水包稠油乳状液稳定性研究Ⅰ.稠油官能团组分分离及其油水界面粘度考察

采用离子交换色谱分离技术将辽河油田杜 -84稠油按化学官能团分为酸性分、碱性分、两性分和中性分 ,同时按极性分离得到胶质和沥青质组分。用元素分析、红外光谱、相对分子质量及酸碱值测定等手段对各组分进行了分析鉴定。又测定了各组分模拟油溶液的油水界面粘度 (IFV) ,考察了油相芳香度、水相 p H值等因素对油水界面粘度的影响。结果表明 ,酸性分和碱性分具有较高的油水界面粘度 ,尤其在水相碱性条件下 ,酸性分的油水界面粘度最高 (p H=1 2时达 0 .1 2 m N· s/m) ,两性分和中性分的油水界面粘度较低 ;沥青质的油水界面粘度明显高于胶质。酸性分的油水界面粘度一般随油相芳香度增大而增大 ,而碱性分油水界面粘度随油相芳香度增大而明显减小 ,两性分和中性分的油水界面粘度随油相芳香度的变化不大。酸性条件下 ,碱性分具有较高的油水界面粘度 ;碱性条件 (p H=1 1以上 )下 ,酸性分具有很高的油水界面粘度。水相碱性条件下稠油中的活性组分主要是官能团组分的酸性分或极性组分的沥青质。油相高芳香度和水相碱性条件有利于 O/W型超稠油乳状液的稳定。官能团组分更能揭示稠油中界面活性组分的内在本质     

380号燃料油的四组分分析及其油水界面张力研究

采用氧化铝吸附色谱柱将380号燃料油分成饱和分、芳香分、胶质和沥青质四组分;用元素分析、凝胶色谱、红外光谱和核磁共振等技术对四组分进行性质分析和结构表征;测定了燃料油及其四组分模拟油的油水界面张力,考察了水相p H、盐浓度对油水界面张力的影响。结果表明:380号燃料油的四组分中芳香分含量最大,沥青质和胶质含量(w)约30%,沥青质比胶质含有更多的杂原子,相对分子质量更大,沥青质的氢碳原子比最小、芳香碳率最大;沥青质比胶质含有更多的羟基、氨基和羧基等官能团,故分子间氢键作用强烈;四组分的油水界面张力由大到小的顺序为饱和分芳香分胶质沥青质,沥青质界面活性最大;由于380号燃料油及其四组分中酸性基团占优势,在强碱性条件下它们与水的界面张力大幅下降;水相盐浓度对380号燃料油及其四组分的界面活性影响不大。     

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。     

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。       

380#燃料油的四组分分析及其油水界面张力研究

采用氧化铝吸附色谱柱将380#燃料油分成饱和分、芳香分、胶质和沥青质四组分;用元素分析、凝胶色谱、红外光谱和核磁共振等技术对四组分进行分析和结构表征;测定了燃料油及其组分模拟油的油水界面张力,考察了水相pH值、盐浓度对燃料油及其组分模拟油油水界面张力的影响。结果表明,380#燃料油中芳香分含量最多,沥青质和胶质含量约30 %。沥青质比胶质含有更多的杂原子,相对分子质量更大。沥青质氢碳原子比n(H)/n(C)最小,芳香碳率fA最大。红外谱图表明,沥青质比胶质含有更多的羟基、氨基和羧基等官能团,故分子间氢键作用强烈。四组分油水界面张力大小顺序为：饱和分>芳香分>胶质>沥青质,沥青质界面活性最大。由于380#燃料油及其组分中酸性基团占优势,在强碱性条件下它们与水的界面张力大幅下降。水相盐浓度对380#燃料油及其组分的界面活性影响不大。     

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。     

一种超稠油模拟油的油水界面扩张黏弹性研究

采用三组分分离法,从一种超稠油中分离出胶质、沥青质和抽余油,配制成不同浓度的模拟油。用OCA20界面张力仪/界面黏弹性仪考察了该种超稠油模拟油的动态界面扩张模量随扩张频率和活性组分浓度的变化规律,研究了从超稠油中分离出的胶质、沥青质和抽余油对模拟油油水界面张力及界面扩张性质的影响。结果表明,当各组分在模拟油中的浓度相同时,抽余油的界面张力最小,胶质的最大,沥青质的居中;含有不同活性组分模拟油的动态界面扩张模量均随扩张频率的升高而增大,胶质模拟油的动态界面扩张模量随活性组分浓度的增大而增大,而沥青质、抽余油模拟油的却先增加后降低;当活性组分浓度为1～4 g/L时,模拟油界面扩张模量的大小顺序为:沥青质胶质抽余油。     

原油乳状液稳定性研究Ⅲ北海原油界面活性组分特性

研究了北海原油界面活性组分在空气中的氧化，红外、紫外光谱，及作为乳化剂对模型乳状液稳定性的影响。研究结果表明，所有胶质、沥青质组分均含有界面活性物质，其中含较多芳香羰基、芳香碳碳双键的化合物对增加油水乳状液的稳定性有重要作用。界面活性组分氧化后羰基浓度增加，作为乳化剂形成的油水乳状液稳定性增大。与胶质相比，沥青质含芳香羰基和芳香碳碳双键较多，分子量较大，在油水界面形成的膜强度较高，所形成的乳状液稳定性也较大。     

原油乳状液稳定性研究：Ⅲ.北海原汪界面活性组分特性

研究了北海原油界面活性组分在空气中的氧化，红外，紫外光谱，及作用乳化剂对模型乳状液稳定性的影响，研究结果表明，所有胶质，沥青质组分均含有界面活性物质，其中含较多芳香羰基，芳香碳－碳双键的化合物对增加油水乳状液的稳定性有重要作用，界面活性组分氧化后羰基浓度增加，作为乳化剂形成的油水乳状液稳定性增大。与胶质相比，沥青质含芳香羰基和芳香碳－碳双键较多，分子量较大，在油水界面形成的膜强度较高，所形成的乳液     

胜利原油活性组分对其与烷基苯磺酸盐溶液组成的体系油-水界面张力的影响

 采用柱色谱四组分分离方法(SARA)对胜利原油进行分离,依次得到沥青质、饱和分、芳香分和胶质;采用碱醇液法萃取胜利原油得到其酸性组分,测定了各原油活性组分模拟油与烷基苯磺酸盐配制的系列标准溶液组成体系的油-水界面张力。结果表明,原油的酸性组分在低质量分数时通过改变油相的等效烷烃碳数（EACN）影响体系的油-水界面张力;高质量分数时则与表面活性剂混合吸附,使得体系油-水界面张力大幅度升高。胶质对其模拟油-表面活性剂标准溶液体系的油-水界面张力的影响与酸性组分的规律一致;沥青质的界面活性弱于酸性组分,混合吸附能力较弱,高质量分数时使体系油-水界面张力小幅度升高;饱和分和芳香分只影响油相的性质。     

杯芳烃基嵌段聚醚的油-水界面粘度

采用界面粘弹仪测量了3类环状对叔丁基酚醛树脂嵌段聚醚(杯芳烃聚醚)在3种沥青质模型油-去离子水体系的界面粘度。结果表明，杯芳烃聚醚具有较高的界面活性，吸附在油-水界面并取代了-部分沥青质，形成界面混合膜，且膜强度变弱，界面粘度减小；将含有杯芳烃聚醚的3种沥青质模型油-水体系的界面压与界面粘度关联后得到，在某一相对分子质量、HLB值范围，聚醚在油-水界面的界面压较高，同时降低界面粘度的能力也较强。     

Influence of the properties of resins on the interactions between asphaltenes and resins

The properties of two resins (Tahe resin and Liaohe resin) and their influences on the dispersion of two asphaltenes (Tahe asphaltene and Liaohe asphaltene) are investigated by laboratory experiments. The results indicate that the adsorption isotherms of two resins are accorded with the Freundlich absorption model. The shape of the curves obtained could be attributed to both multilayer adsorption of resins on asphaltenes surfaces and the penetration of resins into the microporous structure of the asphaltenes. Based on the combined results from the shape of the curves and chemical properties of resins, the relative adsorption quantity of Tahe resin is higher than that of Liaohe resin due to the stronger polarity of Tahe resin, and the effect of Tahe resin on the dispersion of asphaltene is stronger than that of Liaohe rein. The different properties of resin can directly lead to the difference of dispersion performance on asphaltene in crude oil, which is closely related to the chemical structure of resin. The more the number of aromatic structure of the resin, the stronger the effect of resin on the dispersion of asphaltene there is.     

PETROLEUM RESINS: SEPARATION, CHARACTER, AND ROLE IN PETROLEUM

In petroleum science, the term resin generally implies material that has been eluted from various solid adsorbents, whereas the term maltenes (or petrolenes) indicates a mixture of the resins and oils obtained as filtrates from the asphaltene precipitation. Thus, after the asphaltenes are precipitated, adsorbents are added to the n-pentane solutions of the resins and oils, by which process the resins are adsorbed and subsequently recovered by the use of a more polar solvent, and the oils remain in solution. The resin fraction plays an important role in the stability of petroleum and prevents separation of the asphaltene constituents as a separate phase. Indeed, the absence of the resin fraction (produced by a variety of methods) from the maltenes influences the ability of the de-resined maltenes to accommodate the asphaltenes either in solution or as a stable part of a colloidal system. In spite of the fact that the resin fraction is extremely important to the stability of petroleum, there is surprisingly little work reported on the characteristics of the resins. This article summarizes the work that has been carried out in determining the character and properties of the resin constituents. Suggestions are also made regarding current thoughts of the role of these constituents on the structure and stability of petroleum.     

油包水乳状液中胶质和沥青质的界面剪切黏度和乳状液稳定性的关系

 采用红外和紫外光谱分析了胜利原油中胶质和沥青质的结构，采用界面剪切黏度对其油、水界面膜强度进行了表征，测定了胶质和沥青质模拟油油包水乳状液的稳定性。结果表明，沥青质和胶质的结构和相对分子质量不同，沥青质含有更多的芳环结构，相对分子质量比胶质大，界面膜强度也比胶质强，其乳状液更稳定。     

MOLECULAR MECHANICS OF AGGREGATES OF ASPHALTENES AND RESINS OF THE ATHABASCA OIL

An analysis of the effects of an almost continuous chemical distribution of asphaltenes and resins on the molecular recognition processes occurring in crude oil indicates that their aggregates will have a broad distribution both in the chemical composition and in the strength of the intermolecular interactions responsible for the aggregation. Then, crude oil cannot be described just as a sol formed by solid asphaltene particles dispersed by resins or as a simple micellar system of asphaltene and resin molecules. The molecular aggregates may vary from solid particles formed by asphaltenes and resins to loosely bound micelles with quite short lifetimes. These different aggregates may coexist within the crude oil and many will exchange components with others. The entropic contributions to the changes in free energy upon aggregation were also discussed. Molecular mechanics calculations showed that a model asphaltene aggregate from Athabasca exhibits stronger interactions with its resins than with solvents such as toluene and n-octane. The resins showed a considerable selectivity for the different adsorption sites of the asphaltene aggregate. This selectivity was stronger than that found for the solvent molecules, indicating that it is enthalpically more favorable for them to form aggregates with the asphaltenes. The selectivity may also help to explain the specificity of some resins that are able to disperse only the asphaltenes of certain types of crude oils while failing to do the same for others.     

CHARACTERIZATION OF ASPHALTENES AND RESINS FROM PROBLEMATIC MEXICAN CRUDE OILS

Asphaltenes and resins have been separated from four mexican oils suffering from the deposition of asphaltenic material during recovery operations. A SARA separation of the oils was performed and the resins and asphaltenes further analyzed. Characterization methods employed were FTIR, elemental composition both of CHNSO, and trace metals and molecular weight determination using size exclusion chromatography. NMR techniques were applied to two asphaltene samples. The overall scope of the work was to get a better understanding of the nature of the asphaltene stability at a molecular level in these problematic oils. Separation of resin in two fractions indicates that there is no long alkyl chains in these as given by FTIR, which may be the cause of the lack of stability along with the large difference in bubble point and reservoir pressure.     

减压渣油微观相结构特性的分子模拟

选用4种模型化合物代表减压渣油四组分(SARA),采用分子动力学模拟了减压渣油微观相结构,发现不同结构分子间相互作用的差异是减压渣油微观非均匀分布的本质原因,并通过电子分布特性分析了不同结构分子间相互作用差异的本质原因。沥青质分子间强相互作用使得沥青质分子自缔合形成聚集体;而多个胶质分子与沥青质分子的强相互作用封闭了沥青质分子自身进一步发生相互作用的活性位;同时,与胶质分子、饱和烃分子具有强相互作用的芳香烃分子将沥青质 胶质分子形成的聚集体分散在由芳香烃 饱和烃分子构成的连续相内,其中芳香烃分子更靠近胶质分子。因此,增加沥青质、饱和烃分子的含量会促进沥青质聚集,降低减压渣油稳定性;增加胶质、芳香烃分子的含量会阻碍沥青质聚集,提高减压渣油稳定性。     

CHARACTERIZATION OF ASPHALTENES AND RESINS FROM PROBLEMATIC MEXICAN CRUDE OILS

Asphaltenes and resins have been separated from four mexican oils suffering from the deposition of asphaltenic material during recovery operations. A SARA separation of the oils was performed and the resins and asphaltenes further analyzed. Characterization methods employed were FTIR, elemental composition both of CHNSO, and trace metals and molecular weight determination using size exclusion chromatography. NMR techniques were applied to two asphaltene samples. The overall scope of the work was to get a better understanding of the nature of the asphaltene stability at a molecular level in these problematic oils. Separation of resin in two fractions indicates that there is no long alkyl chains in these as given by FTIR, which may be the cause of the lack of stability along with the large difference in bubble point and reservoir pressure.

     

界面扩张流变法研究有机碱与原油活性组分的界面相互作用

从胜利油田渤61原油中分离得到胶质和沥青质,通过滴外形分析方法研究了两种原油组分模拟油（质量分数0.5%,由航空煤油配制）与乙醇胺溶液间的界面张力及界面扩张流变性质。结果表明,乙醇胺与胶质中脂肪酸反应,形成脂肪酸和皂的混合吸附膜,有利于界面张力的降低,但对界面扩张模量影响不大。乙醇胺与沥青质中芳香酸的反应能促进芳香酸的吸附,降低界面张力,同时增加膜强度;但随着乙醇胺浓度的进一步增大,芳香酸皂扩散交换作用对界面膜的影响增强,界面膜黏性部分增加,膜强度有所降低。