Silicone emulsion-enhanced recovery of chlorinated solvents: batch and column studies

Batch and column experiments were conducted to investigate the feasibility of flushing with silicone oil emulsion for the removal of chlorinated solvents, including trichloroethylene (TCE), perchloroethylene (PCE) and 1,2-dichlorobenzene (DCB). In the batch experiments, solubilization potentials of emulsion and effects of surfactants as additives were examined. The emulsion prepared with 2% (v/v) silicone oil could solubilize 90.7% of 10,000 ppm TCE, 97.3% of 4000 ppm PCE and 99.7% of 7,800 ppm DCB. Results of one-dimensional column studies indicated that aqueous solubility and sorption of contaminants determined the flushing efficiency. The addition of surfactants below their critical micelle concentration (CMC) did not affect the removal of chlorinated solvents in batch and column experiments. The results of this study show that flushing with oil-based emulsion can be applied to treat the chlorinated solvents.     

Laboratory tests for reactive barrier design

Owing to limitations of pump-and-treat, several technologies are being investigated for groundwater treatment. One of the most promising is the treatment of contaminants through the use of reactive barriers installed in situ, especially in the case of aquifers contaminated with chlorinated solvents. This work presents results of batch and column tests with metallic iron and some chlorinated solvents (1,2-DCA, 1,1,2-TCA and TCE). Such tests provided means to evaluate the degradation rates of these compounds and their byproducts. It is concluded that the reductive dechlorination with metallic iron can have different results, depending on the type of contaminant. Some contaminants may not present any degradation, or they have a half-life time so high that the use of the reactive barrier technology may not be practical. Furthermore, the formation of chlorinated byproducts, eventually more toxic than the original contaminant and that are not degradable using this same technology, emphasises that the treatment of aquifers should be sequential.     

Field vapor extraction test and long-term monitoring at a PCE contaminated site

The results of a field investigation, vapor extraction tests, and long-term monitoring at a PCE-contaminated site in Saga, Japan, are reported. The field investigation indicated that PCE likely was trapped in a surface clayey sand layer (vadose zone), and soil vapor extraction (SVE) was adopted as the remediation approach. The field test results the effectiveness of SVE in removing volatile organic compounds (VOCs) from contaminated sites. For the case where the radius of influence for an extraction well was 15–20 m, the blower capacity had no obvious effect on the radius of influence possibly due to the short circuiting of air from the ground surface. However, the maximum negative pressure (difference between vapor pressure and ambient pressure) in the extraction well was approximately proportional to blower capacity for the range of blower capacities tested. The long-term monitoring results indicate that PCE concentration varied seasonably, and temperature and rainfall are two of the influencing factors.     

蒸汽渗透法有机溶剂气相脱水

蒸汽渗透法是一种膜法气相脱水技术，与渗透汽化不同，在该过程中，进料的蒸汽与膜直接接触，在高于料液沸点的温度下进行操作，可以采用提高压力和温度等手段提高分离膜的透过通量，并可以与分馏过程集成使用，简化化工操作单元，要求所使用的膜具有更好的高温耐溶性性能。文章综述近几年２５篇有关文献，介绍蒸汽渗透过程的特点、与渗透汽化的对比、使用的膜以及其应用前景。     

用于有机蒸汽分离的PAN—SR复合膜的研究

以聚内烯腈（ＰＡＮ）为膜材料考察了铸膜液浓度、不同添加剂、不同硅橡胶对膜性能的影响，制成了ＰＡＮ基膜和ＰＡＮ复合膜，利用电镜考察了ＰＡＮ基膜的形态和结构，将ＰＡＮ基膜怀ＰＡ复合膜分别浸泡在７种溶剂中２００－１３２０ｈ，观察膜性能及膜失重变化，测定复合地有机蒸汽的分离性能，实验结果表明，ＰＡＮ－ＳＲ 事膜适用于从空气中分离有机蒸汽。     

Subcritical water extraction for the remediation of phthalate ester-contaminated soil

Subcritical water has been used as an environment-friendly extraction fluid for many classes of organic compounds. It was used for the removal of phthalate esters (PEs), such as di-methyl phthalate, DMP; di-ethyl phthalate, DEP; di-iso-propyl phthalate, DIPP; di-n-butyl phthalate, DBP; benzyl butyl phthalate, BBP; di-n-pentyl phthalate, DpentP; di-n-hexyl phthalate, DHXP; di-heptyl phthalate, DheptP; di-2-ethylhexyl phthalate, DEHP; di-n-nonyl phthalate, DNP; di-n-octyl phthalate, DOP; di-n-decyl phthalate, DDP, in soil samples under the optimum condition of 250 °C and 10 MPa in our study. The soil samples cleaned with subcritical water were extracted by homemade accelerated solvent extraction system (ASE) and analyzed by HPLC-UV to check for soil remediation efficiency. Three types of soil collected at different sites in Taiwan have been tested. Although at higher PEs concentration levels, the modification of treatments may be necessary for satisfactory removal of the contaminants, soil samples of different PEs levels treated with subcritical water extraction (SCWE) were analyzed and the results indicated removal efficiency ranges of 80-90% for PEs spiked in soil samples. Soil samples contaminated with native DEHP were treated and gave comparable recovery efficiencies. Our results indicate that the applications of subcritical water as soil remediation for removal of PEs contaminant are feasible.     

Hot water extraction with in situ wet oxidation: kinetics of PAHs removal from soil

Finding environmentally friendly and cost-effective methods to remediate soils contaminated with polycyclic aromatic hydrocarbons (PAHs) is currently a major concern of researchers. In this study, a series of small-scale semi-continuous extractions--with and without in situ wet oxidation--were performed on soils polluted with PAHs, using subcritical water (i.e. liquid water at high temperatures and pressures, but below the critical point) as the removal agent. Experiments were performed in a 300 mL reactor using an aged soil sample. To find the desorption isotherms and oxidation reaction rates, semi-continuous experiments with residence times of 1 and 2 h were performed using aged soil at 250 degrees C and hydrogen peroxide as oxidizing agent. In all combined extraction and oxidation flow experiments, PAHs in the remaining soil after the experiments were almost undetectable. In combined extraction and oxidation no PAHs could be detected in the liquid phase after the first 30 min of the experiments. Based on these results, extraction with hot water, if combined with oxidation, should reduce the cost of remediation and can be used as a feasible alternative technique for remediating contaminated soils and sediments.     

Experimental study of the viscosity of lithium vapor at high temperatures

The viscosity of lithium vapor was measured at temperatures from 1600 to 2000 K and pressures from 0.02 to 0.1 MPa with an experimental setup consisting of a closed circuit with a short annular channel used as a measuring element. The accuracy of the data obtained was estimated to be 3–4%. The characteristic features of the designed apparatus are the following: a high stability of the pressure difference within the viscometer during experiment, the absence of condensate accumulation out of the flowmeter, and a sufficiently large flowmeter volume. Since the length of the measuring section is short, the hydrodynamics of the gas flow through an annular channel were studied carefully. This enabled us to introduce the necesary corrections in the working equation. The results obtained are compared with available experimental data and the results of theoretical calculations.Paper submitted to the Ninth Symposium on Thermophysical Properties, June 24–27, 1985, Boulder, Colorado, U.S.A.     

Removal of copper from industrial sludge by traditional and microwave acid extraction

This work elucidates the removal of copper from industrial sludge by traditional and microwave acid extraction. The effects of acid concentration, extraction time, sludge particle size and solid/liquid (S/L) ratio on copper removal efficiency were evaluated. Leaching with more concentrated acid yielded greater copper content from the industrial sludge. The experimental findings reveal that the most economical traditional extraction conditions were the use of 1N sulfuric or nitric acid for 60 min at an S/L ratio of 1/20; however, at an S/L ratio of 1/6, the extraction time needed to achieve the same copper removal efficiency was increased to 36 h. Increasing the microwave power and reducing the S/L ratio increased the copper extraction efficiency and the effect in the larger S/L ratio system was more significant. A comparison of the results of microwave-assisted (microwave only) and microwave-enhanced (microwave with addition of active carbon) acid extraction demonstrated that under both conditions, S/L ratio = 1/6 and 1/20; adding active carbon shortened the extraction time required to achieve 80% copper extraction efficiency from 20 to 10 min. These experimental results indicate that the most important factors that most strongly affected microwave acid extraction were the addition of a microwave absorber, the microwave power input and the S/L ratio. The sludge particle size did not significantly affect the copper extraction. The results reveal that sulfuric acid was an effective extractant and that the copper fraction in the extracted sludge shifted from being mostly bound to the Fe–Mn oxides and organic matter, to being mostly bound to organic matter and remaining as a residue during acid extraction.     

Natural attenuation of chlorinated organics in a shallow sand aquifer

This work presents the second phase of a groundwater remediation program for the migration control of a 1,2-dichloroethane (1,2-DCA) contaminated plume which includes natural attenuation at a distance downgradient from the source area. The conceived system for the plume migration control, implemented just after a major accidental release of 1,2-DCA in the soil, included a 300 m long physical barrier (cement-bentonite diaphragm wall) and 12 extraction wells. Results of field investigations have provided evidence that 1,2-DCA was naturally biodegrading into vinyl chloride as well as ethene under the natural anaerobic-reducing conditions at the site. In that case, source control measures were implemented to accelerate the overall remediation process. Although the results are favorable, the natural degradation of the 1,2-DCA does not guarantee acceptable levels of concentrations. Therefore, a pilot test to evaluate the enhancement of these processes is being carried out through the use of a biosparging system. This test is being implemented near the source to achieve sequential aerobic–anaerobic treatment zones.     

气相色谱法测定盐酸美金刚原料药中有机溶剂残留量

目的:用毛细管柱气相色谱法建立测定盐酸美金刚原料药中二氯甲烷、乙腈、乙醚、乙醇的残留量的方法。方法:采用内壁涂有5%苯基-95%聚二甲基硅氧烷的毛细管柱(DB-5毛细管色谱柱30m×0.53mm×1.5μm),以氮气为载气,流速1.0ml/min。柱温箱:50℃保持12min,然后以30℃/min升温至230℃,至少保持12分钟。分流直接进样,进样口温度230℃,进样量:1.0μl。FID检测器,检测器温度280℃。按内标法计算残留溶剂的含量。结果:在考察的浓度范围内呈现良好的线性关系(二氯甲烷r=0.99885、乙腈r=0.99975、乙醚r=0.99659、乙醇r=0.99985),方法的精密度良好,回收率较为理想。结论:该法适用于盐酸美金刚原料药中二氯甲烷、乙腈、乙醚、乙醇的残留量的检测。     

Prediction of solubility of long-chain hydrocarbons in various solvents using UNIFAC

The UNIFAC group contribution model has been widely used in the prediction of phase equilibria of various fluid mixtures. We have applied the method to predict the solubility of various long-chain hydrocarbon solids in a number of solvents of industrial importance. The calculated solubilities are compared with measured values and also with the predictions of the regular solution theory of Hildebrand and Scatchard. Some disagreements were found between the measured solubilities and the predicted values of both theories. Overall the UNIFAC scheme appears to be superior to the regular solution theory.Paper presented at the Ninth Symposium on Thermophysical Properties, June 24–27, 1985, Boulder, Colorado, U.S.A.     

Structural transition of a homopolymer in solvents mixture

The present work is aimed at studying the thermodynamic behaviour of a polymer in solvents mixture. Dynamic light scattering is used to measure the hydrodynamic radius of polyvinylpyrrolidone (M_w = 360,000 g/mol), in water/methanol solvents mixture, versus the mixed solvents composition at 25 °C. Then, we show that the polymer conformation adopts the Coil–Globule–Coil structure when the methanol molar fraction X_A is varied. This transition is attributed to solvent quality change which result from water and methanol complex formation. The polymer contraction rate calculated for each composition takes its maximum value at X_A = 0.17. Hildebrand theory assuming the solvents mixture as an equivalent solvent was used to analyze the change in mixed solvents quality. These changes can be attributed to dispersive forces in solvents mixture.     

Sorption of solvents in plastics and solvent desorption and retention

The experiments reported here have studied the following systems within the temperature range 25–50°C: sorption and desorption of solvents on LDPE, OPP, PS, rigid PVC, OPA, PETP and regenerated cellulose with methanol, ethanol, n-propanol, and ethyl acetate. With reference to these, the theory presented indicates the most important aspects related to the tests, refers to identification data on similar problems and enumerates the possibilities of interaction. The application of equation 1 and the reported measuring method allows the determination of diffusion coefficients within a vapour-saturated atmosphere system. As the gravimetric method also allows the determination of solubilities (α_L, the solubility coefficient), the permeation behaviour in the Fick range is calculable from The equation used by the author can be related to other equations from the technical literature, such as for the range Q_(t)Q∞>0.4, or where for the range <0.4 The agreement can be considered as good. The D values provide a calculation base within the scope of the outlined problem definition. The taste limits for solvents in water reveal which solvents could, as residual solvents, become critical. These values—connected with sorption/desorption identification values, evaporation numbers etc. —indicate where there is a risk and those cases where sufficient drying, or even the use of more adequate solvents is essential.     

Computational fluid dynamic modeling of tin oxide deposition in an impinging chemical vapor deposition reactor

A fundamental framework for atmospheric pressure chemical vapor deposition of tin oxide coatings on glass using monobutyltin trichloride as the precursor, developed using computational fluid dynamics (CFD) in an impinging flow geometry, is presented in this paper. The CFD model explicitly accounts for homogenous reaction in the gas phase, heterogeneous reaction on the glass surface, thermal effect of the impinging jet on the glass, and impinging flow characteristics in the confined coating zone. A comparison of modeling results with experimental data is described. It is shown that the experimentally observed spatial distribution in the deposition rate is successfully captured by the model and the wave shape in the deposition profile can be explained with boundary layer separation. The effects of reactor-substrate spacing and glass line speed on the simulated deposition profile are discussed.     

化学气相沉积与渗透过程中热解炭织态结构生成机理研究

为研究热解炭织态结构的生成规律，采用不同压强的甲烷为碳源，在1100℃条件下进行了化学气相沉积和化学气相渗透实验。化学气相沉积以具有不同表面积／自由体积比（[A／V]值）的直通方形多孔陶瓷为基体；化学气相渗透实验在直径为1mm细直孔内表面沉积和对炭纤维体积分数为7％的炭毡进行致密化。借助正交偏光显微镜（消光角）和透射电子显微镜（定向角）对在不同实验条件下制备的热解炭进行分析和定量表征。研究发现：热解炭的织态结构可以在两种不同的沉积条件下形成。当甲烷压强较低时为化学生长阶段；当甲烷压强较高时为物理形核阶段。在化学生长控制阶段，热解炭的织态结构可以利用之前提出的“颗粒填充模型（P-F模型）”加以解释。该模型假设高织构热解炭的沉积一定对应于气相中存在具有合适比例的芳香化合物（例如苯）和线性小分子（主要是C2H2），当二者的浓度比偏离该最优比（或者偏大，或者偏小），均将导致中织构甚至低织构热解炭的生成。在化学生成控制阶段，化学气相沉积和化学气相渗透对热解炭织态结构影响的差别，除了[A／V]值而外，还有氢气的作用。在化学气相渗透过程中，基体内部生成的氢气快速扩散至基体表面，使内外沉积速率和织态结构均发生较大变化。     

低温化学气相沉积法制备SiC纳米粉体

合成了液态碳硅烷并对其结构进行了分析;采用化学气相沉积工艺,以自制的液态碳硅烷为先驱体,分别在850℃和900℃的较低温度下制得了SiC粉体,并对产物进行了IR、XRD和SEM分析.结果表明,850℃产物中含有未分解完全的有机基团,900℃产物为较纯的部分结晶的纳米SiC粉体,粒度为50～70nm.     

Chlorinated precursor study in low temperature chemical vapor deposition of 4H-SiC

Low temperature (1300 °C) chemical vapor deposition (CVD) of SiC has gained interest in the last years for being less demanding in terms of reaction chamber lifetime, but also for allowing higher p-type dopant incorporation. Chloride-based CVD at low temperatures has been studied using chloromethane with tetrachlorosilane or silane, respectively and with or without controlled HCl addition. In this study we explore the use of methyltrichlorosilane (MTS) at growth temperatures (1300 °C) significantly lower than what is commonly used for homoepitaxial growth of SiC (1600 °C). MTS is a molecule containing all the needed precursor atoms; its effects are compared to the standard CVD chemistry, consisting of silane, ethylene, and HCl.Very different chemistries between the two precursor systems are proposed; in the case of MTS, C/Si ratios higher than 1 were required, however using the standard chemistry ratios lower than 1 were needed to obtain a defect-free epitaxial layer. We also demonstrate the need of using Cl/Si ratios as high as 15 to achieve a growth rate of 13 μm/h for 8° off-axis 4H-SiC epitaxial layers at 1300 °C. Limitations due to the low growth temperature are discussed in light of the experimental evidence on the growth mechanism as determined by the morphology degradation and the limited growth rate. Finally a comparison between the epilayers morphology obtained on 4H-SiC substrates with different off-cuts are presented, confirming the importance of lower C/Si ratios for 4° off-axis material and the inevitable growth of the cubic SiC polytype on on-axis substrates.     

Preparation of nanosized silicon carbide powders by chemical vapor deposition at low temperatures

Liquid carbosilane was synthesized and analyzed by infrared (IR) and H-NMR (nuclear magnetic resonance) spectroscopy. Silicon carbide (SiC) powders were prepared by chemical vapor deposition (CVD) at 850°C and 900°C from liquid carbosilanes. The product powders were characterized by IR spectroscopy, X-ray diffractometry (XRD) and scanning electron microscopy (SEM). Results show that liquid carbosilane synthesized was the mixture of several oligomers that had a Si-C backbone. The powders prepared at 850°C contain some organic segments, and those prepared at 900°C are pure nanosized SiC powders, which are partly crystallized, the size of which is about 50–70 nm. Translated from Journal of Functional Materials and Devices, 2006, 12(5): 447–450 (in Chinese)     

MVR系统中离心式蒸汽压缩机与蒸发器的匹配特性研究

为了保证机械式蒸汽再压缩（mechanical vapor recompression, MVR）系统的运行经济性和稳定性,对MVR系统中离心式蒸汽压缩机与蒸发器的匹配特性进行研究。针对蒸发器换热系数在新投、工作和结垢工况下的变化,提出了蒸发器运行温阻特性线的概念,并将其与离心式蒸汽压缩机的温升特性线叠加,从而开展离心式蒸汽压缩机与蒸发器的匹配分析。通过分析发现,离心式蒸汽压缩机的设计流量偏大或蒸发器的换热面积过小会导致匹配不足,易发生喘振,从而影响MVR系统的运行稳定性。而离心式蒸汽压缩机的设计流量偏小或蒸发器的换热面积过大会导致匹配过度,致使MVR系统的运行经济性差,甚至可能造成MVR系统无法建立热力自循环。结果表明,离心式蒸汽压缩机在MVR系统启动过程中会出现不稳定的喘振现象,可以通过系统参数的临时调节或采取辅助措施来避开不稳定区。设计时应保证离心式蒸汽压缩机的喘振裕度大于20%,蒸发器换热面积的设计裕度为30%;MVR系统运行时实际蒸发温度与设计温度的偏差应控制在±5 ℃以内。研究结果可为MVR系统的设计和调试提供参考。