (R)-3-quinuclidinolwith regeneration of cofactors in situ was developed. The magnetic combi-CLEAs were [...] Read more.
Enzymes are biocatalysts. In this study, a novel biocatalyst consisting of magnetic combined cross-linked enzyme aggregates (combi-CLEAs) of 3-quinuclidinone reductase (QNR) and glucose dehydrogenase (GDH) for enantioselective synthesis of (R)-3-quinuclidinolwith regeneration of cofactors in situ was developed. The magnetic combi-CLEAs were fabricated with the use of ammonium sulfate as a precipitant and glutaraldehyde as a cross-linker for direct immobilization of QNR and GDH from E. coli BL(21) cell lysates onto amino-functionalized Fe3O4 nanoparticles. The physicochemical properties of the magnetic combi-CLEAs were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and magnetic measurements. Field emission scanning electron microscope (FE-SEM) images revealed a spherical structure with numerous pores which facilitate the movement of the substrates and coenzymes. Moreover, the magnetic combi-CLEAs exhibited improved operational and thermal stability, enhanced catalytic performance for transformation of 3-quinuclidinone (33 g/L) into (R)-3-quinuclidinol in 100% conversion yield and 100% enantiomeric excess (ee) after 3 h of reaction. The activity of the biocatalysts was preserved about 80% after 70 days storage and retained more than 40% of its initial activity after ten cycles. These results demonstrated that the magnetic combi-CLEAs, as cost-effective and environmentally friendly biocatalysts, were suitable for application in synthesis of (R)-3-quinuclidinol essential for the production of solifenacin and aclidinium with better performance than those currently available. Full article
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Open AccessArticle
On the Impact of the Preparation Method on the Surface Basicity of Mg–Zr Mixed Oxide Catalysts for Tributyrin Transesterification
Catalysts 2018, 8(6), 228; https://doi.org/10.3390/catal8060228 - 28 May 2018
Cited by 4
Abstract
Mixed metal oxides are promising heterogeneous catalysts for biofuel production from lipids via alcoholysis, however, the impact of solid acidity and/or basicity on reactivity is comparatively poorly understood. Two systematically related families of MgO–ZrO2 mixed oxide catalysts were therefore prepared by different [...] Read more.
Mixed metal oxides are promising heterogeneous catalysts for biofuel production from lipids via alcoholysis, however, the impact of solid acidity and/or basicity on reactivity is comparatively poorly understood. Two systematically related families of MgO–ZrO2 mixed oxide catalysts were therefore prepared by different synthetic routes to elucidate the impact of surface acid-base properties on catalytic performance in the transesterification of tributyrin with methanol. The resulting materials were characterized by TGA-MS, ICP-OES, N2 porosimetry, XRD, TEM, XPS, DRIFTS, and CO2-temperature-programmed desorption (TPD). MgO–ZrO2 catalysts prepared by both non-aqueous impregnation and citric acid-mediated sol–gel routes exhibit excellent activity and stability. The citrate routes favor highly dispersed MgO and concomitant Lewis acid-base pair formation at the interface with zirconia. However, for both the citrate and impregnation routes, tributyrin transesterification occurs over a common, strongly basic MgO active site. Full article
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Open AccessArticle
Selective Conversion of Furfural to Cyclopentanone or Cyclopentanol Using Co-Ni Catalyst in Water
Catalysts 2018, 8(5), 193; https://doi.org/10.3390/catal8050193 - 04 May 2018
Cited by 1
Abstract
Co-Ni catalysts, prepared by a typical wetness impregnation method, can selectively convert furfural (FFA) to cyclopentanone (CPO) or cyclopentanol (CPL) in water, respectively. The catalytic performance depends strongly on the support. It is also strongly influenced by the Co-Ni loadings of the catalyst. [...] Read more.
Co-Ni catalysts, prepared by a typical wetness impregnation method, can selectively convert furfural (FFA) to cyclopentanone (CPO) or cyclopentanol (CPL) in water, respectively. The catalytic performance depends strongly on the support. It is also strongly influenced by the Co-Ni loadings of the catalyst. The 10%Co-10%Ni/TiO2 catalyst showed the highest selectivity toward CPO (53.3%) with almost complete FFA conversion, and the main product was CPL (45.4%) over 20%Co/TiO2 at the optimized conditions (150 °C, 4 MPa H2, 4 h). The surface morphology, surface area, composition and reducibility properties of these catalysts were fully characterized by XRD, H2-TPR, ICP-AES and SEM. The factors that influenced the activity of catalysts were also investigated in detail. Additionally, the stability of catalyst for the hydrogenative rearrangement of FFA was studied. Full article
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