STUDY ON BLENDS OF CRUDE OIL WITH SLUDGE LEFT IN KUWAITI OIL LAKES

An attempt has been made to determine the optimum amount of light crude oil (API=37) to be added to sludge left in Kuwaiti oil lakes to make a blend that has acceptable properties for refining purposes. Blends of different proportions were prepared and examined. Tests on selected physical properties such as API gravity, salt content, sulfur content, and viscosity were carried out. Analysis of experimental data indicated that a two weight percent blend of sludge with light crude oil would be the most appropriate proportion that will not jeopardize the specifications required by the refinery.

Experimental values of viscosity were compared with some of the available predictive correlations. The true boiling point (TBP) distillation was conducted to obtain yields of different cuts that could be produced out of the optimum proportion of the blends. Distillation curve for the 2wt% blend of sludge with light crude oil was compared with the distillation curves for each component of the blend.     

原油相容性的测定及与其性质相关性的研究

原油混合时不相容会给加工过程带来不良影响,为弄清原油相容性与性质的关系,测定了不同原油的相容性参数并与原油性质进行关联分析,结果表明：光学检测法可以测定不同类型原油的初始絮凝点,进而计算出原油的相容性参数;两种原油混合时相容性参数呈线性变化,并且原油的混合溶解性参数SBN越大,与其它原油掺混时相容性越好;将原油的密度、特性因数K、胶质和沥青质含量与相容性参数进行关联,所得关系式能用于相容性参数的计算,计算结果与实测值的偏差较小。     

Modeling the Onset of Asphaltene Flocculation at High Pressure by an Association Model

A new thermodynamic model was developed to calculate the onset of flocculation in crude oil systems similarly to the liquid-liquid equilibrium of polymer solutions. The key concept of the model is that asphaltene self-association leads to a polydisperse system of associates characterized by a size distribution function. Using continuous thermodynamics the mass action law is applied to the association equilibrium and an analytical expression for the size distribution function is derived. In contrast to polymer thermodynamics this distribution function depends on temperature, pressure, and concentration. For modeling the high pressure equilibrium the Sako-Wu-Prausnitz equation of state is applied. The model was tested on existing flocculation data for three systems of the type methane + i-octane + maltene + asphaltene with crude oils of different asphaltene contents. The amount of precipitant necessary to provoke flocculation was calculated in good agreement with the experimental data for all three systems up to a pressure of 15 MPa.     

THE COLLOIDAL STABILITY OF CRUDE OILS AND CRUDE OIL RESIDUES

A crude oil and three residues of the crude oil processing were investigated by determination of flocculation points of both the product solutions and the original products. Diverse analytical methods were used for characterizing products and their fractions. The evaluation of results was performed by the theory of regular solutions and its extension by Hansen. It was found, that the colloidal disperse phase shows a behaviour similar to that of polymer solutions. The conditions of the destabilization of the colloids can be defined by the critical Flory-Huggins interaction parameter. The solvation and the low soluble part of the asphaltenes have the greatest influence on the colloidal stability. The lowest stability is found for the visbreaking residue. The influence of the crude oil distillation on the colloidal stability is not significant.     

THE COLLOIDAL STABILITY OF CRUDE OILS AND CRUDE OIL RESIDUES

ABSTRACT

A crude oil and three residues of the crude oil processing were investigated by determination of flocculation points of both the product solutions and the original products. Diverse analytical methods were used for characterizing products and their fractions. The evaluation of results was performed by the theory of regular solutions and its extension by Hansen. It was found, that the colloidal disperse phase shows a behaviour similar to that of polymer solutions. The conditions of the destabilization of the colloids can be defined by the critical Flory-Huggins interaction parameter. The solvation and the low soluble part of the asphaltenes have the greatest influence on the colloidal stability. The lowest stability is found for the visbreaking residue. The influence of the crude oil distillation on the colloidal stability is not significant.     

高压加氢工艺生产冷冻机油研究

克拉玛依具有丰富的环烷基原油资源,为研制适合国际市场需要的冷冻机油产品,在实验室中,参照德国DIN51503VG46冷冻机油标准,以克拉玛依环烷基原油减二线馏分油为原料,利用国产加氢精制催化剂RN-1、临氢降凝催化剂RDW-1,在100mL小型加氢实验装置上,采用高压加氢精制-高压加氢降凝-分馏切割工艺路线开展工艺研究,目标产品收率高,经检测分析产品质量好,各项指标均可满足德国DIN51503 VG46冷冻机油标准要求。     

进口原油掺炼污油的超声波破乳研究

以中国石化齐鲁分公司胜利炼油厂第二常减压装置加工的典型原油为研究对象,在实验室超声波-电脱盐动态模拟评价装置上进行了进口混合原油掺炼胜利重污油的脱盐脱水研究。结果表明:在无超声波作用时,掺炼重污油的混合原油脱后含盐量为4.9mg/L,采用超声波强化破乳后,脱后原油含盐量为2.8mg/L。说明超声波有较好强化破乳脱盐脱水作用。     

酯化高酸原油的腐蚀性研究

研究了石油酸酯和酯化高酸原油的热稳定性及腐蚀性规律。结果表明,石油酸酯在高温下会发生一定的分解,但石油酸经酯化后可有效抑制腐蚀,缓蚀率达95%以上;酯化降酸抑制腐蚀的程度与酯化高酸原油中金属羧酸盐含量有关,通过脱除原油中的金属羧酸盐及采用稳定的非均相催化剂,可降低石油酸酯分解反应速率,达到抑制腐蚀的目的。     

克拉玛依原油中各组分的乳化性质

用沉淀法和色谱分离法将克拉玛依原油分离成沥青质，极性物和抽余油三组分，红外光谱分析表明，沥青质和极性物中存在一些含氧官能团的羧酸类或酚类以及含氮化合物，而抽余油则主要为烃类物质，因而沥青质和极性物的界面活性大于抽余油，沥青质具有较强的油包水（W／O）乳化能力，是造成克拉玛依原油W／O乳化的主要组分，极性物具有较强的水包油（O／W）乳化能力，是造成克拉玛依原油O／W乳化的主要组分，抽余油的乳化能力很弱。     

SULFUR COMPOUND TYPE DISTRIBUTION IN NAPHTHA AND GAS OIL FRACTIONS OF KUWAITI CRUDE

ABSTRACT

The need for detailed information on the types of sulfur compounds present in various petroleum cuts has been well recognized by refiners and environmentalists worldwide. This need is growing in recent years in view of the current environmental regulations that limit the sulfur content of transportation fuels to very low levels. In the present work we have studied the distribution of different kinds of sulfur compounds present in light and middle distillates of Kuwait crude oil. A representative sample of Kuwait crude oil was fractionated into naphtha (15-160°C) and 10-15°C cuts in the gas oil boiling range (210-340°C) using an 80L capacity autodistillation unit “AUTODEST-800” according to ASTM 2892. The distribution of various types of sulfur compounds in each of these cuts was quantitatively estimated by capillary gas chromatography equipped with a sulfur chemiluminescence detector. Thiophene and its alkyl derivatives constituted about 60% of the total sulfur compounds in the naphtha fraction. The remaining 40% was composed of mercaptanes and alkyl sulfides. In the gas oil boiling range (210-340) two groups of sulfur compounds, namely, alkyl benzothiophenes and alkyl dibenzothiophenes were present. A major portion of the alkyl benzothiophenes was found in the fraction boiling in the narrow range 235-257°C. Among the alkyl dibenzothiophenes, the concentration of C, and C₂ DBTs decreased while that of higher alkyl DBTs (< C₃-DBTs) increased with increasing temperature. The C₁ and C₂ alkyl DBTs were highly concentrated in a fraction boiling between 280-325°C and these sulfur compounds were absent in the fraction boiling above 330°C. The industrial implications of these results are discussed.     

原油中有机氯化物脱除方法的研究

利用原油中有机氯化物的极性和亲电性,开展了原油中有机氯化物脱除方法——相转移催化亲核取代反应方法的研究。以四丁基氢氧化铵为相转移剂、乙二胺为碱性试剂、乙醇和水为溶剂,按照一定物质的量的比配制的脱氯剂,可以有效脱除原油中的有机氯化物,脱氯率达90%以上。对于同一种氯化物,脱氯率随脱氯反应条件及电脱条件的变化而变化。脱氯条件一定时,脱氯率因原油中氯化物形态的不同而不同。     

混合原油的相容性

 为探讨混合原油相容性规律,将3种不同基属的原油,新疆塔河(Tahe)原油、委内瑞拉波斯坎(Boscan)原油、哈萨克斯坦库姆克尔(Kumkol)原油进行混合,采用显微镜观察混合原油的相容性,并根据稳定性参数IN、SBN考察混合原油的相容性变化规律。结果表明,将石蜡基的库姆克尔原油分别掺入塔河原油和波斯坎原油的体积分数为60%和85%时,出现不相容现象。根据所测原油和混合原油的稳定性参数IN和SBN可知,随着轻质石蜡基的库姆克尔原油掺入塔河原油或波斯坎原油比例的增大,混合原油对沥青质的溶解能力逐渐下降,最终导致不相容现象发生。从原油组成来分析,两性质差异较大的原油混合时,体系中饱和烃含量增多、芳香烃和胶质含量减少是致使沥青质絮凝的原因,而沥青质的n(H)/n(C)低、芳碳率(fA)高是混合体系更易絮凝的重要原因。     

CHARACTERIZATION OF KUWAITI CRUDE TBF-FRACTIONS WITH EMPHASIS ON KINEMATIC VISCOSITY - TEMPERATURE BEHAVIOR

ABSTRACT

Characterization of Kuwaiti crude oil, has been carried out in terms o API gravity, debutanized gravity, total sulfur content, Reid Vapor pressure ash content, heating value, salt content, viscosity SUS, vanadium content a: V2 O5, pour point and analysis of various metals. The true boiling poinl (TBP) fractions of this crude (IBP - 95^° C, 95 - 205^°C, 205 - 260^° C, 260 - 345^° C and 455^° C⁺;) were also characterized in terms of API gravity, total sulfui content, H₂S content, mercaptans content, molecular weight and elementa analyses for total carbon, hydrogen and nitrogen. The kinematic viscosity temperature data have been obtained for 95^°C⁺; TBP fractions for a wide range of temperatures.     

辽河原油沥青质及胶质油水界面化学性质初探

对由辽河原油中分别提取的沥青质组分,胶质组分配成的模型油与水的界面性质进行了研究,还考察了油相芳香度对涸青质,胶质模型油油水界面粘度的影响及当模型油中沥青质与胶质共存时的油水界面性质。结果表明,含沥青质的模型油的油水界面粘度较高,界面老化现象严重;而仅含胶质的模型油的油水界粘度较小。     

CHARACTERIZATION OF KUWAITI CRUDE TBF-FRACTIONS WITH EMPHASIS ON KINEMATIC VISCOSITY - TEMPERATURE BEHAVIOR

Characterization of Kuwaiti crude oil, has been carried out in terms o API gravity, debutanized gravity, total sulfur content, Reid Vapor pressure ash content, heating value, salt content, viscosity SUS, vanadium content a: V2 O5, pour point and analysis of various metals. The true boiling poinl (TBP) fractions of this crude (IBP - 95^° C, 95 - 205^°C, 205 - 260^° C, 260 - 345^° C and 455^° C⁺;) were also characterized in terms of API gravity, total sulfui content, H₂S content, mercaptans content, molecular weight and elementa analyses for total carbon, hydrogen and nitrogen. The kinematic viscosity temperature data have been obtained for 95^°C⁺; TBP fractions for a wide range of temperatures.     

微生物采油中微生物对原油作用的研究

长庆油田采用美国ＮＰＣ公司的商品微生物，分两次在３２口井上进行了１１６井次的微生物单井吞吐采油试验，效果显著。通过测定微生物处理前后油井产出的原油组成（含蜡量和烃组成）和物性（凝固点、粘度）、原油伴生水中有机酸含量和水的表面张力等的变化，以及在室内将油井产出的含水原油与微生物混合培养后测定生成气体的组成，研究了微生物对原油的作用：产生Ｃ６以下气态烃、少量ＣＯ２、Ｎ２和Ｈ２，使原油轻质化，产生有机酸和其他表面活性物质。本文报告了此项研究的结果。     

水包稠油乳状液中孤岛稠油组分间相互作用初探

 研究了孤岛稠油脱沥青质油、胶质、沥青质及胶质与沥青质混合物对水包稠油乳状液界面性质的影响。结果表明，具有高芳碳率、低烷基碳率、高芳香环缩合程度的沥青质组分界面活性较高。在水包稠油乳状液形成过程中，芳香分的存在有利于以稠合芳香环系为核心的胶质粒子的溶解，促进胶质单元结构在油滴表面的吸附，使脱沥青质油的界面活性高于胶质。胶质对沥青质有很好的分散作用，使沥青质在油相中溶解度增加，沥青质分子以较小的缔合体或以自由分子状态存在，沥青质分子中所有极性基团较易到达表面上，使油水界面张力降低。稠油组分与阴离子乳化剂LAS存在正的协同作用，与非离子乳化剂OP-10存在负的协同作用。稠油各组分共同与乳化剂作用形成稳定的水包稠油乳状液。     

原油储存温度的优化

分别研究了原油储存温度对原油输送功率,罐区加热、维温、散热负荷,以及蒸馏装置冷、热公用工程消耗的影响;结合环境温度变化,建立了相关的能耗和能耗费用计算方程,并以此为基础提出了以总能耗或总能耗费用最小为目标函数的优化原油储存温度计算方法.实例应用表明该方法应用于实际操作,可较大幅度地降低原油罐区和蒸馏装置的相关能耗.     

原油中甾烷的生物降解模拟实验研究

通过喜氧细菌对原油的模拟生物降解实验,以及对模拟产物的饱和烃色谱—质谱分析,对原油饱和烃中规则甾烷和重排甾烷的降解作用进行了研究。研究结果显示,规则甾烷先于重排甾烷发生生物降解,甾烷降解由易到难的顺序为C₂7>C₂8>C₂9。在甾烷被大量降解前,20S/(20S+20R)(甾烷异构化作用)等生物标记化合物的成熟度指标基本无变化,但某些用于油源对比、母源和沉积环境研究的生物标记化合物参数可能会发生变化,如:规则甾烷/17α(H)-藿烷、C₂7-C₂8-C₂9甾烷、C₂7-C₂8-C₂9重排甾烷和重排甾烷/规则甾烷等。     

原油储罐涂料防腐蚀施工质量探讨

讨论了10×104 m3原油储罐防腐蚀施工方案、涂料选择、喷砂除锈、储罐涂装、施工队伍管理等关键环节的质量控制。同时,讨论了金属表面喷砂除锈等级、粗糙度、涂层外观、涂层厚度、涂层针孔等关键技术指标的测量方法及检验标准。