Characterization of Asphalt Fractions by NMR Spectroscopy

Abstract

Petroleum asphalt was separated into saturates, naphthalene aromatics, polar aromatics, and asphaltenes using the Corbett method. These asphalt fractions were characterized by H-1 and C-13 nuclear magnetic resonance spectroscopy (NMR). The spectra of saturates illustrate only traceable quantities of aromatic hydrogen and aromatic carbon. Naphthalene aromatics, polar aromatics, and asphaltenes all have broad bands in the aromatic regions of both H-1 and C-13 NMR spectra. These broad bands demonstrate the presence of polycondensed aromatic rings present in the structure of naphthalene aromatics, polar aromatics, and asphaltenes. Based on available literature, numerous NMR resonance bands are identified. The quantitative estimations for various kinds of protons and carbons in the asphalt fractions are compared.     

Aquathermolysis of heavy oil in reservoir conditions with the use of oil-soluble catalysts: part I – changes in composition of saturated hydrocarbons

Abstract

This paper is devoted to the study of aquathermolysis processes of heavy oil produced by CSS technology on Boca de Jaruco oil field. Various catalysts based on cobalt, nickel, iron and copper were used for intensification of in-situ upgrading processes of heavy oil. The first paper in series is presented results of transformation of crude oil and its saturate fraction after thermal treatment with and without catalysts by SARA analysis, MALDI mass-spectrometry, FTIR-spectroscopy and gas chromatography. It is revealed, that catalysts provide more deep conversion of asphaltenes and resins into lighter hydrocarbons. Particularly, for the given heavy oil, catalysts based on iron and nickel organic salts are more effective to reduce the content of high molecular weight components (asphaltenes). Saturates fraction after thermal treatment in presence of the catalysts is enriched with lighter alkanes in comparison to the crude oil treated without catalysts. Obtained results show that crude oil recovered by catalytic aquathermolysis processes will be better quality than the original oil in the place.     

饱和分和沥青质对渣油流变特性的影响

 通过Rheostress300型流变仪和偏光显微镜测定了大庆常渣(DQAR)的流型、流型转变特点、黏-温关系和蜡晶形貌等流变性特怔,并分析了渣油饱和分和沥青质对DQAR流变特性的影响。结果表明,DQAR在低温下均为假塑性流体,在高温下转型为牛顿流体,其流型转变温度为50℃。饱和分的加入能使大庆常压渣油蜡晶晶粒变大,网状结构更加紧凑,流型转变温度升高, 并使渣油在非牛顿流型区域黏度急剧增加;而沥青质在整个温度范围内,均能使渣油黏度增大,基本不影响DQAR蜡晶形貌。     

原油热裂解过程中的红外光谱演化特征及其主控因素

原油的红外光谱能够反映原油中各种分子基团的信息,对于简单、快速识别原油的成因类型和热演化程度有很大的应用潜力。通过对两个不同有机相来源的原油样品开展热解实验,初步研究了原油热解过程中红外光谱的演化特征及其主控因素。结果表明,随着原油热解程度的增加,不同类型原油的红外光谱具有相似的演化模式,可近似划分为两个阶段。在早期阶段(实验温度<370℃),热解油中甲基/亚甲基吸光度比值(A_CH3/A_CH2)变化不明显,而芳环分子基团吸光度(A_aro)及其与烷基分子基团吸光度比值(A_aro/A_sat)减小,这主要是由于原油中部分热稳定性低的化合物发生脱支链作用,形成了饱和烃组分,降低了芳烃/饱和烃比值。在晚期阶段(实验温度>370℃),热解油中A_CH3/A_CH2,A_aro和A_aro/A_sat     

新疆托里油砂的催化热解

利用固定床热解装置,考察了温度、氢气浓度、催化剂种类及催化剂与油砂的接触方式对新疆托里油砂热解特性和油砂油收率的影响及催化剂对热解反应活化能的影响. 结果表明,在N2气氛下,550℃时,油砂油收率最高,达44.52%(w);热解气氛中H2浓度增加可促进油砂油中饱和分的二次裂解,使油砂油收率减小,烃类气体产率增加,H2浓度为40%(j)时,饱和分含量降至28.96%(w),较纯N2气氛减少25.43%;以2%(w)的NiO, WO3, ZnO和纳米CuO为催化剂,油砂油产率分别增加15.77%, 16.87%, 3.79%和5.62%;金属氧化物催化剂与油砂的接触方式对油砂油收率有较明显的影响,NiO与油砂分层放置时有利于提高油砂油收率及品质,而纳米CuO和WO3更适合与油砂混合热解;ZnO, NiO和纳米CuO可有效降低油砂热解的活化能.     

Towards a multidisciplinary approach to structuring in reduced saturated fat‐based systems – a review

Although many food products are essentially emulsions, interest in the structuring of oil‐continuous emulsions (and in specific cases water‐continuous emulsions) is intense, particularly to meet the continuing challenge of reducing the degree of saturates in food systems. Consequently, it is necessary to observe the effects of structurants and to examine their impacts on current food systems. This is especially the case where novel structuring materials are used to wholly or partially replace traditional structurants. A multidisciplinary approach is discussed encompassing traditional and novel mechanisms considered able to structure within low saturated fat‐based systems and which in themselves could also have emulsification properties. The presence of interfacial compositions as in emulsions requires a crucial understanding of the interactions within these compositions for the creation of building blocks in oil or fat structuring. Where a co‐surfactant structure may be used, together with novel structurants, for example, wax esters, phytosterols, it is necessary to understand how these may influence interfacial film thickness, strength and flexibility. Understanding how to measure mechanical visco‐elastic properties of structurant interactions both in model and real time dynamic measurements will be necessary to account for diffusion, orientation and self‐assembly mechanisms. This review discusses combining traditional techniques with novel structurant technology; developing and validating dynamic measurement techniques; and investigation of real systems as opposed to purely model systems.     

单程焦化－溶剂抽提组合工艺试验

本文提出了单程焦化－溶剂抽提组合新工艺。与常规延迟焦化相比，单程焦化可大大提高焦化装置处理能力，增加液体产物收率，降低焦炭产率。管输原油渣油中型试验结果表明，液收增加５．０７个百分点，焦炭减少３．３５个百分点。但单程焦化蜡油占液体产物的比例增加，且质量更差。采用双溶剂抽提工艺处理单程焦化蜡油，可使其中９７％以上的饱和烃进入抽余油，硫、氮脱除率分别在５０％和８０％左右。抽余油饱和烃含量达７０％以上，是优质催化裂化原料。抽出油主要是重质芳烃，特别是双溶剂抽提的抽出油，芳烃含量可达９８％以上，可用于开发多种化工产品。     

胜利原油各组分对界面膜扩张流变性的影响

 采取经典的四组分分离方法(SARA)将胜利原油分离得到饱和分、芳香分、胶质和沥青质,利用醇碱萃取法得到酸性组分。通过滴外形分析方法系统研究了上述5类原油组分及稀释原油的界面扩张流变性质,考察了振荡频率和各组分质量分数的影响。结果表明,各类活性组分及稀释原油表现出与表面活性剂类似的界面扩张行为,扩张模量均随振荡频率增大而增大,随质量分数的增加先增大后减小;相角随振荡频率增大而降低,随质量分数增大而增加。各组分模拟油及稀释原油形成的界面膜均表现出较强的弹性行为,且按其界面行为可以分为3组：稀释原油和饱和分、酸性组分和胶质、芳香分和沥青质。模量最大值对应的质量分数高低顺序为稀释原油和饱和分、酸性组分和胶质、芳香分和沥青质。沥青质扩张模量的最大值在 25 mN/m 左右,略高于稀释原油和其它活性组分。     

Rapid Nondestructive Analysis of Intact Canola Seeds Using a Handheld Near-Infrared Spectrometer

The near-infrared (NIR) models for canola quality were developed with samples from Canadian canola seeds harvested in 2016 and 2017. All calibration models were first tested on a 2017 external validation sample set. The handheld NIR spectrometer used in this study has a limited wavelength range 908.1–1676.2 nm; however, the validation results showed that it could be used to predict several important parameters that defined canola seed quality. Final testing was performed using calibration models with the least number of factors on a second external canola validation sample set (2018 harvest). Some calibration models showed excellent stability and predictive powers with R²_val values of 0.94–0.99 (i.e., oil, protein, oleic acid and iodine value) and low SEPs for both external validation sample sets. The α-linolenic acid model had an R²_val of 0.93 when applied to the 2017 external validation set, the correlation fell slightly to 0.88 when applied to the 2018 external validation sample set, potentially indicating a slight instability in the model. The prediction model for total glucosinolate was not very good, but still could be used to segregate the samples into low or high glucosinolate samples. Finally, the predictive models for chlorophyll and total saturates were unusable. The chlorophyll model was very unstable, likely due to the instrument's limited wavelength range.     

氮化合物对饱和烃类氧化的作用

A custom built dynamic oxygen uptake tester was used to study the influence of nitrogen compounds on the oxidation characteristics of the saturate fractions from mineral base oils. Expermental results indicate that nitrogen compounds,especially quinoline and indole,take part in the oxidation of saturates.It is also found that indole is more active than quinoline. The latter can be oxidized partly into ketoimine,and the former is more rapidly oxidized into acylamide.The oxidation products, ketoimine or acylamide, could inhibit the oxidation of the saturates by decomposing hydroperoxide.The influences of indole and quinoline on oxidation of saturates are more complex.For lower nitrogen content, the oxidation processes were accelerated.However, at high nitrogen content, the oxidation induction peroids were increased. The oxidation characteristics of saturates were also dependent on the type of catalysts presented.