硫酸-糖蜜酒精废液浸出软锰矿的动力学(英文)

The kinetics of reductive leaching of manganese from low grade pyrolusite in dilute sulfuric acid in the presence of molasses alcohol wastewater was investigated. The shrinking core model was applied to quantify the effects of reaction parameters on leaching rate. The leaching rate increases with reaction temperature, concentrations of H 2 SO 4 and organic matter in molasses alcohol wastewater increase and ore particle size decreases. The leaching process follows the kinetics of a shrinking core model and the apparent activation energy is 57.5 kJ·mol –1 . The experimental results indicate a reaction order of 0.52 for H2SO4 concentration and 0.90 for chemical oxygen demand (COD) of molasses alcohol wastewater. It is concluded that the reductive leaching of pyrolusite with molasses alcohol wastewater is controlled by the diffusion through the ash/inert layer composed of the associated minerals.     

乙醇从葛根中提取黄酮动力学

The kinetics of leaching flavonoids from Pueraria Lobata with ethanol was investigated. The effects of leaching temperature, mechanical agitation rate, concentration of ethanol and feed particle size on leaching kinetics were examined. It is found that the smaller the feed particle size or the higher the leaching temperature, the higher the leaching rate. The leaching process can be described by the shrinking-core model. The apparent activation energy is 10.8kJ·mol^-1, suggesting that the leaching process is controlled by the inner diffusion. An empirical equation relating the flavonoids leaching rate constant to the feed particle size and leaching temperature was expected.     

内部部分润湿催化剂的动力学行为

The global reaction rate of benzene hydrogenation to cyclohexane accompanied by partial internal wetting of catalyst pellets was measured by a new method, which investigated both adsorption and chemical reaction. The adsorption investigation was used to establish a relationship between the extent of liquid filling of the catalyst and the bulk conditions while the chemical reaction investigation was to study the effect of partial internal wetting of the catalyst on the global reaction rate. It was shown that the extent of liquid filling in the catalyst interior showed a significant effect on the global rate, and the current state of the catalyst depended on the history, i.e. whether it was a liquid evaporation process or a vapor condensation process, and two steady states were found under certain circumstances. A mathematical model was developed, which took multicomponent diffusion, chemical reaction, pore size distribution of the catalyst and capillary condensation of condensable components in the catalyst pellet into consideration. The predicted values were in good agreement with the experimental data.     

Reaction kinetics and internal diffusion of Zhundong char gasification with CO2

Mass transfer usually affects the rate of chemical reactions in coal.The effect of internal diffusion on char gasification with CO₂ in the temperature range from 1123 K to 1273 K was investigated via thermo-gravimetric analysis and assessment of char morphology features.The results revealed that the effect of internal diffusion on the initial reaction rate was more significant with an increase of particle size,due to the concentration gradient of the gasification agent within the solid particles.In the early stage of gasification,the generation of new micropores and the opening of closed pores led to an increase in specific surface area.As the reaction proceeded,the openings were gradually expanded and the specific surface area continued to increase.However,with further reaction,disappearance of edge pores,melting and collapse of the pore structure led to a decrease in specific surface area.The intrinsic activation energy and reaction order based on the nth-order model were 157.67 kJ?mol^?1 and 0.36,respectively.Thus,temperature zones corresponding to chemical reaction and diffusion control were identified.Moreover,the calculated effectiveness factor provided a quantitative estimation of internal diffusion in the initial stage.     

煤矸石盐酸浸溶出铝铁的动力学研究（英文）

The extraction of aluminum from coal mining waste (CMW) is an important industrial process. The two major problems in applications are low aluminum dissolution efficiency and high iron content in the raw material, which affect the quantity and quality of products. To improve the aluminum recovery process, the leaching kinet-ics of CMW with hydrochloric acid was studied. A shrinking core model was used to investigate aluminum and iron dissolution kinetics. Based on the kinetic characteristics, a process for recovering aluminum was proposed and tested experimental y. It is found that the aluminum leaching reaction is controlled by surface reaction at low temperatures (40–80 °C) and by diffusion process at higher temperatures (90–106 °C). The iron dissolution process is dominated by surface reaction at 40–100 °C. The results show that iron could be dissolved or separated by concentrated hydrochloric acid. Fine grinding wil improve aluminum dissolution significantly.     

An investigation on dissolution kinetics of single sodium carbonate particle with image analysis method

Dissolution kinetics of sodium carbonate is investigated with the image analysis method at the approach of single particle. The dissolution experiments are carried out in an aqueous solution under a series of controlled temper-ature and pH. The selected sodium carbonate particles are al spherical with the same mass and diameter. The dissolution process is quantified with the measurement of particle diameter from dissolution images. The concentration of dissolved sodium carbonate in solvent is calculated with the measured diameter of particle. Both surface reaction model and mass transport model are implemented to determine the dissolution mecha-nism and quantify the dissolution rate constant at each experimental condition. According to the fitting results with both two models, it is clarified that the dissolution process at the increasing temperature is controlled by the mass transport of dissolved sodium carbonate travelling from particle surface into solvent. The dissolution process at the increasing pH is control ed by the chemical reaction on particle surface. Furthermore, the dissolution rate constant for each single spherical sodium carbonate particle is quantified and the results show that the disso-lution rate constant of single spherical sodium carbonate increases significantly with the rising of temperature, but decreases with the increasing of pH conversely.     

热辅助紫外光催化氧化方法用于总磷检测的实验研究和动力学分析(英文)

A novel thermal-assisted ultra-violet (UV) photocatalysis digestion method for the determination of total phos-phorus (TP) in water samples was introduced in this work. The photocatalytic experiments for TP digestion were conducted using a 365 nm wavelength UV light and TiO2 particles as the photocatalyst. Sodium tripolyphosphate and sodium glycerophosphate were used as the typical components of TP and the digested samples were then determined by spectrophotometry after phosphomolybdenum blue reaction. The effects of operational parameters such as reaction time and temperature were studied for the digestion of TP and the kinetic analysis of two typical components was performed in this paper. The pseudo-first-order rate constants k of two phosphorus compounds at different temperatures were obtained and the Arrhenius equation was employed to explain the effect of temperature on rate constant k. Compared with the conventional thermal digestion method for TP detection, it was found that the temperature was decreased from 120 °C to 60 °C with same conversion rate and time in this thermal-assisted UV digestion method, which enabled the digestion process work at normal pressure. Compared with the individual ultra-violet (UV) photocatalysis process, the digestion time was also decreased from several hours to half an hour using the thermal-assisted UV digestion method. This method wil not lead to secondary pol ution since no oxidant was needed in the thermal-assisted UV photocatalysis digestion process, which made it more compatible with electrochemical detection of TP.     

Sulfation Kinetics in the Preparation of Cellulose Sulfate

In the established apparatus, the converaion ratios of cellaloee sulfation (X) under dif-ferent salfation conditlons were measured. The range of temperature was from -5℃ to 5℃, and the H2SO4 concentration was from 3.1 mol.L^-1 to 4.5 mol.L^-1. The experimental results were used for the establishment of the kinetic model for cellulose sulfation. With the model, X values and the yield of NaCS (Y) can be calculated, thus the reaction with respect to H2SO4 concentration is determined to be third order.     

氢气还原氧化铁动力学的研究(英文)

Kinetics parameters of iron oxide reduction by hydrogen were evaluated by the isothermal method in a differential micro-packed bed.Influence of external diffusion,internal diffusion and heat transfer on the intrinsic reaction rate was investigated and the conditions free of internal and external diffusion resistance have been deter-mined.In the experiments,in order to correctly evaluate the intrinsic kinetics parameters for reducing Fe2O3 to Fe3O4,the reaction temperatures were set between 440 °C and 490 °C.However,in order to distinguish the reduc-tion of Fe3O4 to FeO from that of FeO to Fe,the reaction temperature in the experiment was set to be greater than 570 °C.Intrinsic kinetics of iron oxide reduction by hydrogen was established and the newly established kinetic models were validated by the experimental data.     

惰性粒子喷动床中制备超细碳酸钙的实验与建模

A novel reaction-drying process was carried out in a spouted bed reactor with inert particles and used to prepare ultrafine CaCO3 particles. Effects of concentrations of CO2 and Ca(OH)2, and reaction temperature on Ca(OH)2 conversion were experimentally investigated. The particle sizes and composition of CaCO3 produced were characterized with transmission electron microscopy (TEM) and X-ray diffraction (XRD). The results indicated that ultrafine CaCO3 particles with mean size of 80 nm could be obtained with this novel process.By modifying the Arrhenius Equation and considering the Ca(OH)2 state, a kinetic model was established to describe the process in the spouted bed. The model parameters estimated from the reaction-drying experiments were found to fit well the experimental data, indicating the applicability of the proposed kinetic model.     

一种利用脱氮硫杆菌的同步脱硫反硝化新工艺研究

Thiobacillus denitrificans, a kind of autotrophic facultative bacteria, can oxidize sulfide into elemental sulfur or sulfate when nitrate was adopted as its electron accepter and carbon dioxide as its carbon resource under anoxic or anaerobic environment. In this way, nitrate is converted into nitrogen. In addition, ThiobaciWus denitrificans can accumulate sulfur extracellularly. In this study, in a process of simultaneous desulfurization and denitrification, a strain of Thiobacillus denitriificans is employed as sulfur-producer in the treatment of wastewater containing sulfide and nitrate. The key factors affecting this process are investigated through batch tests. The experimental results indicate that the sulfide concentration and the ratio of sulfide to nitrate (S2-/NO3-) in the influent are the key factors, and their suitable values are suggested to be 5/3 and no more than 300mg·L-1, respectively, in order to achieve high conversion of sulfur.     

超临界反溶剂过程制备槲皮素超细颗粒

Supercritical antisolvent (SAS) process is a recently developed technology to produce micro- and nanoparticles. This paper presents a continuous apparatus to conduct experiment of SAS process. With the apparatus,the effects of pressure, temperature and flow ratio of CO2 to the solution on the shape and size of particles are studied for the quercetin-ethanol-CO2 system. Spherical quercetin microparticles with diameters ranging form i μm to 6μm can be obtained while ethanol is used as organic solvent. The most effective fact on the shape and size of particles is pressure, the next is temperature and the last is the flow ratio of CO2 to solution.     

聚醚与含氢硅油的硅氢加成反应的动力学研究

The hydrosilylation of polyhydrosiloxane and unsaturated allylic polyether terminated with ester group is processed with chloroplatinic acid as catalyst and ethyl acetate as solvent to exclude the mass transfer resistance in the system. The kinetic study is performed by means of Gel Permeation Chromatography. Within the experimental range （mass ratio of the whole reactants to solvent is 1：4, the tool ratio of Si-H bond to carbon-carbon double bond is 1： 1.3, the catalyst concentration from 1.0×10^-4mol·L^-1 （Pt） to 3.1×10^-4mol·L^-1 （Pt）, temperature between 338.15K and 350.35K）, a kinetic model of zero-th order reaction is built up and the evaluated model parameters are found to change linearly with the catalyst concentration.     

SEBS三嵌段共聚物膜的形态研究

Surface morphologies of the films of poly [styrene-b-（ethylene-co-butene）-b-styrene] （SEBS） have been studied by using tapping-mode atomic force microscopy （TM-AFM）. The films of block copolymer were prepared both by spin-coating on mica and by solvent-casting on different solution surfaces. For spin-coating samples, the effect of solution concentration, solvent, and annealing temperature are investigated. It is shown that changing the concentration of the solution makes no difference on the morphology of the film of the block copolymer. The microstructures are quite stable during thermal annealing; only the size of the domains changes toward the equilibrium configuration. However, solvent annealing can notably change the microstructures. When different selective solvents are used for film spin-coating, different morphologies can be obtained and explained by the different solubility parameters of the solvents. As expected, significant different morphologies in the top and the bottom surfaces of the casting films were observed. The images of the top surfaces reveal cylinder microdomains, while those of the bottom surfaces were spherical morphologies.     

N-异丙基丙烯酰胺凝胶在NaCl水溶液中溶胀行为的预测研究

In this paper, a model is presented to correlate and predict the swelling behavior of hydrogels in aqueous solutions of electrolytes. The model is a combination of VERS-model, “phantom network“ theory and “free-volume“ contribution. The VERS-model is used to calculate Gibbs excess energy; “phantom network“ theory to describe the elastic properties of polymer network, and “free-volume“ contribution to account for additional difference in the size of the species. To test the model, a series of N-isopropylacrylamide based hydrogels are synthesized by free radical polymerization in oxygen-free, deionized water at 25~C under nitrogen atmosphere. Then, the degree of swelling of all investigated gels as well as the partition of the solute between the gel phase and the surrounding coexisting liquid phase are measured in aqueous solution of sodium chloride. The model test demonstrates that the swelling behavior correlated and predicted by the model agrees with the experimental data within the experimental uncertainty. The phase transition appeared in the experiment, and the influences of the total mass fraction of polymerizable materials ξgel as well as the mole fraction of the crosslinking agent YCR on the swelling behavior of IPAAm-gels can also be predicted correctly. All these show the potential of such model for correlation and prediction of the swelling behavior of hydrogels in aqueous solutions of electrolytes.     

载体对镍催化剂催化间二硝基苯加氢制间苯二胺反应性能的影响

The hydrogenation of m-dinitrobenzene to m-phenylenediamine in liquid phase was studied with the nickel catalysts supported on SiO2, TiO2, γ-Al2O3, MgO and diatomite carders. Based on the experiments of X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, temperature-programmed reduction （TPR）, temperature-programmed desorption of hydrogen （H2-TPD） and activity evaluation, the physico-chemical and catalytic properties of the catalysts were investigated. Among the catalysts tested, the SiO2 supported nickel catalyst showed the highest activity and selectivity towards m-phenylenediamine, over which 97.3% m-dinitrobenzene conversion and 95.1% m-phenylenediamine yield were obtained at 373K under hydrogen pressure of 2.6MPa after reaction for 6 h when using ethanol as solvent. Although TiO2 and diatomite supported nickel catalysts also presented high activity, they had lower selectivity towards m-phenylenediamine. As for γ-Al2O3 and MgO supported catalysts were almost inactive for the object reaction. It was shown that both the activity and selectivity of the catalysts were strongly depended on the interaction between nickel and the support. The higher activities of Ni/SiO2, Ni/TiO2 and Ni/diatomite could be attributed to the weaker metal-support interaction, on which Ni species presented as crystallized Ni metal particles. On the other hand, there existed strong metal-support interaction in Ni/MgO and Ni γ-Al2O3, which causes these catalysts more difficult to be reduced and the availability of Ni active sites decreased, resulting in their low catalytic activity.     

空间质量作用模型预测小分子离子交换平衡

The steric mass-action (SMA) model has been widely reported in the literature for ion-exchange and metal-affinity interaction adsorption equilibrium of biomacromolecules. In this paper, the usefulness of SMA model is analyzed for describing micromolecule ion-exchange equilibrium onto cation exchangers, CM Sephadex C-25 and Streamline SP. Batch adsorption experiments with ephedrine hydrochloride as a model adsorbate are carried out to determine the model parameters, that is, steric factor, characteristic charge and equilibrium constant. The result shows that the SMA model parameters of micromolecule cannot be obtained using the nonlinear least-square fitting method as protein‘s due to the remarkable difference between the molecular mass and dimension of micromolecule and protein. It is considered that the small size of the adsorbates dealt with in this study justifies the neglect of steric hindrances arising from adsorbate bulkiness. Thus, the three-parameter SMA model is reduced to two-parameter one (i.e., steric factor is equal to zero) for describing micromolecule ion-exchange equilibrium. It is found that the equilibrium constant for CM Sephadex C-25 increases with increasing ionic strength, while the equilibrium constant for Streamline SP shows an opposite trend. This is probably due to the remarkable difference between the physicalpro perties of the two adsorbents. Then, the relationship between the equilibrium constant and ionic strength is described by an expression. The computer simulations show that, the theoretical model with the correlation is promising in the prediction of micromolecule adsorption decrease with increasing ionic strength in a wide range of salt concentration.     

天然气超声波旋流脱水装置的工作性能

A new type of dehydration unit for natural gas was briefly described and its basic structure and working principles were presented. An indoor test rig for testing the unit performance was set up and the experimental results were given. The results showed that the unit could attain a maximum dew point depression of about 20~C without any need of external mechanical power and chemicals. The pressure loss ratio, shock wave and the flow rate had great influence on the dehydration characteristics. From the systematic analysis of the factors that affect the dehydration efficiency of the unit, the suggestions for improving the unit are put forward.     

电化学还原硝基甲烷合成N-甲基羟胺盐酸盐的工业化试验

An industrial electrolytic cell was designed for the electrochemical synthesis of N-methylhydroxylamine hydrochloride （N-MHA）. Copper was used as the cathode, graphite as the anode, and a cation membrane as the separator. The results show that N-MHA with a high purity of 99% can be electrosynthesized directly from nitromethane in HC1 solution. Under a constant current of 1000-2500A.m^-2 in the temperature of 30-50℃, the average yield, current efficiency, and reaction selectivity were 65%, 70%, and 99%, respectively. Graphite electrode and membrane material can be used continuously in the preparative electrolysis for 5000h. Moreover, the effects of the electrode and membrane materials, current intensity, electrolyte temperature, and other associated parameters on the electrosynthesis results were investigated. The direct current power consumption was 8151.3kW-h-（1000kg N-MHA）^ -1. This method is a simple separation process with limited contamination and hence, is a new green synthesis method for the industrial production of N-MHA.     

胞外高分子物质对基质在复合生物膜内传质速率影响的测定

A model, for evaluating the effect of porosity and volume fraction of extracellular polymeric substances (EPS) within multispecies biofilms on the effective diffusivity, is developed and experimentally validated, based on the extraction of EPS from intact biofilms. The amount of EPS in biofilms significantly affects the effective diffusivity. For biofilms with porosity of 77%—95% in the top layers and 54%—58% in the bottom layers, the value of De/Dw decreases from 0.52—0.83 in the top layers to 0.23—0.31 in the bottom layers. Generally, the effective diffusivity in the heterotrophic/autotrophic biofilms is slightly lower than that in the heterotrophic biofilms, due to the lower porosity in the heterotrophic/autotrophic biofilms.