Application of Gaussian quadrature method to characterize heavy ends of hydrocarbon fluids for modeling wax precipitation

The hydrocarbon plus fractions that comprise a significant portion of naturally occurring hydrocarbon fluids create major problems when determining the thermodynamic properties and the volumetric behavior of these fluids by equations of state. These problems arise due to the difficulty of properly characterizing the plus fractions (heavy ends). Proper characterization of the heavier components is important when cubic equations of state and/or solid formation thermodynamic models are used to describe complex phase behavior of reservoir fluids. The effect of heavy fractions characterization on thermodynamic modeling of wax precipitation has been investigated using different models including Won, Pan and proposed models. In order to characterize the plus fraction (heavier part) as a series of pseudocomponents, a probability model that expresses the mole fraction as a continuous function of the molecular weight has been used. The study has been conducted using several mixtures. Two different SCN (single carbon number), C₇₊${\text{C}}_{7^{+}}$ and C₁₀₊${\text{C}}_{{10}^{+}}$ were chosen. The Chosen SCN were distributed to multi-components of five, six, and/or ten using continuous function and Gaussian quadrature method. The results showed that the fractioning is required to be able to predict wax precipitation. Distribution of C₁₀₊${\text{C}}_{{10}^{+}}$ using a proper distribution function has shown improvement in predictions of WAT and the amount of wax deposited in comparison with the characterization of C₇₊${\text{C}}_{7^{+}}$ using semi-continuous approach. In predicting of WAT and the amount of wax build up the developed model showed superiority over the others.     

Synthesis of ultra‐low‐molecular‐weight polyethylene wax using a bulky Ti(IV) aryloxide–alkyl aluminum catalytic system

Complexes of titanium(IV) with bulky phenolic ligands such as 2‐tert‐butyl‐4 methylphenol, 2, 4‐di‐tert‐butyl phenol and 3,5‐di‐tert‐butyl phenol were prepared and characterized. These catalyst precursors, formulated as [Ti(OPh*)_n(OPrⁱ)_4?n] (OPh* = substituted phenol), were found to be active in polymerization of ethylene at higher temperatures in combination with ethylaluminum sesquichloride (Et₃Al₂Cl₃) as co‐catalyst. It was observed that the reaction temperature and ethylene pressure had a pronounced effect on polymerization and the molecular weight of polyethylene obtained. In addition, this catalytic system predominantly produced linear, crystalline ultra‐low‐molecular‐weight polyethylenes narrow dispersities. The polyethylene waxes obtained with this catalytic system exhibit unique properties that have potential applications in surface coating and adhesive formulations. Copyright © 2007 John Wiley & Sons, Ltd.     

Thermal analysis via molecular dynamics simulation

Thermal analysis by classical molecular dynamics simulations is discussed on hand of heat capacity of crystals of 9600 atoms. The differences between quantum mechanical and classical mechanical calculations are shown. Anharmonicity is proven to be an important factor. Finally, it is found that defects contribute to an increase in heat capacity before melting. The energy of conformational gauche defects within the crystal is only about 10% due to internal rotation. The other energy must be generated by cooperative strain. The conclusion is that the next generation of faster computers may permit wider use of molecular dynamics simulations in support of the interpretation of thermal analysis.Dedicated to Professor Bernhard Wunderlich on the occasion of his 65th birthday     

Using Neural Networks or Linear Models to Predict the Characteristics of Microcapsules Containing Phase Change Materials

Summary: Microcapsules with large amount of PRS® paraffin wax encapsulated and narrow size distribution were prepared by shirasu porous glass (SPG) emulsification technique and a subsequent suspension like polymerization process and then examined by DSC, laser diffraction and SEM analyses. An experimental design approach, based on a central composite design, was used to determine quantitatively the effect of PRS® paraffin wax/styrene mass ratio (PRS/St), percentage of polyvinylpyrrolidone/styrene mass ratio (%PVP/St) and water/styrene mass ratio (H₂O/St) on the microparticles properties. The results were fitted using two black-box models. The empirical equations allow the prediction of the amount of the paraffin wax encapsulated and the mean particle size in number as a function of aforementioned synthesis variables. It was observed that both models allowed to drawn the same conclusions. %PVP/St mass ratio was the most important parameter affecting the particle size distribution decreasing the average particle size with the increase of %PVP/St. On the other hand, PRS/St mass ratio has a direct influence on the latent heat of fusion.     

Experimental measurement and modeling study for estimation of wax disappearance temperature

Wax deposition is a frequent problem in oil pipelines and down-stream industries. Correct prediction of wax formation conditions is required to prevent this phenomenon. In this study, wax appearance temperature (WAT) of 12 Iranian oil and condensate samples were measured using viscometry data and differential scanning Calorimetry (DSC) analysis. Also, a new empirical correlation and intelligent artificial neural network (ANN) model were developed to estimate wax disappearance temperature (WDT) of crude oils. Specific gravity, pressure, and molecular weight of oil sample were used as input variables for these models. The ANN model was trained using different hidden neurons and training algorithms. Experimental measurements studies were used for validation of the new correlation. Comparing the results indicated that the ANN model has 0.27% error while most thermodynamic models have an average error of 0.35% to 2.19%. Also, the proposed correlation can predict WDT with good accuracy and minimum input data. Results show that this correlation has a maximum error of 1.16% for 310 published experimental data and 1.19% for 9 Iranian samples.     

Wax deposition rate model for heat and mass coupling of piped waxy crude oil based on non-equilibrium thermodynamics

In this paper, wax deposition in waxy crude oil transportation process was regarded as an irreversible process. Based on the entropy production rate equations, the linear phenomenological equations for the diffusion of wax molecules were derived by using the theory and method of non-equilibrium thermodynamics and heat-mass transfer. Combined with the mass and energy conservation laws, the differential equations of heat and mass transfer in the process of pipeline transportation were established, and the molecular diffusion rate of dissolved wax was solved. On the basis of this, the mathematical model of actual wax deposition rate was established by considering the attachment process and scouring process of the wax molecules. Taking an oil pipeline in Daqing as an example, the change law and influencing factors of the wax molecular diffusion coefficient, the wax deposition rate, and the net wax deposition rate were studied by numerical simulation. The wax deposition rate test results of the laboratory loop test were compared with the theoretical calculation results in order to analyze the accuracy and the adaptability of heat and mass coupling mechanism and to provide a theoretical basis for further study of wax deposition in the process of waxy oil pipeline transportation.     

PREPARATION OF MICROPOROUS ULTRA HIGH MOLECULAR WEIGHT POLYETHYLENE (UHMWPE) BY THERMALLY INDUCED PHASE SEPARATION OF A UHMWPE/LIQUID PARAFFIN MIXTURE

Ultra-high molecular weight polyethylene (UHMWPE) with a microporous structure was prepared via thermally induced phase separation (TIPS).Liquid paraffin (LP) was used as a diluent in the preparation of microporous UHMWPE. Small angle laser light scattering (SALLS) and differential scanning calorimetry (DSC) were used to determine the phase separation temperatures,i.e.the cloud points and the dynamic crystallization temperatures,respectively.It was found that the cloudI points were coincident with the cr...     

木蜡油涂饰对檀香紫檀易混树种的红外光谱影响分析

卢氏黑黄檀和染料紫檀木材特征与檀香紫檀相似,特别是两者经过加色精的木蜡油涂饰后,用肉眼很难与珍贵的檀香紫檀分辨。市场上销售的很多红木家具为了达到防腐、防尘、防开裂的性能以及提高红木表面光泽度和显现珍贵木材的纹理,大都进行了木蜡油表面涂饰加工,因而只研究木材本身的鉴别不能满足市场需求。借助红外光谱（FTIR）结合二阶导数红外光谱（SDIR）和二维相关红外光谱（2D-IR）技术,对经过木蜡油涂饰的檀香紫檀（Pterocarpus santalinus）、染料紫檀（P.tinctoricus Welw）和卢氏黑黄檀（Dalbergia louuelii）进行了红外光谱分析。通过打磨-涂底油-打磨-涂面油-干燥的涂饰工艺对3个树种进行表面涂饰。分别取3个树种素材的木粉和经过表面涂饰的木材表面的木粉进行FTIR,SDIR和2D-IR三级鉴别分析,同时测定了木蜡油的FTIR谱图。结果表明：(1）木蜡油FTIR谱图在2 925,1 733,1 465和1 378 cm-1较强的特征峰出峰位置与3个树种木材本身的出峰位置基本重合,且在2 854 cm-1处归属于亚甲基C-H对称伸缩振动,1 233 cm-1处归属于羧基C-O伸缩振动,729 cm-1处归属于长链的亚甲基C-H弯曲振动的特征峰在涂饰后三种样品的FTIR谱图中有相同的体现,说明木蜡油涂饰未对3个树种红外谱图的特征峰产生影响;3个树种表面涂饰前后FTIR谱图的相关系数同时可以对木蜡油涂饰未对3个树种的特征峰产生影响进行佐证;(2）FTIR谱图在1 595,1 060和836 cm-1处可以将染料紫檀与檀香紫檀和卢氏黑黄檀两个树种区分开;SDIR谱图可以在1 551 cm-1将卢氏黑黄檀区分开,并能进一步对染料紫檀的特征峰进行验证;在2D-IR光谱中,在1 425~1 800和850~1 300 cm-1两个波段范围,檀香紫檀的自动锋明显区别于其他两个树种,在1 250 cm-1处归属于醚类化合物的吸收峰可以将檀香紫檀区分开。目前红木识别主要利用木材解剖方法,表面涂饰大多集中在木材材色变化研究。借助红外光谱技术,最终利用各个树种和木蜡油在红外光谱谱图中不同的特征峰体现的官能团差异直接推测特征成分的含量差异,无须测定其特征成分的具体物质,进而实现准确、快速地把经木蜡油表面涂饰的檀香紫檀及与其易混淆的染料紫檀和卢氏黑黄檀区分鉴别。     

多级孔HZSM-5分子筛催化剂的制备及低碳烃芳构化应用

采用0.2 mol/L的NaOH溶液对HZSM-5分子筛进行了不同时间的碱改性处理, 并对分子筛的结构和酸性进行表征, 考察了碱改性对HZSM-5催化剂的低碳烃芳构化活性的影响. 结果表明, HZSM-5分子筛经碱改性后会产生少量介孔, 且随改性时间延长, 介孔数量增加, 平均孔径增大, 总酸量降低, B酸/L酸比值降低. 120 min碱改性HZSM-5催化剂的活性、 稳定性以及目标产物苯、 甲苯、 乙苯和二甲苯(统称BTEX)的选择性最高.     

偶氮胂Ⅲ-镝(Ⅲ)反射散射光度法测定蛋白质

研究了微晶石蜡吸萃蛋白质—偶氮胂Ⅲ-镝(Ⅲ)复合物的条件,并设计了固相反射散射分光光度直接测定石蜡相中牛血清白蛋白(BSA)的方法,所拟定的方法有较好的选择性,可以用于25—300μg／25mLBSA的测定．