SOLUBILISED WAXES AND THEIR INFLUENCE ON THE FLOW PROPERTIES OF LUBE OIL BASE STOCKS

ABSTRACT

The physico-chemical properties of Lubricating oil base stocks (LOBS) are generally influenced by the type/nature and concentration of solubilised waxes present in them. Detailed composition of the solubilised waxes, saturates and aromatics present in LOBS and its distillate fractions has been sludied. Further the influence of these solubilised waxes and as well of saturates/aromatics on the flow properties particularly pour point, viscosity and viscosity temperature relationship of LOBS sample and its distillate fractions have been investigated. The response of a commercial pour point depressant additive with varying composition of solubilised waxes in lube oil base stock sample has also been studied.     

ROLE OF COMPOSITION ON THE VISCOSITY AND SHEAR STRESS TEMPERATURE BEHAVIOUR OF SOME LUBE OIL BASE STOCKS

Lubricating oil base stocks differ greatly in their chemical composition and consequently in their physical properties and applications. Influence of waxes and various hydrocarbon type constituents viz saturates and aromatic components on the viscosity and shear stress as a function of temperature in different lube oil base stocks has been studied in the present paper.     

The Influence of Separated Fractions on Crude Oil Viscosity

Abstract

To solve the problem of heavy oil production, the properties of heavy oil and separated fractions of oil (saturates, aromatics, resin, asphaltene) were determined by the technologies of scanning electron microscope, energy spectrum analysis, and so on. The results show that the heavy oil viscosity decreased significantly with temperature increase and the turning point of temperature will change with different properties of heavy oil. The sequence of the influences of heavy oil components on its viscosity is: asphaltenes > resins > aromatics > saturates. The asphaltene is a primary influential factor among them. The contents of S, Cl, O, N, and mental elements (Ni, V) in Tahe heavy oil are relatively higher than that of ordinary crude oil. The viscosity of heavy oil will increase when the transition metal ions and organic heterocyclic elements form a stable complex. Now, there are few systematic studies on the influence of heavy oil separated fractions on its viscosity. The research will provide guidance for the exploitation technology of other heavy oil fields.     

矿物基础油对锂基润滑脂流变性的影响

选用不同类型与黏度的11种矿物基础油,以锂基润滑脂为对象,系统研究基础油对流变性的影响,并基于烃类分子水平进行深入探讨。结果表明,同皂量下,线性黏弹区内润滑脂的表观黏度与基础油高度相关,关键决定因素是基础油的倾点,其次是黏度。随链烷烃含量增加,基础油倾点升高,润滑脂的表观黏度随之增大;而芳烃影响则相对复杂,其含量增加时,在降低油品倾点的同时,却增大了黏度,两者的综合作用决定着润滑脂的表观黏度,一般黏度占主导地位。     

加氢处理进料中的芳烃含量对润滑油基础油质量的影响

为使加氢处理后所得润滑油基础油符合质量要求,对一种中东原油的减压馏分油及其精制深度不同的两表制在实验室进行了加氢处理试验研究,探讨了了原料中的芳烃含量对中压在加氢处理过程的反应类型,所得基础油产吕的组成分布及粘度指数的影响,结果表明：加氢处理进料中的芳烃含量的多少,会影响加氢处理过程中所发生的反应,从而通过所得基础油的烃类分布影响基础油的质量,适当降低进料中的芳烃含量,可以优化加氢处理过程,提高基础油中的饱和烃含量,并使芳烃和环烷烃以单环烃为主,获得较高粘度指数的润滑油基础油产品。／     

LOW TEMPERATURE FLOW CHARACTERISTICS OF SOME WAXY CRUDE OILS IN RELATION TO THEIR COMPOSITION : PART I WITH AND WITHOUT POUR POINT DEPRESSANT ADDITIVES

The yield stress, plastic viscosity and apparent viscosity and the dependence of the latter on the shear rate have been studied at different temperatures below pour point of Lingala (Krishna-Godavari basin, Eastern coast), Duliajan (Eastern region of Assam), Rava (Godavari basin) and Bombay-High (off-shore western region) indigenous crude oils

Four different commercial pour point depressant additives have been used to study their effects on the pour point, yield stress and plastic viscosity

From this study it has been found that wax concentration and its composition are primarily responsible for the variation in the pour point, and crude base composition has a small effect. However, the response of the pour point depressant additive in effecting the change in the pour point is primarily governed by the liquid matrix. As the temperature is lowered both the yield stress and plastic viscosity increase in case of each crude oil. However, the magnitude is dependent on the nature of the crude oil. With pour point depressant additives, the yield stress and plastic viscosity are decreased and this decrease is a function of nature of the liquid matrix of the crude oil and concentration of the additive     

Hydrocracking of Polyolefin Thermal Cracking Waxes Over Ni-loaded Molecular Sieve Catalysts

The hydrocracking of thermal cracking waxes obtained from pyrolysis of polyolefin at 360°C for 120 min has been studied using Ni-loaded molecular sieves catalysts. According to XRD, TPR, and BET data, the presence of nickel oxide did not seem to damage the crystalline framework of the catalytic supports. Hydrocracking experiments were carried out in a stirred autoclave reactor at 300°C for 120 min under 2.0 MPa of hydrogen. The results suggested the existence of a balance between the acid and metal function over bifunctional catalysts, which affects hydrogenation and hydroisomerization of thermal cracking waxes. Hydrocracking reactions took place extensively over mixture of Ni/HBeta and ZSM-5, leading toward higher fractions of gases (30.2%) and diesel (23.5%). The higher fractions of gasoline (33.5%) and lube base oil (19.0%) were obtained over mixture of Ni/HSAPO-11 and ZSM-5. In contrast, hydrocracking reaction occurred in a lower extent over mixture of Ni/NMCM-41 and ZSM-5, which produces lube base oil with lower pour point (–10°C), gasoline and diesel with lower bromine numbers (1.1 and 0.8 g Br₂/100 g sample). The viscosity index of lube base oil was in the range of 131–171 over all three mixed catalysts.     

Rheological Properties and Composition of Some Vacuum Distillates Derived from Indian Crudes

Abstract

Three vacuum distillates boiling range 400°C–530°C derived from Bakrola, Dholka, and PY-3 crudes of Gujarat region (India) were subjected to urea adduction to isolate n-paraffin components from them. The deparaffinized base oils obtained after removal of n-paraffin components from the distillate fractions were further fractionated into various hydrocarbon-type constituents viz iso + cyclo paraffins, aromatics, and polar components by column chromatography. The influence of various hydrocarbon-type components thus separated on rheological characteristics (pour point and viscosity temperature behavior) of deparaffinized base oil was investigated. This study was done by preparing base oil blends by adding separated hydrocarbon-type constituents in various concentrations to different base oils and characterizing them. The effect of change of solvent matrix on the rheological characteristics was also determined. The study demonstrated the role of solid n-paraffins for variation in pour point and viscosity temperature behavior of the waxy distillate fractions.     

Boiling Point Distribution of Hydrocarbon Types in Diesel Using Solid-Phase Extraction Followed by GC/FID-EIMS

In this paper, a method was established to determine the boiling point distribution of hydrocarbon types in diesel. The diesel sample was separated into the saturate and aromatic fractions by means of solid-phase extraction （SPE）, and each fraction was analyzed by GC/FID-EIMS. According to the relationship between boiling point and retention time of n-paraffins in the chromatogram, the percentages of saturates and aromatics at each temperature interval were calculated. According to the average mass spectra of the saturate and aromatic fractions at each temperature interval, the hydrocarbon types of the sample were identified through summation of characteristic mass fragments. Using this method, the changes in composition of diesel during hydrotreating process were studied. The results showed that hydrogenation of aromatics is the main reaction during the hydrotreating process. The more rings the aromatics have, the easier the hydrogenation reactions would take place. The aromatics were converted into cycloparaffins via the hydrogenation and saturation process, leading to an increase in low boiling point fractions in the hydrotreated oil.     

LOW TEMPERATURE FLOW CHARACTERISTICS OF SOME WAXY CRUDE OILS IN RELATION TO THEIR COMPOSITION : PART II EFFECT OF WAX COMPOSITION AND CONCENTRATION ON THE DEW AXED CRUDE OILS WITH / WITHOUT ADDITIVES

In this part of the work the effect of wax concentrations on the rheologica! properties of the dewaxed Duliajan (Assam) and Lingaia crude oils have been studied. The dewaxing of the crude oil was done by removing n-paraffins from the crude oil by urea adduction. The urea adducted n-paraffins concentrate-the wax- was characterized by its carbon number distribution. The urea non adducted oil portion - the denormalized crude oil (DNO)- was characterized for its pour point. The wax in different concentration was then added in the DNO and the change in the rheological properties like pour point, yield stress and plastic viscosity were studied using a Haake Rota Viscometer. The effect of carbon number distribution, i.e. the composition of the wax, on these rheological properties was also investigated. Four different commercial pour point depressanl additives have been used to study their effects on the pour point, yield stress and plastic viscosity of the reconstituted (wax mixed DNO) crude oils.

From this study it has been found that wax concentration and its composition are primarily responsible for the variation in the pour point of the DNO, and the DNO composition has a small effect. However, as seen in the Part I of this paper, the response of the pour point depressant additive in effecting the change in the pour point is primarily governed by the composition of the DNO. The additives have shown better response in the DNO having more aromatic concentrate, as has been found in the case of Duliajan (Assam) DNO.     

LOW TEMPERATURE FLOW CHARACTERISTICS OF SOME WAXY CRUDE OILS IN RELATION TO THEIR COMPOSITION : PART I WITH AND WITHOUT POUR POINT DEPRESSANT ADDITIVES

ABSTRACT

The yield stress, plastic viscosity and apparent viscosity and the dependence of the latter on the shear rate have been studied at different temperatures below pour point of Lingala (Krishna-Godavari basin, Eastern coast), Duliajan (Eastern region of Assam), Rava (Godavari basin) and Bombay-High (off-shore western region) indigenous crude oils

Four different commercial pour point depressant additives have been used to study their effects on the pour point, yield stress and plastic viscosity

From this study it has been found that wax concentration and its composition are primarily responsible for the variation in the pour point, and crude base composition has a small effect. However, the response of the pour point depressant additive in effecting the change in the pour point is primarily governed by the liquid matrix. As the temperature is lowered both the yield stress and plastic viscosity increase in case of each crude oil. However, the magnitude is dependent on the nature of the crude oil. With pour point depressant additives, the yield stress and plastic viscosity are decreased and this decrease is a function of nature of the liquid matrix of the crude oil and concentration of the additive     

体相催化剂在加氢裂化装置中的应用

中国石化金陵分公司加氢裂化装置第六周期采用FF-66加氢精制催化剂及FC-16B/FC-14组合加氢裂化催化剂,装置运行36个月后,产品变压器油氧化安定性降低,倾点较高,尾油黏度指数无法满足润滑油基础油的需求。为了改善产品质量,提高加氢能力,装置第七周期精制剂采用FF-66级配体相催化剂FTX-1,裂化剂采用FC-16B/FC-14级配体相催化剂FTXC-1。标定结果表明,与第六周期相比,第七周期产品重石脑油硫质量分数从4.0μg/g降低至1.3μg/g,喷气燃料烟点从25.4 mm升高至26.8 mm,变压器油倾点从-9℃降低至-12℃。芳烃含量高是变压器油氧化安定性差的主要原因,通过加氢饱和处理,变压器油的芳烃质量分数从约10%降至最低约0.5%,氧化安定性得以改善。但是,第七周期尾油黏度指数为91,未能满足润滑油基础油的要求,可以通过掺炼石蜡基油种的蜡油和提高裂化剂的开环能力来提升尾油黏度指数。     

LOW TEMPERATURE FLOW CHARACTERISTICS OF SOME WAXY CRUDE OILS IN RELATION TO THEIR COMPOSITION : PART II EFFECT OF WAX COMPOSITION AND CONCENTRATION ON THE DEW AXED CRUDE OILS WITH / WITHOUT ADDITIVES

ABSTRACT

In this part of the work the effect of wax concentrations on the rheologica! properties of the dewaxed Duliajan (Assam) and Lingaia crude oils have been studied. The dewaxing of the crude oil was done by removing n-paraffins from the crude oil by urea adduction. The urea adducted n-paraffins concentrate-the wax- was characterized by its carbon number distribution. The urea non adducted oil portion - the denormalized crude oil (DNO)- was characterized for its pour point. The wax in different concentration was then added in the DNO and the change in the rheological properties like pour point, yield stress and plastic viscosity were studied using a Haake Rota Viscometer. The effect of carbon number distribution, i.e. the composition of the wax, on these rheological properties was also investigated. Four different commercial pour point depressanl additives have been used to study their effects on the pour point, yield stress and plastic viscosity of the reconstituted (wax mixed DNO) crude oils.

From this study it has been found that wax concentration and its composition are primarily responsible for the variation in the pour point of the DNO, and the DNO composition has a small effect. However, as seen in the Part I of this paper, the response of the pour point depressant additive in effecting the change in the pour point is primarily governed by the composition of the DNO. The additives have shown better response in the DNO having more aromatic concentrate, as has been found in the case of Duliajan (Assam) DNO.     

ANALYSIS AND PHYSICO-CHEMICAL CHARACTERIZATION ON CHINESE OIL SAND BITUMENS

The extraction of four Chinese oil sands from Sinjiang and Inner Mongolia Autonomous Regions with Dean-Stark extractor were investigated. The mineral composition and sand grain distribution were determined and the bitumens were separated into saturates, aromatics, resin-I and resin-II, asphaltenes. The structure parameters and molecular model were made for the bitumens. Elemental analysis, molecular weight, FTIR, 1H-NMR were made for the bitumen fractions. The results show that the molecular structure of Mongolia bitumens have more polycyclic aromatics than that of Sinjiang bitumen. It is believed that the extraction of Sinjiang oil sand bitumen by hot alkaline water is much easier than Mongolia oil sand due to the difference of the viscosity of bitumen, the molecular structure and other physico-chemical properties of the bitumens.     

ANALYSIS AND PHYSICO-CHEMICAL CHARACTERIZATION ON CHINESE OIL SAND BITUMENS

Abstract

The extraction of four Chinese oil sands from Sinjiang and Inner Mongolia Autonomous Regions with Dean-Stark extractor were investigated. The mineral composition and sand grain distribution were determined and the bitumens were separated into saturates, aromatics, resin-I and resin-II, asphaltenes. The structure parameters and molecular model were made for the bitumens. Elemental analysis, molecular weight, FTIR, 1H-NMR were made for the bitumen fractions. The results show that the molecular structure of Mongolia bitumens have more polycyclic aromatics than that of Sinjiang bitumen. It is believed that the extraction of Sinjiang oil sand bitumen by hot alkaline water is much easier than Mongolia oil sand due to the difference of the viscosity of bitumen, the molecular structure and other physico-chemical properties of the bitumens.     

全氢型工艺再生废润滑油技术的开发

介绍了中国石化抚顺石油化工研究院开发的废润滑油高压加氢处理与补充精制两段加氢组合工艺再生润滑油基础油技术。以废润滑油小于510℃馏分油为原料,在小型加氢反应装置上进行试验,在最大限度保留废润滑油中大部分优质基础油组分的同时脱除杂质和芳烃饱和。结果表明:在反应压力为(基准+5)MPa、加氢处理/补充精制反应温度为(基准+20)℃/(基准+10)℃、加氢处理/补充精制体积空速为基准/(基准+1.0)h~(-1)、氢油体积比为800的条件下,废润滑油可再生为润滑油基础油,生成油色度达到+30号,分馏得到大于400℃馏分的倾点为-18℃,100℃黏度为6.856mm~2/s,黏度指数为100,可生产HVIⅡ6号基础油产品;320~400℃馏分的倾点为-23℃,100℃黏度为3.218mm~2/s,可作为HVIⅡ3号基础油产品或3号工业白油;280~320℃馏分的40℃黏度为6.725mm~2/s,倾点为-45℃,可作为40号通用变压器油;大于320℃基础油的收率在80%以上,总液体收率大于98%。     

异构脱蜡润滑油基础油组成对其性质的影响

以加氢裂化尾油和加氢处理重质减压馏分油为原料,采用异构脱蜡工艺制备润滑油基础油。分析基础油的性质,并采用质谱和¹³C核磁共振分析异构脱蜡基础油的烃组成和烃结构,考察异构脱蜡润滑油基础油的烃组成和烃结构对其性质的影响。结果表明,对于异构脱蜡润滑油基础油,在多环环烷烃质量分数、链烷碳质量分数和平均碳数相近的条件下,黏度指数随着异构烷碳与正构烷碳质量分数之比的增大而减小,倾点随着异构烷碳与正构烷碳质量分数之比的增大而降低;在多环环烷烃质量分数、异构烷碳与正构烷碳质量分数之比相近的条件下,黏度指数和倾点随着分子的平均碳数减少而降低。     

Compositional Changes in Hydrotreated Naphthenic Oil under Ultraviolet Radiation

Compositional changes of hydrotreated naphthenic oil during ultraviolet (UV) radiation were studied in detail. First, liquid-solid chromatography was used to separate the initial oil and the UV-irradiated oil into three different fractions: saturates, aromatics, and polars. Then, each fraction's compositional changes were evaluated using a series of instrument technologies including gas chromatography-mass spectroscopy (GC-MS), infrared spectroscopy (IR), atmospheric pressure chemical ionization mass spectroscopy (APCI/MS), and X-ray photo electron spectroscopy (XPS), respectively. The results show that after UV radiation, the UV-irradiated sample exhibited a decrease in saturates concomitant with an increase in the aromatic and polar fractions. For saturates and aromatics, the UV-irradiated sample exhibited a decrease in alkanes, diaromatics, and polyaromatics concomitant with an increase in other aromatics. The UV light had no significant effect on the cycloalkanes. For polars, a relatively large amount of oxygen-containing compounds, such as hydroxyl, carbonyl, and carboxyl groups, was formed in the presence of UV light. XPS data show that a type of S 2pa compound in the initial oil disappears and could be converted to SO₄^2-. No obvious changes of molecular weight distribution were observed. A part of polar compounds in the UV-irradiated oil might come from aromatic photooxidation in the initial oil.     

环烷基基础油和石蜡基基础油混合中的自降凝现象研究

针对润滑油基础油混合中出现的自降凝现象,即混合油品倾点低于两种组分油品各自倾点的现象,将不同环烷基基础油和石蜡基基础油调合,测定其低温性能,并结合油品理化性质进行分析,提出自降凝现象的作用机理。结果表明：自降凝现象在环烷基原油精制油品与石蜡基原油精制油品间混兑时比较明显;两种油品混合时,自降凝现象的明显程度取决于基础油类型、两种油品间的倾点差距及运动黏度（100 ℃）差距,3种因素对自降凝的影响依次减弱。两种油品的凝固方式差别越大、倾点越接近、运动黏度（100 ℃）越接近,则自降凝现象越明显。KN4010为环烷基基础油,HVIP8为石蜡基基础油,两者倾点都是-24 ℃,运动黏度（100 ℃）接近,其混合油品的倾点可以降低到-42 ℃。     

Compositional Changes of Hydrotreated Naphthenic Rubber Base Oil Under High Temperature

Abstract

This article discusses the compositional changes of hydrotreated naphthenic rubber base oil under high temperature. First, we adopted liquid–solid chromatography to separate the initial oil and the heated oil into three different fractions (i.e., saturates, aromatics, and polars). Next, each fraction's compositional change was respectively evaluated through a series of instrument technology including gas chromatography-mass spectroscopy (GC-MS), infrared spectroscopy (IR), and x-ray photoelectron spectroscopy (XPS). The results show that under high temperature, the heated sample exhibits a decrease in the saturate and aromatic fractions concomitant with an increase in the polar fraction. For saturates, the content of alkanes in the heated sample exhibits a relatively substantial decrease. On the other hand, the content of cycloalkanes shows a little increase in trend, and the heated oil sample exhibits a decrease in aromatics. Regarding polars, a relatively large amount of oxygen-containing compounds such as hydroxyl, carbonyl, and carboxyl groups was formed under high temperature. XPS data show that a type of S 2pa compounds in the initial oil disappears and could be converted to SO42?. A part of polar compounds in the heated oil could come from aromatic thermo-oxidation in the initial oil.