轻烃在改性ZSM－5催化剂上转化成芳烃与低碳烯烃的选择性控制

研究了Ｃ３－Ｃ９烷烃在不同的改性ＺＳＭ－５沸石上的反应规律．过渡金属离子改性的ＺＳＭ－５沸石显示了较高的芳烃选择性，芳烃的选择性还取决于改性金属离子的脱氧能力并可通过预硫化得到改进．钾、钡改性的沸石显示了较高的烯烃选择性，增加钾含量，烯烃选择性显著提高，但也明显抑制了催化剂的活性；提高Ｂａ含量，同样可提高烯烃选择性，但对活性影响不大．环己烯的模型反应结果表明，Ｋ，Ｂａ的作用在于抑制了双分子氢转移反应和提高了脱氢能力．红外表征结果表明，沸石表面的羟基，因不同金属改性而发生不同的变化．此外，气相氧对提高烯烃和芳烃的收率有明显作用     

Evaluation of pressure on the crystallization of waxes using microcalorimetry

Petroleum composition contains various sizes and quantities of paraffins. Their crystallization and deposition cause many of the problems of oil production. The determination of the wax appearance temperature (WAT) is a useful method of predicting the behavior of oil in production lines. The measured WAT value depends on factors such as: oil composition, thermal history, pressure, measurement technique and cooling rate. There are hardly any studies in the literature that have analyzed the effect of pressure and light fractions on the WAT of oils. Moreover, given the diversity of factors involved in the analysis of the results, the studies that do exist do not enable one to evaluate the effect of light fractions on paraffins with specific sizes and size distributions. This study characterized commercial paraffins with different features according to size and distribution of the molecule size. The paraffins were analyzed using high-pressure microcalorimetry (HPμDSC), and the saturation gas characteristics were varied. The results showed that the fractions heavier than C3, contained in the saturation gas, were more efficient at solubilizing paraffins with lower molar masses. Regarding the commercial paraffins with higher melting points, methane had a solvency that was slightly lower than the blend of gases with the highest levels of fractions >C3.     

THE ADSORPTION OF AN ANIONIC SURFACTANT AT THE OIL WATER INTERFACE DURING EMULSION HOMOGENIZATION

Adsorption of sodium dodecylbenzene sulfonate (NaDBS) on the surfaces of dispersed oil globules during homogenization of paraffin oil in water emulsions has been studied. NaDBS concentration was changed over a wide interval comprising critical micelle concentration. For the emulsions homogenized for different time intervals the total quantity and the percentage of NaDBS adsorbed, the amount and number of NaDBS molecules adsorbed per unit inter-facial area, as well as the specific surface area of dispersed phase and the area per emulsifier molecule have been determined.

The amount adsorbed and density of the emulsifier layer, I.e., the area per NaDBS molecule adsorbed on the oil globule surfaces, depend not only on Initial NaDBS concentration but also, on the homogenization time and the homogenization action. This makes a difference between the adsorption behaviour under the conditions of emulsion formation and its subsequent homogenization, and the adsorption behaviour of the emulsifier at a plane quiescent Interface.     

Dimethylbenzothiophenes and methyldibenzothiophenes in crude oils from different sources

A method is presented for the identification and quantification of C₂-substituted benzothiophenes in crude oil. The method will enable analysis of the pattern of these compounds, for example as a basis for differentiating crude oils from one another (fingerprinting) and for investigation of their suitability as indicators of oil maturity. Here results are reported for five crudes from Iraq, Venezuela, Saudi Arabia, the former Soviet Union, and the North Sea. The aromatic fraction of the crudes was oxidized and the dioxides of the heterocycles separated according to the number of carbon atoms in the side chains. The final separation was by capillary GC with atomic emission or flame ionization detection. A fluorinated analog was synthesized and used as internal standard. The concentrations of 2,3-, 2,4-, 2,7-, and 3,7-dimethylbenzothiophene ranged between 11 and 272 ppm. Three other dimethylated benzothiophenes present in lower amounts were also identified.     

杯芳烃交联聚硅氧烷热稳定性能研究

聚有机硅氧烷是一类主链由硅-氧键连接而成,侧链为有机基团的聚合物,兼具有机聚合物和无机聚合物的特性,性能优异,尤以卓越的耐高温性能而著称,在大气中于-50~250℃可以长期使用[1].为了进一步提高聚有机硅氧烷的热稳定性,主要有以下几种方法,(1)添加各种耐热性添加剂,或可与聚     

UNIQUAC model for wax solution with pour point depressant

It had been shown that after adding pour point depressant (PPD), the diffraction line intensities of paraffin mixtures progressively decreased without any significant variation of the Bragg angle values. This phenomena is due to the structure of paraffin mixture is partly transformed from orthorhombic into hexagonal form. Owing to the crystal lattice transformation, the amount of wax precipitated from oil treated with PPD in the experimental range is lower than that from untreated oil and the wax precipitated from treated oil is richer in the higher melting point paraffins than that from untreated oil. A thermodynamic model is established in this work to predict these experimental results. The liquid phase behavior is described by the LCVM mixing rule and an equation of state-G^E model while the solid-phase non-ideality is represented by the UNIQUAC equation, respectively. New correlations for the melting points and solid–solid transition temperatures of treated paraffins are established based on the experimental results by differential scanning calorimeter (DSC). The experimental results indicated that the melting points and solid–solid transition temperatures of treated paraffins were both decreased. The calculation results for the amount and composition of wax precipitated from treated and untreated solutions at different temperatures have been compared with experimental observations. It has been shown that the predicted results agree well with the experimental ones.     

气体中微量油分析方法研究

对GJB 3403—98气体中微量油分析方法存在的不足进行了分析,对技术指标、标准物质、冷源、流速、取样量、油含量单位进行了探讨,并以实验证明了用冷凝富集-紫外分光光度法测定氦气、氮气、空气中微量油含量的可行性。方法改进后可以提高氮气、氦气、空气等气体中油含量分析的可靠性。     

醇酸树脂热炼过程中分子量分布的研究

<正> 涂料工业中醇酸树脂基料分子量分布的研究,通常采用萃取分级法和沉淀分级法,近年来发展了高速凝胶色谱法。我们曾报道了高效GPC法测定醇酸树脂的分子量分布的方法。本文就醇酸树脂热炼过程产物作了物性表征和研究。 实验所测试样系取自5吨反应釜热炼生产中酯化过程各阶段和反应终点的产物。各品种醇酸树脂的配方见表1。     

On the flow characteristics of highly concentrated oil-in-water emulsions

The laminar flow characteristics of oil-in-water emulsions with oil concentrations greater than 59% by volume have been investigated experimentally. Up to an oil concentration of 65% by volume, the emulsions exhibited power-law non-newtonian behaviour. At a higher oil concentration, of 72.21% by volume, a dramatic change in the flow behaviour of the emulsion was observed. The flow curve, i.e. shear stress vs. shear rate plot on a log-log scale, clearly exhibited the presence of a yield-stress.The rheological data on the emulsions were used to correlate the laminar pipeline transport data on the same emulsions. For power-law emulsions, values of the drop in pipeline pressure could be accurately predicted from simple rheological measurements. For a yield-stress emulsion, the experimental pipeline data deviated from the predicted values especially at low values of shear stress.     

Effect of solvent properties on permeate flow through nanofiltration membranes. Part I: investigation of parameters affecting solvent flux

The objective of the present study was to characterize transport properties of solvents permeating through solvent resistant nanofiltration membranes that have only recently become available. Permeation flows of a number of solvents of different chemical families were measured in a batch cell. The solvents studied were alcohols, paraffins, ketones, acetates, and water, as well as their binary mixtures. The experimental data revealed a marked variation in the level of permeate flux among the various solvents. For instance, permeation flow of pentane was about 60-times faster compared to that of water while permeation flow of ethanol was about 10-times faster than that of water. The dependence of solution flux on the fractional composition of the solvents in the mixture was found to be highly non-linear. The flux of either pure or mixed solvents was mainly affected by surface tension and viscosity of the solvents. The flux of paraffins mixtures in particular was affected by the dielectric constant also.     

Supercritical fluid extraction of Moroccan (Timahdit) oil shale with water

Timahdit oil shale was subjected to supercritical water extraction. The results reveal significant difference in oil yields and composition when compared with those obtained from conventional pyrolysis. In addition, the effect of temperature and residence time on the supercritical water extraction of oil was investigated in a set of three experiments. The results revealed that the yield and the fraction of paraffins and aromatics increase while the percentage of asphaltenes decreases as the temperature is increased from 380 to 400°C. The residence time was found to affect the yield and the fraction of asphaltenes and polar compounds.     

煤中无机矿物组分的溶出性及其对水煤浆流变特性的影响

用等离子体原子发射光谱考察了１４种不同变质程度煤中的无机矿物质在煤浆分散体系中的溶出性，并就其对浆体流变特性的影响进行了讨论。结果发现；煤中无机矿物质的溶出性视煤种和煤中矿物质含量的不同而有很大差异，而且，除个别煤熔出相当数量的铝离子外，其余煤在浆体分散体系中溶出的无机矿物离子均主要以钙出子为主，其次为镁，铁离子。     

Analysis of Alaskan crude oils by glass capillary gas chromatography/mass spectrometry

Glass capillary gas chromatography/mass spectrometry is used to profile Alaskan crude oil for purposes of origin verification. Alaskan oil, sampled at Valdez, Alaska, and transshipped to the U.S. East Coast, is compared with 21 samples of foreign crude oil using GC/MS techniques in which original data is reconstructed at selected parent and fragment ions to generate a series of chromatographic profiles. Comparison of selected profiles and compositional parameters derived from peak ratios allows distinction of Alaskan oil from many foreign crudes and may be applied to the examination of crude mixtures.     

Supercritical fluid chromatography of industrial paraffins and waxes

Summary The application of capillary SFC for SIMDIST investigations of paraffins and waxes is reported. Pressure, density and temperature of the mobile phase are optimized to obtain high chromatographic resolution of complex mixtures of industrial products. Isothermal linear pressure programming and asymptotic pressure and density programming are used in the range from 15 to 35 MPa in the isothermic mode above 100°C. SFC chromatograms of natural and synthetic paraffins, microcrystalline wax and candle wax are compared. The retention behaviour of paraffin mixtures and waxes has been investigated on methyl/phenyl and biphenyl capillary columns. The polarity of the stationary phases influences the absolute retention time more than it influences the chromatographic resolution.     

A new quick method of determining the group hydrocarbon composition of crude oils and oil heavy residues based on their oxidative distillation (cracking) as monitored by differential scanning calorimetry and thermogravimetry

A calorimetric-thermogravimetric method is described of determining mass percent contents of distillate fractions, paraffins, base oils, resins, asphaltenes and carbines in various crude oils. The method is based on recording DSC curves of a 10–15 mg sample heated in air in a calorimetric-cell at a rate of 40–50 °C/min. Additionally, weight loss of sample is found at temperatures before and after the reaction. At temperatures from 220 °C or higher distillation of the hydrocarbon mixture starts to be accompanied by its exothermic oxidation, thereby making possible monitoring the distillation (oxidation) of consecutive HC fractions by simple calorimetric-techniques. Differential scanning calorimeter “Thermodat” of high-calorimetric-resolution and sensitivity equipped with dedicated software was used for conducting the experiments and performing all the calculations. Percent contents of the main constituents in a number of heavy and light crude oils were determined and formulas for establishing paraffinic, base oil and coke-forming potentials of crude oils and oil residues derived. One full analysis of a sample takes no longer than 1.0–1.5 h. The method can be used for on-line quality control of various petroleum products, such as atmospheric and vacuum oil residues, cracking residues, lubricants, ceresins and paraffins.     

气相色谱-场电离飞行时间质谱测定中间馏分油中链烷烃的形态分布

利用气相色谱-场电离飞行时间质谱技术( GC-FI TOF MS)建立了中间馏分油中不同异构程度链烷烃的碳数分布表征方法。首先利用GC-FI TOF MS技术对不同异构程度的链烷烃进行分离、鉴别,然后建立了中间馏分油沸点范围内正构烷烃、异构烷烃在GC-FI TOF MS测定时的相对响应因子算法及不同异构程度链烷烃的碳数分布算法,最后考察此定量方法的精密度和准确度。结果表明,GC-FI TOF MS可以将同碳数链烷烃区分为异构程度不同的3部分：多取代基异构烷烃、单取代基异构烷烃和正构烷烃;可利用GC-FI TOF MS对异构程度不同的链烷烃进行定量分析,精密度较好,相对偏差小于15%。此方法无需进行样品预分离,可直接进样分析,缩短了分析时间,且首次提供了不同异构程度异构烷烃的碳数分布信息。     

Change in the Rheological Properties of Oil Disperse Systems upon a Vibrational Treatment

The effect of a vibrational treatment on the rheological properties of highly structured oil disperse systems is studied. A maximal decrease in the rheological parameters is observed after 20-min vibrational treatment for paraffin-rich and highly resinous oils and after 5-min treatment for mazut. The vibrational treatment is shown to be the most effective for oils with an increased content of paraffins. It is revealed that the magnetic treatment decreases the congelation temperature of oil.     

Selective inhibition of paraffin deposition under high flow rate as a function of the crude oil paraffin type and content by fluorescence depolarization: polypropylene and high-density polyethylene

High-density polyethylene (HDPE) and polypropylene (PP) were studied to identify tailor-made materials for walls of pipelines and ducts for crude paraffinic oil that inhibit paraffin depositions. The interfacial interaction was investigated from 50 to 70 degrees C and as a function of the n-C(36)H(74) paraffin concentration added to the paraffinic crude oil. The static and the dynamic interfacial tensions were observed, respectively, by traditional contact angle measurements and by fluorescence depolarization of the natural fluorescent probes of the crude oil, flowing at a high rate. The static interaction showed a low dependence on the n-paraffin content for both surfaces. For PP, it decreased slightly as the n-paraffin concentration increased, evidencing an increase in the liquid-liquid interaction. The dynamic interfacial tension with PP clearly decreased as temperature and n-paraffin concentration increased, the latter effect being attributed to the PP methyl groups hindering the interaction between the n-paraffin and the PP main chain. For the flow on HDPE, the interaction proved to be highly dependent on the n-paraffin concentration and temperature. It increased as n-paraffin was added and temperature decreased. The former effect is attributed to the alignment of the n-paraffin chains within the high rate flowing liquid and the similar molecular geometry of the n-paraffin and the linear polymer surface (almost without branches), which increases the number of sites available for interaction. PP proved to be more suitable for transportation of crude oil rich in paraffins with more than 36 carbon atoms, while HDPE was more suitable for those with smaller paraffinic chains.     

Further considerations on oxidative processes

Refuting recent criticisms by Russell, modification of the currently accepted mechanism of formation of benzyl chloride from toluene is introduced and current interpretation of the reactivity of carbonyl compounds is broadened. The results of the photochemical interaction of benzophenone, isopropyl alcohol, and nitric oxide are shown to accord with classical as against the hydrogen-abstraction theory of oxidation. Supplementary discussion of the behaviour of ethers, amines and paraffins is also contributed.     

Hydrocarbon Formation in the Catalytic Conversion of Methanol Over Zeolite ZSM-5

The reaction mechanism of methanol conversion to hydrocarbons on HZSM-5 zeolite was studied. From the selectivity plots of products in an integral fixed-bed flow reactor, paraffins were classified as primary and secondary stable products, light olefins as primary unstable products, aromatics as primary and secondary unstable or stable products. The results of the ¹⁴C-labelled methanol reaction indicated that the C₁–C₅ surface intermediates generated by dimethyl ether / methanol equilibrium gave paraffins and olefins at 300°C. The concentration of intermediates and adsorbed methanol on ZSM-5 decreased with increasing temperature. The distribution of radioactivity showed that propylene played an important role in the autocatalysis of the reaction.