辽河低凝原油润滑油糠醛精制油蜡含量分布研究

采用自行开发的润滑油蜡含量测定方法，考察了辽河低凝原油各润滑油馏分糠醛精制油在不同温度下的蜡含量分布情况。试验结果表明：辽河低凝原油润滑油糠醛精制油蜡含量很低，脱除少许环烷蜡即可生产出合格的LVI基础油，润滑油溶剂脱蜡有一最佳油剂比，随着脱蜡温度的下降，润滑油脱蜡量增加，脱蜡油凝点明显降低。     

Improvement of Egyptian vacuum distillates by urea dewaxing

The dewaxing of paraffinic lube stocks is an essential step in the production of lubricants to improve the operability of machines especially in winter. The present work deals with study of the urea dewaxing process of two types of Egyptian vacuum distillates. The effect of different compositions of methanol to water saturated with urea and yield of the oil, percent of wax, pour point, refractive index, viscosity, viscosity index and specific gravity of the oil produced from the two types of distillates (I and II) were evaluated. The operating conditions of the urea adduct formation with n-paraffins using methanol to water mixture achieved the best pour point at −3.88 °C from an initial temperature of 4.4 °C for distillate I at (25/75) methanol to water. At the same ratio of methanol to water the best specific gravity of oil produced changed from 0.865 to 0.867, with viscosity index of 80. Percent yield of 50% for oil and percent wax of 50% were obtained. Results for distillate II, of higher specific gravity, are comparatively higher than those for distillate I. Experiments were carried out at room temperature.     

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.     

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.     

Experience in Manufacture of Hard Waxes. Combined Dewaxing and Deoiling Unit

Most of the country's oil units are primarily oriented toward production of lube oils. The by–products formed are used as components of furnace residual fuel oil. Even the slack wax obtained in dewaxing of selectively refined raffinates goes into furnace residual fuel oil. The slack wax contains from 80 to 90% hard waxes which, like dewaxed oil, are a valuable petroleum product.     

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.     

溶剂脱蜡——尿素脱蜡生产低凝润滑油的研究

研究利用溶剂脱蜡一尿素脱蜡组合工艺生产低凝润滑油的可行性,并研究了不同脱蜡方法对润滑油低温性能的影响,研究表明,采用溶剂脱蜡－尿素脱蜡组合工艺生产低凝润滑油是可行的,尿素脱蜡所脱蜡对润滑油低温性能的影响程度要比溶剂脱蜡的大,相同脱错量时;尿素脱蜡油的低温性能要远比溶剂脱蜡油好;达到相同的凝点时,原东脱蜡油的收率要高于溶剂脱蜡油．     

Clarified Oil from Fluid Catalytic Cracking as an Additional Source of Group II Base Oil Components

Abstract

Clarified oil (CLO) from a commercial fluid catalytic cracking unit was subjected to solvent extraction followed by solvent dewaxing and adsorption chromatography to analyze its various components for different end-use applications. The clarified oil was first solvent extracted using N-methyl pyrrolidone (NMP) to produce paraffinic rich raffinate (68.9 wt% yield). The raffinate thus obtained was dewaxed using methyl isobutyl ketone (MIBK) to get an oil of pour point 0°C. This dewaxed oil was then subjected to adsorption chromatography to determine group II base oil potential through yield v/s viscosity index (VI) curve. The results revealed that clarified oil has an actual potential of around 27.1 wt% of group II base oil components, suggesting that clarified oil can be used as an additional source of feed for production of group II base oil. This article also describes the potential of other components in clarified oil such as slack wax (24.2 wt%), aromatics (31.1 wt%), and low VI oil (17.6 wt%).     

Exhaustive Processing of Low-viscosity Raffinate

In exhaustive dewaxing of raffinate from the 300 – 400°C cut, the yield of MS–8 lube stock with a solid point of –55°C does not exceed 40%. The slack wax obtained contains 30 – 40% oils. As a result of deoiling the slack wax at a temperature of –24°C, soft wax with a melting point of +43°C and dewaxed oil with a solid point of –2°C were obtained. The first product is used as a component of the feedstock for production of synthetic fatty acids and the second is used for production of cooling fluids. The scheme for exhaustive refining of raffinate and the material balance of the process are reported.     

高倾点富芳烃原料生产环保橡胶填充油的技术开发

根据高倾点富芳烃含量溶剂精制抽出油的组成特点和性质,以及其中高凝点组分的分子结构特点,开发出具有自主知识产权的添加脱蜡助剂抽出油溶剂脱蜡技术,该技术可以有效提高抽出油溶剂脱蜡的过滤速度和滤布蜡饼厚度,使得溶剂脱蜡装置可以连续加工抽出油。抽出油脱除高凝点组分后的脱蜡油经环保芳烃油溶剂抽提制备出环保型芳烃橡胶填充油,填充油中多环芳烃含量、苯并(a)芘含量和苯并(a)芘等八种稠环芳烃总含量均满足欧盟2005/69/EC指令中环保指标要求,该填充油的橡胶充油过程良好,没有游离的油珠,充油胶性能均满足SBR1723橡胶优级品的质量要求。     

Combined process for production of base oils and exhaustively deoiled waxes. Use of oscillating crystallizers

The analysis of the results obtained suggests the following conclusions: a process for fabricating lube oils and exhaustively deoiled waxes using recrystallization of dewaxing stage-two slack wax in an oscillating crystallizer was developed. The possibility of stable manufacture of wax with an oil content at more than 1 wt. % in processing raffinate from the 420–490°C cut was demonstrated. __________ Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 2, pp. 13–15, March–April, 2006.     

脱蜡助剂对加氢处理油溶剂脱蜡助滤效果的评价

以兰炼加氢处理的125N、200N、400N及120BS润滑油基础油为原料，对不同相对分子质量的聚烯烃／聚丙烯酸脱蜡助剂DEW－6、DEW－7、DEW－8的脱蜡助滤效果在实验室进行了评价。评选工艺采用关键单元的间歇式过程。试验结果表明，对于125N，DEW－6加剂量为0．05％时，过滤速度提高60％－80％，油收率提高5个百分点，蜡含油降低70％；对于200N，DEW－7加剂量为0．01％时，过滤速度能提高50％，油收率提高5个百分点，蜡含油降低30％；对于400N，DEW－7加剂量为0．09％时，过滤速度能提高150％，油收率提高10个百分点，蜡含油降低30％、对于120BS，DEW－8加剂量为0．09％时，过滤速度提高60％，油收率提高3个百分点，蜡含油降低30％。     

Determination of wax content in crude oil

Wax deposition is one of the chronic problems in the petroleum industry. The various crude oils present in the world contain wax contents of up to 32.5%. Paraffin waxes consist of straight chain saturated hydrocarbons with carbons atoms ranging from C18 to C36. Paraffin wax consists mostly with normal paraffin content (80–90%), while, the rest consists of branched paraffins (iso-paraffins) and cycloparaffins. The sources of higher molecular weight waxes in oils have not yet been proven and are under exploration. Waxes may precipitate as the temperature decreases and a solid phase may arise due to their low solubility. For instance, paraffinic waxes can precipitate out when temperature decreases during oil production, transportation through pipelines, and oil storage. The process of solvent dewaxing is used to remove wax from either distillate or residual feedstocks at any stage in the refining process. The solvents used, methyl-ethyl ketone and toluene, can then be separated from dewaxed oil filtrate stream by membrane process and recycled back to be used again in solvent dewaxing process.     

OCCURRENCE AND DISTRIBUTION OF n-ALKANESAND n-FATTY ACIDS IN SAUDI ARABIAN CRUDE OILS

ABSTRACT

Ten crude oil samples, covering wide range of maturity (API gravity = 18·5–36·1), were assembled from Safaniya, Abqiq, Ain Dar, Wafra. Marjan and Zuluf oil fields in the area of Arabian Gulf. n-Alkanes of were separated from the petroleum distillate ((150°C–450°C) of the crude oils by urea adduction. n-Fatty acids were separated from the fraction of n-alkanes by treatment with aqueous solution of KOH. Distribution of n-alkanes and n-fatty acids has been investigated by means of gas chromatography. The studied crude oils showed symmetrical distribution curves of n-paraffins and fatty acids of low molecular weight were abundant as compared with n-paraffins. The n-paraffins distribution curve of Wafra/Iucene biodegraded immature crude oil showed three maxima at C₁₇, C₁₉, and C₃₁ whereas the maxima of n-fatty acids are located at C₁₄,C₂₂and C₂₄. The results were interpreted in terms of origin, maturation and depositional environments of the crude oils.     

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。     

Hydroisomerization of n-Hexane Using Unloaded and Low-Platinum-Loaded H-ZSM-5 and H-MOR Catalysts

Abstract

The applicability for investing and comparing two zeolites (H-ZSM-5 and H-MOR) as supports for low-platinum (less expensive) catalysts used principally for hydroisomerization of n-paraffins in light petroleum naphtha is investigated using n-hexane as a model n-paraffin feed at temperatures of 250°C–500°C in a flow-type reactor with a hydrogen flow of 20 cm³ min^?1 at atmospheric pressure. H-ZSM-5 zeolite acquires higher density of strong acid sites, which are still somewhat weaker than the respective sites in H-MOR. These milder sites in H-ZSM-5 zeolite enhanced hydroisomerization and dehydrocyclization but suppressed hydrocracking after incorporating 0.15% Pt. Hydrochlorination (HCl) and hydrofluorination (HF) of 0.15% Pt/H-ZSM-5 were carried out to modify its acidity and Pt dispersion with the goal of maximizing n-hexane hydroisomerization. The HCl treatment seems to have significantly approached the requirement for optimum catalytic bifunctionality, whereas HF treatment appears mostly deteriorative.     

Rheology of Middle Distillate. I. Role of Composition

Abstract

The rheological behavior of middle distillate (250–375°C) fraction, obtained from the waxy Bombay-High Off-shore crude oil, and its five narrow sub-fractions of 25°C interval each, i.e., Fr 1 (250–275°C), Fr 2 (275–300°C), Fr 3 (300–325°C), Fr 4 (325–350°C), and Fr 5 (350–375°C), have been studied below their ASTM pour point temperatures. The rheograms (the shear stress vs. rate of shear) of the fraction and sub-fractions, at various temperatures below their pour points, are recorded on a Haake RV-12 Co-axial Rota Viscometer fitted with a NV sensor and a temperature programmer (PG-20) and attached with a programmed heating/cooling system. From these rheograms the flow parameters like plastic viscosity, apparent viscosity, and yield stress are obtained and their variations with temperature and shear rate have been studied in terms of compositions of the fraction/sub-fractions. These results might be useful in devising methodology for overcoming the wax separation phenomenon from middle distillates at low temperatures.     

润滑油加氢处理装置的设计及工业生产

介绍了引进法国石油研究院专利技术,我国自行设计的润滑油加氢处理装置的设计、建设及生产情况。工业生产表明,采用“一段加氢处理－常减压蒸馏－二段加氢精制－溶剂脱蜡”新工艺,可用低粘度指数原料生产全型谱热稳定性和紫外稳定性均较好的高粘度指数或超高粘度指数润滑油基础油。装置标定结果显示,利用新疆混合原油的减三线油（粘度指数为４２～６５）,可生产粘度指数大于１２５的润滑油基础油,含蜡基础油收率可达６６％;切换为减四线油或丙烷脱沥青油后,可生产２００Ｎ,５００Ｎ和１５０ＢＳ含蜡基础油,脱蜡油的粘度指数均大于９５。     

Preparation of synthetic hydrocarbon oil by high-pressure hydrocracking of ethylene-propylene copolymers

Degradation reactions of ethylene-propylene copolymers at a high temperature (380–430°C) and a high pressure (180–220 atm) in the presence of a nickel catalyst and hydrogen have been studied. In contrast to the previously known processes, the degradation reactions have been conducted simultaneously with hydrogenation reactions. The effects of temperature, pressure, and time on the yield of each fraction have been examined. As a result, optimal process conditions have been found for each fraction. The physicochemical properties of the lube oil fraction (C₁₈–C₂₅) used as a base oil have been studied. It has been found that as in the case of oils derived from ethylene-propylene copolymers by other methods, these oils have a high viscosity index (VI > 95), a high flash point (T _f > 210°C), and a low pour point (T _p < ?50°C).     

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.