Catalytic combustion of toluene on Cu-Mn/MCM-41 catalysts: Influence of calcination temperature and operating conditions on the catalytic activity

Catalytic combustion of toluene on Cu-Mn/MCM-41 catalyst was performed in tubular flow reactor operated at atmospheric pressure. The effect of catalyst pre-treatment temperatures on the catalytic activity and stability was investigated. Some reaction variables, such as inlet concentration of toluene and oxygen, reaction temperatures and space velocities were varied over wide ranges, and the influence of different reaction conditions on toluene conversion was discussed. It is showed that the catalytic activity was significantly affected by calcination temperatures between 300 and 800 °C, and oxygen concentration, toluene concentration and space velocity are all key experimental factors to optimize the toluene combustion activities. The objective of this study was to investigate catalytic properties of Cu-Mn/MCM-41 catalysts prepared at different calcination temperatures, in order to obtain additional information to prepare an efficient and highly active catalyst at low temperature.     

Effect of coke formation on catalytic activity tests for catalytic combustion of toluene: the difficulty of measuring TOF and T98 accurately

Catalytic combustion is considered as one of the most efficient routes for removing volatile organic compounds. In recent years, the catalytic activities of catalysts have usually been evaluated by the values of TOF and T₉₈. It is difficult, however, to measure the values accurately because the influencing factors are numerous and easy to be overlooked. In this work, the influence of the catalytic test procedure on TOF and T₉₈ values was investigated. Supported Pd or Pt catalysts were prepared via the incipient wetness impregnation method. The catalytic activities of the same catalyst were very different when evaluated in different catalytic test procedures. Indeed, the catalytic test procedures affected the TOF and T₉₈ values remarkably. It was found that the different coking behavior in different catalytic test procedures is the major cause. The influences on coke formation in toluene combustion – such as reaction temperature, reaction time, and catalyst type – were investigated.     

A comparative study on citrate sol-gel and combustion synthesis methods of CoAl2O4 spinel

CoAl₂O₄ spinel was successfully synthesized by combustion synthesis method using glycine and urea by 1:1 molar ratio as fuels and sol-gel process using citric acid as a chelating agent. The as-synthesized powders were calcined at desired temperatures to obtain CoAl₂O₄ spinel as a single phase. X-ray diffraction, thermogravimetric, and differential thermal analysis results revealed that the formation of CoAl₂O₄ spinel in combustion method needs 300°C higher temperatures than those of sol-gel. Scanning electron microscopy and transmission electron microscopy analysis results revealed that “sol-gel spinel” had nanometric particle size which was smaller than those of “combustion spinel.” Temperature programed reduction with hydrogen and Fourier transform infrared spectroscopy results declared that there was a little residual cobalt oxide in combustion spinel while there is no oxide resided in “sol-gel spinel.” Consequently, the sol-gel method has more benefit in synthesizing spinel with sulfate precursors than combustion.     

Stability and performance of catalytic microreactors: Simulations of propane catalytic combustion on Pt

A pseudo-two-dimensional (2D) model is developed to analyze the operation of platinum-catalyzed microburners for lean propane-air combustion. Comparison with computational fluid dynamics (CFD) simulations reveals that the transverse heat and mass transfer is reasonably captured using constant values of Nusselt and Sherwood numbers in the pseudo-2D model. The model also reasonably captures the axial variations in temperatures observed experimentally in a microburner with a gap size. It is found that the transverse heat and mass transport strongly depend on the inlet flow rate and the thermal conductivity of the burner solid structure. The microburner is surface reaction limited at very low velocities and mass transfer limited at high velocities. At intermediate range of velocities (preferred range of reactor operation), mass transfer affects the microburner performance strongly at low wall conductivities, whereas transverse heat transfer affects stability under most conditions and has a greater influence at high wall conductivities. At sufficiently low flow rates, complete fuel conversion occurs and reactor size has a slight effect on operation (conversion and temperature). For fast flows, propane conversion strongly depends on residence time; for a reactor with gap size of , a residence time higher than 6 ms is required to prevent propane breakthrough. The effect of reactor size on stability depends on whether the residence time or flow rate is kept constant as the size varies. Comparisons to homogeneous burners are also presented.     

High temperature stable magnesium oxide catalyst for catalytic combustion of methane: A comparison with manganesesubstituted barium hexaaluminate

The activity of magnesium oxide for catalytic combustion of methane was examined and the results were compared with experimental results for manganese-substituted barium hexaaluminate. The catalysts were calcined at temperatures up to 1 500°C and the effects of temperature, space velocity and calcination temperature were examined. The catalysts were also characterized with BET and XRD. For magnesium oxide calcined at 1 100°C the ignition temperature T_10% was decreased by 270°C compared to the non-catalyzed reaction. For the same catalyst T_50% was measured to be 795°C. The corresponding temperature for the hexaaluminate was 640°C. The difference between the two catalysts decreased after calcination at 1 500°C. For the magnesium oxide the influence of catalytically initiated homogeneous gas phase reactions was studied by varying the post catalytic volume of the reactor (and hence the residence time in the heated zone after the catalyst). It was shown that these catalytically initiated homogeneous gas phase reactions are significant for the methane conversion.     

Pd catalysts supported on silicon nitride for the combustion of methane: Influence of the crystalline and amorphous phases of the support and of the preparation method on the catalytic performances

Non-oxide refractory materials, such as silicon nitride having high thermal stability and thermal conductivity can be used as catalytic supports. The influence of the Si₃N₄ support nature and of the chemical compounds used for preparations on the physical-chemistry and catalytic properties of the palladium systems in the total oxidation of methane was investigated. A strong influence of the phase composition and the crystalline state of supports on the catalytic properties in the total oxidation of methane of the Pd catalysts was found. The activity of Pd catalysts increases with the -Si₃N₄ content and crystallization state of the support. The catalytic activity of Pd/-Si₃N₄ is also strongly affected by the preparation procedure. The Pd/-Si₃N₄ catalyst obtained by aqueous impregnation is less active and less stable. It was proposed that if water is used as an impregnation solvent, the surface acid-based properties of Si₃N₄ support and/or of the Pd active phase are irreversibly damaged. Pd supported on -Si₃N₄, prepared by impregnation of the Pd precursors in toluene solutions are found to be the most active and stable under reaction conditions.     

A comparative reactivity and kinetic study on the combustion of coal-biomass char blends

The combustion behavior and kinetics of various biomass chars, a lignite and a hard coal char and their blends were investigated. Pure fuel chars were compared to blended chars with respect to their performance during combustion. Non-isothermal thermogravimetry experiments were performed in air atmosphere, over a temperature range of 25-850 °C and at a heating rate of 10 °C/min. Kinetic evaluation was performed using a power law model. Reaction kinetic parameters were obtained by modeling the combustion of biomass and coal chars as a single reaction, with the exception of lignite and olive kernel chars, the combustion of which was modeled by two partial reactions. A single reaction model was used in the case of coal-wood char blends, while for the lignite-biomass char blends two partial reactions were used. Reactivity was assessed using the specific reaction rate, as a function of conversion. Biomass chars were generally more reactive than those of hard coal and lignite. The combustion behavior of the blends was greatly influenced by the rank of each coal (hard coal or lignite) and the proportion of each component in the blend. Combustion performance of the blends showed some deviation from the expected weighted average of the constituent chars. An attempt was made to estimate the kinetics of the blends using, as a basis, the parameters estimated for the individual components. In this case, because of the interactions between the components of the blends, the kinetic parameters needed to be slightly modified. Alteration in reactivity was more pronounced in the case of lignite-biomass chars than coal-wood chars.     

Al18B4O33 aluminium borate: A new efficient support for palladium in the high temperature catalytic combustion of methane

Well crystallised aluminium borate Al₁₈B₄O₃₃ has been synthesised from alumina and boric acid with a BET area of 18 m²/g after calcination at 1100 °C. Afterwards, 2 wt.% Pd/Al₁₈B₄O₃₃ was prepared by conventional impregnation of Pd(NO₃)₂ aqueous solution and calcination in air at 500 °C. The catalytic activity of Pd/Al₁₈B₄O₃₃ in the complete oxidation of methane was measured between 300 and 900 °C and compared with that of Pd/Al₂O₃. Pd/Al₁₈B₄O₃₃ exhibited a much lower activity than Pd/Al₂O₃ when treated in hydrogen at 500 °C or aged in O₂/H₂O (90:10) at 800 °C prior to catalytic testing. Surprisingly, a catalytic reaction run up to 900 °C in the reaction mixture induced a steep increase of the catalytic activity of Pd/Al₁₈B₄O₃₃ which became as active as Pd/Al₂O₃. Moreover, the decrease of the catalytic activity observed around 750 °C for Pd/Al₂O₃ and attributed to PdO decomposition into metallic Pd was significantly shifted to higher temperatures (820 °C) in the case of Pd/Al₁₈B₄O₃₃. The existence of two distinct types of PdO species formed on Al₁₈B₄O₃₃ and being, respectively, responsible for the improvement of the activity at low and high temperature was proposed on the basis of diffuse reflectance spectroscopy and temperature-programmed desorption of O₂.     

A comparative study of liquid product on non-catalytic and catalytic degradation of waste plastics using spent FCC catalyst

Non-catalytic and catalytic degradation of waste plastics (high-density polyethylene (HDPE), low-density polyethylene (LDPE), polypropylene (PP) and polystyrene (PS)) using spent fluid catalytic cracking (FCC) catalyst into liquid product were comparatively studied with a stirred semi-batch reactor at 400 ‡C, under nitrogen stream. Liquid product characteristics were described by cumulative distribution as a function of lapse time of reaction, paraffin, olefin, naphthene and aromatic (PONA) composition, and also carbon number distribution on plastic type of reactant. For degradation of waste PE with relatively high degradation temperature, the effect of adding spent FCC catalyst greatly appeared on cumulative distribution of liquid product with a reaction lapse time, whereas those for waste PP and PS with low degradation temperature showed a similar trend in both non-catalytic and catalytic degradation at 400 ‡C. In PONA and carbon number distribution of liquid product, the characteristics of waste PS that was mainly degraded by end chain scission mechanism were not much altered in presence of spent FCC catalyst. However, waste polyolefinic polymer that was degraded by a random chain scission mechanism significantly differed on PONA and carbon number distribution of liquid product with or without spent FCC catalyst. The addition of spent FCC catalyst in degradation of polyolefinic polymer, which economically has a benefit in utilization of waste catalyst, significantly improved the light olefin product by its high cracking ability and also the aromatic product by cyclization of olefin as shape selectivity in micropore of catalyst.     

A comparative study of the thermal and hydrothermal aging effect on Cu-SSZ-13 for the selective catalytic reduction of NOx with NH3

In this work, the characterizations of Cu-SSZ-13 after hydrothermal aging(HTA) and thermal aging(TA)at different temperatures(750, 800, and 850 °C) are compared, and the differences between those two serious aged samples are analyzed. With this data, the effect of steam on catalysts deactivation during hydrothermal aging is analyzed. The TA at 750 and 800 °C causes the dealumination and the agglomeration of Cu2+ions to Cu O, resulting in the activity loss of Cu-SSZ-13. The presence of steam upon...     

Vm/MOx催化剂对柴油碳烟催化燃烧抗硫中毒性能的比较

用柠檬酸络合助溶的等体积浸渍法制备了不同载体(γ-Al2O3 、SiO2 、TiO2、ZrO2和CeO2)负载的系列钒氧化物催化剂,使用红外光谱对催化剂硫中毒老化后的结构进行表征,采用程序升温氧化反应技术评价了硫老化后的催化剂对柴油碳烟催化燃烧的活性.结果表明,负载钒基氧化物催化剂硫老化后,催化剂表面主要以亚硫酸盐物种...     

Plasma-assisted surface engineering for value added in starch bioplastics: A study on enhanced surface properties and natural dye immobilization

This study examines the enhancement of starch-based bioplastic sheets for immobilizing natural dyes (ND) using plasma processes. The effects of poly(vinyl alcohol) (PVA) as a binder for ND were also assessed. Starch substrates were treated with air plasma, air plus 1,7-octadiene (OD) plasma, and air plus 2-methy-2-oxazoline (Ox) plasma before immobilizing curcumin and telang NDs, followed by an OD overcoating. Surface morphology, wettability, chemical composition, tensile strength, and surface charge were analyzed. Results showed improved wettability and dye immobilization, particularly for telang with a PVA binder and plasma treatment. OD overcoating prevented dye leaching. Air plasma reduced, while OD plasma maintained the starch's negative charge. XPS analysis indicated increased oxygen and nitrogen presence after air plasma and enhanced aliphatic carbon from OD overcoating. Tensile strength was largely unaffected, but elongation at break was reduced, especially after air and OD plasma treatment.     

Searching for the active sites of Co-H-MFI catalyst for the selective catalytic reduction of NO by methane: A FT-IR in situ and operando study

A Co-H-MFI sample has been studied through FT-IR spectroscopy of in situ adsorption and co-adsorption of probe molecules (o-toluonitrile, CO, NO) and has been tested in the CH₄-SCR process under IR operando conditions. The o-toluonitrile (oTN) adsorption and the oTN and NO co-adsorption, show that both Co²⁺ and Co³⁺ species are present on the catalyst surface. Co³⁺ species are located inside the zeolitic channels while Co²⁺ ions are distributed both at the external and at the internal surfaces. The operando study show the activity of Co³⁺ species in the reaction. The existence of three parallel reactions, CH₄-SCR, CH₄ total oxidation and NO to NO₂ oxidation, has been confirmed. Isocyanate species and nitrate-like species appear to be intermediates of CH₄-SCR and NO oxidation, respectively. A mechanism for CH₄-SCR has been proposed. Co²⁺ substitutional sites, very evident and predominant in the catalyst, which are very hardly reducible, seem not to play a key role in the SCR process.     

Pt catalysts supported on zeolitized-pumice for the selective hydrogenation of campholenic aldehyde: A characterization and kinetic study

A detailed characterization study of Pt catalysts supported on a novel zeolitized-pumice (Z-PM) support is reported. Two catalysts, named Pt(Cl)/Z-PM and Pt(Ac)/Z-PM, prepared by impregnation from H₂PtCl₆ and Pt(acac)₂ as precursors and subsequent reduction under H₂ at 623 K, were investigated in terms of microstructure, chemical and surface properties by using X-ray diffraction (XRD), transmission electron microscopy (TEM), temperature programmed reduction (TPR) and X-ray photoelectron spectroscopy (XPS).Characterization data showed that the microstructural stability of the support was preserved by using Pt(acac)₂ as precursor. It was verified instead that, by using H₂PtCl₆, the microstructure of the support changed during the thermal activation step under hydrogen, favouring a strong interaction between Pt and support as well as the formation of bimetallic Pt–Fe alloys. Moreover, a moderate increase of Pt d-band vacancies with respect to metallic Pt was observed in this catalyst by XPS.The above catalysts were tested in the selective hydrogenation of campholenic aldehydes to the corresponding unsaturated alcohol, naturanol. In comparison to the Pt(Ac)/Z-PM sample, the ex-chloride Pt(Cl)/Z-PM catalyst showed a higher selectivity to naturanol. This behaviour was interpreted on the basis of the different microstructural and electronic properties as evinced by the characterization data.     

Incorporating life cycle assessment and ecodesign tools for green chemical engineering: A case study of competences and learning outcomes assessment

Chemical engineers assume a broad range of roles in industry, spanning the development of new process designs, the maintenance and optimization of complex systems, and the production of intermediate materials, final products and new technologies. The technical aptitude that enables chemical engineers to fulfill these various roles along the value chain makes them compelling participants in the environmental assessment of the product in question. Therefore, the introduction of life cycle assessment (LCA) and ecodesign concepts into the chemical engineering curriculum is essential to help these future professionals to face design problems with a holistic view of the technical, economic, social and environmental impacts of their solutions. The teaching of these and other disciplines by means of student-centered methods, based on a holistic structure, have demonstrated better teamwork and communication skills. For that reason, this paper proposes a Micro (Assess-Analyze-Act) (M-3A) model of assessment mainly focused on closing the loop of the learning activities. This model has been applied to an ecodesign case study of the “University master’s Degree in chemical engineering” of the University of Cantabria/University of the Basque Country, with positive feedback of the students. They felt that the approach has allowed them to utilize their analytical skills in quantifying a situation before applying other subjective measures, and that the public discussion of the results was a satisfactory element for improving their communication skills. Moreover, the students found that the workload was nicely adjusted, highlighting the acquisition of 4 competences preferentially: teamwork, creativity; relevance of environmental issues and initiative and entrepreneurship. Finally, the students suggest that the application of this methodology into their degree could motivate future students improving their performance.     

A comparative study of electrocoagulation and electro-Fenton for food industry wastewater treatment: Multiple response optimization and cost analysis

ABSTRACT

In this study, response surface methodology was applied for food wastewater by electrocoagulation (EC) and electro-Fenton (EF) processes. The optimum conditions for the chemical oxygen demand (COD) removal were found to be 21.36 min, pH 10 and 86 mA/cm² in EC, whereas 27.11 min, pH 2.38, 86 mA/cm² and H₂O₂/COD:2 in EF process. COD removal efficiencies were determined to be 29.4% for EC and 59.1% for EF processes and higher than 99% total suspended solids removal efficiencies were achieved. It can be concluded that high COD removal was obtained (4998 mg/L COD removal by EC and 10,047 mg/L COD removal by EF).     

A comprehensive review on the preparation and application of calcium hydroxyapatite: A special focus on atomic doping methods for bone tissue engineering

Hydroxyapatite (HAP) has been considered to be one of the most preferred scaffold materials among many in the last decade for the bone tissue engineering. Be it prosthetic implants, scaffolds or artificial bone cement, hydroxyapatite has received highest attraction among all due to its chemical and physical properties similar to that of human bone. Although it can be used in the bone tissue engineering as the original composition; for enhancing its different properties relevant to in vivo applications, the calcium in HAP may also be replaced by other atomic dopants depending on usage. Here, we review various HAP coating agents and methods, their merits and demerits. We also review various HAP doping materials, including both cationic as well as anionic materials. We discuss the effects and usage of substitution of hydroxyapatite and their subsequent usage in both bone tissue engineering and maxillofacial surgeries. We consider various research articles published in recent times to accomplish detailed discussion on the subject.     

A comparative study of Ag/Al2O3 and Cu/Al2O3 catalysts for the selective catalytic reduction of NO by C3H6

The selective catalytic reduction (SCR) of NO by C₃H₆ in excess oxygen was evaluated and compared over Ag/Al₂O₃ and Cu/Al₂O₃ catalysts. Ag/Al₂O₃ showed a high activity for NO reduction. However, Cu/Al₂O₃ showed a high activity for C₃H₆ oxidation. The partial oxidation of C₃H₆ gave surface enolic species and acetate species on the Ag/Al₂O₃, but only an acetate species was clearly observed on the Cu/Al₂O₃. The enolic species is a more active intermediate towards NO + O₂ to yield—NCO species than the acetate species on the Ag/Al₂O₃ catalyst. The Ag and Cu metal loadings and phase changes on Al₂O₃ support can affect the activity and selectivity of Ag/Al₂O₃ and Cu/Al₂O₃ catalysts, but the formation of enolic species is the main reason why the activity of the Ag/Al₂O₃ catalyst for NO reduction is higher than that of the Cu/Al₂O₃ catalyst.     

A novel method for enhancing on-stream stability of fluid catalytic cracking (FCC) gasoline hydro-upgrading catalyst: Post-treatment of HZSM-5 zeolite by combined steaming and citric acid leaching

This article describes a novel modification method consisting of steaming and subsequent citric acid leaching to finely tune acidity and pore structure of HZSM-5 zeolite and thereby to enhance the on-stream stability of the zeolite derived fluid catalytic cracking (FCC) gasoline hydro-upgrading catalyst. A series of dealuminated HZSM-5 zeolites and their derived catalysts were prepared and characterized by X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), ²⁷Al MAS NMR, nitrogen adsorption, temperature programmed desorption of ammonium (NH₃-TPD) and infrared (IR) spectroscopy of chemisorbed pyridine. The results showed that the citric acid leaching could preferentially remove the extra-framework Al (EFAl) species formed by steaming treatment and thus reopen the EFAl-blocked pore channels of the steamed zeolite. The steaming treatment at a suitable temperature and subsequent citric acid leaching not only decreased the strength of acid sites to a desirable degree but also increased the ratio of medium and strong Lewis acidity to medium and strong Brönsted acidity, both of which conferred the resulting catalyst with superior selectivity to aromatics, good hydroisomerization activity and gasoline research octane number (RON) preservability, as well as enhanced on-stream stability. The results fully demonstrated that the treatments by steaming and followed citric acid leaching can serve as an important method for adjusting the physicochemical properties of HZSM-5 zeolite.     

A comparative study on catalytic performances of chromium incorporated and supported mesoporous MSU-x catalysts for the oxidehydrogenation of ethane to ethylene with carbon dioxide

Two kinds of Cr-based mesoporous materials, Cr incorporated and supported silicate MSU-1, were synthesized at room temperature and characterized with XRD, N₂ adsorption–desorption, FT-IR, DR UV–vis and H₂-TPR techniques. Both Cr-based catalysts exhibited similar mesoporous channels and textural properties. The catalytic performances of two catalysts for the oxidative dehydrogenation of ethane to ethylene with CO₂ were investigated. They both showed high activities, providing 58.0 and 68.1% ethane conversion and 53.4 and 55.6% ethylene yield at 700 °C, respectively. The catalysts were prone to deactivate in the reaction but could be partially regenerated by oxygen. Cr species formed in high oxidation state were reduced during the reaction. It was proposed that these high-valent Cr species were responsible for the high activities of catalysts.