VOC — or not? Determination of an important environmental parameter

Conclusions  The DSC method has been shown to be a fast method for measurements of boiling points of organic solvents at normal atmospheric pressure. The boiling point temperatures obtained by the DSC method are in very good agreement with existing data, especially concerning solvents of low volatility. These boiling points, together with the definition of a VOC given by the EU directive, enables a rapid characterisation of a solvent as a VOC or not. In a few cases, where the boiling point is between 170–260°C, the vapour pressure must be determined experimentally. The DSC method can be used to measure the boiling points of mixtures and commercial products. If more than one boiling point is measured for a mixture or commercial product the lowest boiling point can be used to define whether the product is a VOC or not. Measurements can also be performed on commercial products containing solids if the solvent content is not too low. Whether or not a product can be described as a VOC is of great significance, especially for the coatings industry. This method can be used in connection with other environmental definitions of VOC, where boiling point is used instead of vapour pressure, for example in connection with labelling. The presentation by Charlotte Nielsen of the paper on which this article is based received the CSI Medallion at the SLF Congress in Lillehammer, Norway, May 1997. The paper is published with the permission of the SLF.     

有机化合物沸点估算的复合基团拓扑空间方法

基于传统基团划分方法进行了有机化合物分子的空间设计,用基团模指数表征基团在分子中的位置,用基团-邻接原子对增加对基团环境影响的考虑,建立了有机化合物物性估算的复合基团拓扑空间方法。提出了估算正常沸点的表达式,使用了1171种有机化合物拟合出了相应的基团和基团．邻接原子对的参数,其估算的平均相对偏差为1．58％,为与前期工作进行比较,故用前期工作所用的669种物质进行了估算,其平均相对偏差为1．29％。将本方法和常用的方法以及本工作前期提出的方法进行了比较,结果表明本方法有更高的准确度和可靠性。     

BP网络预测胺类衍生物常压沸点

论文采用误差反传前向人工神经网络模型,优选结构因子作为输入特征参数,对胺类衍生物的常压沸点进行预测,网络自相容能力和交叉检验结果良好。该方法还可作为对有机化合物构性关系研究及其它性质进行预测的一种有效手段。     

Assessment of in situ butanol recovery by vacuum during acetone butanol ethanol (ABE) fermentation

BACKGROUND: Butanol fermentation is product limiting owing to butanol toxicity to microbial cells. Butanol (boiling point: 118 °C) boils at a higher temperature than water (boiling point: 100 °C) and application of vacuum technology to integrated acetone–butanol–ethanol (ABE) fermentation and recovery may have been ignored because of direct comparison of boiling points of water and butanol. This research investigated simultaneous ABE fermentation using Clostridium beijerinckii 8052 and in situ butanol recovery by vacuum. To facilitate ABE mass transfer and recovery at fermentation temperature, batch fermentation was conducted in triplicate at 35 °C in a 14 L bioreactor connected in series with a condensation system and vacuum pump. RESULTS: Concentration of ABE in the recovered stream was greater than that in the fermentation broth (from 15.7 g L^?1 up to 33 g L^?1). Integration of the vacuum with the bioreactor resulted in enhanced ABE productivity by 100% and complete utilization of glucose as opposed to a significant amount of residual glucose in the control batch fermentation. CONCLUSION: This research demonstrated that vacuum fermentation technology can be used for in situ butanol recovery during ABE fermentation and that C. beijerinckii 8052 can tolerate vacuum conditions, with no negative effect on cell growth and ABE production. Copyright © 2011 Society of Chemical Industry     

Heats of vaporization of then-fatty acid esters

Heats of vaporization at both 25°C and normal boiling points are given for then-fatty acid methyl and ethyl esters and then-alkyl acetates. The validity of the reported heats of vaporization is supported by: (i) their agreement with those estimated by alternate methods, and (ii) the equations correlating heats of vaporization with homolog carbons have the proper slopes (approximately 4.96). Equations also are given for correlating heats of vaporization with boiling points, and boiling points and molar volumes with homolog chainlength.     

估算有机物正常沸点的基团贡献法的研究进展

有机物的正常沸点是重要的物性数据之一。尽管文献中有很多化合物正常沸点的实验值,但一些物质的正常沸点不能由实验获得,可以通过建立数学模型来估算缺少的有机物正常沸点,其中基团贡献法是人们获得正常沸点的最重要研究方法。本文对估算有机物正常沸点的基团贡献法进行了综述。主要介绍了Joback法、C—G法、许文法、定位分布贡献法、元素和化学键法等方法的原理、优缺点及应用范围;并对这些方法进行简单的比较;最后指出了有机物正常沸点的基团贡献法的发展趋势。     

池内水沸腾状态的声发射测量

采用声发射技术,结合频域和时域分析手段,研究了池内水沸腾过程中声信号变化与沸腾状态转变的对应关系。结果表明,当过热度为5℃时,沸腾由自然对流状态转变为核态沸腾状态,此时声信号能量、标准偏差和平均绝对偏差值均达到极值点;当过热度为30℃时,沸腾由核态沸腾状态转变为过渡沸腾状态,此时声信号能量、标准偏差和平均绝对偏差值开始出现剧烈的波动。与此同时,随过热度的增加,沸腾过程中声信号主频出现两次明显的阶跃性下降,分别对应于沸腾状态转变为核态沸腾和过渡沸腾。因此,声信号主频的阶跃性变化可作为沸腾状态转变的判据。与该领域的其他工作相比,不仅考察了自然对流状态和核态沸腾状态,还考察了核态沸腾向过渡沸腾的转变过程,同时提出了沸腾状态转变的判据。与传统方法相比,该法相对简单准确,具有灵敏度高、非侵入式、实时在线的优点。     

卤代乙烷沸点与分子结构的关联及预测

探讨了卤代乙烷沸点的变化规律 ,发展了一种根据分子结构计算和预测卤代乙烷沸点的方法。对74种卤代乙烷的计算结果表明 ,沸点计算值与实验值的一致性令人满意 ,平均误差 1.10 %。并应用该方法预测了一些卤代乙烷的沸点 ,供有关研究者参考和实践的进一步检验。     

High yield production and purification of 5‐hydroxymethylfurfural

Conversion of carbohydrates to 5‐hydroxymethylfurfural (HMF) will provide a new step toward achieving renewable biomass‐based chemicals and fuels platform. Recently, the excellent yield of HMF (91.0%) in dimethyl sulfoxide (DMSO) catalyzed by sulfonated carbon was demonstrated, but the separation of HMF from the reaction mixture remains challenging because of the high boiling point of DMSO. As a solution, herein, low boiling point solvent tetrahydrofuran (THF) mixed with DMSO was used for the fructose dehydration and high yield of HMF (98.0%) was still obtained. Besides, the stability of the sulfonated carbonaceous catalyst was also confirmed. More importantly, HMF from the reaction solution was successfully separated by using simple extraction method, and high purity of HMF (ca. 96.4%) was obtained. Compared with pure DMSO solvent, the combination of low boiling point THF with DMSO not only gives higher yield of HMF, but also improves the separation efficiency and reduces environmental risk. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2558–2566, 2013     

Vapor pressure and normal boiling point predictions for pure methyl esters and biodiesel fuels

Temperature dependent vapor pressures of the methyl esters of fourteen fatty acids that are commonly present in biodiesel fuels were predicted by the Antoine equation and a group contribution method. The predicted boiling points of these esters up to a pressure of 100 mmHg were within ±1.0% of reported data for these two methods. Normal boiling points were determined from both the predicted vapor pressure and a correlation equation and the prediction errors were less than 5 K comparing to available published data. The vapor pressure and normal boiling points of 19 real-world biodiesel fuels were predicted and compared with reported data where available. The prediction errors of normal boiling points were less than 1.0%, and the predicted vapor pressures were also observed to closely match the reported data among the methyl esters of soybean oil, rapeseed oil and tallow. The predicted results showed that, except for coconut and butterfat, most of the methyl esters of the vegetable oils and animal fats had a normal boiling point in the range of 620–630 K. A sensitivity analysis indicated that the variation of fatty acid composition and the uncertainty of the normal boiling point of C18:2 were the main factors that affected the predicted normal boiling points of the biodiesel fuels.     

Measurements of normal boiling points of fatty acid ethyl esters and triacylglycerols by thermogravimetric analysis

At present, a large number of studies of biodiesel production process using simulation packages are being developed. In these studies, vegetable oils and biodiesels are characterized in the software through representative compounds because of they are not in the compounds database of commercial simulators. With the aim to achieve a successfully characterization in these kinds of software, some properties of the substances must be available. The normal boiling point (NBP) is the most important property due to the fact that this property along with group contribution methods allows other properties calculation such as, e.g., critical properties and temperature dependency properties. In this work, a thermogravimetric analysis (TGA) method for rapid measurement of normal boiling points of two triacylglycerols and four ethyl esters, i.e., triolein, tripalmitin, ethyl oleate, ethyl palmitate, ethyl linoleate and ethyl ricinoleate, was used. Nowadays, in the open literature exists few data available about ethyl esters properties; hence, the results obtained here will contribute in the proposal, analysis, and evaluation of ethyl esters (biodiesel) virtual plants using reliable simulation packages. In addition, a more accurate characterization of compounds and therefore more accurate simulation results can be obtained when they are used.     

Enzymatic Synthesis of Ether Lipids Rich in Docosahexaenoic Acid with Squalene as Reaction Medium

Using squalene as reaction medium was tried for the enzymatic synthesis of ether lipids rich in docosahexaenoic acid (DHA) via transesterification of alkylglycerols (AKG) obtained from shark liver oil and DHA-enriched ethyl esters (DHA-EE) from Schizochytrium sp. The effects of reaction time, temperature, molar ratio (AKG /DHA-EE), and enzyme dosage were investigated. DHA conversion of 74.47% was achieved for 48 hours of reaction at 60 °C using a molar ratio of 1:2 and an enzyme dosage of 30% based on AKG in the presence of squalene with Lipozyme® 435 (Novozymes, Tianjin, China) as the catalyst. With a high boiling point, squalene could act as a solvent without being vaporized from the reaction system under vacuum and improve the operational stability of immobilized lipase, which may be useful for enzymatic reactions under vacuum for lipid modification with byproducts of low boiling points.     

沸点蒸发焓估算的基团拓扑空间方法

本文提出了有机物正常沸点蒸发焓估算的基团拓扑空间方法。给出了沸点蒸发焓的估算表达式和相应的基团参数值。沸点蒸发焓估算的平均相对偏差为1 052%。把本方法和广泛应用的其它方法进行了比较,结果表明本方法有更高的准确度和可靠性。     

Prediction of isobaric and isothermal vapour–liquid equilibria from limited experimental data

Malesinski's method for prediction of isobaric vapour–liquid equilibrium data using a single experimental datum on a T–x isobar has been modified and extended to a more general case where the molar entropies of vaporisation of the components are not necessarily equal and the non-ideality in the vapour phase is considered. However, it is assumed that the solution behaves like a strictly regular one over the temperature range in question, that is, the constant A in the expression for excess free energy: g^E=Ax₁x₂ is independent of temperature. The method has been illustrated for several systems and is found to be highly satisfactory for non-polar–non-polar as well as polar–non-polar systems in which the boiling points of the pure components are not much different. Incorporating temperature dependence of the constants in the Redlich–Kister equation for excess free energy, a method has been developed for predicting isothermal vapour–liquid equilibrium data at several temperature levels from equilibrium values at a single pressure. For testing the validity of this method, predicted results have been compared with the available experimental data for zeotropic as well as azeotropic systems comprising non-polar–non-polar, polar–non-polar and polar–polar mixtures, and the method has been found to be satisfactory for all systems.     

Thermal isomerization of (all-E)-lycopene and separation of the Z-isomers by using a low boiling solvent: Dimethyl ether

Thermal isomerization of (all-E)-lycopene and the separation of generated Z-isomers were conducted using a low boiling solvent, dimethyl ether (DME). Because of the low boiling point (–24.8°C), DME is easily separated from lipids and other residues and is extremely low residual. The efficiency of thermal Z-isomerization of (all-E)-lycopene in DME was almost equivalent to using hexane. The thermally generated lycopene Z-isomers were separated by utilizing the solubility differences among lycopene isomers and a characteristic of DME that allows the solubility of compounds to be controlled by changing the temperature. Finally, a lycopene mixture containing 72.0% Z-isomers was obtained from (all-E)-lycopene.     

Effect of process distillation on mutagenicity and cell-transformation activity of solvent-refined,coal-derived liquids

Blended SRC-II process streams, representing a full boiling range distillate material, were fractionally distilled into non-overlapping 50 °F cuts with boiling points between 300 and 850 °F. Another set of 18 distillate cuts were obtained with boiling points ranging between 138 and 1055 °F. Distillate cuts were assayed for mutagenic activity using the histidine reversion assay with Salmonella typhimurium strains TA98, TA100, TA1535 and TA1537, as well as for mammalian-cell transformation activity in the Syrian hamster embryo test, and DNA damage in the prophage induction assay. Samples were also separated into chemical class fractions by alumina column chromatography and analysed by high resolution gas chromatography so that the chemical composition of the cuts could be related to their relative activity in the different assays. In the mammalian cell transformation and microbial mutagenicity assays, significant activity was found almost exclusively in distillate cuts with components boiling > 700 °F, with the highest activity in the transformation assay observed for cuts > 800 °F. All of the distillate cuts showed increased levels of DNA damage as expressed by lambda prophage induction in Escherichia coli 8177. However, the greatest activity was associated with distillate cuts with boiling points in the 800 °F + range. Chemical analysis of the 50 °F distillate cuts showed a variety of polycyclic aromatic hydrocarbons (PAH) and amino-PAH compounds to be present in the distillate cuts boiling > 700 °F and essentially absent from cuts boiling < 700 °F. The sample set of non-overlapping (50 °F) cuts were reblended according to the proportions of each cut found in the original blend material. These reblended composites were then assayed to compare their activity with that predicted from the activities of the component distillate cuts. The reblending experiments indicated the microbial mutagenicity response was essentially additive. Mammalian cell transformation activities were non-additive, indicating a compositional effect on the expression of transforming agents in the complex mixture.     

Effect of boiling water aging on strength and fracture properties of chopped strand mat–polyester laminates

Four types of unsaturated polyesters and chopped strand mat laminates prepared from these resins were examined for their durability after immersion in boiling water. The boiling water aging of fiber-reinforced plastics (FRP) by use of a pressure cooker was found to be 3–4 times faster than boiling water immersion at atmospheric pressure. The weight gain of neat resins increased, and their tensile strength decreased with an increase in immersion time. No variation in the plane strain fracture toughness, K_Ic of the neat resins was observed after boiling water immersion. The elastic–plastic fracture toughness J_Ic of the immersed FRP was measured by a partial unloading procedure. Although J_Ic showed considerable scatter, on the whole, J_Ic of FRP was found to be independent of the four types of matrix resins and also was not effected by immersion in boiling water at 116°C for 24 h.     

Vapour pressure and vapourisation enthalpy of pyridine N‐oxide

The vapour pressure of pyridine N‐oxide was measured using a boiling point method at different temperatures from 389.02 to 546.33 K and the constants of the Antoine equation for the substance were determined. The vapourisation enthalpy of pyridine N‐oxide at the normal boiling point is calculated to be 58.8 ± 1.8 kJ mol^?1. Based on Othmer's method, the standard enthalpy of vapourisation is estimated to be 66.6 ± 0.1 kJ mol^?1 by using pyridine as the reference substance. Furthermore, Watson equation is employed to verify the reliability of and the results demonstrate that the value of is acceptable. © 2011 Canadian Society for Chemical Engineering     

基团贡献人工神经网络法估算有机物常压沸点

基于基团贡献应用人工神经网络法对有机物的常压沸点进行了估算 ,输入参数为有机物的基团数 ,输出为常压沸点 ,本方法具有很好的灵活性 ,并能考虑到基团的相互作用 ,189个样本估算的平均相对误差仅为 1.5 9%     

蒸发焓及沸点估算的基团拓扑空间方法

基于传统基团划分方法提出了描述有机化合物分子拓扑结构的新方法,用基团模指数表征基团在分子中的位置,建立了有机化合物物性估算的基团拓扑空间方法.提出了估算正常沸点下蒸发焓ΔH_vb和沸点T_b的表达式,并分别用503种和669种有机化合物拟合出了相应的基团参数.蒸发焓ΔH_vb和沸点T_b估算的平均相对偏差分别为0.962%和1.40%.与广泛应用的其他方法进行比较,结果表明本方法具有更高的准确度和可靠性.