Concentration of mixed acid by electrodialysis for the intensification of absorption process in acrylic acid production

The absorption process in acrylic acid production was water-intensive. The concentration of acrylic acid before distillation process was low, which induced to large amount of wastewater and enormous energy consumption.In this work, a new method was proposed to concentrate the side stream of absorption column and thus increase the concentration in bottom product by electrodialysis. The influence of operating conditions on concentration rate and specific energy consumption were investigated by a laboratory-scale device. When the voltage drop was 1 V·cP~(-1)(1 cP=10~(-3) Pa·s), flow velocity was 3 cm·s~(-1) and the temperature was 35 °C, the concentration rates of acrylic acid and acetic acid could be 203.3% and 156.6% in the continual-ED process. Based on the experimental data, the absorption process combined with ED was simulated, in which the diluted solution from ED process was used as spray water and the concentrated solution was feed back to the absorption column. The results shown that the flow rate of spray water was decreased by 37.1%, and the acrylic acid concentration at the bottom of the tower was increased by 4.56%. The ions exchange membranes before and after use 1200 h were tested by membrane surface morphology(scanning electron microscope), membrane chemical groups(infrared spectra), ion exchange capacity, and membrane area resistance, which indicated the membrane were stable in the acid system. This method provides new method for energy conservation and emission reduction in the traditional chemical industry.     

Desulfurization of gasoline by condensation of thiophenes with formaldehyde in a biphasic system using aqueous phase of acids

Aqueous phase of acids as catalysts for the desulfurization of gasoline by condensation of thiophenes with formaldehyde in a biphasic system was investigated. Two types of model gasoline with and without aromatics and olefins were employed in this work. The desulfurization rates were above 90% on these two types of model gasoline using formic acid and H_3PW_(12)O_(40)(0.8 mol·L~(-1)), indicating that the presence of aromatics and olefins has no effect on the desulfurization rate. High temperature(above 90 °C) was more favorable to the process for desulfurization. Four hours was considered to be the proper treating time for the sulfur removal. In addition,aqueous phase of acids could be recycled at least 4 times without decreasing desulfurization rate. Finally, the possible process for the integration of condensation desulfurization into the existing refinery process for the production of gasoline with low sulfur content was proposed.     

活性白土对模拟油脂中β-胡萝卜素和叶绿素的吸附动力学研究

The textural properties of acid-activated bentonite (AAB), which were prepared using four different concentrations of sulfuric acid, were analyzed by adsorption-desorption isotherm of nitrogen using an automated specific surface area and porosity analyzer. The total pore volume, specific surface area and average pore diameter of these four kinds of AAB show a regular changing trend, increasing first and then decreasing, the optimum of which can be achieved at a sulfuric acid concentration of 25% (sample A25). The kinetic analysis of the adsorption ofβ-carotene and chlorophyll in model oil solutions, namely, xylene and edible oil solution, has been investigated by using AAB. Experimental results indicated that the adsorption data fit the pseudo-second-order model well. The whole adsorption process of the two pigments on AAB was divided basically into two parts the initial adsorption of pigments was rapid in the first 10 min, followed by a slower adsorption process till equilibrium was attained at 60 min. In addition, the amount and rate of adsorption on A25 increase synchronously with the initial pigment concen-tration and temperature. The results showed that the adsorption kinetics behavior of AAB with respect to the pig- ments is not influence by the xylene and edible oil solution.     

Experimental and Theoretical Studies on Desulfurization Efficiency of Dual-alkali FGD System in a RST Scrubber

The effects of operating parameters on desulfurization efficiency of a dual-alkali FGD process in a rotating-stream-tray (RST) scrubber are investigated. A dimensionless factor, e, is proposed in this study to predict desulfurization efficiency of this dual-alkali FGD system. e represents the desulfurization ability of a dual alkali FGD system, determined by five main operating parameters such as sodium ion concentration, ratio of absorbent flow rate to flue gas flow rate, pH value of absorbent solution, ratio of sulfate ion to total sulfur ion in absorbent solution, and sulfur dioxide concentration of inlet flue gas. The empirical expression for predicting desulfurization efficiency at different temperatures is obtained through the experimental study and theoretical calculation. It provides useful guide for engineering design.     

Measurement and Correlation of Liquid–Liquid Equilibrium Data for Ethanol–Water–KF and Ethanol–Water–K2CO3 Systems

The liquid–liquid equilibrium data for two ternary systems, ethanol–water–KF and ethanol– water–K2CO3, were determined at 25℃. Experiments show that by adding KF or K2CO3 into the ethanol–water system two phases are formed: an ethanol-rich phase with negligible salt and a water-rich phase with negligible ethanol, thus water can be separated out easily. A mathematical calculation of the liquid–liquid equilibrium data was carried out with the Pitzer theory on water activity in the aqueous phase, and with the Wilson or NRTL or UNIQUAC equations for that in the ethanol phase, which is in good agreement with experimental data.     

Chemical dehydration coupling multi-effect evaporation to treat waste sulfuric acid in titanium dioxide production process

In order to concentrate the diluted sulfuric acid from the titanium dioxide(TiO_2) production of sulphate process,a new concentration process was proposed by coupling chemical dehydration and multi-effect evaporation. The ferrous sulfate monohydrate(FeSO_4·H_2O), as the dehydrant, was added to the diluted sulfuric acid to form ferrous sulfate heptahydrate(FeSO_4·7H_2O) according to the H_2SO_4-FeSO_4-H_2O phase diagrams, which partially removes the water. This process was named as Chemical Dehydration Process. The residual water was further removed by two-effect evaporation and finally 70 wt% sulfuric acid was obtained. The FeSO_4·H_2O can be regenerated through drying and dehydration of FeSO_4·7H_2O. The results show that FeSO_4·H_2O is the most suitable dehydrant, the optimal reaction time of chemical dehydration process is 30 min, and low temperature is favorable for the dehydration reaction. 45.17% of the entire removed water can be removed by chemical dehydration from the diluted sulfuric acid. This chemical dehydration process is also energy efficient with 24.76% saving compared with the direct evaporation process. Furthermore, 51.21% of the FeSO_4 dissolved originally in the diluted sulfuric acid are precipitated out during the chemical dehydration, which greatly reduces the solid precipitation and effectively alleviates the scaling in the subsequent multi-effect evaporation process.     

采用增大凝结液滴方法的锥芯超音速旋流分离装置性能研究

To improve the separation performance of a supersonic gas separation device for the treatment of gas mixture with a single heavy component, a novel structure with shorter settlement distance was constructed and a method of droplet enlargement was applied. A series of experiments were carried out in the improved separation device under various conditions, using air-ethanol vapor as the medium and micro water droplets as nucleation centers. The effects of the inlet pressure, temperature and relative humidity, the swirling intensity, and mass flow rate of water on the separation performance were investigated. The separation was improved by increasing the inlet pressure and relative humidity. With the decrease of swirling intensity and mass flow rate of water, the separation efficiency increased first and then decreased. The inlet temperature had a slight effect on the separation. The results showed that the separation performance was effectively improved using the proposed structure and method, and the best separation in this study was obtained with the ethanol removal rate about 55% and dew point depression 27 K. The addition of water had little pollution to the air-ethanol vapor system since the water carry-over rate was within the range of %-0 in most cases.     

Experimental and simulation of the reactive dividing wall column based on ethyl acetate synthesis

Reactive dividing wall column(RDWC) is a highly integrated unit which combines reaction distillation(RD) with dividing wall column separation technology into one shell, and it realized the chemical reaction and the separation of multiple product fractions simultaneously. In this paper, the reaction of esterification with acetic acid and ethanol to produce ethyl acetate was used as the research system, experiments and simulations of the RDWC were carried out. This system in the traditional process mostly used the homogeneous catalyst(e.g. sulfuric acid). However, in view of the corrosion of the equipment caused by the acidity of the catalyst, we used the heterogeneous catalysts – iron exchange resins – Amberlyst15 and proposed a novel catalyst loading method. Firstly,the reliability of the model of the simulation was verified by the experimental study on the change of liquid split ratio and reflux ratio. After that, the four-column model was established in Aspen Plus to analyze the effects of the amount of azeotropic agent, reflux ratio and acetic acid concentration. Finally, for a fair comparison, the economic analysis was conducted between traditional RD column and RDWC. The results showed that RDWC can save34.7% of total operating costs and 18.5% of TAC.     

Determination of Vapor Pressures for Binary and Ternary Mixtures Containing Ionic Liquid 1-propyl-3-methylimidazolium Bromide

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.     

固定化Candida sp. 99-125脂肪酶催化合成蜡酯(英文)

Wax esters were synthesized in a solvent free system catalyzed by immobilized lipase from Candida sp. 99-125, with oleic acid and cetyl alcohol. The effects of substrate molar ratio, lipase dosage and water removal were investigated in a 50 ml flask incubated in a thermostatic cultivation cabinet. The optimized conditions were: temperature 40 ℃, shaking at 170 r·min-1, acid/alcohol molar ratio 1:0.9, lipase dosage in 10% (by mass) of oleic acid, and open reaction for water removal. As a result, the conversion rate reached 98% for reaction of 8 h. The volume of reactor was scaled up to 1 L three-neck flask. The optimized parameters were: 200 r·min-1 agitation speed, 2.5% (by mass) lipase dosage, others were the same as the parameters described above. The conversion rate reached 95% for reaction of 24 h. The lipase retained 46% conversion rate after reuse for 6, 7 batches. The products were purified by removing remained cetyl alcohol and fatty acids with ethanol and saturated sodium carbonate so-lution, respectively. The purity of the wax ester, cetyl oleate, was 96%. The physical and chemical properties of cetyl oleate were tested and compared with those of jojoba oil. The results show that the product cetyl oleate has great potential to use as the substitute of natural jojoba oil.     

铁基离子液体湿法氧化硫化氢的反应性能

以氯化丁基甲基咪唑(BmimCl)和六水合三氯化铁(FeCl3.6H2O)为原料合成了铁基离子液体。分析表明,铁基离子液体具有非定量组成[Bmim]Fe0.9Cl4.7,表现出较强的疏水特性,而且具有良好的氧化性和热稳定性。以铁基离子液体为脱硫剂,对其氧化脱除硫化氢及再生工艺进行了初步研究,考察了硫化氢流量、硫化氢浓度、反应温度和氧气流量对脱硫效率的影响。结果表明,铁基离子液体的硫容达到0.31g.L-1,氧化脱硫过程中无须添加辅助试剂和调控pH值,反应温度和硫化氢流量是对脱硫率影响最为显著的两个因素,铁基离子液体脱硫剂可以在氧气中再生并循环使用。因此,铁基离子液体作为脱硫剂可以氧化硫化氢生成硫磺并在氧气中再生并生成水。基于产物水与疏水脱硫剂的不溶性,可以构建基于疏水性铁基离子液体作为脱硫剂的非水相湿法氧化脱硫新工艺,避免了水相湿法氧化脱硫过程中二次污染及操作复杂的难题,对研究发展绿色湿法脱硫工艺具有积极意义。     

复合离子液体组成对硫化氢的氧化脱硫性能的影响

针对纯铁基离子液体（Fe-IL）在脱硫过程中气液传质效率较低、铁活性不高等缺陷导致的脱硫液易被击穿、硫容小和再生缓慢等问题,以铁基离子液体（Fe-IL）为基质,选用锌基离子液体（Zn-IL）、锰基离子液体（Mn-IL）和1,3-二甲基咪唑啉酮（DMI）为助剂,调节相互之间的质量比配制复合离子液体基脱硫液,并试验上述混合溶液的脱硫效果。实验结果表明,复合金属离子液体之间具有协同强化脱硫的作用,1,3-二甲基咪唑啉酮对铁基离子液体脱硫有着较好的活化作用,其中铁锌基离子液体与1,3-二甲基咪唑啉酮组成的复合液脱硫效果更为理想。     

电石渣湿法脱硫中结晶产物的影响因素研究

电石渣湿法脱硫中结晶产物的品质直接影响后续脱硫石膏的资源化利用。基于此,系统研究了pH、氧化时间和电石渣粒径对电石渣湿法脱硫中结晶产物含水率、亚硫酸盐含量、矿相组成和微观形貌的影响。结果表明,较高pH会限制亚硫酸钙与溶解氧的接触,当pH在4.00~4.50时亚硫酸钙的氧化效果较好;初始阶段氧化速率受时间影响显著,6 h后氧化速率趋于平稳;电石渣粒径过大会导致比表面积减小,降低亚硫酸钙与溶解氧的接触面积,粒径过小则在生成亚硫酸钙时容易发生静电团聚现象,导致粒径增大、氧化率降低。因此,当电石渣粒径为75.00~93.75 μm、pH为4.0、氧化时间为6 h时,结晶产物（二水合硫酸钙）的结晶效果最好。     

亚硫酸钙两步法制备高浓度亚硫酸氢钠溶液

利用湿法烟气脱硫中间产物亚硫酸钙（CaSO₃）和氯碱工业副产物芒硝和废硫酸制备高浓度亚硫酸氢钠（NaHSO₃）溶液,以简化亚硫酸氢钠溶液的后续处理工序并降低能耗。以亚硫酸氢钠溶液质量浓度为考察指标,采用两步法制备高浓度的亚硫酸氢钠。首先考察亚硫酸钙加入量、反应温度、反应时间、亚硫酸钙悬浮液质量分数等因素对第一步制备的低浓度亚硫酸氢钠溶液质量浓度的影响。其次考察第一步制备的低浓度亚硫酸氢钠溶液质量浓度对第二步制备的高浓度亚硫酸氢钠溶液质量浓度的影响。研究结果表明,实验中当亚硫酸钙加入量为0.068 mol、反应温度为13 ℃、反应时间为30 min、亚硫酸钙悬浮液质量分数为25%时,第一步制备的低浓度亚硫酸氢钠溶液质量浓度达到198.2 g/L;当第一步制备的低浓度亚硫酸氢钠溶液质量浓度为170 g/L时,第二步制备的高浓度亚硫酸氢钠溶液质量浓度达到264.2 g/L。采用两步法制备高浓度的亚硫酸氢钠溶液,节省了蒸发能源,具有显著的经济效益,为亚硫酸钙的利用提供了一条可行的路径。     

Stabilization of bioethanol recovery with silicone rubber‐coated ethanol‐permselective silicalite membranes by controlling the pH of acidic feed solution

In order to produce highly concentrated bioethanol by pervaporation using an ethanol‐permselective silicalite membrane, techniques to suppress adsorption of succinic acid, which is a chief by‐product of ethanol fermentation and causes the deterioration in pervaporation performance, onto the silicalite crystals was investigated. The amount adsorbed increased as the pH of the aqueous succinic acid solution decreased. The pervaporation performance also decreased with decreasing pH when the ternary mixtures of ethanol/water/succinic acid were separated. Using silicalite membranes individually coated with two types of silicone rubber, pervaporation performance was significantly improved in the pH range of 5 to 7, when compared with that of non‐coated silicalite membranes in ternary mixtures of ethanol/water/succinic acid. Moreover, when using a silicalite membrane double‐coated with the two types of silicone rubber, pervaporation performance was stabilized at lower pH values. In the separation of bioethanol by pervaporation using the double‐coated silicalite membrane, removal of accumulated substances having an ultraviolet absorption maximum at approximately 260 nm from the fermentation broth proved to be vital for efficient pervaporation. Copyright © 2005 Society of Chemical Industry     

Calcium sulfate whisker prepared by flue gas desulfurization gypsum: A physical-chemical coupling production process

In this paper, the solid waste desulfurization gypsum produced by coal-fired power plants was used as a raw material to prepare calcium sulfate whiskers with high application prospects. Calcium sulfate whiskers with uniform morphology and high aspect ratio can be prepared by hydrothermal method in sulfuric acid solution. A new process of desulfurization gypsum activated by high-energy grinding to reduce the reaction temperature and sulfuric acid concentration was developed. Through the comparison of product morphology, the best grinding time was determined to be 3.5 h. The mechanism of desulfurization gypsum through physical-chemical coupling to reduce energy consumption was clarified. The activation of desulfurization gypsum by grinding and the acidic environment provided by the sulfuric acid solution made the calcium sulfate solution reached rapid saturation and accelerated the nucleation rate. By calculating the conversion and crystallization rate of calcium sulfate whiskers, it was found that there were obvious “autocatalytic” kinetic characteristics during the crystallization process.     

不同亚临界溶剂从微拟球藻湿藻泥中提取油脂

以微拟球藻(Nannochlorsis sp.)湿藻泥为原料,研究了亚临界乙醇、亚临界乙醇-正己烷共溶剂及硫酸辅助亚临界乙醇-正己烷共溶剂3种萃取体系对微藻油脂提取的影响. 结果表明,亚临界乙醇-正己烷比亚临界乙醇对湿藻细胞有更高的油脂萃取率和低的溶剂用量,加入少量硫酸可进一步提高油脂的提取率、降低溶剂用量. 微拟球藻湿藻泥(含水约70%)优化提取条件为,正己烷/乙醇体积比3:1,液固比(溶剂/藻细胞干重)7 mL/g,加入藻细胞干重6%的硫酸,1.5 MPa下90℃萃取30 min,在此条件下油脂提取率可达90%以上. 3种萃取体系获得的微藻油脂均以甘油三酯为主,甘油三酯的脂肪酸主要为C16:0, C18:1和C16:1,其中硫酸辅助亚临界共溶剂萃取的微藻油脂中甘油三酯含量最高,约占总脂的86%以上.     

Calcium sulfate whisker prepared by flue gas desulfurization gypsum: A physical–chemical coupling production process

In this paper, the solid waste desulfurization gypsum produced by coal-fired power plants was used as a raw material to prepare calcium sulfate whiskers with high application prospects. Calcium sulfate whiskers with uniform morphology and high aspect ratio can be prepared by hydrothermal method in sulfuric acid solution. A new process of desulfurization gypsum activated by high-energy grinding to reduce the reaction temperature and sulfuric acid concentration was developed. Through the comparison of product morphology, the best grinding time was determined to be 3.5 h. The mechanism of desulfurization gypsum through physical–chemical coupling to reduce energy consumption was clarified. The activation of desulfurization gypsum by grinding and the acidic environment provided by the sulfuric acid solution made the calcium sulfate solution reached rapid saturation and accelerated the nucleation rate. By calculating the conversion and crystallization rate of calcium sulfate whiskers, it was found that there were obvious “autocatalytic” kinetic characteristics during the crystallization process.     

盐溶液种类和浓度对α-半水脱硫石膏合成的影响

为了解决脱硫石膏的大量堆存对环境造成的潜在危害,同时提高脱硫石膏的附加值,采用常压盐溶液水热法以电厂脱硫石膏为原料探究α-半水石膏的最佳合成工艺,重点研究了盐溶液种类及浓度对α-半水石膏的合成过程、合成产物组成及结构的影响。结果表明：在氯化钙、氯化镁盐溶液中,由于同离子效应和硫酸镁离子对的形成,导致半水石膏的形成过程受阻。较高浓度氯化钾和氯化钠盐溶液可使二水石膏发生转晶,其中氯化钾会致使半水石膏过度脱水生成无水钾石膏,氯化钠盐溶液可以使二水石膏转变为半水石膏并维持较长时间,通过比较得出最佳合成工艺为氯化钠溶液质量分数为15%、体系反应温度为95 ℃、固液质量比为1∶4、搅拌速率为150 r/min、合成时间为3 h,可以制得长径比约为5∶1的六方短柱状α-半水石膏。     

硫酸改性核桃壳处理含Cr(Ⅵ)模拟废水研究

在100 mL 8 mol·L-1硫酸溶液中,核桃壳加入量为9 g,核桃壳颗粒度为100目,反应时间为3 h,反应温度为25℃的条件下制备得到硫酸改性核桃壳.硫酸改性核桃壳对Cr(Ⅵ)具有优异的吸附性能.详细探讨了硫酸改性核桃壳处理含Cr(Ⅵ)模拟废水的影响因素:废水pH值、Cr(Ⅵ)离子浓度、硫酸改性核桃壳用量、处理...