Thermal analysis of Beypazari lignite

Beypazari lignite was investigated by differential scanning calorimetry (DSC), thermogravimetry (TG), high pressure thermogravimetry (HPTG) and combustion cell experiments. All the experiments were conducted at non-isothermal heating conditions with a heating rate of 10°C min^?1, in the temperature range of 20–700°C. DSC-TG data were analysed using an Arrhenius-type reaction model assuming a first-order reaction. For the HPTG data the Coats and Redfern equation was used for kinetic analysis. In the combustion cell experiments the Fassihi and Brigham approach was used in order to calculate kinetic data. Finally a comparison is made between the kinetic results.     

原油组分低温氧化机理和反应活性实验研究

分析了原油和原油组分低温氧化的机理,通过实验进行了不同油品低温氧化反应,考察了氧化反应前后原油族组成的变化,并研究了单组分(正十六烷、蜡、蒽、沥青质)在不同温度下的低温氧化速率和反应活性,得出了不同原油组分的低温氧化反应的活化能。结果表明,稠油较轻质油有更好的氧化反应活性,在较低温度下稠油更容易被氧化,原油中不同组分及含量是影响氧化反应活性和氧化反应速率的重要因素,重组分的沥青质和长链烷烃在低温下(70~90℃)氧化活性较高,正十六烷和蒽反应活性较之重组分低。揭示了原油组分低温氧化反应机理以及不同组分氧化反应活性的区别,为油田注空气工艺方案设计提供基础。     

Kinetics of crude oil combustion

In this research, thermal characterization and kinetics of Karakus crude oil in the presence of limestone matrix is investigated. Thermogravimetry (TG/DTG) is used to characterize the crude oil in the temperature range of 20-900°C, at 10°C min ^-1 heating rate using air flow rate of 20 mL min ^-1. In combustion with air, three distinct reaction regions were identified known as low temperature oxidation (LTO), fuel deposition (FD) and high temperature oxidation (HTO). Five different kinetic methods used to analyze the TG/DTG data to identify reaction parameters as activation energy and Arrhenius constant. On the other hand different f(α) models from literature were also applied to make comparison. It was observed that high temperature oxidation temperature (HTO) activation energy of Karakus crude oil is varied between 54.1 and 86.1 kJ mol ^-1, while low temperature oxidation temperature (LTO) is varied between 6.9 and 8.9 kJ mol ^-1.     

Characterization of Oil Shales by High Pressure DSC

Pressurised differential scanning calorimeter (PDSC) has been used to obtain information on the pyrolysis and combustion characteristics of oil shales. Two distinct exothermic peaks were identified in combustion experiments known as low temperature oxidation (LTO) and high temperature oxidation (HTO) reaction regions. The pyrolysis process of all studied oil shale samples showed one exothermic effect at each total pressure studied. Kinetic data were analysed by Roger & Morris and Arrhenius methods and the results are discussed. This revised version was published online in August 2006 with corrections to the Cover Date.     

马瑞原油在空气和氮气中的热解-氧化性能

低温氧化是注空气采油及原位燃烧采油技术中的重要化学反应,为深入认识原油在有氧环境下复杂热反应过程中的低温氧化特性,我们采用热重/差热分析法(TG/DTA)研究了线性升温和等温条件下马瑞(Merey)原油的热反应行为。 结果表明,Merey原油在空气及线性升温条件下的受热过程分4个阶段:气化段、低温氧化段、热解段和高温氧化段;相邻阶段的物理、化学主导过程的重叠增加了分析原油热反应特征的难度。 升温速率提高,气化段和低温氧化段的终止温度不变;热解段和高温氧化段的终止温度以及热解段的峰温随升温速率的增加而升高。 N₂气与空气下Merey原油的热重/微分热重(TG/DTG)数据对比表明,升温速率越高,空气下的高温氧化段与热解段重叠程度越大,这有利于燃烧但会降低原油采收率。 空气下等温时的TG/DTA结果表明随升温速率增加,升温至300 ℃时的失重率降低,不利于原油轻组分的气化。 反应温度越高,气化过程时间越长,失重分数越大。 Merey原油在低于300℃时低温氧化反应不是主导反应。     

Investigation of the properties of oil at the bleaching unit of an oil refinery

Color removal from neutralized sunflower oil was studied with different kinds of commercial bleaching earths. The effect of changes in time (25 and 35 min), temperature (80-125 degrees C), and bleaching earth dosage (0.1-0.9% by weight) on color, chlorophyll and carotene concentrations, and oxidation degree were investigated. To obtain adsorption curves from coloring compounds adsorbed onto activated bleaching earths, the Langmuir and Freundlich equations was used, the constant parameters and correlation coefficient R were calculated for each type of bleaching earth, and color changes were explained by both adsorption isotherms. It was observed that an increase in bleaching earth dosage decreases color. Its effect on oxidation state, however, is complex and related to both primary and secondary oxidation products. In addition, an increase in temperature seems to decrease chlorophyll and carotene adsorptions. Generally, time beyond equilibrium is considered useless for the removal of unwanted components. This study also confirms this claim and reveals that the peroxide value does not indicate the oxidation state of the oil completely.     

酯类基础油热氧化过程中的拉曼光谱分析

将DXR激光显微拉曼光谱仪与Linkam FTIR600控温台联用,测定了连续加热、恒温氧化过程中三羟甲基丙烷油酸酯(TMPTO)、偏苯三酸三异酸酯(TDTM)、己二酸二异辛酯(DOA)等酯类基础油的拉曼特征峰的变化规律,探讨了热氧化过程中酯类油分子结构的变化特点。研究发现,随着加热温度的提高,酯类基础油的部分拉曼峰的峰位与峰强均发生了明显变化;酯类基础油的甲基与亚甲基的C—H伸缩振动峰及亚甲基的剪式振动峰对温度很敏感,随着温度的升高发生了不同程度的峰强衰减,冷却后可基本恢复;C‖O振动峰随温度的升高变化不明显;TMPTO酯类基础油的C‖C双键伸缩振动峰随着温度升高逐渐向高波区移动冷却后可恢复,‖C—H和C‖C的伸缩振动峰强冷却后不能完全恢复;恒温下随着氧化时间的延长,TDTM和DOA基础油的拉曼峰无明显变化,与TMPTO基础油的‖C—H、C‖C及—CH2—相关的拉曼峰呈规律性衰减。因此可运用原位拉曼光谱法对不饱和酯类基础油中连续氧化进行监测。而原位光谱法对饱和酯类油和芳香酯类油高温连续氧化过程的监测具有一定的局限性。     

稠油的可控氧化热采：MnO2催化剂上的重油低温氧化分解行为

采用MnO2纳米催化剂促进稠油重组分的低温氧化裂解及高温氧化生热,进而促进火烧油层技术在超稠油油藏开发中的应用,提高火烧油层技术的采收率.结果表明, MnO2促进了稠油的低温裂解,高温生热量并不随燃料沉积量的减少而降低. MnO2的加入促进了低温下小分子的生成,并使高温氧化反应更加温和,提高了高温产物的氧化度.相比无催化剂的氧化反应, MnO2使稠油的低温氧化和高温氧化的表观活化能分别降低了10–30 kJ/mol和20–40 kJ/mol.     

Survey on ionic liquids effect based on metal anions over the thermal stability of heavy oil

A survey on the effect of ionic liquids (ILs) over the thermal stability of a heavy Mexican oil was performed. ILs used were based on [C_nim]⁺ and [C_npyr]⁺ organic cations with FeCl₄⁻ metal anion. Mixtures of heavy crude oil (HCO) with ILs show three oxidation zones: low temperature oxidation (LTO), full deposition (FD) and high temperature oxidation (HTO). Thermal stability and mass loss decrease in the LTO zone but increase in the FD and HTO zones for every ILs used. The activation energy of the oxidation is influenced by the ILs in the HTO zone. It decreases when increasing the size of the organic radical substitute in the cation of the ILs while it increases with the presence of hydroxyl groups. The influence of electronic structure and reactivity indexes are rationalized to understand the variations of activation energy obtained of the reaction systems. Among all cations used, cation-3 (IL-3) shows the greater value of HOMO-LUMO gap as well as the lower activation energy.     

Headspace Solid-Phase Microextraction Analysis of Volatile Components in Peanut Oil

Peanut oil is favored by consumers due to its rich nutritional value and unique flavor. This study used headspace solid-phase microextraction (HS-SPME) combined with gas chromatography (GC) and gas chromatography–mass spectrometry (GC-MS) to examine the differences in the peanut oil aroma on the basis of variety, roasting temperatures, and pressing components. The results revealed that the optimal conditions for extracting peanut oil were achieved through the use of 50/30 μm DVB/CAR/PDMS fibers at 60 °C for 50 min. The primary compounds present in peanut oil were pyrazines. When peanuts were roasted, the temperature raised from 120 °C to 140 °C and the content of aldehydes in peanut oil increased; however, the content of aldehydes in No. 9 oil at 160 °C decreased. The components of peanut shell oil varied depending on the peanut variety. The most marked difference was observed in terms of the main compound at the two roasting temperatures. This compound was a pyrazine, and the content increased with the roasting temperature in hekei oils. When the roasting temperature was lower, No. 9 oil contained more fatty acid oxidation products such as hexanal, heptanal, and nonanal. When the roasting temperature increased, No. 9 oil contained more furfural and 5-methylfurfural. Heren oil was easier to oxidize and produced nonanal that possessed a fatty aroma.     

Evaluation and Optimization of the Oxidation efficiency of a UV-Persulphate-Oxidation Toc-Analyzer for the Determination of Oil Contamination from Forestry in Ground Water

Different chain oils (tall, rape seed and mineral oils) have been used as model compounds to evaluate and optimize the applicability of UV-persulphate TOC-analyzer for quantitative determination of forestry oils and to follow the progress of their biodegradability. It was shown, that K 2 S 2 O 8 -UV-oxidation method is not sufficient to oxidize chain oils completely. There were differences in oxidation efficiency between different oils, changing from about 46% measured for tall oil to about 25% observed for rape seed chain oil. The addition of Triton X-100 surfactant up to 2% (w/w) was observed to increase the oxidation efficiency, e.g. to 75% for tall oil. The observations can be explained by assuming that in the presence of surfactant the emulsions are more homogeneous and stable. Optimization using two-level full factorial design (temperature of the oxidation chamber and the amount of persulphate) was studied. The results show that the UV-persulphate-oxidation TOC-analyzer is not suitable method to monitor biodegradability of chain oils.     

Modelling relation between oxidation resistance and tribological properties of non-toxic lubricants with the use of artificial neural networks

The lubricants based on vegetable oils, as environmental friendly, are urgently sought. However, in addition to ecological characteristics, the lubricating properties have to be met. To meet these requirements the active additives influencing the lubricating properties and oxidation resistance are used. The useful lifetime of lubricants is determined largely by their abilities to resist oxidation. The article presented the results of new, ecological lubricants development. The oxidation performances of different developed lubricants have been tested. The experimentally determined oxidation stability of the compositions based on vegetable oils are presented. Analysed oxidation onset temperature was obtained from the differential scanning calorimetry (DSC) curves, which provides the rapid prediction of the oxidative stability of lubricants. Besides the lubricating composition based on vegetable oils, the developed greases-based mineral, or synthetic oil were investigated. The properties of these greases were evaluated using the measurement of parameters describing structure (penetration) and resistance to high temperature (dropping point). The lubricating properties of both the greases and vegetable oil compositions were tested on four-ball testing machine. In the results of the modelling of the lubricating properties the neural network models for the both types of the lubricants were developed. A discussion of the research results and analysis of models validity is given below. The experimental results are compared with the calculated using the neural models. An acceptable agreement was achieved.     

Catalytic Effects of Metallic Additives on The Combustion Properties of Crude Oils by Thermal Analysis Techniques

Differential scanning calorimetry (DSC) was applied to crude oil combustion in the presence and absence of metal chlorides. It was observed that in the presence of smaller ratios of metallic additives, the surface reactions were predominant and the catalyst did not affect the reactions much. Three reaction regions were identified as low temperature oxidation (LTO), middle temperature oxidation (MTO) and high temperature oxidation (HTO). Kinetic parameters of the reaction regions were determined with two different methods and the results are discussed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Effect of different clay concentrations on crude oil combustion kinetics by thermogravimetry

The objective of this research was to investigate the effect of different clay composition and concentrations on the thermal behaviour and kinetics of heavy crude oil in limestone matrix by thermogravimetry (TG/DTG). In TG/DTG experiments, three distinct reaction regions were identified in all of the crude oil + limestone mixture known as low temperature oxidation (LTO), fuel deposition (FD) and high temperature oxidation (HTO) respectively. Addition of clay to porous matrix significantly affected the reaction regions. Significant reduction of activation energy due to addition of clay to crude oil indicates the catalytic effect of clay on crude oil combustion.     

Influence of reservoir rock composition on the combustion kinetics of crude oil

In this research, the effect of different lithology (limestone and sandstone) on the combustion of light crude oils was investigated using thermal analysis techniques. Three distinct reaction regions were identified in all of the crude oil+limestone and sandstone mixtures, known as low temperature oxidation (LTO), fuel deposition (FD) and high temperature oxidation (HTO), respectively. Kinetic analysis of the crude oil+limestone and sandstone mixtures was performed using Coats and Redfern method and the results are discussed.     

抗氧剂对植物油氧化稳定性影响的高压差示扫描量热法评价

利用高压差示扫描量热法（ＰＤＳＣ）研究了二烷基二硫代氨基甲酸锌（ＶＡＺ）、２,２′－亚甲基双（４－甲基－６特丁基苯酚）（２２４６）、苯江三唑（ＢＴＺ）和二烷基对苯二胺（ＤＢＡ）４种抗氧添加剂对菜子油氧化稳定性的影响,得到了它们抗氧化作用的大小顺序。别外,根据队仑尼乌斯公式计算了不同油样氧化反应的活化能,证明了ＰＤＳＣ是一种快速简便评价基础油氧化稳定性的方法,适用于抗氧添加剂配方的设计工作。     

不同酯基结构的棕榈油生物柴油的性能研究

以棕榈油为研究对象,分别与甲醇、乙醇、异丙醇和异丁醇进行酯交换反应制备了不同酯基结构的生物柴油。利用差示扫描量热仪和应力控制流变仪分析了不同酯基结构棕榈油生物柴油的结晶行为和低温流变性能,同时分析了酯基结构对生物柴油的氧化稳定性,40℃时的动力黏度、20℃时的密度等重要性质的影响。结果表明,随着醇的碳链长度的增加,棕榈油生物柴油的析蜡点和胶凝点均降低,特别是棕榈油异丁酯的析蜡点和胶凝点分别降低到了-2.57和-8.09℃,低温流动性得到了明显改善,且氧化诱导期略有延长,氧化稳定性有所改善。生物柴油的密度和黏度随着酯基结构的不同而有所变化,但其数值都符合中国生物柴油标准。     

Non-isothermal kinetic analysis and feasibilty study of medium grade crude oil field

In this research, non-isothermal kinetics and feasibility study of medium grade crude oil is studied in the presence of a limestone matrix. Experiments were performed at a heating rate of 10°C min⁻¹, whereas the air flow rate was kept constant at 50 mL min⁻¹ in the temperature range of 20 to 600°C (DSC) and 20 to 900°C (TG). In combustion with air, three distinct reaction regions were identified in all crude oil/limestone mixtures, known as low temperature oxidation (LTO), fuel deposition (FD) and high temperature oxidation (HTO). The activation energy values were in the order of 5–9 kJ mol⁻¹ in LTO region and 189–229 kJ mol⁻¹ in HTO region. It was concluded that the medium grade crude oil field was not feasible for a self-sustained combustion process.     

Determination of oxidation parameters of fatliquored leather by DSC

The oxidation of a number of fatliquoring formulations, of different iodine index, derived from fish oil, rapeseed oil, neatsfoot oil, lecithin, paraffin, sulphited and sulphated variants was studied. The formulations included dispersing agents, stabilizers and/or anti-oxidants. Sheepskins were treated with fatliquoring agents at 5% of fatty matter. The oxidation of the fatliquoring formulations and the fatliquored skins was studied by non-isothermal differential scanning calorimetry (DSC). The onset thermoxidation temperature and the enthalpy of the thermoxidation peak located between 195 and 265 °C were determined and then related to the different fatliquoring standard formulations. The skins were subjected to ageing treatments using UV radiation and temperature. The fall in the denaturation temperature of the skin due to ageing was related to the oxidability of the fatliquoring agent.     

Photo‐Electrochemical C−H Bond Activation of Cyclohexane Using a WO3 Photoanode and Visible Light

The photo‐electrochemical C?H bond activation of cyclohexane to produce cyclohexanol and cyclohexanone (KA oil) with high partial oxidation selectivity (99 %) and high current utilization ratio (76 %) was achieved in air at room temperature at atmospheric pressure. The production rate of KA oil was accelerated by applying a bias. The incident photon to current efficiencies at 365 and 420 nm were 57 % and 24 %, respectively.