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.     

Measurement and correlation of solubility of trimethylolethane in different pure solvents and binary mixtures

The solubilities of trimethylolethane in butanol,methyl acetate,ethyl acetate as well as in mixed solvents of (methanol + ethyl acetate) and (ethanol + ethyl acetate) were measured with the gravimetTic method in the temperature range from 283.15 K to 318.15 K under atmosphere pressure.The experiment results showed that the solubility of trimethylolethane increased with the temperature,or along with the concentration of methanol or ethanol in the solvents of (methanol + ethyl acetate) and (ethanol + ethyl acetate).In addition,the experiment values were correlated by the van't Hoffequation,Modified Apelblat Equation,λh Equation,CNIBS/R-K equation and Jouyban-Acree Model.The Modified Apelblat Equation provided the best fitting results of the solubility data of TME in the pure solvents while the CNIBS/R-K model showed the best estimation of the solubility in the binary solvent mixtures.Furthermore,the density functional theory (DFT) calculations showed that solubility in different solvents related to the strength of the interaction between the trimethylolethane and the solvent molecules.Finally,the standard molar enthalpy and molar entropy of trimethylolethane during the dissolving process was also calculated by Modified Apelblat equation in this work.     

Batch Extractive Distillation in a Column with a Middle Vessel

Batch extractive distillation was studied in a column with a middle vessel. The process was simulated by a constant holdup model and solved by two point implicit method. Acetone and methanol mixture was separated in such a setup using water as solvent. The simulation agrees well with experimental results. The experimental and simulation results show that the solvent at the bottom and the product at the top of the column can be withdrawn simultaneously for a long period of time. It needs more time for the solvent to reach high purity than that required for the more volatile component to reach high purity, so that the time to withdraw solvent from the bottom is delayed.     

1,6-二磷酸果糖三钠盐·8H2O结晶新方法的研究

In order to overcome the elementary heterogeneous nucleation while octahydro trisodium salt of fructose-1,6-diphosphate(FDPNa3 8H2O) is crystallized with ethanol precipitation at low temperature, a new crystallization method with alcohol precipitation combined with salt precipitation has been presented. The ethanol-sodium acetate system for crystallization of salt of fructose-1,6-diphosphate is based on the mechanism of crystallization of FDPNa3 8H2O in the ethanol-low temperature system. It is found that crystal size may be controlled by regulating temperature or pH value of solution in the crystallization process, and the crystal yield increases to 95% from 78% which obtained in the ethanol-low temperature system.     

乙酸乙酯与CnH2n+1OH（n=1,2,3）双系统在0.3MPa下的气液平衡（英文）

Vapor-liquid equilibrium data for the binary systems of ethyl acetate + methanol,ethyl acetate + ethanol and ethyl acetate + 1-propanol at 0.3 MPa were determined.The experimental data were verified with the point-to-point test of van Ness(1973).All these systems present an azeotropic point at 0.3 MPa that increases in ester composition for longer alcohol chains.The UNIFAC in different versions and ASOG prediction models were applied.     

关于CO2有机溶剂体系液相体积膨胀的研究

The supercritical antisolvent （SAS） process has been developed in recent years for the tormation of nanoand micro-particles. It is necessary to study the liquid phase volume expansion （LPVE） and find the relationships between the operating conditions and the LPVE in order to develop a practical method for determining the operation conditions and selecting an organic solvent for SAS process. The PR equation of state with vdW-1 mixing rule is used to calculate the LPVE for CO2/toluene, CO2/acetone and CO2/ethyl acetate systems, and the results show that the LPVE for each CO2/organic solvent system decreases as the temperature increases. The relationship between the LPVE and the solubility of CO2 in the liquid phase for CO2/organic solvent systems is investigated, and the results show that the LPVE is determined directly by the solubility of CO2 in the liquid phase, xCO2, and can be related to xCO2 independently. No matter what system of CO2/organic solvent is and how different the temperature is, the LPVEs have little difference as long as the solubility of CO2 in the liquid phase, xCO2, keeps constant. The lower temperature is always favorable to the SAS process. The higher the solubility of CO2 in an organic solvent under certain operation condition, the more suitable it is to the SAS process.     

Catalytic ozonation of volatile organic compounds (ethyl acetate) at normal temperature

Catalytic treatments of VOCs at normal temperature can greatly reduce the cost and temperature of processing, and improve the safety factor in line with the requirements of green chemistry. Activated carbon fiber(ACF) was pretreated with 10% H_2SO_4 by single factor optimization to increase specific surface area and pore volume obviously. The catalytic ozonation performance of ACF loaded with Au, Ag, Pt and Pd noble metals on ethyl acetate was investigated and Pd/ACF was selected as the optimal catalyst which had certain stability. Pd is uniformly distributed on the surface of ACF, and Palladium mainly exists in the form of Pd~0 with a amount of Pd~(+2). The specific surface area of the catalysts gradually decreases as the loading increases. The activation energy of ethyl acetate calculated by Arrhenius equation is 113 kJ·mol~(-1). With 1% Pd loading and the concentration ratio of ozone to ethyl acetate is 3:1, catalytic ozonation performance is maximized and the conversion rate of ethyl acetate reached to 60% in 30–50 ℃ at 15,000–30,000 h~(-1).     

含离子液体溴化1-丙基-3-甲基咪唑的二元和三元体系的蒸气压测定

Vapor pressure values of binary systems water ＋ ethanol, water ＋ ionic liquid 1-propyl-3- methylimidazolium bromide （[PMIM] [Br]）, ethanol ＋ [PMIM] [Br] and ternary system water ＋ ethanol ＋ [PMIM] [Br] at different temperatures were measured by using a modified boiling point method in various concentrations of （16.66%, 33.7%）, （17.4%, 33.9%） and （16.5%, 32%） mass percent of ionic liquid, respectively. The experimental vapor pressures of solvent were well correlated by the Antoine-type equation, and the overall average absolute deviation （AAD） was found to be 0.39%. The experimental results for mixtures containing ionic liquid indicate that the vapor pressure of the solvents can be decreased noticeably to different extent due to the affinity difference between ionic liquid and solvent, which is similar to the salt effect of common inorganic salts. As a result, ionic liquid may find industrial applications in extractive distillations for the system with a low separation factor or even for an azeotropic mixture.     

(S)-(+)-2,2-二甲基环丙烷甲酰胺在不同溶剂中溶解度的测定与关联

（S）-（＋）-2,2-dimethylcyclopropane carbox amide is a key intermediate of Cilastatin, an inhibitor of dehydropeptidase-I. Its corresponding solid-liquid equilibrium data will provide essential support for industrial design and further theoretical studies. The solubilities of （S）-（＋）-2,2-dimethylcyclopropane carbox amide in toluene, dichloromethane, trichloromethane, ethyl acetate, ethanol and pure water at different temperature were measured using the synthetic method by a laser monitoring observation technique. The solubility data were correlated with the modified Apelblat equation.The calculated values were good in agreement with the experimental values.     

Determination and correlation solubility of m-phenylenediamine in (methanol,ethanol, acetonitrile and water) and their binary solvents from 278.15 K to 313.15 K

In this study, the solubility of m-phenylenediamine in four pure solvents(methanol, ethanol, acetonitrile and water) and three binary solvent(methanol + water),(ethanol + water) and(acetonitrile + water) systems were determined in the temperature ranging from 278.15 K to 313.15 K by using the gravimetric method under atmospheric pressure. In the temperature range of 278.15 K to 313.15 K, the mole fraction solubility values of m-phenylenediamine in water, methanol, ethanol, and acetonitrile are 0.0093–0.1533, 0.1668–0.5589,0.1072–0.5356, and 0.1717–0.6438, respectively. At constant temperature and solvent composition, the mole fraction solubility of o-phenylenediamine in four pure solvents was increased as the following order:water b ethanol b methanol b acetonitrile; and in the three binary solvent mixtures could be ranked as follows:(ethanol + water) b(methanol + water) b(acetonitrile + water). The relationship between the experimental temperature and the solubility of m-phenylenediamine was revealed as follows: the solubility of mphenylenediamine in pure and binary solvents could be increased with the increase of temperature. The experimental values were correlated with the Jouyban–Acree model, van't Hoff–Jouyban–Acree model, modified Apelblat–Jouyban–Acree model, Sun model and Ma model. The standard dissolution enthalpy, standard dissolution entropy and the Gibbs energy were calculated based on the experimental solubility data. In the binary solvent mixtures, the dissolution of m-phenylenediamine could be an endothermic process. The solubility data,correlation equations and thermodynamic property obtained from this study would be invoked as basic data and models regarding the purification and crystallization process of m-phenylenediamine.     

D-樟脑-10-磺酸拆分西布曲明及其中间产物的研究

以D-樟脑-10-磺酸与西布曲明作为起始原料,用D-樟脑-10-磺酸拆分西布曲明.西布曲明与D-樟脑-10-磺酸在乙酸乙酯中成盐后,得到非对映异构体盐.通过红外、核磁对中间产物进行表征,证实中间产物为未见报道化合物.纯化后用饱和Na2CO,溶液处理,用乙醚溶解,旋转蒸发之后得到左旋西布曲明,拆分收率23.6%.     

乙醇-乙酸乙酯体系的间歇萃取精馏研究

在常规的间歇萃取精馏实验装置中,研究了以N,N-二甲基酰胺(DMF)和二甲亚砜(DMSO)作萃取剂;在间歇萃取精馏塔中分离乙醇-乙酸乙酯体系的过程。对全回流时间、不同萃取剂、恒沸物组成、溶剂和混合物的体积比、加盐及加碱等因素考察,分析萃取精馏分离乙醇-乙酸乙酯共沸体系的影响,从而得出最佳的萃取条件。     

Synthesis of R-(+)-α-lipoic acid

以6,8-二氯辛酸为原料,S-(-)-α-苯乙胺为拆分剂进行拆分反应得到R-(+)-6,8-二氯辛酸;经酯化制得R-(+)-6,8-二氯辛酸乙酯;后经硫化水解一步合成R-(+)-α-硫辛酸。考察了投料比、溶剂、催化剂、温度等条件对产物收率、比旋光度的影响。结果表明：拆分反应较佳条件为n[S-(-)-α-苯乙胺]∶n（6,8-二氯辛酸）=0.45∶1,溶剂为乙酸乙酯;酯化反应较佳条件为催化剂为对甲苯磺酸,反应时间7 h;硫化反应较佳条件为温度为65 ℃;相转移催化剂用量0.4 g,总收率为44.3%。通过红外光谱、比旋光度、核磁共振等对产物和中间产物进行了表征。     

(R,S)-酮基布洛芬的拆分研究

以N-辛基-D-葡糖胺为拆分剂,研究了(R,S)-酮基布洛芬的拆分及碱解,以及(R)酮基布洛芬的消旋;单轮拆分率达40%。     

右旋酮洛芬的生产工艺进展

酮洛芬是一种非甾类抗炎药。介绍了生产酮洛芬单一对映体常用的动力学拆分法及该工艺过程存在的不足。指出了单一控制酶的细胞膜反应器的工艺技术更为经济,得到的对映异构体纯度高,产率大于50%。综述了当前右旋酮洛芬的不同生产工艺及存在的问题,并提出相应的整改措施。     

减压渣油在常压乙酸乙酯脱沥青溶解度研究

采用实验方法确定了减压渣油、乙酸乙酯的溶解度参数随温度的变化规律,关联出一个适用于低温下减压渣油在乙酸乙酯溶剂中的溶解公式,揭示了减压渣油在常压溶剂乙酸乙酯中的溶解度参数与萃取温度的规律,建立了萃取温度与摩尔分数之间关系,为进一步的减压渣油在常压溶剂脱沥青过程的研究提供了一定的数据基础。     

R-(+)-α-硫辛酸的合成工艺

以6,8-二氯辛酸为原料,S-(-)-α-苯乙胺为拆分剂进行拆分反应得到R-(+)-6,8-二氯辛酸;经酯化制得R-(+)-6,8-二氯辛酸乙酯;后经硫化水解一步合成R-(+)-α-硫辛酸。考察了投料比、溶剂、催化剂、温度等条件对产物收率、比旋光度的影响。结果表明:拆分反应较佳条件为n[S-(-)-α-苯乙胺]∶n(6,8-二氯辛酸)=0.45∶1,溶剂为乙酸乙酯;酯化反应较佳条件为催化剂为对甲苯磺酸,反应时间7 h;硫化反应较佳条件为温度为65℃;相转移催化剂用量0.4 g,总收率为44.3%。通过红外光谱、比旋光度、核磁共振等对产物和中间产物进行了表征。     

有机溶剂萃取加拿大油砂应用研究

介绍了溶剂作为萃取剂分离油砂的技术,溶剂萃取油砂过程包含两个阶段:沥青相向溶剂的溶解过程和沥青、溶剂与砂粒的分离过程。考察了单一溶剂甲苯、丙酮、乙酸乙酯和甲苯/正庚烷、丙酮/正庚烷、乙酸乙酯/正庚烷组成的复合溶剂体系在相同条件下对油砂沥青的萃取率,在此基础上进一步对比了不同溶剂体系对沥青四组分饱和分、芳香分、胶质和沥青质的萃取效果,同时考察了不同浓度的沥青-溶剂溶液的表面张力,结果表明在油砂萃取过程中沥青-溶剂体系的表面张力主要取决于所选溶剂的种类,而沥青的浓度对溶液表面张力的影响不大。混合溶剂体系甲苯/正庚烷、丙酮/正庚烷、乙酸乙酯/正庚烷相比纯溶剂萃取率较高,其沥青溶液表面张力较低,是良好的分离油砂溶剂体系。     

Measurement,Correlation and Thermodynamics of Solubility of 2,6‐Diamino‐3,5‐Dinitropyrazine‐1‐Oxide (LLM‐105) in Eight Solvents

The solubility of insensitive explosive 2,6‐diamino‐3,5‐dinitropyrazine‐1‐oxide (LLM‐105) in dimethyl sulphoxide (DMSO), N,N‐dimethylformamide (DMF), N‐methyl‐2‐pyrrolidone (NMP), N,N‐diethylformamide (DEF), 1,4‐dioxane, 1,4‐butyrolactone, ethyl acetate and 1‐butyl‐3‐methylimidazolium trifluoromethanesulfonate ([Bmim]CF₃SO₃), were measured by a polythermal method in the temperature range of 293.15 K to 375.15 K at the atmospheric pressure. The solubility of LLM‐105 decreased in the order of DMSO, NMP, DMF, DEF, 1,4‐butyrolactone, [Bmim]CF₃SO₃, 1,4‐dioxane, ethyl acetate. With higher temperature, the solubility of LLM‐105 increased in all solvents. The solubility data was correlated against temperature with the modified Apelblat equation and Ideal solution model. In addition, the dissolution enthalpy, entropy, and mole Gibbs free energy of LLM‐105 in each solvent were also calculated from the experimental solubility data by using van′t Hoff equation with the temperature dependence. The results show that the dissolution process of LLM‐105 in these solvents is endothermic and the mechanism is the entropy‐driving. DMSO is suggested as the appropriate solvent for the cooling crystallization or drowning‐out crystallization of LLM‐105.     

废聚苯乙烯泡沫塑料胶粘剂的制备与性能分析

以废PS(聚苯乙烯)泡沫塑料为主要原料,乙酸乙酯、甲苯、丙酮和四氯化碳为混合溶剂,制备溶剂型PS胶粘剂。采用单因素试验法和正交试验法探讨了PS含量、低毒性混合溶剂的选择及配比等对PS胶粘剂性能的影响。研究结果表明:当V(四氯化碳)∶V(乙酸乙酯)∶V(甲苯)∶V(丙酮)=1∶8∶3∶2或2∶4∶3∶4时,相应溶剂型PS胶粘剂的综合性能优于市售白乳胶;该PS胶粘剂对木材、铁片、玻璃和塑料的剪切强度依次为4.8、4.0、3.0、1.0 MPa,并且其制备工艺简单,不产生二次污染,具有良好的应用前景。