乳化剂对超稠油四组分乳化性能的影响

通过乳状液透光率和界面张力考察胜利油田罗家超稠油极性四组分质量分数为2％的甲苯模型油加OP乳化剂前后与地层水、碱水的乳化性能，发现乳化荆对四组分都起到了强烈的乳化促进作用。加200mg／LOP乳化荆后，四纽分模型油透光率变化由大到小的顺序是：沥青质〉芳香分〉肢质≈饱和分；与地层水的界面张力降幅由大到小的顺序是：饱和分≈胶质〉芳香分〉沥青质：与碱水的界面张力降幅由大到小的顺序是：沥青质〉饱和分≈胶质〉芳香分。0P乳化荆使W／O型乳状液转变为0／W型，提高了稠油乳化程度，便于稠油的化学乳化开采和输送。     

酸化-混凝-催化氧化联合处理钻井废液研究

采用灰色关联熵分析法研究了胜利油田稠油黏度与其极性四组分含量和极性组分偶极矩的关联。同时通过改变实验油样乳状液的含水率及温度,探究了稠油组成性质与其乳状液反相点的关联。结果表明：稠油极性四组分含量与其黏度关联度的顺序是：沥青质〉胶质〉芳香分〉饱和分;稠油极性组分偶极矩与其黏度的关联度顺序是：沥青质〉胶质〉芳香分。随着稠油胶质、沥青质含量的增大,油水界面张力的降低、油滴Zeta电位绝对值的增大,乳状液含水率的反相点及温度的反相点逐渐升高。     

SV值表征的稠油W/O乳状液稳定性研究

采用灰色关联熵分析法研究了胜利油田典型区块稠油W/O乳状液稳定性与稠油组成(极性四组分、有机杂原子与过渡金属含量)和油品性质(稠油极性组分偶极矩)的关联,结合稠油W/O乳状液液滴的粒径大小分布及稠油极性四组分Zeta电位,分析了乳状液的稳定机理。用SV值表征乳状液稳定性,SV值越大,乳状液稳定性越好。结果表明,极性四组分、有机杂原子与过渡金属含量与乳状液SV值的关联度从大到小分别为:胶质(0.9945)>饱和分(0.9928)>芳香分(0.9901)>沥青质(0.9597),N(0.9993)>O(0.9918)>S(0.9667),Ni(0.9891)>Fe(0.9852)>V(0.9845),胶质、N及Ni含量与SV值的关联度最大,对乳状液稳定性有重要影响。稠油极性组分偶极矩与SV值的关联度依次为:胶质(0.9929)>沥青质(0.9916)>芳香分(0.9796),胶质的偶极矩是影响乳状液稳定性的关键因素。3-12-182区块稠油的极性四组分Zeta电位绝对值最大,W/O乳状液中液滴粒径最小、尺寸分布最集中(0.5~1.5),SV值最大(1026.70),乳状液最稳定。表2参10     

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。     

稠油W/O型乳状液转相特性研究

为揭示稠油W/O型乳状液转相机理、指导稠油开采及运输,以胜利油田五种稠油样品为研究对象,通过测定不同含水率稠油乳状液的黏度及稠油视HLB值并结合灰熵关联方法,研究分析了稠油由W/O型乳状液向O/W型乳状液的转化过程、稠油乳状液黏度与四组分(饱和分、芳香分、胶质、沥青质)的关系,尝试用稠油的视HLB值解释了不同稠油乳状液乳化转相点的差异原因。按灰熵关联法排列乳化稠油黏度与其极性组分的关联度由大到小的顺序为:重质组分(胶质+沥青质)芳香分饱和分,重质组分是影响乳化稠油高黏的主要因素。对于同一种稠油来说,随着含水率的增加,乳状液表观黏度呈先增大后减小的趋势;随着温度的升高,稠油乳状液转相点增大。胜利油田5种脱水稠油黏度(50℃)由大到小顺序为:草20-平124(14400 m Pa·s)王152-1(22400m Pa·s)草20-平149(24000 m Pa·s)草20-平131(76800 m Pa·s)草南平40(89400 m Pa·s);含水率30%的5种稠油乳状液黏度的大小顺序与脱水稠油黏度的顺序一致,稠油乳状液的乳化转相点(50℃)由高到底的顺序为:草20-平124(59.1%)王152-1(55.5%)草20-平149(53.5%)草20-平131(47.9%)草南平40(45.7%);随着脱水稠油黏度的增大,乳化转相点减小。     

水包稠油乳状液稳定性研究Ⅲ.稠油官能团组分与极性组分的油-水界面张力考察

从稠油官能团组分与极性组分油…水界面张力的角度,研究了稠油各组分的界面活性及其在水包油型乳状液中的作用机理和影响因素.测定了官能团四组分以及极性四组分的油-水界面张力,考察了组分浓度、水相pH值、温度、盐度等因素对油-水界面张力的影响.结果表明,稠油极性四组分的甲苯溶液-水的界面张力大小顺序为饱和分>芳香分>胶质>沥青质;官能团四组分的顺序为中性分>碱性分>酸性分和两性分.酸性分、两性分及沥青质均具有低界面张力的特性,尤其在碱性(pH=11～12)条件下,界面张力很低,是稠油中主要的界面活性组分.碱性条件下更有利于O/W型超稠油乳状液的稳定.官能团组分更能揭示稠油中活性组分的内在本质.     

渤海典型稠油活性组分对油水界面性质及乳状液稳定性的影响

为了揭示原油组分分子组成与各组分界面性质、乳化性能间的关系,阐明油水界面性质变化和原油乳化机理,用极性分离法将渤海某油田稠油分离为沥青质、胶质、剩余分三个组分,含量分别为5.45%、26.5%、57.13%。通过红外光谱、元素分析和高分辨质谱分析了三组分的分子组成,采用界面张力仪、界面黏弹性仪测定了各组分与模拟水间的界面特性。研究结果表明,沥青质、胶质中含有大量酸性化合物,其中沥青质中酸性化合物的相对分子量高、缩合度高且富集多杂原子化合物。0.55%沥青质、5%胶质、5%剩余分模拟油与模拟水间界面张力分别为11.5、20、28 mN/m,说明酸性化合物是原油中主要活性物质,且多杂原子酸性化合物的界面活性更强。原油三组分模拟油的剪切黏度随剪切速率增加而下降,在剪切速率为0.02~0.4 rad/s时,原油三组分/模拟水界面剪切黏度排序为沥青质胶质剩余分,说明各组分形成的界面膜具有明显的结构特性,沥青质尤为明显。原油与乙醇胺溶液能形成稳定的W/O型乳状液,一周后仍无水相析出;除去原油中沥青质后,乳状液稳定性明显变差,11 h后油水完全分层;除去沥青质、胶质后,不能产生乳化现象,说明沥青质、胶质是渤海某油田稠油乳化的活性组分。     

水包稠油乳状液稳定性研究：Ⅲ．稠油官能团组全与极性组分的油—水界面张力考察

从稠油官能团组分与极性组分油－水界面张力的角度,研究了稠油各组分的界面活性及其在水包油型乳状液中的作用机理和影响因素。测定了官能团四组分以及极性四组分的油－水界面张力,考察了组分浓度,水相pH值,温度,盐度等因素对油－水界面张力的影响。结果表明,稠油极性四组分的甲苯溶液－水的界面张力大小顺序为：饱和分＞芳香分＞胶质＞沥青质;官能团四组分的顺序为：中性分＞碱性分＞酸性分和两性分。酸性分,两性分及沥青质均具有低界面张力的特性,尤其在碱性（qH=11-12)条件下,界面张力很低,是稠油中主要的界面活性组分。碱性条件下更有利于O／W型超稠油乳状液的稳定。官能团组分更能揭示稠油中活性组分的内在本质。     

降黏剂对罗家超稠油及其极性四组分模型油乳化性能的影响

实验油样为20℃密度1.0072 g/cm3、50℃黏度40.96 Pa.s、凝点26.5℃的胜利罗家超稠油,乳化降黏剂为非离子表面活性剂OP-10。含水50%的W/O型乳化稠油用600 mg/L OP-10处理后,变为O/W型乳化稠油,在40、50、60、70、80、90℃下的降黏率,以脱水稠油计为99.30%~96.24%,以W/O乳化稠油计为99.58%~96.95%。按行业标准方法将稠油分离为四组分:饱和分20.17%,芳香分39.28%,胶质20.67%,沥青质19.88%,摄取了四组分的IR谱并指认了可能的官能团。将各组分在甲苯中配成2%的模型油,将模型油分散于25倍体积的0.6%Na2CO3碱水中,由加OP-10前后透光率的变化确定各组分乳化能力大小顺序:沥青质>芳香分>饱和分≈胶质。各组分模拟油与地层水、碱水间50℃、10~40分钟动态界面张力高低顺序为:沥青质>饱和分>胶质>芳香分,加OP-10处理后界面张力的降低率,与地层水间为82%~93%,按降低率排列的顺序为:饱和分≈胶质>芳香分>沥青质,与碱水间为22%~89%,按降低率排列的顺序为:沥青质>饱和分≈胶质>芳香分,对这一结果作了分析讨论,包括OP-10引起的芳香分、胶质、沥青质甲基与芳香烃次甲基IR吸收峰面积比和反映更强氢键生成的3600~3000 cm-1土丘状IR吸收峰的变化。图8表7参7。     

稠油组分在水包油乳状液中作用机理的研究——Ⅰ．稠油组分分离及基本性质研究

本文主要研究了稠油的组分分离及其基本性质,为稠油组分在水包油乳状液中的作用机理研究提供基础数据.首次建立了将稠油分为酸性分、碱性分、两性分和中性分四组分的离子交换色谱分离技术.采用该分离技术对辽河杜-84稠油和胜利孤岛垦西稠油进行了组分分离,同时用极性分离法将稠油分为饱和分、芳香分、胶质和沥青质四组分.之后对这些纽分进行了元素、酸碱值、相对分子质量及红外光谱等组成结构测定.结果表明,杜-84稠油中酸性分、碱性分、两性分含量达36.92%;孤岛垦西稠油中酸性分、碱性分、两性分含量达20.65%.元素分析、酸碱值和红外光谱分析结果表明,分离效果较好,离子交换色谱分离法收率可达95%以上.极性四组分以沥青质相对分子质量最高(2000-3000),且辽河沥青质比孤岛沥青质要大许多,反映出辽河稠油的超稠油特性;相对分子质量大小顺序为沥青质＞胶质＞芳香分＞饱和分;官能团四组分中,碱性分相对分子质量最大(1150-1222),其它由大到小依次为两性分、酸性分、中性分.     

克拉玛依风城油田稠油低温氧化过程

风城油田稠油胶质含量高,随着开采的不断深入,部分油井出现吞吐效果变差、含水率升高的现象。为提高克拉玛依风城区稠油油藏注空气采油过程的安全性,进行了低温氧化实验。实验模拟了克拉玛依风城稠油油藏压力（8 MPa）,分别考察油样在不同温度（80~250 ℃）条件下的低温氧化过程,对火烧油层初始低温氧化阶段的油样物性变化、组分变化规律、气体变化进行研究。结果表明,低温氧化反应使稠油密度增加了2%,黏度增加0.72倍;IR分析表明,稠油与空气发生的低温氧化反应使含氧类官能团（-C=O、脂肪醚）的吸收强度明显增强;SARA组分活性强弱为:芳香分＞饱和分＞胶质,250 ℃反应后,沥青质增加较多;气体中N₂含量基本没变,O₂含量由21%降至5%,CO、CH₄和CO₂气体含量升高,由键能法计算结果可知,每消耗1 moL的O₂平均放热量391.54~420.58 kJ。该研究为现场试验设计和应用提供了理论基础数据和技术指导。     

郑王稠油四组分组成和油-水界面膜黏弹性的关系

采用化学分离和元素分析方法分析了郑王稠油的饱和分、芳香分、胶质、沥青质（SARS）的组成,测定了含有分离的四组分的油 水体系的界面扩张黏弹性,考察了振荡频率及组分浓度对油 水体系界面扩张黏弹性的影响。结果表明,含郑王稠油四组分的油 水体系的界面扩张模量均随振荡频率增大而增大,随组分质量分数的增大先增加后减小。含胶质、沥青质组分的油 水体系所形成的界面膜以弹性膜为主,抵抗形变能力更强;油 水体系中饱和分浓度增大,主要体现在其体相浓度增加,弹性模量变化不大,而黏性模量逐渐增大。含郑王稠油四组分的油 水体系的扩张相角均随振荡频率的增加逐渐减小,扩张相角由小到大的油 水体系为含沥青质的、含芳香分的、含胶质的、含饱和分的油 水体系。沥青质是四组分中对油 水体系界面膜黏弹性影响最大的组分。       

Prediction of asphaltene precipitation from n-alkane diluted crude oil by using PC-SAFT equation of state

The precipitation tendency of heavy organics such as asphaltene has posed great challenges for petroleum industry, and thus study of asphaltene precipitation amount and formation conditions seems to be necessary. One of the most common approaches for prediction of asphaltene precipitation is using thermodynamic models. In this study a PC-SAFT equation of state (EOS) is used to predict asphaltene precipitation in two Iranian dead oil samples. Asphaltene content is obtained by filtration method of the oil samples diluted with specific concentrations of different normal alkanes. Also liquid-liquid equilibrium is used for characterization of oil sample into one heavy phase (asphaltene) and another light phase (saturates, aromatics, and resin). Calculations show that the developed model is highly sensitive to interaction parameter between oil fractions. Prediction results were improved due to using Chueh-Prausnitz equation. The results indicate good potential of PC-SAFT EOS in the prediction of asphaltene precipitation in crude oil samples diluted with different normal alkanes. The model error is <5% and the model precision is increased by reducing the number of normal alkane carbons.     

An Experimental Investigation of Asphaltene Precipitation During Natural Production of Heavy and Light Oil Reservoirs: The Role of Pressure and Temperature

Abstract

Many oil reservoirs encounter asphaltene precipitation as a major problem during natural production. In spite of numerous experimental studies, the effect of temperature on asphaltene precipitation during pressure depletion at reservoir conditions is still obscure in the literature. To study their asphaltene precipitation behavior at different temperatures, two Iranian light and heavy live oil samples were selected. First, different screening criteria were applied to evaluate asphaltene instability of the selected reservoirs using pressure, volume, and temperature data. Then, a high pressure, high temperature filtration (HPHT) setup was designed to investigate the asphaltene precipitation behavior of the crude samples throughout the pressure depletion process. The performed HPHT tests at different temperature levels provided valuable data and illuminated the role of temperature on precipitation. In the final stage, the obtained data were fed into a commercial simulator for modeling and predicting purposes of asphaltene precipitation at different conditions. The results of the instability analysis illustrated precipitation possibilities for both reservoirs which are in agreement with the oil field observations. It is observed from experimental results that by increasing the temperature, the amount of precipitated asphaltene in light oil will increase, although it decreases precipitation for the heavy crude. The role of temperature is shown to be more significant for the light crude and more illuminated at lower pressures for both crude oils. The results of thermodynamic modeling proved reliable applicability of the software for predicting asphaltene precipitation under pressure depletion conditions. This study attempts to reveal the complicated role of temperature changes on asphaltene precipitation behavior for different reservoir crudes during natural production.     

A comprehensive experimental evaluation of asphaltene dispersants for injection under reservoir conditions

As the efficiency of dispersants with different origins is questionable for each typical oil sample, the present study provides a reproducible and reliable method for screening asphaltene dispersants for a typical asphaltenic crude oil. Four different asphaltene dispersants (polyisobutylene succinimide, polyisobutylene succinic ester, nonylphenol-formaldehyde resin modified by polyamines, and rapeseed oil amide) were prepared and their performance on two oils from an Iranian field under laboratory and reservoir conditions was studied. A thorough analysis including ash content and SARA tests was performed on the solid asphaltene particles to characterize the nature of deposits. Then a highly efficient carrier fluid, which is crucial when injecting dispersant into the wells, was selected from a variety of chemicals by comparing their solubility. In the next step, using an optical microscope, a viscometer, and a Turbiscan, the screening of dispersants under laboratory conditions was done on a mixture of dead oil and dispersant to evaluate the onset of asphaltene precipitation and its stability when titrating by a precipitant. Finally, two different mixtures of the efficient dispersants, live oil, and carrier fluid were used with the solid detection system (SDS) and the filtration method to examine their effects on the onset pressure of asphaltene precipitation and the asphaltene content of the crude oil under reservoir conditions. The results show that the combination of experimental methods used in this work could be consistently applied to screening asphaltene dispersants. Among the four different dispersants applied here, the dispersant based on nonylphenol-formaldehyde resin modified by polyamines showed the best performance on the available live oils. This chemical modified the onset pressure of asphaltene precipitation of light oil from 4300 psi to about 3600 psi and decreased the precipitated asphaltene of heavy oil by about 30 %.     

辽河超稠油的化学组成特征及其致黏因素探讨

 基于对辽河油田2个超稠油化学组成的系统剖析,研究了辽河油田超稠油的致黏因素,以及化学成分的结构类型、极性和相对分子质量大小对稠油黏度的影响。结果表明,辽河盆地曙光油田超稠油具有成熟度低,胶质、沥青质含量特别高,低相对分子质量组分特别少,并且遭受过严重生物降解等特征。胶质和沥青质的总质量分数接近70%,尤其是沥青质质量分数在40％以上,明显高于国内一般稠油。气相色谱可检测物的总质量分数在饱和烃、芳烃馏分中低于22%,在酸性非烃和中性非烃馏分中分别低于15%和1%。饱和烃中正构烷烃及支链、开链烷烃接近消耗殆尽,GC-MS检测到的几乎全部是孕甾烷、重排甾烷和降藿烷系列化合物。低成熟度和强烈的次生降解作用是其形成的石油地球化学条件,极高含量的大分子组分和极性非烃组分是其具有高黏度的化学组成基础。     

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.     

Catalytic Aquathermolysis of Heavy Oil With Oil-soluble Multicomponent Acrylic Copolymers Combined With Cu2+

A kind of oil-soluble multicomponent acrylic copolymer combined with Cu²⁺ was synthesized and used for catalytic aquathermolysis of heavy oil. This work showed this copper-bearing copolymer led to 84.52% viscosity reduction for the Lukeqin heavy oil at 513.15 K, and converted 10.01% of the resin fraction and 2.85% of the asphaltene fraction into light oil content. After aquathermolysis with this catalyst, some parts of the long-chain saturated hydrocarbons were broken into short-chain ones, and the aromaticity and aromaticity condensation of the resin and asphaltene decreased.     

塔河超稠油胶质、沥青质形貌分析

用环境扫描电子显微镜观察稠油非烃组分胶质和沥青质的形貌,分析结果表明,胶质分子之间、沥青质分子之间以及二者之间可以发生相互作用,形成结构较大的颗粒,胶质颗粒之间连接紧密,沥青质颗粒之间较分散。胶质和沥青质的含量和平面堆砌结构是影响稠油粘度的因素。