Sorption and permeation of solutions of chloride salts, water and methanol in a Nafion membrane

The sorption of water–methanol mixtures containing a dissolved chloride salt in a Nafion 117 membrane, and their transport through the membrane under the driving force of a pressure gradient, have been studied. Both type of experiments was performed by using five different salts: lithium chloride, sodium chloride, cesium chloride, magnesium chloride and calcium chloride. It was observed that both the permeation flow through the membrane and the membrane swelling increase significantly with the methanol content of the solutions. These facts are attributed to the increase in wet membrane porosity, which brings about the increase of the mobility of solvents in the membrane, besides the increase of the mobility of the polymer pendant chains. In contrast, the influence of the type of electrolyte on the membrane porosity and permeability is not very important, with the exception of the CsCl solutions, which is probably due to the small hydration ability of the Cs⁺ ion.     

Effect of water on the solubility and diffusivity of hydrocarbons in polyethylene

There are indications in the literature that the devolatilization of some polymers, particularly polyethylene, can be enhanced by the addition of water, generally in the form of steam. In this study three different experimental methods were used with three different solvent–polyethylene systems to evaluate this effect. The results indicated that no measureable differences were found in either the solubility or the diffusivity of the systems between the dry or wet polymer samples. POLYM. ENG. SCI., 55:1459–1462, 2015. © 2015 Society of Plastics Engineers     

Separation of Azeotropic Dimethylcarbonate/Methanol Mixtures by Pervaporation: Sorption and Diffusion Behaviors in the Pure and Nano Silica Filled PDMS Membranes

In this article, polydimethylsiloxane and hydrophobic nano-silica filled polydimethylsiloxane membranes were prepared and employed in dimethylcarbonate (DMC) removal from the DMC/methanol mixture via pervaporation. The sorption and diffusion behavior of the binary molecule were discussed separately to provide qualitative estimation of the PV performance in both membranes. Compared with the polydimethylsiloxane membrane, hydrophobic nano-silica filled polydimethylsiloxane membranes had a little lower sorption selectivity but higher diffusion selectivity. In both membranes, the sorption value was obtained by both experimentation and model prediction. The Flory-Huggins model was performed to predict the solvent uptakes and the sorption concentrations based on the experimental results. The sorption behavior of DMC was predictable, while the methanol solubility was a little higher than the experimental results. Moreover, the diffusion behavior was studied by Fick's law, the calculated diffusion coefficients of the permeates demonstrated a diffusion-coupling phenomenon, especially in hydrophobic nano-silica filled polydimethylsiloxane membranes. Methanol molecules diffused faster than DMC, suggesting the low diffusion selectivity. The PV performance was affected by both sorption and diffusion. Sorption was demonstrated to be a decisive factor in this pervaporation process.     

Sorption and diffusion of water vapor in poly(ethylene terephthalate) film

The sorption and diffusion of water vapor in poly(ethylene terephthalate) (PET) film were measured by applying a thermogravimetric analyzer (TG‐DTA), which customarily has been used to detect the weight loss of a sample with the increase of temperature under a given atmosphere. In this case, we detected the weight gain of PET film by sorption of water vapor under a given humidity at a constant temperature. Sorption‐rate curves were successfully obtained in spite of the low solubility of PET film and the presence of Fickian‐type curves. The solubility was better described according to the dual‐mode sorption model. The diffusion coefficients were determined in their initial slopes by the short‐time method. We found that the diffusion coefficient depended on vapor pressure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 67–74, 2000     

Solubilities and diffusivities of water vapor in poly(methylmethacrylate), poly(2-hydroxyethylmethacrylate), poly(N-vinyl-2-pyrrolidone) and poly(acrylonitrile)

Sorption and diffusion data were obtained for water vapor in four different polymers: poly (methylmethacrylate) (PMMA), poly (2-hydroxyethylmethacrylate) (PHEMA), poly (N-vinyl-2-pyrrolidone) (PVP) and poly (acrylonitrile) (PAN) at 35 °C using a gravimetric sorption method. Highest sorption was for PVP, followed by PHEMA. PMMA and PAN sorbed very little water. All the polymers exhibit a BET type III sorption isotherm; the large upturn at high activity for PVP and PHEMA is probably due to plasticization of the polymers by water vapor. Sorption data were interpreted using Flory-Huggins theory and the Zimm and Lundberg cluster integral.Fickian diffusion is observed for PHEMA. For PVP, the fractional uptake M_t/M_∞ is linear with the square root of the time up to M_t/M_∞=0.6−0.8 for all water activities a_w, but it shows a clear water sorption overshoot at a_w=55.3% and a_w=72.1%, probably due to macromolecular relaxation. PMMA sorption kinetics is also characterized by a maximum in the water uptake. The diffusion coefficient increases significantly with water concentration for PVP and PHEMA, weakly for PMMA, but it is independent of concentration for PAN.     

Effect of water sorption on the structure and mechanical properties of an epoxy resin system

The characteristics of sorption and diffusion of water in an amine‐cured epoxy system based on tetraglycidyl diaminodiphenylmethane and a novolac glycidyl ether resin were studied as a function both of the polymer microstructure, known from previous works, and the temperature. Water‐sorption experiments and dynamic mechanical analysis (DMA) were performed. Tensile stress–strain and Rockwell hardness tests were conducted to investigate the effects of absorbed water on the mechanical properties of the material. Competing effects of the sorption of water in the free volume and of strong interactions between water molecules and polar groups of the network were used to explain the diffusional behavior observed, which followed Fick's second law. DMA analysis seemed to be sensitive to the water effects and the viscoelastic behavior was related both to the water‐sorption processes and to the microstructure of the system. An important impact of water uptake on the tensile properties at break was also appreciated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 71–80, 2001     

几种高级氧化技术处理造纸黄液的比较研究

比较研究了工业废水处理中使用较多的几种高级氧化技术处理造纸黄液的情况,只有催化氧化混凝体系效果较好,其余不是太理想。分析了可能的原因,并提出了有待改进的方法。     

Toward efficient water/oil separation material: Effect of copolymer composition on pH‐responsive wettability and separation performance

Interest in functional soft matter with stimuli‐responsive wettability has increasingly intensified in recent years. From the chemical product engineering viewpoint, this study aims to fabricate reversible pH‐responsive polymeric surfaces with controllable wettability using [poly(2,2,3,4,4,4‐hexafluorobutyl methacrylate)‐block‐ poly(acrylic acid) (PHFBMA‐b‐PAA)] block copolymers. To attain this aim, three block copolymers with different PAA segment lengths were synthesized for the first time through Cu(0)‐mediated reversible‐deactivation radical polymerization and hydrolysis reaction. pH‐induced controllable wettability was achieved by spin‐coating the resulting block copolymers onto silicon wafers. Results showed that the pH‐responsive wetting behavior was introduced by incorporating the PAA block, and that the responsiveness of as‐fabricated surfaces was greatly influenced by PAA content. All three evolutions of water contact angle with pH shared a similar inflection point at pH 5.25. Furthermore, on the basis of the wetting properties and mechanism understanding, the application of copolymer coated meshes in layered water/oil separation was exploited. Given their superhydrophilicity and underwater superoleophobicity, PHFBMA₇₀‐b‐PAA₁₄₈ and PHFBMA₇₀‐b‐PAA₂₁₁ coated stainless steel meshes (SSMs) can efficiently separate water from different mixtures of organic solvent and water with high flux. However, considering long‐term use, the PHFBMA₇₀‐b‐PAA₁₄₈ coated SSM with good stability may be the best copolymer for water/oil separation. Therefore, a coordination of structure, composition, and functionality was necessary to enable practical applications of the functional materials. © 2016 American Institute of Chemical Engineers AIChE J, 62: 1758–1771, 2016     

山西发展甲醇制烯烃产业的探讨与思考

论述了甲醇制烯烃产业兴起的背景、国内外代表性技术发展概况、国内部分甲醇制烯烃项目的开展情况。针对实际情况,对山西发展甲醇制烯烃的必要性、可行性、政策支持等进行了探讨和分析,提出了一些思考和建议。     

KF对微米铝粉在水蒸气中着火燃烧特性的影响

为改善微米铝粉在水蒸气中的着火特性和燃烧效率,采用自行设计的管式炉实验平台研究了KF对30 ?m铝粉在1000℃水蒸气中着火燃烧特性的影响。用高速摄影系统记录了样品着火燃烧过程,并通过X射线衍射、扫描电镜技术和化学分析方法分析了产物组分、形貌和燃烧效率。结果表明,加入KF可显著降低30 ?m铝粉的点火延迟时间,与加入5wt% (0.003 g) KF相比,加入15wt% (0.009 g) KF后,样品的点火延迟时间减少了47.58 s;微米铝粉在1000℃水蒸气中不能着火,加入KF后能着火,这是因为KF与水蒸气反应生成KOH,KOH与Al2O3反应会破坏铝粉的氧化壳,加快铝与水蒸气的反应,促进铝粉着火。随KF加入量提高,样品的燃烧效率显著上升,最高为82.24%,比未添加KF样品的燃烧效率提升了38.75%。提高KF加入量,可产生更多的KOH,对氧化壳的破坏效果更显著,进一步促进铝与水蒸气反应,提高铝粉燃烧效率。     

Effect of hygroscopic materials on water vapor permeation and dehumidification performance of poly(vinyl alcohol) membranes

In this study, two hygroscopic materials, inorganic lithium chloride (LiCl) and organic triethylene glycol (TEG) were separately added to poly(vinyl alcohol) (PVA) to form blend membranes for air dehumidification. Water vapor permeation, dehumidification performance and long‐term durability of the membranes were studied systematically. Membrane hydrophilicity and water vapor sorbability increased significantly with higher the hygroscopic material contents. Water vapor permeance of the membranes increased with both added hygroscopic material and absorbed water. Water permeation energy varied from positive to negative with higher hygroscopic content. This observation is attributed to a lower diffusion energy and a relatively constant sorption energy when hygroscopic content increases. Comparatively, PVA/TEG has less corrosive problems and is more environmentally friendly than PVA/LiCl. A membrane with PVA/TEG is observed to be highly durable and is suitable for dehumidification applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44765.     

Effect of inlet mass loading,water and total bacteria count on methanol elimination using upward flow and downward flow biofilters

An upward flow biofilter and a downward flow biofilter using compost for removing methanol from air were investigated to compare the biofilter performance and to realize the advantages of using downward flow biofilters for accessibility to water make‐up. Both the upward flow and downward flow columns showed similar performance in terms of elimination capacity (EC) versus inlet mass loading (IC). The maximum elimination capacity (EC) from these two biofilters was approximately 101 g m⁻³ h⁻¹ with an optimum methanol loading rate at inlet (IC) of 169 g m⁻³ h⁻¹ (7.5 g m⁻³ of methanol with superficial velocity of 7.6 m h⁻¹). The effect of water movement within the bed on elimination capacity was monitored. In addition, it was found that when the water content in the compost was below 35% by weight, microbial activity was impaired. Once the compost media had dried, it became hydrophobic and could be rewetted only with great difficulty. Total bacteria count was performed on compost samples during the entire operation. The relationship between elimination capacity and total bacteria count was reported. Similar trends were shown by the variations of elimination capacity and total bacteria count with methanol loading: both initially increase, go through a plateau, then decrease with loading. © 2000 Society of Chemical Industry     

膜分离过滤过程中膜相内扩散动力学研究

基于与传统膜分离技术对物质进行分离过滤的共性,对这种便捷的迁移过程进行了动力学方程的推导,考察了物质穿过膜相的扩散作用和膜相内的运移规律,并用菲克第一定律建立了动力学方程。在此研究中,假定整个体系是瞬时和稳态的反应。最后,对膜相过滤过程的总压力损失和各部分压力损失的关系做了简要的介绍。     

SAPO-34分子筛硅铝比对甲醇制烯烃反应性能及积炭组成的影响

为了研究硅铝比对甲醇制烯烃反应性能及积炭组成的影响,控制合成中的原料配比制备了一系列不同硅铝比的SAPO-34分子筛。对合成的SAPO-34分子筛上的总酸量、酸强度和酸中心的分布进行了表征,发现成对的酸性位点随硅铝比的增大而增加。在固定床反应器中,系统地研究了SAPO-34分子筛的硅铝比对MTO反应性能的影响。由于成对的酸性中心是氢转移、低聚和成环的主要活性中心,能够增加副产物丙烷选择性及焦炭的生成速率,降低SAPO-34催化剂的烯烃选择性和催化剂的寿命。反应失活分析表明,在350℃、常压、空速为10 h^-1的条件下,催化剂可用一级反应失活方程描述,失活与硅铝比的3次方呈正比。采用原位热重质谱分析结合溶炭色谱质谱联用分析,发现硅铝比较高的SAPO-34分子筛笼内萘及其同系物乃至蒽、菲等稠环芳烃产物的生成速度较快,堵塞产物扩散的通道,导致催化剂的快速失活。     

PCL–PEG–PCL triblock copolydiol-based waterborne polyurethane. I. Effects of the soft-segment composition on the structure and physical properties

This article examines the effects of the soft-segment composition on the structure and physical properties of waterborne polyurethane (WBPU) based on polycaprolactone–poly(ethylene glycol)–polycaprolactone (PCL–PEG–PCL) triblock copolydiol as the soft segment. The molecular weight of PEG in the soft-segment composition and soft-segment content (SSC) are varied in this study. The water-vapor permeability (WVP) for the WBPU-coated nylon fabric is also studied. The results showed that the glass transition temperatures (T_g's) of the soft segment decreased and its temperature range (ΔT_g's) narrowed with increase of SSC up to 63 wt % and decrease of the PEG molecular weight. The dynamic mechanical analysis results showed that the α-peak height of the soft segment increased with SSC when the SSC was less than 63 wt %. However, when SSC was more than 63 wt %, the α-peak height became smaller with increasing SSC due to the crystallization of the soft segment. At the same SSC, the number of spherulites was reduced and the spherulites become larger with decrease of the PEG molecular weight. As for the mechanical properties of the WBPU cast film, the breaking stress decreased and the breaking elongation increased with increasing SSC or decreasing PEG molecular weight. For the WBPU-coated nylon fabrics, either higher SSC or higher PEG molecular weight improves the WVP. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:883–892, 1997     

催化剂组成对酸-碱交替沉淀法制备铜基甲醇合成催化剂的影响

采用酸-碱交替沉淀法制备了一种新型的低压甲醇合成催化剂。研究了催化剂组成的影响。当Al和Zr含量固定,随着Cu/Zn摩尔比的增加,催化剂活性先升高后下降,当Cu/Zn摩尔比为1时,活性最高。XRD结果表明,Cu/Zn摩尔比为1时制备的催化剂CuO与ZnO组分间相互均匀分散程度最大。Zr较明显地提高催化剂的活性和耐热性,Mn对催化剂的耐热性提高有一定的作用,La和Ce对提高催化剂活性的作用不大。     

凝固浴组成对SMA/CPVC共混超滤膜的结构与性能影响

通过非溶剂致相分离（NIPS）法制备了苯乙烯-马来酸酐共聚物（SMA）/氯化聚氯乙烯（CPVC）共混超滤膜,探讨了凝固浴中不同溶剂（DMAc）含量对其超滤膜表面酸酐基团偏析程度、微观结构、亲水性、水通量、截留率和抗污染的影响。结果表明：凝固浴中溶剂含量的增加抑制了酸酐基团向膜表面的偏析,导致亲水性减弱;同时,铸膜液中溶剂与水分子之间扩散速率的变小引起延迟分相,使得膜表面孔径变小和分布变窄。当溶剂质量分数为3%时,超滤膜对牛血清白蛋白（BSA）截留率提升至98.10%、通量恢复率为96.82%,且不可逆污染率降为3.77%,表明凝固浴中适量的溶剂可进一步提高超滤膜抗污染性能。     

Impact of fouling,cleaning and faecal contamination on the separation of water from urine using thermally driven membrane separation

In this study, membrane distillation is evaluated as a technology for non-sewered sanitation, using waste heat to enable separation of clean water from urine. Whilst membrane fouling was observed for urine, wetting was not evident and product water quality met the proposed discharge standard, despite concentration of the feed. Fouling was reversible using physical cleaning, which is similar to previous membrane studies operating without pressure as the driving force. High chemical oxygen demand reduction was achieved following faecal contamination, but mass transfer was impeded and wetting occurred which compromised permeate quality, suggesting upstream intervention is demanded to limit the extent of faecal contamination.     

Immobilization influence on the water sorption and diffusion in poly(3-hydroxybutyrate)

The temperature dependency of water vapor sorption and diffusion in poly(3-hydroxybutyrate) (PHB) was studied for the first time. Equilibrium sorption and diffusion kinetics were determined by a quartz McBain's vacuum microbalance technique in the temperature range of 303–333 K. A probability of water molecule interaction with the polymer matrix was analyzed for wet PHB films by FTIR spectroscopy technique. Sorption isotherms are interpreted as the solution of free water molecules estimated by the Flory–Huggins equation and the sorption of water molecules immobilized on the carbonyl groups of PHB. The immobilization effect was described by a Langmuir-type equation. The dependency of diffusivity on water concentration was described in the frames of Fujita's immobilization model in which the growing function D_w versus C_w characterized the filling degree of carbonyl groups as sites of immobilization in the polymer. Enthalpy of free water sorption (12 kJ/mol) and water immobilization (42 kJ/mol), as well as the activation energy of water diffusion coefficients (71 kJ/mol), in noncrystalline areas of PHB were determined. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 981–985, 1999