Influence of alkali metal doping on surface properties and catalytic activity/selectivity of CaO catalysts in oxidative coupling of methane

Surface properties （viz. surface area, basicity/base strength distribution, and crystal phases） of alkali metal doped CaO （alkali metal/Ca= 0.1 and 0.4） catalysts and their catalytic activity/selectivity in oxidative coupling of methane （OCM） to higher hydrocarbons at different reaction conditions （viz. temperature, 700 and 750 ℃; CH4/O2 ratio, 4.0 and 8.0 and space velocity, 5140-20550 cm^3 ·g^-1·h^-1） have been investigated. The influence of catalyst calcination temperature on the activity/selectivity has also been investigated. The surface properties （viz. surface area, basicity/base strength distribution） and catalytic activity/selectivity of the alkali metal doped CaO catalysts are strongly influenced by the alkali metal promoter and its concentration in the alkali metal doped CaO catalysts. An addition of alkali metal promoter to CaO results in a large decrease in the surface area but a large increase in the surface basicity （strong basic sites） and the C2＋ selectivity and yield of the catalysts in the OCM process. The activity and selectivity are strongly influenced by the catalyst calcination temperature. No direct relationship between surface basicity and catalytic activity/selectivity has been observed. Among the alkali metal doped CaO catalysts, Na-CaO （Na/Ca = 0.1, before calcination） catalyst （calcined at 750 ℃）, showed best performance （C2＋ selectivity of 68.8% with 24.7% methane conversion）, whereas the poorest performance was shown by the Rb-CaO catalyst in the OCM process.

Molecular dynamics study on growth of carbon dioxide and methane hydrate from a seed crystal

In the current work,molecular dynamics simulation is employed to understand the intrinsic growth of carbon dioxide and methane hydrate starting from a seed crystal of methane and carbon dioxide respectively.This comparison was carried out because it has relevance to the recovery of methane gas from natural gas hydrate reservoirs by simultaneously sequestering a greenhouse gas like CO2.The seed crystal of carbon dioxide and methane hydrate was allowed to grow from a super-saturated mixture of carbon dioxide or methane molecules in water respectively.Two different concentrations(1:6 and 1:8.5)of CO2/CH4 molecules per water molecule were chosen based on gas–water composition in hydrate phase.The molecular level growth as a function of time was investigated by all atomistic molecular dynamics simulation under suitable temperature and pressure range which was well above the hydrate stability zone to ensure significantly faster growth kinetics.The concentration of CO2 molecules in water played a significant role in growth kinetics,and it was observed that maximizing the CO2 concentration in the aqueous phase may not result in faster growth of CO2 hydrate.On the contrary,methane hydrate growth was independent of methane molecule concentration in the aqueous phase.We have validated our results by performing experimental work on carbon dioxide hydrate where it was seen that under conditions appropriate for liquid CO2,the growth for carbon dioxide hydrate was very slow in the beginning.

Oxidation of propane to acrylic acid and acetic acid over alkaline earth-doped Mo-V-Sb-O_x catalysts

Alkaline earth metal （Mg,Ca,Sr and Ba）-doped Mo-V-Sb-O x catalysts,prepared by a dry-up method,have been investigated for their catalytic performance in the oxidation of propane under different reaction conditions.The catalysts have been characterized by N2 adsorption-desorption,temperature-programmed desorption （TPD） of NH3,SEM and XRD.Influence of water vapor on the catalytic performance,particularly on the selectivities to acetic acid and acrylic acid,has also been studied.The selectivity to acrylic acid was improved significantly by the doping of alkaline earth metals to Mo-V-Sb-O x catalysts.The surface acidic sites of the catalyst decreased with the doping of the catalyst with alkaline earth metals,which ultimately was found to be beneficial for obtaining high selectivity to acrylic acid.The catalytic activity and product selectivities were found to be influenced by the reaction temperature,C3H8/O2 ratio and space velocity.A significant improvement in the selectivity to acrylic acid has also been observed by the addition of water vapor in the feed of propane and oxygen in the oxidation of propane.

Oxidative coupling of methane over La-promoted CaO catalysts:Influence of precursors and catalyst preparation method

The oxidative coupling of methane to C2 hydrocarbons has been studied over a series of La-promoted CaO （La/Ca = 0.05） catalysts, prepared using different precursor salts for CaO and La2O3 （viz. acetates, carbonates, nitrates and hydroxides） and catalyst preparation methods （viz. physical mixing of precursors, co-precipitation using ammonium carbonate/sodium carbonate as a precipitating agent）, under different reaction conditions （temperature： 700-850 ℃, CH4/O2 ratio： 4.0 and 8.0, and GHSV： 51360 cm^3·g^-1·h^- 1）. The surface area and surface basicity/base strength distribution of the catalysts have also been investigated. The surface properties and catalytic activity/selectivity of the La-promoted CaO catalysts vary from catalyst to catalyst depending on the catalyst precursors used and catalyst preparation method. The basicity/base strength distribution is strongly influenced by the precursors （for CaO and La2O3） and catalyst preparation method. Basicity （total and strong basic sites measured in terms of CO2 chemisorbed at 50℃ and 500 ℃, respectively） observed for the catalyst prepared by co-precipitation method is higher than that of the catalysts prepared by physical mixing method. The catalysts prepared by the nitrates of La- and Ca- and co- precipitated by the solution of sodium carbonate and ammonium carbonate exhibit different catalytic performance in OCM. The finding that no direct relationship between the surface basicity and catalytic activity/selectivity in OCM exists indicates that basicity is not solely responsible for obtaining high selectivity to C2 hydrocarbons.

Transport of Indium, Gallium and Thallium Metal Ions Through Chromatographic Fiber Supported Solid Membrane in Acetylacetone Containing Mixed Solvents

The transport of metal ions of indium, gallium and thallium from source solution to receiving phase through the chromatographic fiber supported solid membrane in the acetylacetone （HAA） containing mixed solvent system has been explored. The fibers supported solid membranes were prepared with chemical synthesis from cellulose fibers and citric acid with the carboxylic acid ion exchange groups introduced. The experimental variables, such as concentration of metal ions （10^-2 to 10^-4 mol.L^-1） in the source solution, mixed solvent composition [for exampl, e, acetylacetone, （2,4-pentanedione）, （HAA） 20% （by volume）, 1,4-dioxane 10% to 60% and HC1 0.25 to 2 mol.L^-1] in the receiving phase and stirring speed （50-130 r.min ） of the bulk source and receiving phase, were explored. The efficiency of mixed solvents for the transport of metal ions from the source to receiving phase through the fiber supported solid membrane was evaluated. The combined ion exchange solvent extraction （CIESE） was observed effective for the selective transport of thallium, indium and gallium metal ions through fiber supported solid membrane in mixed solvents. The oxonium salt formation in the receiving phase enhances thallium, indium and gallium metal ion transport through solid membrane phase. The selective transport of thallium metal ions from source phase was observed from indium and gallium metal ions in the presence of hydrochloric acid in organic solvents in receiving phase. The separation of thallium metal ions from the binary mixtures of Be（II）, Ti（IV）, AI（III） Ca（II）, Mg（II）, K （I）, La（III） and Y（III） was carried out in the mixed solvent system using cellulose fiber supported solid membrane.

ZnO-beta zeolite:As an effective and eco-friendly heterogeneous catalyst for the synthesis of benzothiazole derivatives

A cheap and recyclable ZnO-beta zeolite was used as catalyst for the synthesis of benzothiazole derivatives.This method provides several advantages such as environmental friendliness,short reaction times,high yields,simple work-up procedure and catalyst was successfully reused for four cycles without significant loss of activity.

Facile Synthesis of Nitriles and Amides from Aldehyde over Heterogeneous Reusable Copper Fluorapatite (CuFAP) Catalyst under Neat Reaction Condition

A new robust heterogeneous, versatile, an environmentally benign, eco-friendly, recyclable CuFAP catalyst has been developed for the direct synthesis of nitriles and amides from aldehydes at 100°C for 6 h and 4 h, respectively, under neat reaction condition using hydroxylamine hydrochloride in the presence and the absence of tosyl chloride, respectively. Also the recyclability of catalyst as well as influence of solvents, additives on catalysts performance was investigated. The protocol can be considered as an alternative to conventional method for the synthesis of nitriles and amides in good to excellent yields. A highlight of our protocol is the easy separation of catalyst from reaction mixture, hence the catalyst is reused several times without significant loss of its catalytic activity.

Highly Efficient Cobalt (II) Catalyzed O-Acylation of Alcohols and Phenols under Solvent-Free Conditions

Solvent free, highly efficient method has been developed using ecofriendly, heterogeneous reusable cobalt chloride catalyst at ambient reaction conditions for the O-acylation of various alcohols and phenols with acetyl chloride in excellent yield in a short reaction time. The catalyst is recycled several times without loss of catalytic activity.

Prediction of coal ash fusion temperatures using computational intelligence based models

In the coal-based combustion and gasification processes, the mineral matter contained in the coal (predominantly oxides), is left as an incombustible residue, termed ash. Commonly, ash deposits are formed on the heat absorbing surfaces of the exposed equipment of the combustion/gasification processes. These deposits lead to the occurrence of slagging or fouling and. consequently, reduced process efficiency. The ash fusion temperatures (AFTs) signify the temperature range over which the ash deposits are formed on the heat absorbing surfaces of the process equipment. Thus, for designing and operating the coal-based processes, it is important to have mathematical models predicting accurately the four types of AFTs namely initial deformation temperature, softening temperature, hemispherical temperature, and flow temperature. Several linear/nonlinear models with varying prediction accuracies and complexities are available for the AFT prediction. Their principal drawback is their applicability to the coals originating from a limited number of geographical regions. Accordingly, this study presents computational intelligenee (CI) based nonlinear models to predict the four AFTs using the oxide composition of the coal ash as the model input. The CI methods used in the modeling are genetic programming (GP), artificial neural networks, and support vector regression. The no table features of this study are that the models with a better AFT prediction and generalization performanee, a wider application potential, and reduced complexity, have been developed. Among the Ci-based models, GP and MLP based models have yielded overall improved performanee in predicting all four AFTs.

Layered Clay-Alginate Composites for the Adsorption of Anionic Dyes: A Biocompatible Solution for Water/Wastewater Treatment

Adsorption properties of layered anionic clay-composites for the removal of anionic dyes from water were studied. The dye adsorption capacities of the composites were higher than the pristine clay. The clay-alginate composite with 5.9% alginate showed highest adsorption for both the dyes. The maximum adsorption capacity of the composite was enhanced by 51% for Acid Green 25 and 160% for Acid Green 27, compared to the pristine layered clay sample. The adsorption isotherm data were fitted to the Langmuir, Freundlich and Temkin isotherm models. The isotherm data could be explained well using the Freundlich isotherm model. Adsorption kinetics was analyzed using normal first order and Lagergren first order kinetic models.

Novel synthesis and characterization of CuO nanomaterials:Biological applications

CuO nanoparticles were synthesized at a relatively low temperature（80 ℃） for 2 h using polyethylene glycol-glycerol mixture which acts as a capping agent.A detailed characterization of the synthesized nanomaterials were performed utilizing X-ray diffraction（XRD）,infra-red spectroscopy（IR）,thermogravimetric analysis（TGA-DTA）,transmission electron microscopy（TEM）,photoluminescence（PL） by studying its crystalline phase,vibrational mode,thermal analysis,morphology and photoluminescence properties.The effect of annealing on the as-prepared nanoparticles were studied and compared with their corresponding bulk counterpart.The synthesized nanoparticles have been screened for in vitro cytotoxicity（1C_（50）） studies against the human cervical adenocarcinoma cell line（HeLa） using WITT assay methods.The as-prepared nanoparticle inhibits the proliferation of this HeLa cell.The standard disc diffusion method has been used to study the antibacterial activity of the samples against the human pathogenic bacteria Escherichia coli（MTCC 729）,Proteus mirabilis（MTCC 425） and Klebsiella pneumoniae subsp.pneumoniae（MTCC 432）.The results have been compared with the positive control antibiotic gentamycin.The synthesized nanoparticles would provide a potential alternative to antibiotics for controlling some of the microorganisms causing urolithiasis.

The capture of carbon dioxide by transition metal aluminates, calcium aluminate, calcium zirconate, calcium silicate and lithium zirconate

The capture of CO_(2) by transition metal(Mn,Ni,Co and Zn)aluminates,calcium aluminate,calcium zirconate,calcium silicate and lithium zirconate was carried out at pre-and post-combustion temperatures.The prepared metal adsorbents were characterized by X-ray diffraction(XRD),scanning electron microscope(SEM),surface area analysis and acidity/alkalinity mea-surements.The different experimental variables affecting the adsorbents ability to capture CO_(2),such as the mol ratio of metal ions,the pressure of CO_(2),the exposure time and the temperature of the adsorbent were also investigated.Calcium zirconate captured 13.85 wt-%CO_(2) at 650℃ and 2.5 atm and calcium silicate captured 14.31 wt-%at 650℃.Molecular sieves(13X)and carbon can only capture a negligible amount of CO_(2) at high temperatures(300℃–650℃).However,the mixed metal oxides captured reasonable amount of CO_(2) at these higher temperatures.In addition,calcium aluminate,calcium zirconate,calcium silicate and lithium zirconate adsorbents captured CO_(2) at both pre and post-combustion temperatures.The trend for the amount of captured carbon dioxide over the adsorbents was calcium aluminate<lithium zirconate<calcium zir-conate<calcium silicate.