scholarly journals Biodiesel: Modified Mixed Oxides as Catalyst for Transesterification of Rapeseed Oil

Catalysts ◽  
2020 ◽  
Vol 10 (12) ◽  
pp. 1397
Author(s):  
Vávra Aleš ◽  
Tišler Zdeněk ◽  
Kocík Jaroslav ◽  
Smutek Jakub
Keyword(s):  
Active Sites ◽  
Heterogeneous Catalysts ◽  
Fossil Fuels ◽  
Mixed Oxides ◽  
Catalyst Activity ◽  
Textural Properties ◽  
Carbon Fibres ◽  
Key Factor ◽  
Double Hydroxides

Biodiesel, as one of the alternative biofuels replacing the common fossil fuels, is prepared by transesterification of oils and fats. Commonly, the reaction is catalysed by either acidic or basic catalysts. The availability of the active sites to large triglyceride molecules is the key factor of the heterogeneous catalysts. The use of carbon fibres during the synthesis of Mg/Fe layered double hydroxides results in the formation of macropores during the calcination. The amount of carbon fibres showed an important effect on the textural properties of the resulting mixed oxides. The texture was determined by N2-adsorption and Hg-porosity. The catalyst activity in the studied reaction was examined by determination of ester amount by gas chromatography and the activity was compared with unmodified mixed oxides. The highest ester yield (40 wt.%) was achieved by adding 1 wt.% of carbon fibres to the catalyst with the largest size of macropores.

scholarly journals Bio-DEE Synthesis and Dehydrogenation Coupling of Bio-Ethanol to Bio-Butanol over Multicomponent Mixed Metal Oxide Catalysts

Catalysts ◽  
2021 ◽  
Vol 11 (6) ◽  
pp. 660
Author(s):  
Izabela S. Pieta ◽  
Alicja Michalik ◽  
Elka Kraleva ◽  
Dusan Mrdenovic ◽  
Alicja Sek ◽  
...  
Keyword(s):  
Active Sites ◽  
Internal Combustion Engines ◽  
Mixed Oxides ◽  
Catalyst Activity ◽  
Product Distribution ◽  
Coke Deposition ◽  
Precipitation Method ◽  
Mixed Metal Oxide ◽  
Low Carbon ◽  
Municipal Solid Wastes

Within the Waste2Fuel project, innovative, high-performance, and cost-effective fuel production methods from municipal solid wastes (MSWs) are sought for application as energy carriers or direct drop-in fuels/chemicals in the near-future low-carbon power generation systems and internal combustion engines. Among the studied energy vectors, C1-C2 alcohols and ethers are mainly addressed. This study presents a potential bio-derived ethanol oxidative coupling in the gas phase in multicomponent systems derived from hydrotalcite-containing precursors. The reaction of alcohol coupling to ethers has great importance due to their uses in different fields. The samples have been synthesized by the co-precipitation method via layered double hydroxide (LDH) material synthesis, with a controlled pH, where the M(II)/M(III) ≈ 0.35. The chemical composition and topology of the sample surface play essential roles in catalyst activity and product distribution. The multiple redox couples Ni2+/Ni3+, Cr2+/Cr3+, Mn2+/Mn3+, and the oxygen-vacant sites were considered as the main active sites. The introduction of Cr (Cr3+/Cr4+) and Mn (Mn3+/Mn4+) into the crystal lattice could enhance the number of oxygen vacancies and affect the acid/base properties of derived mixed oxides, which are considered as crucial parameters for process selectivity towards bio-DEE and bio-butanol, preventing long CH chain formation and coke deposition at the same time.

scholarly journals Aldol Condensation of Cyclohexanone and Furfural in Fixed-Bed Reactor

Catalysts ◽  
2019 ◽  
Vol 9 (12) ◽  
pp. 1068
Author(s):  
Zdeněk Tišler ◽  
Pavla Vondrová ◽  
Kateřina Hrachovcová ◽  
Kamil Štěpánek ◽  
Romana Velvarská ◽  
...  
Keyword(s):  
Inductively Coupled Plasma ◽  
Heterogeneous Catalysts ◽  
Mixed Oxides ◽  
Aldol Condensation ◽  
Condensation Reaction ◽  
Catalyst Activity ◽  
Fixed Bed ◽  
Chemical Properties ◽  
Fixed Bed Reactor ◽  
Molar Ratio

Aldol condensation reaction is usually catalysed using homogeneous catalysts. However, the heterogeneous catalysis offers interesting advantages and the possibility of cleaner biofuels production. Nowadays, one of the most used kinds of heterogeneous catalysts are hydrotalcites, which belong to a group of layered double hydroxides. This paper describes the aldol condensation of cyclohexanone (CH) and furfural (F) using Mg/Al mixed oxides and rehydrated mixed oxides in order to compare the catalyst activity after calcination and rehydration, as well as the possibility of its regeneration. The catalysts were synthesized by calcination and subsequent rehydration of the laboratory-prepared and commercial hydrotalcites, with Mg:Al molar ratio of 3:1. Their structural and chemical properties were determined by several analytical methods (inductively coupled plasma analysis (ICP), X-ray diffraction (XRD), diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), specific surface area (BET), thermogravimetric analysis (TGA), temperature programmed desorption (TPD)). F-CH aldol condensation was performed in a continuous fixed-bed reactor at 80 °C, CH:F = 5:1, WHSV 2 h−1. The rehydrated laboratory-prepared catalysts showed a 100% furfural conversion for more than 55 h, in contrast to the calcined ones (only 24 h). The yield of condensation products FCH and F2CH was up to 68% and 10%, respectively. Obtained results suggest that Mg/Al mixed oxides-based heterogeneous catalyst is suitable for use in the aldol condensation reaction of furfural and cyclohexanone in a fixed-bed reactor, which is an interesting alternative way to obtain biofuels from renewable sources.

scholarly journals Mg-Fe-mixed oxides derived from layered double hydroxides: A study of the surface properties

2011 ◽  
Vol 76 (12) ◽  
pp. 1661-1671 ◽  
Author(s):  
Milica Hadnadjev-Kostic ◽  
Tatjana Vulic ◽  
Radmila Marinkovic-Neducin ◽  
Aleksandar Nikolic ◽  
Branislav Jovic
Keyword(s):  
Surface Properties ◽  
Layered Double Hydroxides ◽  
Active Sites ◽  
Mixed Oxides ◽  
Lower Surface ◽  
Multiphase System ◽  
Fischer Tropsch ◽  
Acid And Base ◽  
Phase Range ◽  
Double Hydroxides

The influence of surface properties on the selectivity of the synthesized catalysts was studied, considering that their selectivity towards particular hydrocarbons is crucial for their overall activity in the chosen Fischer- -Tropsch reaction. Magnesium- and iron-containing layered double hydroxides (LDH), with the general formula: [Mg1-xFex(OH)2](CO3)x/2?mH2O, x = = n(Fe)/(n(Mg)+n(Fe)), synthesized with different Mg/Fe ratio and their thermally derived mixed oxides were investigated. Magnesium was chosen because of its basic properties, whereas iron was selected due to its well-known high Fischer-Tropsch activity, redox properties and the ability to form specific active sites in the layered LDH structure required for catalytic application. The thermally less stable multiphase system (synthesized outside the optimal single LDH phase range with additional Fe-phase), having a lower content of surface acid and base active sites, a lower surface area and smaller fraction of smaller mesopores, showed higher selectivity in the Fischer-Tropsch reaction. The results of this study imply that the metastability of derived multiphase oxides structure has a greater influence on the formation of specific catalyst surface sites than other investigated surface properties.

scholarly journals Synthesis of Chalcone Using LDH/Graphene Nanocatalysts of Different Compositions

2019 ◽  
Vol 3 (1) ◽  
pp. 29 ◽  
Author(s):  
Mayra Álvarez ◽  
Dana Crivoi ◽  
Francesc Medina ◽  
Didier Tichit
Keyword(s):  
Active Sites ◽  
Mixed Oxides ◽  
Catalytic Properties ◽  
Condensation Reaction ◽  
Nanocomposite Materials ◽  
Acid Base ◽  
Basic Sites ◽  
Base Catalysts ◽  
Reduced Graphene ◽  
Double Hydroxides

Layered double hydroxides (LDH) or their derived mixed oxides present marked acid-base properties useful in catalysis, but they are generally agglomerated, inducing weak accessibility to the active sites. In the search for improving dispersion and accessibility of the active sites and for controlling the hydrophilic/hydrophobic balance in the catalysts, nanocomposite materials appear among the most attractive. In this study, a series of nanocomposites composed of LDH and reduced graphene oxide (rGO), were successfully obtained by direct coprecipitation and investigated as base catalysts for the Claisen–Schmidt condensation reaction between acetophenone and benzaldehyde. After activation, the LDH-rGO nanocomposites exhibited improved catalytic properties compared to bare LDH. Moreover, they reveal great versatility to tune the selectivity through their composition and the nature or the absence of solvent. This is due to the enhanced basicity of the nanocomposites as the LDH content increases which is assigned to the higher dispersion of the nanoplatelets in comparison to bulk LDH. Lewis-type basic sites of higher strength and accessibility are thus created. The nature of the solvent mainly acts through its acidity able to poison the basic sites of the nanocatalysts.

scholarly journals Critical Review of Low-Temperature CO Oxidation and Hysteresis Phenomenon on Heterogeneous Catalysts

Catalysts ◽  
2018 ◽  
Vol 8 (12) ◽  
pp. 660 ◽  
Author(s):  
Rola Al Soubaihi ◽  
Khaled Saoud ◽  
Joydeep Dutta
Keyword(s):  
Low Temperature ◽  
Co Oxidation ◽  
Active Sites ◽  
Heterogeneous Catalysts ◽  
Catalyst Activity ◽  
Cost Effective ◽  
Hysteresis Phenomenon ◽  
Reaction Conditions ◽  
Kinetic Oscillations ◽  
Low Temperature Co Oxidation

There is a growing demand for new heterogeneous catalysts for cost-effective catalysis. Currently, the hysteresis phenomenon during low-temperature CO oxidation is an important topic in heterogeneous catalysis. Hysteresis provides important information about fluctuating reaction conditions that affect the regeneration of active sites and indicate the restoration of catalyst activity. Understanding its dynamic behavior, such as hysteresis and self-sustained kinetic oscillations, during CO oxidation, is crucial for the development of cost-effective, stable and long-lasting catalysts. Hysteresis during CO oxidation has a direct influence on many industrial processes and its understanding can be beneficial to a broad range of applications, including long-life CO2 lasers, gas masks, catalytic converters, sensors, indoor air quality, etc. This review considers the most recent reported advancements in the field of hysteresis behavior during CO oxidation which shed light on the origin of this phenomenon and the parameters that influence the type, shape, and width of the conversion of the hysteresis curves.

scholarly journals Use of Co/Fe-Mixed Oxides as Heterogeneous Catalysts in Obtaining Biodiesel

Catalysts ◽  
2019 ◽  
Vol 9 (5) ◽  
pp. 403 ◽  
Author(s):  
Norma Gutiérrez-Ortega ◽  
Esthela Ramos-Ramírez ◽  
Alma Serafín-Muñoz ◽  
Adrián Zamorategui-Molina ◽  
Jesús Monjaraz-Vallejo
Keyword(s):  
Fourier Transform ◽  
Active Sites ◽  
Heterogeneous Catalysts ◽  
Mixed Oxides ◽  
Resonance Spectroscopy ◽  
Scanning Calorimetry ◽  
X Ray ◽  
Catalyst Composition ◽  
Catalyst Type ◽  
Diffuse Reflectance Infrared

Catalyst-type mixed metal oxides with different compositions and Co/Fe ratios were obtained from layered double hydroxides to be used as heterogeneous catalysts in the production of biodiesel. The effect of the Co/Fe ratio on the precursors of the catalysts was analyzed, considering their thermal, textural and structural properties. The physicochemical properties of the catalysts were determined by thermogravimetric analysis (differential scanning calorimetry and thermogravimetric), X-ray diffraction, Fourier-transform infrared spectroscopy, Scanning Electron Microscopy-Energy Dispersive X-ray spectroscopy and N2-physisorption. The conversion to biodiesel using the different catalysts obtained was determined by diffuse reflectance infrared Fourier-transform spectroscopy and 1H-Nuclear magnetic resonance spectroscopy, allowing us to correlate the effect of the catalyst composition with the catalytic capacity. The conditions for obtaining biodiesel were optimized by selecting the catalyst and varying the percentage of catalyst, the methanol/oil ratio and the reaction time. The catalysts reached yields of conversion to biodiesel of up to 96% in 20 min of reaction using only 2% catalyst. The catalyst that showed the best catalytic activity contains a mixture of predominant crystalline and amorphous phases of CoFe2O4 and NaxCoO2. The results suggest that cobalt is a determinant in the activity of the catalyst when forming active sites in the crystalline network of mixed oxides for the transesterification of triglycerides, with high conversion capacity and selectivity to biodiesel.

scholarly journals A study of thermally activated Mg-Fe layered double hydroxides as potential environmental catalysts

2010 ◽  
Vol 75 (9) ◽  
pp. 1251-1257 ◽  
Author(s):  
Milica Hadnadjev-Kostic ◽  
Tatjana Vulic ◽  
Radmila Marinkovic-Neducin
Keyword(s):  
Layered Double Hydroxides ◽  
Active Sites ◽  
Single Phase ◽  
Mixed Oxides ◽  
Precipitation Method ◽  
Test Reaction ◽  
Thermally Activated ◽  
Fe Content ◽  
Multiphase Systems ◽  
Double Hydroxides

Layered double hydroxides (LDHs) and mixed oxides derived after thermal decomposition of LDH with different Mg-Fe content were investigated. These materials were chosen because of the possibility to tailor their various properties, such as ion-exchange capability, redox and acid-base properties and surface area. Layered double hydroxides, [Mg1-x Fex (OH)2](CO3)x/2 ? m H2O, (where x presents the content of trivalent ions, x = M(III)/[M(II) + M(III)]) were synthesized, using low supersaturation precipitation method. The influence of different Mg/Fe ratio on the structure and surface properties of LDH and derived mixed oxides was investigated in correlation to catalytic properties in chosen test reaction (Fischer-Tropsch synthesis). It was determined that the presence of active sites in the mixed oxides is influenced by structural properties of the initial LDH and by the presence of additional Fe phases. Furthermore, the synthesis outside the optimal range for the synthesis of single phase LDHs leads to the formation of metastable, multiphase systems with specific characteristics and active sites.

scholarly journals Effect of MAF-6 Crystal Size on Its Physicochemical and Catalytic Properties in the Cycloaddition of CO2 to Propylene Oxide

Catalysts ◽  
2021 ◽  
Vol 11 (9) ◽  
pp. 1061
Author(s):  
Maria N. Timofeeva ◽  
Ivan A. Lukoyanov ◽  
Valentina N. Panchenko ◽  
Biswa Nath Bhadra ◽  
Evgenii Yu Gerasimov ◽  
...  
Keyword(s):  
Particle Size ◽  
Propylene Oxide ◽  
Active Sites ◽  
Heterogeneous Catalysts ◽  
Binary Systems ◽  
Crystal Size ◽  
Tetrabutylammonium Bromide ◽  
Textural Properties ◽  
Similar Reaction ◽  
Zeolitic Imidazolate Frameworks

Zeolitic imidazolate frameworks MAF-5 and MAF-6 based on Zn2+ and 2-ethylimidazole were demonstrated to be efficient heterogeneous catalysts in solvent-free coupling of CO2 and propylene oxide (PO) to produce propylene carbonate (PC) at 0.8 MPa of CO2 and 80 °C. Activity of MAF-5 was lower in comparison with MAF-6 due to the difference in their structural and textural characteristics. MAF-6 samples with particle size of 190 ± 20, 360 ± 30, and 810 ± 30 nm were prepared at room temperature from [Zn(NH3)4](OH)2 and 2-ethylimidazole. Control of particle size was achieved by variation of type of alcohol in alcohol/cyclohexane media for the preparation of MAF-6. According to this comprehensive study, the yield of PC was found to decrease with increasing crystal size of the MAF-6 material, which was related to the change in textural properties and the number and localization of active sites. The combination of MAF-6 with particle size of with particle size of 190 ± 20 nm and tetrabutylammonium bromide ([n-Bu4N]Br) as co-catalyst led to an approximately 4-fold enhancement in the yield of PC (80.5%). Compared with reported ZIFs catalysts, the efficiencies of MAF-5/[n-Bu4N]Br and MAF-6/[n-Bu4N]Br binary systems were comparable and higher under similar reaction conditions.

scholarly journals A one-step rapid synthesis of TS-1 zeolites with highly catalytically active mononuclear TiO6 species

2020 ◽  
Vol 8 (19) ◽  
pp. 9677-9683 ◽  
Author(s):  
Wenjing Xu ◽  
Tianjun Zhang ◽  
Risheng Bai ◽  
Peng Zhang ◽  
Jihong Yu
Keyword(s):  
Active Sites ◽  
High Performance ◽  
Rational Design ◽  
Heterogeneous Catalysts ◽  
Rapid Synthesis ◽  
Catalytically Active ◽  
One Step

The modulation and determination of the coordination environments of Ti active sites in titanosilicate zeolites are key challenges in the rational design of high-performance heterogeneous catalysts.

What catalysis needs from the electron microscopist

1988 ◽  
Vol 46 ◽  
pp. 694-695
Author(s):  
Alexis T. Bell
Keyword(s):  
Active Sites ◽  
Heterogeneous Catalysts ◽  
Catalyst Deactivation ◽  
Surface Composition ◽  
Internal Surface ◽  
Active Phase ◽  
Atomic Scale ◽  
Metal Catalyst ◽  
Internal Surface Area ◽  
Porous Support

Heterogeneous catalysts, used in industry for the production of fuels and chemicals, are microporous solids characterized by a high internal surface area. The catalyticly active sites may occur at the surface of the bulk solid or of small crystallites deposited on a porous support. An example of the former case would be a zeolite, and of the latter, a supported metal catalyst. Since the activity and selectivity of a catalyst are known to be a function of surface composition and structure, it is highly desirable to characterize catalyst surfaces with atomic scale resolution. Where the active phase is dispersed on a support, it is also important to know the dispersion of the deposited phase, as well as its structural and compositional uniformity, the latter characteristics being particularly important in the case of multicomponent catalysts. Knowledge of the pore size and shape is also important, since these can influence the transport of reactants and products through a catalyst and the dynamics of catalyst deactivation.

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