Catalytic Hydrodeoxygenation of Fatty Acids for Biodiesel Production

This paper is devoted to the production of second generation biodiesel via catalytic hydrodeoxygenation of fatty acids. Pd/C catalysts with different metal loading were used. The palladium catalysts were characterized using low-temperature nitrogen physisorption and X-ray photoelectron spectroscopy. It was revealed that the most active and selective catalyst was 1%-Pd/C which allowed reaching up 97.5% of selectivity (regarding to n-heptadecane) at 100% conversion of substrate. Moreover, the chosen catalyst is more preferable according to lower metal content that leads the decrease of the process cost. The analysis of the catalysts showed that 1%-Pd/C had the highest specific surface area compared with 5%-Pd/C. Copyright © 2016 BCREC GROUP. All rights reservedReceived: 31st July 2015; Revised: 9th December 2015; Accepted: 30th December 2015How to Cite: Stepacheva, A.A., Sapunov, V.N., Sulman, E.M., Nikoshvili, L.Z., Sulman, M.G., Sidorov, A.I., Demidenko, G.N., Matveeva, V.G. (2016). Catalytic Hydrodeoxygenation of Fatty Acids for Biodiesel Production. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (2): 125-132 (doi:10.9767/bcrec.11.2.538.125-132)Permalink/DOI: http://dx.doi.org/10.9767/bcrec.11.2.538.125-132Article Metrics: (click on the button below to see citations in Scopus)

Phytocenosis biodiversity at various water levels in mesotrophic Lake Arakhley, Lake Baikal basin, Russia

Small lakes have lower water levels during dry years as was the case in 2000–2020. We sought to show the biodiversity of plant communities at various water levels in Lake Arakhley. Changes in moisture content are reflected in the cyclical variations of the water level in the lake, which decreased approximately 2 m in 2017–2018. These variations affect the biological diversity of the aquatic ecosystems. We present the latest data on the state of the plant communities in this mesotrophic lake located in the drainage basin of Lake Baikal. Lake Arakhley is a freshwater lake with low mineral content and a sodium hydrocarbonate chemical composition. Changes in the nutrient concentration were related to precipitation; inflow volume and organic matter were autochtonous at low water levels. The most diverse groups of phytoplankton found in the lake were Bacillariophyta, Chlorophyta, and Chrysophyta. High biodiversity values indicate the complexity and richness of the lake’s phytoplankton community. A prevalence of Lindavia comta was observed when water levels were low and Asterionella formosa dominated in high-water years. The maximum growth depth of lacustrine vegetation decreased from 11.0 m to 4.0 m from 1967 to 2018. Decreasing water levels were accompanied by a reduction in the littoral zone, altering the communities of aquatic plants. The hydrophyte communities were monodominant in the dry years and were represented by Ceratophyllum demersum. The vegetation cover of the lake was more diverse in high-water years and variations in the lake’s water content altered the composition of biogenic substances. These changes were reflected in the lake’s phytocenosis

Promotion Effect of Alkali Metal Hydroxides on Polymer-Stabilized Pd Nanoparticles for Selective Hydrogenation of C–C Triple Bonds in Alkynols

Postimpregnation of Pd nanoparticles (NPs) stabilized within hyper-cross-linked polystyrene with sodium or potassium hydroxides of optimal concentration was found to significantly increase the catalytic activity for the partial hydrogenation of the C–C triple bond in 2-methyl-3-butyn-2-ol at ambient hydrogen pressure. The alkali metal hydroxide accelerates the transformation of the residual Pd(II) salt into Pd(0) NPs and diminishes the reaction induction period. In addition, the selectivity to the desired 2-methyl-3-buten-2-ol increases with the K- and Na-doped catalysts from 97.0 up to 99.5%. This effect was assigned to interactions of the alkali metal ions with the Pd NPs surfaces resulting in the sites’ separation and a change of reactants adsorption

Влияние степени окисления и распределения частиц рутения на гидрирование левулиновой кислоты в присутствии Ru-содержащих катализаторов на основе цеолитов

The paper presents data on the synthesis of ruthenium catalysts based on the zeolites HBeta, HΥ, HMordenite and HZSM‑5 and their testing in the hydrogenation reaction of levulinic acid to gamma- valerolactone in an aqueous medium at a temperature of 100 oC and partial hydrogen pressure of 1 MPa. For the initial zeolites and synthesized catalysts, physicochemical study was carried out using low- temperature nitrogen physisorption, XPS, DRIFT spectroscopy using CD3CN as a probe molecule, and electron microscopy. The dependence of the activity of Ru/zeolite composites on the surface content of RuO2 was establishedВ работе представлены данные по синтезу рутениевых катализаторов на основе цеолитов HBeta, HΥ, HMordenite и HZSM‑5 и их тестированию в реакции гидрирования левулиновой кислоты до гамма-валеролактона в водной среде при температуре 100 о С и парциальном давлении водорода 1 МПа. Для исходных цеолитов и катализаторов на их основе проведено физико-химическое исследование методами низкотемпературной адсорбции азота, РФЭС, ИК‑спектроскопии с адсорбцией CD3CN, а также электронной микроскопии. Установлена зависимость активности композитов Ru/цеолит от поверхностного содержания RuO

Magnetic Nanoparticle-Containing Supports as Carriers of Immobilized Enzymes: Key Factors Influencing the Biocatalyst Performance

In this short review (Perspective), we identify key features of the performance of biocatalysts developed by the immobilization of enzymes on the supports containing magnetic nanoparticles (NPs), analyzing the scientific literature for the last five years. A clear advantage of magnetic supports is their easy separation due to the magnetic attraction between magnetic NPs and an external magnetic field, facilitating the biocatalyst reuse. This allows for savings of materials and energy in the biocatalytic process. Commonly, magnetic NPs are isolated from enzymes either by polymers, silica, or some other protective layer. However, in those cases when iron oxide NPs are in close proximity to the enzyme, the biocatalyst may display a fascinating behavior, allowing for synergy of the performance due to the enzyme-like properties shown in iron oxides. Another important parameter which is discussed in this review is the magnetic support porosity, especially in hierarchical porous supports. In the case of comparatively large pores, which can freely accommodate enzyme molecules without jeopardizing their conformation, the enzyme surface ordering may create an optimal crowding on the support, enhancing the biocatalytic performance. Other factors such as surface-modifying agents or special enzyme reactor designs can be also influential in the performance of magnetic NP based immobilized enzymes

Cellulase Immobilization on Nanostructured Supports for Biomass Waste Processing

Nanobiocatalysts, i.e., enzymes immobilized on nanostructured supports, received considerable attention because they are potential remedies to overcome shortcomings of traditional biocatalysts, such as low efficiency of mass transfer, instability during catalytic reactions, and possible deactivation. In this short review, we will analyze major aspects of immobilization of cellulase—an enzyme for cellulosic biomass waste processing—on nanostructured supports. Such supports provide high surface areas, increased enzyme loading, and a beneficial environment to enhance cellulase performance and its stability, leading to nanobiocatalysts for obtaining biofuels and value-added chemicals. Here, we will discuss such nanostructured supports as carbon nanotubes, polymer nanoparticles (NPs), nanohydrogels, nanofibers, silica NPs, hierarchical porous materials, magnetic NPs and their nanohybrids, based on publications of the last five years. The use of magnetic NPs is especially favorable due to easy separation and the nanobiocatalyst recovery for a repeated use. This review will discuss methods for cellulase immobilization, morphology of nanostructured supports, multienzyme systems as well as factors influencing the enzyme activity to achieve the highest conversion of cellulosic biowaste into fermentable sugars. We believe this review will allow for an enhanced understanding of such nanobiocatalysts and processes, allowing for the best solutions to major problems of sustainable biorefinery

Thermal behavior of a catalytic packed-Bed Milli-reactor operated under radio frequency heating

An approach for analysis of thermal gradients in a catalytic packed bed milli-reactor operated under radio frequency (RF) heating has been presented. A single-point temperature measurement would cause the misinterpretation of the catalytic activity in an RF-heated reactor, because of the presence of a temperature gradient. For reliable data interpretation, the temperature should be measured at three positions along the reactor length. The temperature profile can be accurately estimated with the exact analytical solution of a one-dimensional (1D) convection and conduction heat-transfer model, and it can also be approximated with a second-order polynomial function. The results revealed that the position of maximum temperature in the catalytic bed shifts toward a downstream location as the flow rate increases. The relative contribution of conduction and convection to the overall heat transport has been discussed. The design criteria for a near-isothermal milli-reactor have been suggested

Recent Progress in Chitosan-Containing Composite Materials for Sustainable Approaches to Adsorption and Catalysis

In recent years, composite materials including organic–inorganic systems have drawn special attention due to their enhanced properties such as adsorbents and heterogeneous catalysts. At the same time, large-scale production of environmentally benign functionalized biopolymers, such as chitosan (CS), allows for constantly developing new materials, since CS reveals remarkable properties as a stabilizing agent for metal-containing compounds and enzymes and as an adsorbent of organic molecules. This review is focused on CS-based materials and on the composite systems including CS-oxide and CS-metal composites in particular for application as adsorbents and supports for catalytically active metal nanoparticles and enzymes

Cellulose Conversion Into Hexitols and Glycols in Water: Recent Advances in Catalyst Development

Conversion of biomass cellulose to value-added chemicals and fuels is one of the most important advances of green chemistry stimulated by needs of industry. Here we discuss modern trends in the development of catalysts for two processes of cellulose conversion: (i) hydrolytic hydrogenation with the formation of hexitols and (ii) hydrogenolysis, leading to glycols. The promising strategies include the use of subcritical water which facilitates hydrolysis, bifunctional catalysts which catalyze not only hydrogenation, but also hydrolysis, retro-aldol condensation, and isomerization, and pretreatment (milling) of cellulose together with catalysts to allow an intimate contact between the reaction components. An important development is the replacement of noble metals in the catalysts with earth-abundant metals, bringing down the catalyst costs, and improving the environmental impact

Pd-Nanoparticles Confined Within Hollow Polymeric Framework as Effective Catalysts for the Synthesis of Fine Chemicals

Encapsulation of metal nanoclusters in porous solid polymer materials is a promising approach to combine the outstanding properties of both, heterogeneous and homogeneous catalysts. We report heterogeneous nano-engineered catalysts containing Pd-nanoparticles (NPs) confined within highly-porous hollow polymeric framework of hyper cross-linked polystyrene (HPS). HPS with different surface functionalities (amine vs. sulfonate) were used for impregnation by Pd precursors of different nature and followed by a variety of catalyst post-treatments. The catalysts have been tested in two model key reactions for the synthesis of fine chemicals: selective hydrogenation of 2-methyl-3-butyne-2-ol to 2-methyl-3-butene-2-ol (MBE) and Suzuki cross-coupling of 4-bromoanisole with phenylboronic acid. Optimization of the Pd/HPS preparation and reaction conditions allowed attaining high selectivity (similar to 99 %) to target MBE at close to full conversion. For Suzuki cross-coupling more than 90 % yield of coupling product was obtained under mild reaction conditions and the absence of phase transfer agent. Our results demonstrate the potential of HPS as a suitable support for tailoring metal NPs properties and circumvent undesirable metal leaching