Highly selective hydrogenation of furfural over supported Pt nanoparticles under mild conditions

The selective liquid phase hydrogenation of furfural to furfuryl alcohol over Pt nanoparticles supported on SiO₂, ZnO, γ-Al2O₃, CeO₂ is reported under extremely mild conditions. Ambient hydrogen pressure, and temperatures as low as 50 °C are shown sufficient to drive furfural hydrogenation with high conversion and >99% selectivity to furfuryl alcohol. Strong support and solvent dependencies are observed, with methanol and n-butanol proving excellent solvents for promoting high furfuryl alcohol yields over uniformly dispersed 4 nm Pt nanoparticles over MgO, CeO₂ and γ-Al₂O₃. In contrast, non-polar solvents conferred poor furfural conversion, while ethanol favored acetal by-product formation. Furfural selective hydrogenation can be tuned through controlling the oxide support, reaction solvent and temperature

Hydrogenation of furfural over supported Pd catalysts

Lignocellulosic biomass is the most abundant and economical non-fossil carbon source. Furthermore, it is not competitive with the food chain, coming from lignocellulosic wastes including agricultural and food processing, local urban solid and forestry wastes. However, these are made up of complex carbohydrates (mainly, cellulose and hemicellulose), which require to be broken down in their respective monomers. The hemicellulose is mainly composed of pentosans, which, after an initial hydrolysis step, are dehydrated to furfural. Furfural is an important platform molecule, since it has a wide range of applications, being considered the main chemical, aside from bioethanol, obtained from the sugar platform for the synthesis of chemicals, for plastics, agrochemical and pharmaceutical industries. In the present work, the hydrogenation of furfural in gas phase has been studied by using Pd as active phase, and different metal oxides as support, in order to elucidate the influence of the support on the catalytic performance. Furfural can be converted into chemicals with important applications in many different industrial fields. Thus, reduction of furfural can proceed through different pathways depending on the experimental conditions, where the nature of the catalysts plays a key role. In the case of Pd-based catalysts, the main products come from the decarbonylation of furfural.The catalytic results reveals that the nature of the support exerts an important influence on furfural conversion and yield. The highest conversion (92% after 5 h of TOS at 463 K) was attained with a Pd-SiO2 catalyst, with a furan yield of 70 mol%. This catalyst is the most selective to furan and a moderate deactivation is only observed after 5 h reaction. The catalytic performance demonstrates that decarbonylation reaction was the main pathway, although the formation of furfuryl alcohol and 2-methylfuran also suggests that the hydrogenation of the carbonyl group of furfural takes place.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tec

Identification of furfural resistant strains of Saccharomyces cerevisiae and Saccharomyces paradoxus from a collection of environmental and industrial isolates

Background Fermentation of bioethanol using lignocellulosic biomass as a raw material provides a sustainable alternative to current biofuel production methods by utilising waste food streams as raw material. Before lignocellulose can be fermented it requires physical, chemical and enzymatic treatment in order to release monosaccharides, a process that causes the chemical transformation of glucose and xylose into the cyclic aldehydes furfural and hydroxyfurfural. These furan compounds are potent inhibitors of Saccharomyces fermentation, and consequently furfural tolerant strains of Saccharomyces are required for lignocellulosic fermentation. Results This study investigated yeast tolerance to furfural and hydroxyfurfural using a collection of 71 environmental and industrial isolates of the baker’s yeast Saccharomyces cerevisiae and its closest relative Saccharomyces paradoxus. The Saccharomyces strains were initially screened for growth on media containing 100 mM glucose and 1.5 mg ml-1 furfural. Five strains were identified that showed a significant tolerance to growth in the presence of furfural and these were then screened for growth and ethanol production in the presence of increasing amounts (0.1-4 mg ml-1) of furfural. Conclusions Of the five furfural tolerant strains S. cerevisiae NCYC 3451 displayed the greatest furfural resistance, and was able to grow in the presence of up to 3.0 mg ml-1 furfural. Furthermore, ethanol production in this strain did not appear to be inhibited by furfural, with the highest ethanol yield observed at 3.0 mg ml-1 furfural. Although furfural resistance was not found to be a trait specific to any one particular lineage or population, three of the strains were isolated from environments where they might be continually exposed to low levels of furfural through the on-going natural degradation of lignocelluloses, and would therefore develop elevated levels of resistance to these furan compounds. Thus these strains represent good candidates for future studies of genetic variation relevant to understanding and manipulating furfural resistance and in the development of tolerant ethanologenic yeast strains for use in bioethanol production from lignocellulose processing

Fuels and chemicals from biomass using solar thermal energy

The significant nearer term opportunities for the application of solar thermal energy to the manufacture of fuels and chemicals from biomass are summarized, with some comments on resource availability, market potential and economics. Consideration is given to the production of furfural from agricultural residues, and the role of furfural and its derivatives as a replacement for petrochemicals in the plastics industry

Mesoporous niobium oxide for dehydration of D-xylose into furfural

Se ha demostrado que el óxido de niobio mesoporoso es un catalizador eficaz para la deshidratación de D-xilosa a furfural, alcanzando una conversión del 92% y un rendimiento de furfural 49,3% a 170º C y 90 minutos. La lixiviación de Nb, determinada por ICP-MS, era inferior al 0,5% en peso de la concentración de Nb inicial, confirmando de este modo la estabilidad del catalizador ácido sólido.El furfural posee un gran potencial como molécula plataforma de origen renovable para la síntesis de una alta variedad de compuestos químicos. Se obtiene mediante la deshidratación de pentosas, principalmente a partir de D-xilosa, proceso catalizado por ácidos minerales en fase homogénea. Por tanto, dentro de la química verde y la búsqueda de sostenibilidad de los procesos catalíticos, es necesaria su sustitución por catalizadores sólidos ácidos que sean tolerantes al agua, ya que es el disolvente más utilizado para esta reacción. El óxido de niobio posee propiedades ácidas y es insoluble en agua, pero su superficie específica es muy baja. Por lo tanto, resulta muy interesante la síntesis de un óxido de niobio mesoporoso para emplearlo como catalizador en esta reacción. En este trabajo, se ha sintetizado un Nb2O5 mesoporoso y se ha evaluado su comportamiento catalítico en la obtención de furfural a partir de D-xilosa.Spanish Ministry of Science and Innovation (ENE2009-12743-C04-03 project)Junta de Andalucía (P09-FQM-5070).Ministry of Science and Innovation for the financial support under the Program Ramón y Cajal (RYC-2008-03387)

Key schedule algorithm based on coordinate geometry of a three-dimensional hybrid cube

Cryptographic algorithms play an important role in information security where it ensures the security of data across the network or storage. A key schedule algorithm is the mechanism that generates and schedules all session-keys for the encryption process. The 2-dimensional hybrid cube is generated based on permutation and combination of integer numbers that are utilized in the construction of encryption and decryption key in the non-binary block cipher. The generation of key space by using the 2-dimensional hybrid cubes are not sufficient to resist attacks and could easily be exploited. Therefore, the large key space is more desirable to resist any attack on the secret key. This research proposed a new Key Schedule Algorithm based on the coordinate geometry of a Hybrid Cube (KSAHC) for the non-binary block cipher. By using the three-dimensional hybrid cube in KSAHC transformation, encryption keys are represented as n × n × n matrix of integer numbers and used in the development of the permutation and substitution of order 4 square matrix. Triangular Coordinate Extraction (TCE) technique has also been introduced to extract the coordinates during the rotation of Hybrid Cube surface (HCs) and plays an important role in the development of KSAHC algorithm. The Hybrid Cube Encryption Algorithm (HiSea) has been implemented to validate the encryption keys that are generated from the proposed algorithm. The strength of the keys and ciphertext are compared with the Advanced Encryption Standard (AES), HiSea, and Dynamic Key Schedule Algorithm (DKSA). The proposed KSAHC algorithm has been validated using the randomness test proposed and recommended by NIST, the average result of avalanche test is 93%, entropy is 0.9968, correlation assessment test is -0.000601 and having large key space 2.70 × 1067 keys that makes the Brute Force attack difficult and time-consuming. Therefore, it can be concluded that the strength and validity of KSAHC algorithm have been enhanced as compared to other algorithms and can serve as the alternative algorithm in designing security systems

Honey volatiles as a fingerprint for botanical origin: a review on their occurrence on monofloral honeys

Honeys have specific organoleptic characteristics, with nutritional and health benefits, being highly appreciated by consumers, not only in food but also in the pharmaceutical and cosmetic industries. Honey composition varies between regions according to the surrounding flora, enabling its characterization by source or type. Monofloral honeys may reach higher market values than multifloral ones. Honey's aroma is very specific, resulting from the combination of volatile compounds present in low concentrations. The authentication of honey's complex matrix, according to its botanical and/or geographical origin, represents a challenge nowadays, due to the different sorts of adulteration that may occur, leading to the search for reliable marker compounds for the different monofloral honeys. The existing information on the volatiles of monofloral honeys is scarce and disperse. In this review, twenty monofloral honeys and honeydews, from acacia, buckwheat, chestnut, clover, cotton, dandelion, eucalyptus, fir tree, heather, lavender, lime tree, orange, pine, rape, raspberry, rhododendron, rosemary, strawberry tree, sunflower and thyme, were selected for volatile comparison purposes. Taking into consideration the country of origin, the technique of isolation and analysis, the five main volatiles from each of the honeys are compared. Whereas some compounds were found in several types of monofloral honey, and thus not considered good volatile markers, some monofloral honeys revealed characteristic volatile compounds independently of their provenance.Funding: SFRH/BD/117013/2016, UID/AGR/00690/2019, UID/AMB/50017/2019, MED (UIDB/05183/2020), FEDER, PT2020 PACompete 2020info:eu-repo/semantics/publishedVersio

Supported nickel nitride catalysts for the gas-phase hydrogenation of furfural

A series of catalysts with different nickel loading (2.5-30 wt%) has been prepared by UGR. The preparation of Ni3N phase was ascertained via Powder X-rays diffraction together with cubic nickel . The elemental chemical analysis and XPS data confirm the presence of the nitride phase. Their catalytic performance points out that catalysts with loading of 5-10 wt% Ni exhibit a higher stability, maintaining furfural conversion values higher than 75% after 5 h of time-on-stream at 170ºC, and the main products detected were furfuryl alcohol (hydrogenation) and furan (decarbonylation). This would indicate that two types of active sites are present on the catalyst surface. It is noteworthy the high catalytic activity of this family of catalyst, since they exhibit a better performance than Cu-ZnO catalysts, but using a lower reaction temperature and H2/furfural molar ratio, as well as a higher furfural concentration and WHSV values. The experimental conditions have been optimized in order to achieve the maximum yield in the target product, but preserving a high activity and stability. The fresh and spent catalysts have been characterized in order to elucidate structure-activity-stability relationships.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tec

Gas phase selective hydrogenation of furfural to furfuryl alcohol and 2-methylfuran over Cu-CeO2 coprecipitated catalysts

Furfural is an important chemical derived from lignocellulosic biomass, in particular from C5 sugars like xylose, and it is considered as a platform molecule of great potential for the synthesis of a broad spectrum of chemicals. In this sense, furfuryl alcohol and 2-methylfuran are two important chemicals which can be produced through furfural hydrogenation, either in liquid or vapor phase, although the latter is preferred because it can be carried out at atmospheric pressure. Industrially, a copper chromite catalyst is used, although this catalyst can become very toxic due to the presence of chromium. Therefore, much attention is being paid to the development of chromium-free catalysts, more sustainable and environmentally friendly, as those based on Cu or Ni which are active and selective towards the formation of furfuryl alcohol and 2-methylfuran. Furfuryl alcohol is mainly used for the production of thermostatic resins, intermediate in the manufacture of lysine, vitamin C and dispersing agents. Meanwhile, 2-methyl furan is used in the synthesis of pesticides, or in the pharmaceutical and fragrance industries. The aim of this work is the synthesis of a series of copper based catalysts, which have been synthesized by coprecipitation of copper and cerium(IV) and subsequent thermal programmed reduction. This method allows increasing the dispersion of Cu particles, while the use of a support like CeO2 can modify the electronic density of the active phase, which can influence the catalytic activity and resistance to deactivation.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech. Economy and Competitiveness Ministry (Project CTQ2012-38204-C03-02), Junta de Andalucía (Project: RNM-1565) and FEDER funds of the European Unio