Catalytic kinetics of dimethyl ether one-step synthesis over CeO_2–CaO–Pd/HZSM-5 catalyst in sulfur-containing syngas process

CeO_2–CaO–Pd/HZSM-5 catalyst was prepared for the dimethyl ether(DME) one-step synthesis in a continuous fixed-bed micro-reactor from the sulfur-containing syngas. The catalytic stability over hybrid catalyst of CeO_2–CaO–Pd/HZSM-5 was investigated to ensure that the kinetics experimental results were not significantly influenced by induction period and catalytic deactivation. A large number of kinetic data points(40 sets) were obtained over a range of temperature(240–300 °C), pressure(3–4 MPa), gas hourly space velocity(GHSV)(2000–3000 L·kg~(-1)·h~(-1)) and H_2/CO mole ratio(2–3). Kinetic model for the methanol synthesis reaction and the dehydration of methanol were obtained separately according to reaction mechanism and Langmuir–Hinshelwood mechanism. Regression parameters were investigated by the method combining the simplex method and Runge–Kutta method. The model calculations were in appropriate accordance with the experimental data.     

EXPERIMENTAL MEASUREMENT OF SUPERCRITICAL CO_2-LOW VOLATILITY LIQUID PHASE EQUILIBRIA

Extraction equilibria of three low volatility liquids (benzyl alcohol,2-phenethyl alcohol and citronellol)separately with supercritical CO_2 were determined in a semi-flow apparatus at two temperatures(308.2K and318.2K)and pressures up to 20MPa.The solubility data of CO_2 in methyl benzoate were also obtained at thetwo temperatures in two-phase region.The experimental data were correlated by means of the Peng-Robinsonequation of state with two characteristic parameters.     

New process development and process evaluation for capturing CO2 in flue gas from power plants using ionic liquid [emim][Tf2N]

Using the ionic liquid [emim][Tf_2N] as a physical solvent, it was found by Aspen Plus simulation that it was possible to attempt to capture CO_2 from the flue gas discharged from the coal-fired unit of the power plant.Using the combination of model calculation and experimental determination, the density, isostatic heat capacity,viscosity, vapor pressure, thermal conductivity, surface tension and solubility of [emim][Tf_2N] were obtained.Based on the NRTL model, the Henry coefficient and NRTL binary interaction parameters of CO_2 dissolved in[emim][Tf_2N] were obtained by correlating [emim][Tf_2N] with the gas–liquid equilibrium data of CO_2. Firstly,the calculated relevant data is imported into Aspen Plus, and the whole process model of the ionic liquid absorption process is established. Then the absorption process is optimized according to the temperature distribution in the absorption tower to obtain a new absorption process. Finally, the density, constant pressure heat capacity,surface tension, thermal conductivity, and viscosity of [emim][Tf_2N] were changed to investigate the effect of ionic liquid properties on process energy consumption, solvent circulation and heat exchanger design. The results showed that based on the composition of the inlet gas stream to the absorbers, CO_2 with a capture rate of 90% and a mass purity higher than 99.5% was captured. These results indicate that the [emim][Tf_2N] could be used as a physical solvent for CO_2 capture from coal-fired units. In addition, the results will provide a theoretical basis for the design of new ionic liquids for CO_2 capture.     

Ni-Zn/C催化剂上乙醇气相羰基化动力学研究

A novel heterogeneous Ni-Zn/C catalyst was used for vapor-phase carbonylation of ethanol under atmospheric pressure.Experiments were designed with the elimination of mass-transfer resistances.The data of primary reaction in the carbonylation were collected with a differential tubular reactor.Power law rate models were emplyed to express the conversion of ethanol and the yields of ethyl propionated and diethyl ether.The results obtained with the models were in agreement with the experimental data.     

CO2 absorption performance in a rotating disk reactor using DBU-glycerol as solvent

Gas–liquid mass transfer of rotating disk reactor was studied in CO_2 absorption using 1,8-diazabicyclo-[5.4.0]-undec-7-ene(DBU)-glycerol solution as solvent. Effects of the rotating disk structure and various operation parameters on the CO_2 absorption rate and CO_2 removal efficiency were investigated. The rotating disk with optimal holes is conducive to mass transfer of CO_2 and the formation of thin liquid film at the opening increases the gas–liquid contact area. With the increase of rotating speed, the liquid flow pattern on the rotating disk surface changes from thin film flow to separated streams and creates extra liquid lines attached to the rim of the disk,which leads to a very complicated change on the CO_2 absorption rate and CO_2 removal efficiency. The overall gas-phase mass transfer coefficient increases 138% as the rotating speed increasing from 250 to 1400 r·min~(-1).Increasing temperature from 298 to 338 K can enhance the CO_2 absorption rate due to lowering the viscosity of the solvent. The rate-determined step for the absorption is focused on the gas side. The rotating disk reactor can effectively enhance the absorption of CO_2 with viscous DBU-glycerol solvents.     

Measurements and correlation of liquid–liquid equilibrium data for the ternary(methyl tert-butyl ketone + o,m, p-benzenediol + water)system at(333.2, 343.2 and 353.2) K

In this work, liquid–liquid equilibria(LLE) data for the ternary system methyl tert-butyl ketone(MTBK) + o, m,p-benzenediol + water were investigated at 333.2 K, 343.2 K and 353.2 K under 101.3 kPa. The performance of MTBK to extract o, m, p-benzenediol from wastewaters was estimated by partition coefficients and separation factors. The Hand and Bachman equations were both applied to check the reliability of the experimental LLE data. Furthermore, the Non-Random Two-Liquid(NRTL) and Universal Quasi Chemical(UNIQUAC) models were applied to correlate the measured LLE data. The results showed a good agreement with the determined ternary LLE data with the root-mean-square error(RMSE) values below 0.71%. MTBK was proved to be a promising extracting agent in extracting benzenediols from effluents.     

Kinetic contribution of CO2/O2 additive in methane conversion activated by non-equilibrium plasmas

A temperature-controlled and pressure-controlled coaxial dielectric barrier discharge(DBD) reactor was developed to decouple the thermal and kinetic effects of radio frequency(RF) discharge on methane conversion,and further to compare the kinetic behaviors of the mechanistically similar reactions of methane conversion with O_2 and CO_2 additives. A kinetic mechanism for RF plasma assisted methane conversion was assembled. The formation of products in the RF plasma reactor was measured with Gas Chromatography(GC–TCD) and the data were used to validate the kinetic model. The experimental and computational results showed the different kinetic roles of carbon dioxide and oxygen additives in methane conversion, due to the different dissociation and ionization energy of the two additive gases, as well as the thus produced electron energy distribution function(EEDF). Fuel oxidation by plasma generated O, O(~1 D), O_2(a~1Δg), O_2(b~1Σ_g~+) and O+in partial oxidation of methane was observed essential for methane consumption, which resulted in an increase in methane conversion rate,compared to pure methane pyrolysis and dry reforming of methane with CO_2 additive. It was also found that dry reforming of methane with CO_2 was by far the easier to produce the syngas as well as C_2 hydrocarbon species,due to the weak oxidation ability of CO_2 and also the significant deposition of the electron energy on CH_4 dissociation in a dry reforming discharge mixture. This kinetic study produced comparative data to demonstrate the contribution of CO_2/O_2 additive in non-equilibrium plasma assisted methane conversion.     

A robust predictive tool for estimating CO2 solubility in potassium based amino acid salt solutions

The acid gas absorption in four potassium based amino acid salt solutions was predicted using artificial neural network(ANN). Two hundred fifty-five experimental data points for CO_2 absorption in the four potassium based amino acid salt solutions containing potassium lysinate, potassium prolinate, potassium glycinate, and potassium taurate were used in this modeling. Amine salt solution's type, temperature, equilibrium partial pressure of acid gas, the molar concentration of the solution, molecular weight, and the boiling point were considered as inputs to ANN to prognosticate the capacity of amino acid salt solution to absorb acid gas. Regression analysis was employed to assess the performance of the network. Levenberg–Marquardt back-propagation algorithm was used to train the optimal ANN with 5:12:1 architecture. The model findings indicated that the proposed ANN has the capability to predict precisely the absorption of acid gases in various amino acid salt solutions with Mean Square Error(MSE) value of 0.0011, the Average Absolute Relative Deviation(AARD) percent of 5.54%,and the correlation coefficient(R~2) of 0.9828.     

鼓泡塔中低浓度表面活性剂对CO2吸收传质系数的影响（英文）

The effect of different surfactants (n-octyltrimethylammonium bromide (OTABr), sodium dodecyl benzene sulfonate (SDBS) and Tween 80) with different critical micelle concentrations (CMC) on the CO2 absorption into aqueous solutions in a bubble column is analyzed in the present work. The presence of these surfactants in-creased the gas–liquid interfacial area, and decreased the liquid phase mass transfer coefficient, but with signif-icant different extent. The results indicated that the CMC can be a key parameter affecting the mass transfer of CO2 absorption into a dilute aqueous solution of a surfactant. Sardeing's model was used to fit the experimental data successfully by re-correlating the parameters.     

Measurements and thermodynamic modeling of liquid–liquid equilibria in ternary system 2-methoxy-2-methylpropane+p-cresol+water

Liquid–liquid equilibrium(LLE)data for the ternary system 2-methoxy-2-methylpropane(methyl tert-butyl ether)+ p-cresol + water was measured at atmospheric pressure and temperatures of 298.15 K and 313.15 K.From the distribution coefficients and selectivity,it was found that 2-methoxy-2-methylpropane is an efficient solvent to extract p-cresol from wastewater.The consistency of the experimental tie-line data was verified with the Hand and Bachman equations.These data were also correlated with the non-random two liquid(NRTL)and universal quasi-chemical correlation activity coefficient(UNIQUAC)models to yield binary interaction parameters for p-cresol extraction process evaluation.Both models agreed with experiments very well,yet the NRTL model showed even smaller average deviation than the UNIQUAC model.     

常压下二乙二醇单乙醚和水二元体系不同温度下的密度、黏度及过量性质

Densities and viscosities were measured as a function of composition for binary liquid mixture of diethylene glycol monoethyl ether [CH3CH2O(CH2)2O(CH2)2OH] + water from 293.15 to 333.15 K at atmospheric pressure, with a capillary pycnometer and Ubbelohde capillary viscometer respectively. From the experimental data, the excess molar volume VE, viscosity deviation η, and the excess energy of activation for viscous flow G*E were calculated. These data were correlated by the Redlich-Kister type equa-tions to obtain the coefficients and standard deviations. The results showed a strong molecular interaction between diethylene glycol monoethyl ether and water.     

含CaCl2的乙酸2-甲基-1-丁酯溶液饱和蒸汽压的测定及关联

The CaCl2 solubility in 2-methyl-butanol acetate and the vapor pressure of 2-methyl-butanol acetate containing CaCl2 were measured in the range of 90-135°C and from very low salt concentration to saturation.The experimental data were correlated with two equations,a modified Antoine equation with the dissolved salt taken into account and a nonrandom two liquid-electrolyte(e-NRTL)model.Both models are in good agreement with the experimental data.This study provides essential physical data for further investigation of vapor-liquid equilibrium system containing salt.     

Hydrogen sulfide removal by catalytic oxidative absorption method using rotating packed bed reactor

Using catalytic oxidative absorption for H_2S removal is of great interest due to its distinct advantages. However,traditional scrubbing process faces a great limitation in the confined space. Therefore, there is an urgent demand to develop high-efficiency process intensification technology for such a system. In this article, H_2S absorption experimental research was conducted in a rotating packed bed(RPB) reactor with ferric chelate absorbent and a mixture of N_2 and H_2S, which was used to simulate natural gas. The effects of absorbent p H value, gas–liquid ratio, gravity level of RPB, absorption temperature and character of the packing on the desulfurization efficiency were investigated. The results showed that H_2S removal efficiency could reach above 99.6% under the most of the experimental condition and above 99.9% under the optimal condition. A long-time continuous experiment was conducted to investigate the stability of the whole process combining absorption and regeneration. The result showed that the process could well realize simultaneous desulfurization and absorbent regeneration, and the H_2S removal efficiency kept relatively stable in the whole duration of 72 h. It can be clearly seen that high gravity technology desulfurization process, which is simple, high-efficiency, and space intensive, has a good prospect for industrial application of H_2S removal in confined space.     

Mass transfer characteristics in a rotating packed bed with split packing

The rotating packed bed (RPB) with split packing is a novel gas–liquid contactor, which intensifies the mass transfer processes controlled by gas-side resistance. To assess its efficacy, the mass transfer characteristics with adjacent rings in counter-rotation and co-rotation modes in a split packing RPB were studied experimentally. The physical absorption system NH3–H2O was used for characterizing the gas volumetric mass transfer coeffi-cient (kyae) and the effective interfacial area (ae) was determined by chemical absorption in the CO2–NaOH sys-tem. The variation in kyae and ae with the operating conditions is also investigated. The experimental results indicated that kyae and ae for counter-rotation of the adjacent packing rings in the split packing RPB were higher than those for co-rotation, and both counter-rotation and co-rotation of the split packing RPB were superior over conventional RPBs under the similar operating conditions.     

Physicochemical properties of aqueous solutions of sodium glycinate in the non-precipitation regime from 298.15 to 343.15 K

The physicochemical properties, including the density, viscosity, and refractive index of aqueous solutions of sodium glycinate as a solvent for CO2 absorption in the non-precipitation regime were measured under the wide temperature range of 298.15 to 343.15 K. The concentration of the sodium glycinate in an aqueous form in the non-precipitation regime was identified up to 2.0 mol·L?1. The coefficients of thermal expansion values were estimated from measured density data. It was found that, the densities, viscosities and refractive indices of the aqueous sodium glycinate decrease with an increase in temperature, whereas with increasing sodium glycinate concentration in the solution, all three properties increase. Thermal expansion coefficients slightly increase with rising temperature and concentration. The measured values of density, viscosity and refractive index were correlated as a function of temperature by using the least squares method. The predicted data obtained from correlation equations for all measured properties were in fairly good agreement with the experimental data.     

Solvent extraction of lanthanum and cerium ions from hydrochloric acidic aqueous solutions using partly saponified 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester

In order to clarify the extraction process with saponified extractant, the solvent extraction experiments of rare earth elements(REEs), lanthanum and cerium, by using partly saponified 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester(EHEHPA, HL) from hydrochloric acidic solutions have been performed. The concentration of initial aqueous rare earth ion was in a range of 0.0010–0.1000 mol·L~(-1); EHEHPA in a range of 0.2877–0.8631 mol·L~(-1) with saponification rate of 0.3(mole fraction), and the initial aqueous p H in a range of 1.00–4.00. Firstly, the extracted species were determined by the saturation extraction capacity method. Secondly, according to the equilibrium aqueous pH values, the extraction processes were divided into three different categories: extraction with saponified EHEHPA, extraction with un-saponified EHEHPA, and hydrolysis process. Finally, for the first two processes, in order to predict the distribution ratio, two semi-empirical calculation models were developed with.The calculation results are in good agreement well with the experimental data.     

Salt effect on the liquid–liquid equilibrium of the ternary (water + phenol + methyl isobutyl ketone) system: Experimental data and correlation

The effects of NaCl, KCl and Na_2SO_4 on the liquid–liquid equilibrium(LLE) data for the ternary system, water+ phenol + methyl isobutyl ketone, were determined at 0.101 MPa and 333.15 K and 343.15 K.The nonrandom two-liquid(NRTL) model was used to correlate the experimental data and to yield corresponding binary interaction parameters for these salt containing systems.The Hand and Othmer–Tobias equations were used to confirm the dependability of the determined LLE data in this work.Distribution coefficient and selectivity were used to evaluate the extraction performance of methyl isobutyl ketone with the existence of salt.The magnitude of salt effect on the water + phenol + methyl isobutyl ketone(MIBK) system is in the following order: Na_2SO_4NaClKCl.     

Heat of absorption of CO2 in aqueous N,N-diethylethanolamine + N-methyl-1,3-propanediamine solutions at 313 K

Differential heat of absorption of CO_2 in aqueous solutions of N,N-diethylethanolamine(DEEA) and activated DEEA solutions up to a total concentration of 2 mol·L~(-1) was measured as a function of CO_2 loading at 313.15 K using a reaction calorimeter. In order to analyze the performance of N-methyl-1,3-propanediamine(MAPA)as an activator, DEEA blended solutions containing 0.05, 0.1 and 0.2 mol·L~(-1) MAPA were studied. The heat of CO_2 absorption in single DEEA solutions was unaffected by changing the DEEA concentration in the range of(0.5–2) mol·L~(-1). On the other hand, increasing the concentration of MAPA in aqueous amine mixtures of(DEEA + MAPA) raised the heat of absorption.     

An experimental approach for measuring carbon dioxide diffusion coefficient in water and oil under supercritical conditions

Several direct or indirect approaches have been proposed to measure diffusion coefficient of gases into liquids. The main complexity of indirect techniques such as pressure decay method is interpreting early pressure–time data which strongly affected by incubation period effect or convective instability. In the current approach, accurate apparatus and precise experimental setup including a high pressure and temperature PVT cell, a high precision Sanchez pump, heating and recording sub-system are implemented and a novel data analysis procedure is applied to modify pressure decay method. The effect of incubation period is reduced remarkably and diffusion coefficient of carbon dioxide in water in wide range of pressures and temperatures is determined and the effects of temperature, pressure and carbon dioxide phase alteration from gas to supercritical are investigated and the value of uncertainty is estimated.Furthermore, diffusion coefficient of CO_2 and methane in an oil sample from one of the Iranian southwest oil formations is determined precisely using the experimental approach while no incubation period is detected. The results showed that incubation period duration decreases with increasing diffusion coefficient. Additionally, when CO_2 state is gas, rate of increasing diffusion coefficient with pressure is decreased with temperature and when CO_2 state is supercritical, the rate of increasing diffusion coefficient with pressure is decreased significantly.     

甲基二氯硅烷-甲基乙烯基二氯硅烷-甲苯三元体系等压汽液平衡

Vapor-liquid euilibrium (VLE) for a ternary system of Methyldichlorosilane methylvinyldichlorosilane toluene and constituent binary systems were measured at 101.3kPa using a new type of magnetical pump-ebulliometer,The equilibrium conpositions of the vapor phase of binary systems were calculated indirectly from the total pressure-temperature-liquid composition(pTx).The experimental data were correlated with the Wilson and NRTL(non-random two liquid )equations.The parameters of the Wilson moldel were employed to predict the ternary VLE data .The calculated boiling points were in good agreement with the experimental ones.