Catalytic conversion of chloromethane to methanol and dimethyl ether over mesoporous γ-alumina

Mesoporous γ-alumina, mp-γ-Al₂O₃, possessing surface area around 385 m²/g and total pore volume of 2.0 cm³/g was prepared via template-free sol-gel synthesis. The catalytic activity of the prepared alumina for the conversion of chloromethane to dimethyl ether, DME, in the presence of water or methanol was studied in the temperature range of 170-450 °C employing FTIR spectroscopy. In the absence of water and methanol, the fresh surface of mp-γ-Al₂O₃ showed 100% conversion of chloromethane to DME at temperatures between 250 and 350 °C. However, rapid deactivation of the catalyst resulted in a sharp decrease in the conversion to < 5% within a few minutes of reaction. The catalytic activity was noticeably enhanced by adding water vapor to the gas feed resulting in higher conversions to DME and methanol. The catalytic activity and DME selectivity were further enhanced in the presence of methanol instead of water. In the temperature range of 200-300 °C, complete conversions were obtained at the beginning of reactions before they declined to values between 31 and 45% depending on the reaction temperature. It was proposed that the surface hydroxyl groups are the active sites where chloromethane molecules dissociatively adsorb forming adsorbed methoxy ion intermediates. The adsorption of molecular methanol regenerates the surface hydroxyl groups and enhances the formation of adsorbed methoxy ions on the surface which react further with chloromethane or methanol molecules to produce more DME.     

Catalytic dehydration of methanol to dimethyl ether over modified γ-Al2O3 catalyst

A γ-Al₂O₃ catalyst was modified with metal oxide (Nb₂O₅) in order to improve its activity and stability for dimethyl ether (DME) synthesis from methanol. A series of modified γ-Al₂O₃ catalysts were prepared with Nb₂O₅ and characterized by X-ray diffraction and temperature programmed desorption of ammonia. Results showed that the γ-Al₂O₃ catalyst containing 10 wt.% of Nb₂O₅ exhibited the highest surface area among the modified ones. The number of acid sites of the modified catalysts was increased by the Nb₂O₅ modification. In the chemical reaction of DME synthesis, it was found that the Nb₂O₅ modified γ-Al₂O₃ catalyst exhibited a higher activity in the low temperature region (240 °C-260 °C) and a higher activity than did the untreated γ-Al₂O₃ catalyst.     

Investigation of different precipitating agents effects on performance of γ-Al2O3 nanocatalysts for methanol dehydration to dimethyl ether

This research includes synthesis of nano-sized γ-Al₂O₃ catalyst for methanol dehydration reaction to produce DME. A co-precipitation method with four precipitants including sodium carbonate, sodium bicarbonate, ammonium carbonate and ammonium bicarbonate was used for this purpose. The catalysts were characterized by XRD, FTIR, NH₃-TPD, SEM, TEM and N₂ adsorption–desorption techniques. In order to investigate the catalyst activity, they were used in the fixed bed micro reactor for methanol dehydration reaction at different operating conditions. Also, a commercial γ-Al₂O₃ nanocatalyst was utilized for comparison purposes. The catalyst prepared by ammonium carbonate showed the highest yield of DME in comparison with other ones.     

From laboratory experiments to simulation studies of methanol dehydration to produce dimethyl ether reaction—Part II: Simulation and cost estimation

The vapor phase dimethyl ether (DME) synthesis is simulated by Hysys process simulation software and relevant cost analysis is also conducted. Based on cost estimation results, it is found that capital investment of the classic DME process is greatly influenced by the distillation towers and operating costs. Accordingly, to solve these problems an innovative DME process based on a top-wall dividing-wall column (DWC) in vapor phase is proposed, in this work. It is shown that the novel proposed DWC process leads to 44.53% reduction in operating costs compared to the conventional one, while both schemes predict almost the same output specifications.     

From laboratory experiments to simulation studies of methanol dehydration to produce dimethyl ether—Part I: Reaction kinetic study

Most of the reaction rate equations for methanol dehydration are derived from the experiments conducted for crude methanol as feed and laboratory prepared catalysts, which are not exactly the same as industrial reactors conditions. In the present contribution, it is attempted to find suitable rate of reactions for pure methanol with no water as feed and commercial catalysts of HZSM-5 and γ-alumina at industrial conditions in methanol dehydration process. In addition, a comparison between the performances of the catalysts is performed. It is found that HZSM-5 has superior performances compared to the γ-alumina in terms of conversion. Modeling results are also indicated that the proposed rate of reaction predicts the behavior of the process, properly.     

Influence of Gas Phase Reactions on DME-SCR over γ-alumina

Abstract  

Above 300 °C, gas phase reactions occur between dimethyl ether (DME), NO and O₂ generating NO₂. The influence of these reactions on DME-SCR was studied in a setup that decoupled the occurrence of gas phase reactions from catalyst temperature. NO_x conversion decreased at 350 °C and increased at 250 °C due to less DME available and higher NCO conversion with NO₂, respectively.     

Study of the deactivation and regeneration of copper chromite on γ-alumina and magnesium chromite on γ-alumina catalysts for fuel combustion

The causes of the deactivation of catalysts for fuel combustion MeCr₂O₄/ -Al₂O₃ (Me = Cu or Mg) have been investigated using a variety of complex physical-chemical methods: IRS, ESDR, XPS, TPD and a pulse microcatalytic method. It has been concluded that the observed deactivation of catalysts during fuel combustion is due to the combined effect of high temperatures and reduction media.     

Fluorinated γ-alumina aerogels and xerogels: characterisation and catalytic behaviour

The porosity of -alumina-based materials is an important parameter affecting the extent of fluorination (aerogels > commercial -Al₂O₃ > xerogels) and, consequently, also the textural, acidic and catalytic properties of the final fluorinated materials. Only the highly fiuorinated aluminas having strong Lewis acidic sites catalyse the isomerisation of CHF₂CHF₂ to CF₃CH₂F.     

Alkylation of phenol with anisole over zeolites or γ-alumina

The reaction of phenol with anisole was carried out over three X-, six Y-, a ZSM-5 and a ZSM-11 zeolites, and over γ-Al₂O₃, in a fixed-bed continuous reactor. Alkylation products were cresols (o>p>m), xylenols and methylanisoles; also some dealkylation of anisole to phenol occurred. Selectivity to cresols and xylenols in the range 45–60% and 25–30%, respectively, at anisole conversions of around 90%, were reached with HY and HNaY zeolites, and with γ-Al₂O₃, when operating over fresh catalysts. Alkylations were particularly ortho-selective over γ-Al₂O₃.     

Liquid phase catalytic dehydration of glycerol to acrolein over Brønsted acidic ionic liquid catalysts

Liquid phase dehydration of glycerol to acrolein catalyzed by Brønsted acidic ionic liquids (BAILs) using semi-batch reaction technique was investigated. For the BAILs catalysts, the acrolein yields were in an order of [Bmim]H₂PO₄ > [Bmim]HSO₄ > [BPy]HSO₄ > [PSPy]HSO₄ > [N₂₂₂₄]HSO₄ > [PSPy]H₂PO₄ > [BPy]H₂PO₄ > [N₂₂₂₄]H₂PO₄. When [Bmim]H₂PO₄ and [Bmim]HSO₄ were used as the catalysts at 270 °C with the molar ratio of catalyst to glycerol of 1:100, the acrolein yields were 57.4% and 50.8%, respectively, at complete conversion of glycerol. The BAILs with [Bmim] cation and moderate acidity favored the formation of acrolein in liquid phase glycerol dehydration.     

Effects of particle size on catalytic conversion of ethanol to propylene over H-ZSM-5 catalysts—Smaller is better

In this study, H-ZSM-5 catalysts with different particle sizes were prepared by adding different amount of water to the starting gel before crystallization. These H-ZSM-5 catalysts were characterized by scanning electron microscopy, N₂ adsorption/desorption measurements, X-ray fluorescence, X-ray diffraction, and temperature programmed desorption of ammonia. It was found that the olefin (ethylene, propylene and butene) yield decreased with the increase in the particle size of the catalysts. The paraffin (ethane, propane and butane) yield trended to increase with the increase of particle size. The C₅ + products yield increased considerably with the increase of particle size. The results implied that the formation of the C₅ + products and hydrogen was inhibited over the smaller particle size catalyst, furthermore the formation of paraffin decreased. So the propylene yield could be increased over smaller H-ZSM-5 catalyst.     

Binary vapour—liquid equilibria of methanol with sulfolane. Tetraethylene glycol dimethyl ether and 18-crown-6

The activity coefficients of methanol in sulfolane, tetraethylene glycol dimethyl ether (TEGDME) and 18-crown-6 under conditions of equilibrium have been determined in the temperature range 423–503 K and in the pressure range 0.28–3.5 MPa. A minimum in the activity coefficient was found for the methanol—TEGDME and methanol—18-crown-6 solutions.     

Steam reforming of dimethyl ether over Cu–Ni/γ-Al2O3 bi-functional catalyst：Effect of calcination temperature

采用沉积-沉淀法制备了一系列不同焙烧温度的二甲醚水蒸气重整制氢催化剂2Cu-1Ni/5g-Al₂O₃（摩尔比）,考察了焙烧温度对催化剂2Cu-1Ni/5g-Al₂O₃的结构及催化性能的影响,并运用N₂吸附-脱附（BET）、H₂程序升温还原（H₂-TPR）、X射线衍射（XRD）等手段对催化剂进行了表征与分析。结果表明,500 ℃焙烧的催化剂BET比表面积及孔容、孔径适中。随着焙烧温度的升高,以尖晶石态存在的铜组分比例逐渐增加,金属Cu的粒径也从12.6 nm增至33.2 nm。适当的焙烧温度可保证金属和载体之间的强度适中的作用力,从而保证催化剂具有较优的活性和稳定性。催化剂活性随着焙烧温度的增加先升高后减小,较优的焙烧温度为500 ℃。     

Effects of imidazolium-based ionic liquids on the isobaric vapor–liquid equilibria of methanol + dimethyl carbonate azeotropic systems

The separation of methanol(MeOH) and dimethyl carbonate(DMC) is important but difficult due to the formation of an azeotropic mixture. In this work, isobaric vapor–liquid equilibrium(VLE) data for the ternary systems containing different imidazolium–based ionic liquids(ILs), i.e. MeOH + DMC + 1-butyl-3-methy-limidazolium bis[(trifluoromethyl)sulfonyl]imide([Bmim][Tf_2N]), MeOH + DMC + 1-ethyl-3-methyl-imidazolium bis[(trifluoromethyl)sulfonyl]imide([Emim][Tf_2N]), and MeOH + DMC + 1-ethyl-3-methylimidazolium hexafluorophosphate([Emim][PF6])) were measured at 101.3 kPa. The mole fraction of IL was varied from0.05 to 0.20. The experimental data were correlated with the NRTL and Wilson equations, respectively. The results show that imidazolium-based ILs were beneficial to improve the relative volatility of MeOH to DMC,and [Bmim][Tf_2 N] showed a much more excellent performance on the activity coefficient of MeOH. The interaction energies of system components were calculated using Gaussian program, and the effects of cation and anion on the separation coefficient of the azeotropic system were discussed.     

Supercritical antisolvent processing of γ-Indomethacin: Effects of solvent, concentration, pressure and temperature on SAS processed Indomethacin

γ-Indomethacin (IMC) is successfully processed with the supercritical antisolvent (SAS) technique. Pure, acicular (needle-like) particles of the α-polymorph are consistently obtained with SAS as the solvent, concentration, temperature and pressures are varied. Controlled changes in process parameters yield significant changes in particle size. Enhanced dissolution profiles are observed with IMC processed with SAS as opposed to the unprocessed IMC. The reduced particle size, as well as the α-polymorphic form of IMC, contributes to the enhanced dissolution rate.     

Effects of various rare-earth additives on the sintering and transmittance of γ-AlON

Several rare earth elements (Sc, La, Pr, Sm, Gd, Dy, Er, and Yb) were evaluated to develop a sintering additive for transparent γ-AlON. After adding 0.2 wt. % of each of the rare earth additives to the α-Al₂O₃ and AlN starting material, hot pressing was performed at 1850 °C for 1 h under 20 MPa as a screening test, whereby the γ-AlON with Pr-nitrate showed the highest transmittance of 60.4 % at 632 nm. Two-step pressureless sintering was conducted as a separate test for the same starting material after adjusting the amount of Pr-nitrate to 0, 0.1, or 0.2 wt. % to enhance transmittance. The γ-AlON with 0.1 wt. % Pr-nitrate showed the highest transmittance of 80.36 % after 1st and 2nd sintering steps at 1610 and 1940 °C, respectively, indicating that Pr can be an alternative sintering additive to conventional Y₂O₃, MgO, and La₂O₃ for the fabrication of transparent γ-AlON.     

The structure of vanadium oxide species on γ-alumina; an in situ X-ray absorption study during catalytic oxidation

The mechanism of catalytic oxidation reactions was studied using in situ X-ray absorption spectroscopy (XAFS) over a 17.5 wt% V₂O⁵/Al₂O₃ catalyst, i.e., at reaction temperatures and in the presence of reactants. It was found that X-ray absorption near-edge structure (XANES) is a powerful tool to study changes in the local environment and the oxidation state of the vanadium centres during catalytic oxidation. At 623 K, the catalyst follows the associative mechanism in CO oxidation. XAFS revealed that the Mars–van Krevelen mechanism is operative at 723 K for CO oxidation. The extended X-ray absorption fine structure (EXAFS) results showed that the structure of the supported V₂O⁵ phase consists of monomeric tetrahedral (Al–O)₃–V=O units after dehydration in air at 623 K. However, the residuals of the EXAFS analysis indicate that an extra contribution has to be accounted for. This contribution probably consists of polymeric vanadate species. The structure remains unchanged during steady-state CO oxidation at 623 and 723 K. Furthermore, when oxygen was removed from the feed at 623 K, no changes in the spectra occurred. However, when oxygen is removed from the feed at 723 K, reduction of the vanadium species was observed, i.e., the vanadyl oxygen atom is removed. The V³⁺ ion subsequently migrates into the γ-Al₂O₃ lattice, where it is positioned at an Al³⁺ octahedral position. This migration process appears to be reversible; so the (Al–O)₃–V=O units are thus restored by re-oxidation. This revised version was published online in June 2006 with corrections to the Cover Date.     

Effects of boron and fluorine modified γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> with tailored surface acidity on catalytic ethanol dehydration to ethylene

The effect of boron and fluorine modified γ-Al₂O₃ was investigated during ethanol dehydration to ethylene. The conventional and modified γ-Al₂O₃ were prepared by a sol–gel method and characterized by various techniques. The results showed that boron modified γ-Al₂O₃ possessed decreased amount of Lewis acid sites by increasing the boron content. Fluorine modified γ-Al₂O₃ created new Brönsted acid sites with increasing the fluorine content, which resulted in the coexistence of Brönsted and Lewis acid sites, at the same time, strong acid sites appeared. Boron modified γ-Al₂O₃ catalyst (Al-B1) at 340 °C exhibited excellent catalytic stability and good selectivity for ethanol conversion to ethylene. The improvement in the catalytic stability could be attributed to the lower acidity after boron modification. The results indicated that on γ-Al₂O₃ catalyst, strong acid sites especially Brönsted acid sites were responsible for coking deactivation and unfavorable to ethanol dehydration to ethylene.     

Effects of α- and γ-tocopherols on the autooxidation of purified sunflower triacylglycerols

The antioxidant effects of α- and γ-tocopherols were evaluated in a model system based on the autooxidation of purified sunflower oil (p-SFO) triacylglycerols at 55°C for 7 d. Both tocopherols were found to cause more than 90% reduction in peroxide value when present at concentrations >20 ppm. α-Tocopherol was a better antioxidant than γ-tocopherol at concentrations ≤40 ppm but a worse antioxidant at concentrations >200 ppm. Neither α- nor γ-tocopherol showed a prooxidant effect at concentrations as high as 2000 ppm. The amount of tocopherols consumed during the course of oxidation was positively correlated to the initial concentration of tocopherols, and the correlation was stronger for α- than for γ-tocopherol. This correlation suggested that, besides reactions with peroxyl radicals, destruction of tocopherols may be attributed to unknown side reactions. Addition of FeSO₄, as a prooxidant, caused a 12% increase in the peroxide value of p-SFO in the absence of tocopherols. When tocopherols were added together with FeSO₄, some increase in peroxide value was observed for samples containing 200, 600 or 1000 ppm of α- but not γ-tocopherol. The addition of FeSO₄, however, caused an increase in the amount of α- and γ-tocopherols destroyed and led to stronger positive correlations between the amount of tocopherols destroyed during oxidation and initial concentration of tocopherols. No synergistic or antagonistic interaction was observed when α- and γ-tocopherols were added together to autooxidizing p-SFO.