Effects of specific surface area of metallic nickel particles on carbon deposition kinetics

Carbon deposition on nickel powders in methane involves three stages in different reaction temperature ranges. Temperature programing oxidation test and Raman spectrum results indicated the formation of complex and ordered carbon structures at high deposition temperatures. The values of I（D）/I（G） of the deposited carbon reached 1.86, 1.30, and 1.22 in the first, second, and third stages, respectively. The structure of carbon in the second stage was similar to that in the third stage. Carbon deposited in the first stage rarely contained homogeneous pyrolytic deposit layers. A kinetic model was developed to analyze the carbon deposition behavior in the first stage. The rate-determining step of the first stage is supposed to be interfacial reaction. Based on the investigation of carbon deposition kinetics on nickel powders from different resources, carbon deposition rate is suggested to have a linear relation with the square of specific surface area of nickel particles.

Study of the gas sources of the Ordovician gas reservoir in the Central-Eastern Ordos Basin

The source of the natural gas in the Lower Paleozoic Ordovician strata in the Ordos Basin,China is a controversial issue.In the present study,the genesis and distribution characteristics of the Ordovician natural gas were qualitatively investigated based on the composition of the natural gas and the hydrocarbon isotopic composition.Then,the kinetics of the carbon isotope were analyzed to determine the proportions of the gas in the Ordovician gas reservoir contributed from the Carboniferous-Permian and Ordovician strata.The results show the following.Compared to the Upper Paleozoic natural gas,the Ordovician natural gas has a large dryness coefficient.In core areas where gypsum-salt rocks are developed,the gypsum-salt rocks completely isolate the gas sources.The weathering crust of the reservoir in the fifth member of the Majiagou Formation(Ma_(5)^(1+2))originates primarily from the Upper Paleozoic coal-measure source rocks,while the Ma_(5)^(5)and the pre-salt natural gas are mainly derived from the Ordovician source rocks.In the areas where the gypsum-salt rocks are relatively well-developed,the gypsum-salt rocks isolate the gas source to some extent,the pre-salt gas reservoir is mainly derived from the Lower Paleozoic source rocks,and this contribution gradually increases with increasing depth.In the areas where the gypsum-salt rocks are not developed,the proportion of the contribution of the Upper and Lower Paleozoic source rocks to the gas source of the Ordovician gas reservoir is mainly controlled by the volume of gas generated and the other accumulation conditions,and it does not reflect the isolation effect of the gypsum-salt rocks on the gas source.The Ordovician natural gas accumulation models in the central-eastern Ordos Basin can be divided into four types according to the differences in the gas sources.

Simulation Experiments on the Reaction of CH_4-CaSO_4 and Its Carbon Kinetic Isotope Fractionation

Thermochemical sulfate reduction (TSR) in geological deposits can account for the accumulation of H2S in deep sour gas reservoirs. In this paper, thermal simulation experiments on the reaction of CH4-CaSO4 were carried out using an autoclave at high temperatures and high pressures. The products were characterized with analytical methods including carbon isotope analysis. It is found that the reaction can proceed to produce H2S, H2O and CaCO3 as the main products. Based on the experimental results, the carbon kinetic isotope fractionation was investigated, and the value of Ki (kinetic isotope effect) was calculated. The results obtained in this paper can provide useful information to explain the occurrence of H2S in deep carbonate gas reservoirs.

Removal of diclofenac from aqueous solution with multi-walled carbon nanotubes modified by nitric acid

Modified multi-walled carbon nanotubes(MWCNTs) were used as adsorbents for removal of diclofenac. The reaction conditions were examined. Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich isotherm models were applied to determine appropriate equilibrium expression. The results show that the experimental data fit the Freundlich equation well. Thermodynamic parameters show that the adsorption process is spontaneous and exothermic. The kinetic study indicates that the adsorption of diclofenac can be well described with the pseudo-second-order kinetic model and the process is controlled by multiple steps.

Adsorption of acid and basic dyes by sludge-based activated carbon:Isotherm and kinetic studies

A batch experiment was conducted to investigate the adsorption of an acid dye(Acid Orange 51) and a basic dye(Safranine) from aqueous solutions by the sludge-based activated carbon(SBAC). The results show that the adsorption of Acid Orange 51 decreases at high p H values, whereas the uptake of Safranine is higher in neutral and alkaline solutions than that in acidic conditions. The adsorption time needed for Safranine to reach equilibrium is shorter than that for Acid Orange 51. The uptakes of the dyes both increase with temperature increasing, indicating that the adsorption process of the dyes onto SBAC is endothermic. The equilibrium data of the dyes are both best represented by the Redlich-Peterson model. At 25 °C, the maximum adsorption capacities of SBAC for Acid Orange 51 and Safranine are 248.70 mg/g and 525.84 mg/g, respectively. The Elovich model is found to best describe the adsorption process of both dyes, indicating that the rate-limiting step involves the chemisorption. It can be concluded that SBAC is a promising material for the removal of Acid Orange 51 and Safranine from aqueous solutions.

Recovery of carbon monoxide from flue gases by reactive absorption in ionic liquid imidazolium chlorocuprate(I): Mass transfer coefficients

Recovery of carbon monoxide from flue gases by selective absorption of carbon monoxide in an imidazolium chlorocuprate（l） ionic liquid is considered in this work as an alternative to the use of molecular volatile solvents such as aromatic hydrocarbons. The present work evaluates the CO mass transfer rates from the gas phase to the ionic liquid solutions in the absence of chemical reaction. To that end, carbon dioxide was employed as an inert model gas and absorption experiments were performed to assess the influence of different process variables in a batch reactor with fiat gas-liquid interface. The experimental mass transfer coefficients showed significant var- iation with temperature, （3.4-10.9） × 10^-7 m·s^-1 between 293 and 313 K; stirring speed, （10.2- 33.1）× 10^-7 m.s 1 between 100 and 300 r·min^-1; and concentration of copper（1）, （6.6-10.2） × 10^-7 m·s^-1 between 0.25 and 2 mol· L^- 1. In addition, the mass transfer coefficients were eventually found to follow a poten- tial proportionality of the type kL ∝μ^-0.5 and the dimensionless correlation that makes the estimation of the mass transfer coefficients possible in the studied range of process variables was obtained： Sh=10^-2.64 Re^1.07 , Sc^0.75,These results constitute the first step in the kinetic analysis of the reaction between CO and imidazolium chlorocuprate（I） ionic liquid that determines the design of the separation units.

Experimental Design Technique on Removal of Hydrogen Sulfide using CaO-eggshells Dispersed onto Palm Kernel Shell Activated Carbon：Experiment,Optimization,Equilibrium and Kinetic Studies

This study presents the use of chicken eggshells waste utilizing palm kernel shell based activated carbon（PKSAC） through the modification of their surface to enhance the adsorption capacity of H2S. Response surface methodology technique was used to optimize the process conditions and they were found to be： 500 mg/L for H2S initial concentration, 540 min for contact time and 1 g for adsorbent mass. The impacts of three arrangement factors（calcination temperature of impregnated activated carbon（IAC）, the calcium solution concentration and contact time of calcination） on the H2S removal efficiency and impregnated AC yield were investigated. Both responses IAC yield（IACY, %） and removal efficiency（RE, %） were maximized to optimize the IAC preparation conditions. The optimum preparation conditions for IACY and RE were found as follows： calcination temperature of IAC of 880 ℃, calcium solution concentration of 49.3% and calcination contact time of 57.6 min, which resulted in 35.8% of IACY and 98.2% RE. In addition, the equilibrium and kinetics of the process were investigated. The adsorbent was characterized using TGA, XRD, FTIR, SEM/EDX, and BET. The maximum monolayer adsorption capacity was found to be 543.47 mg/g. The results recommended that the composite of PKSAC and Ca O could be a useful material for H2S containing wastewater treatment.

Morphology of Oxide Scale and Oxidation Kinetics of Low Carbon Steel

The oxidation kinetics and composition of oxide scales on low carbon steel （SPHC） were studied during i- sothermal oxidation. Thermogravimetric analyzer （TGA） was used to simulate isothermal oxidation process of SPHC for 240 min under air condition, and the temperature range was from 500 to 900 ℃. Scanning electron microscope （SEM） was used to observe cross-sectional scale morphology and analyze composition distribution of oxide scales. The morphology of oxide scale was classical three-layer structure. Fe2 03 developed as whiskers at the outermost lay- er, and interlayer was perforated-plate Fe3 04 while innermost layer was pyramidal FeO. From the oxidation curves, the oxidation mass gain per unit area with time was of parabolic relation and oxidation rate slowed down. On the ba- sis of experimental data, the isothermal oxidation kinetics model was derived and oxidation activation energy of SPHC steel was 127. 416 kJ/mol calculated from kinetics data.

Effect of thickness on the photophysics and charge carrier kinetics of graphitic carbon nitride nanoflakes

We investigated the thickness effect on the photophysics and charge carrier kinetics of graphitic carbon nitride nanoflakes （g-CNN） by using ultraviolet visible diffuse reflectance spectroscopy, atomic force microscopy, femtosecond transient absorption spectroscopy, and picosecond time-correlated single photon counting measurement. For the first time, we found that g-CNN displays a layer-dependent indirect bandgap and layer-dependent charge carrier kinetics.

Removal of perfluorinated surfactants from wastewater by adsorption and ion exchange--Influence of material properties,sorption mechanism and modeling

Perfluorooctane sulfonate（PFOS） has attracted increasing concern in recent years due to its world-wide distribution, persistence, bioaccumulation and potential toxicity. The influence of sorbent properties on the adsorptive elimination of PFOS from wastewater by activated carbons, polymer adsorbents and anion exchange resins was investigated with regard to their isotherms and kinetics. The batch and column tests were combined with physicochemical characterization methods, e.g., N2 physisorption, mercury porosimetry, infrared spectroscopy, differential scanning calorimetry, titrations, as well as modeling. Sorption kinetics was successfully modelled applying the linear driving force（LDF） approach for surface diffusion after introducing a load dependency of the mass transfer coefficient βs.The big difference in the initial mass transfer coefficient βs,0, when non-functionalized adsorbents and ion-exchange resins are compared, suggests that the presence of functional groups impedes the intraparticle mass transport. The more functional groups a resin possesses and the longer the alkyl moieties are the bigger is the decrease in sorption rate.But the selectivity for PFOS sorption is increasing when the character of the functional groups becomes more hydrophobic. Accordingly, ion exchange and hydrophobic interaction were found to be involved in the sorption processes on resins, while PFOS is only physisorptively bound to activated carbons and polymer adsorbents. In agreement with the different adsorption mechanisms, resins possess higher total sorption capacities than adsorbents. Hence, the latter ones are rendered more effective in PFOS elimination at concentrations in the low μg/L range, due to a less pronounced convex curvature of the sorption isotherm in this concentration range.

Evolution of Al2O3 inclusions by cerium treatment in low carbon high manganese steel

The influence of cerium（Ce）treatment on the morphologies,size and distributions of Al_2O_3 inclusions in low carbon high manganese steel was investigated by OM,SEM-EDS and theoretical calculation.The results showed that Ce can modify the morphologies and types of Al_2O_3 inclusions.After Ce treatment,the irregular Al_2O_3 inclusions were replaced by smaller and dispersive spherical cerium oxysulfides.The effects of treatment time and Ce content on the evolution of Al_2O_3 inclusions were examined.It indicated that Al_2O_3 inclusions were wrapped by rare earth inclusions to form a ring like shape Ce-enriched band around the inclusions.Model was established to elucidate the evolution mechanism of Al_2O_3 inclusions.Evolution kinetics of inclusions was discussed qualitatively to analyze the velocity controlled step.It was found that diffusion of Ce^（3＋）and Al^（3＋）in solid inclusion core and the formed intermediate layer would be the limited step during the evolution process.

Adsorption of chlorophenols from aqueous solutions by pristine and surface functionalized single-walled carbon nanotubes

The adsorption of six kinds of chlorophenols on pristine, hydroxylated and carboxylated single-walled carbon nanotubes（SWCNTs） has been investigated. Pseudo-first order and pseudo-second order models were used to describe the kinetic data. All adsorption isotherms were well fitted with Langmuir, Freundlich and Polanyi–Manes models, due to surface adsorption dominating the adsorption process. The close linear relationship between log Kowand log Kdsuggested that hydrophobicity played an important role in the adsorption. The SWCNTs＇ adsorption capacity for chlorophenols was weakened by addition of oxygen-containing functional groups on the surface, due to the loss of specific surface area, the increase of hydrophilicity and the reduction of π–π interaction. The best adsorption capacity of pristine SWCNTs, SWCNT-OH and SWCNT-COOH for six chlorophenols varied from 19 to 84 mg/g, from 19 to 65 mg/g and from 17 to 65 mg/g,respectively. The effect of pH on the adsorption of 2,6-dichlorophenol（2,6-DCP）, was also studied. When p H is over the pK aof 2,6-dichlorophenol（2,6-DCP）, its removal dropped sharply. When ionic strength increased（Na Cl or KCl concentration from 0 to 0.02 mmol/L）,the adsorption capacity of 2,6-DCP on pristine SWCNTs decreased slightly. The comparison of chlorophenols adsorption by SWCNTs, MWCNTs and PAC was made, indicating that the adsorption rate of CNTs was much faster than that of PAC. The results provide useful information about the feasibility of SWCNTs as an adsorbent to remove chlorophenols from aqueous solutions.

Mechanism of Methylene Blue adsorption on hybrid laponite-multi-walled carbon nanotube particles

The kinetics of adsorption and parameters of equilibrium adsorption of Methylene Blue（MB）on hybrid laponite-multi-walled carbon nanotube（NT）particles in aqueous suspensions were determined.The laponite platelets were used in order to facilitate disaggregation of NTs in aqueous suspensions and enhance the adsorption capacity of hybrid particles for MB.Experiments were performed at room temperature（298 K）,and the laponite/NT ratio（Xl）was varied in the range of 0–0.5.For elucidation of the mechanism of MB adsorption on hybrid particles,the electrical conductivity of the system as well as the electrokinetic potential of laponite-NT hybrid particles were measured.Three different stages in the kinetics of adsorption of MB on the surface of NTs or hybrid laponite-NT particles were discovered to be a fast initial stage Ⅰ（adsorption time t=0–10 min）,a slower intermediate stage Ⅱ（up to t=120 min）and a long-lasting final stage Ⅲ（up to t=24 hr）.The presence of these stages was explained accounting for different types of interactions between MB and adsorbent particles,as well as for the changes in the structure of aggregates of NT particles and the long-range processes of restructuring of laponite platelets on the surface of NTs.The analysis of experimental data on specific surface area versus the value of Xl evidenced in favor of the model with linear contacts between rigid laponite platelets and NTs.It was also concluded that electrostatic interactions control the first stage of adsorption at low MB concentrations.

Gas Generation from Coal and Coal-Measure Mudstone Source Rocks of the Xujiahe Formation in the Western Sichuan Depression,Sichuan Basin

The Triassic and Jurassic tight sandstone gas in the western Sichuan depression,Sichuan Basin has attracted much attention in recent years,and the Upper Triassic coal-bearing Xujiahe Formation is believed to be the major source rock.However,there are relatively few studies on the carbon isotopic heterogeneity of methane generated from coal-measure source rocks and the origin of the natural gases in Xinchang Gas Field is still controversial.In this study,one coal-measure mudstone sample and one coal sample of the Xujiahe Formation in western Sichuan Basin were selected for gold tube pyrolysis experiment to determine their gas generation characteristics.Geological extrapolation of gas generation and methane carbon isotope fractionation parameters reveals that the main gas generation stage of Xujiahe Formation ranges from Late Jurassic to Cretaceous in the Xinchang Gas Field.The natural gas in the 5th member of Xujiahe Formation in Xinchang Gas Field is mainly derived from the 5th member of Xujiahe Formation itself,i.e.,self-generation and self-reservoir,however,the gas in the Jurassic gas pools is mainly derived from the source rocks of the 3rd member of Xujiahe Formation rather than the 5th member of Xujiahe Formation.