Article(id=1156949366956184156, tenantId=1146029695717560320, journalId=1146123166801305609, issueId=1156949362480861758, articleNumber=null, orderNo=null, doi=10.12404/j.issn.1671-1815.2308634, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1699027200000, receivedDateStr=2023-11-04, revisedDate=1730736000000, revisedDateStr=2024-11-05, acceptedDate=null, acceptedDateStr=null, onlineDate=1753767824162, onlineDateStr=2025-07-29, pubDate=1738944000000, pubDateStr=2025-02-08, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1753767824162, onlineIssueDateStr=2025-07-29, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1753767824162, creator=13701087609, updateTime=1753767824162, updator=13701087609, issue=Issue{id=1156949362480861758, tenantId=1146029695717560320, journalId=1146123166801305609, year='2025', volume='25', issue='4', pageStart='1312', pageEnd='1751', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=0, createTime=1753767823094, creator=13701087609, updateTime=1755171161273, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1162835389472424814, tenantId=1146029695717560320, journalId=1146123166801305609, issueId=1156949362480861758, language=EN, specialIssueTitle=, coverIllustrator=, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1162835389472424815, tenantId=1146029695717560320, journalId=1146123166801305609, issueId=1156949362480861758, language=CN, specialIssueTitle=, coverIllustrator=, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=1428, endPage=1437, ext={EN=ArticleExt(id=1156949367904096874, articleId=1156949366956184156, tenantId=1146029695717560320, journalId=1146123166801305609, language=EN, title=Effects of Oil Composition and Phase Change on the Stability of Water-in-waxy Model Oil Emulsions, columnId=1156262729003422020, journalTitle=Science Technology and Engineering, columnName=Papers·Petroleum and Natural Gas Industry, runingTitle=null, highlight=null, articleAbstract=

In the process of oilfield development, the formation of emulsion between crude oil and water is quite common, which increases the difficulty of crude oil treatment. The composition of crude oil, especially the precipitation of paraffin wax, has significant influence on the stability of the emulsion. From the unique perspective that the oil composition affects the phase change and then further determines the emulsion stability, a systematic study was carried out with the methods of emulsion stability test, oil-water interfacial characteristic test, wax precipitation test, asphaltene dispersion stability test, and microscopic observation. It is observed that increasing the amount of liquid paraffin in the solvents leads to a change in the form of wax crystals from fine particles to larger agglomerated wax crystals, and the asphaltenes dispersion stability decreases along with it. Test temperature can significantly affect emulsion stability. At 30 ℃, increasing the percentage of liquid paraffin reduces the interfacial tension, increases the interfacial dilatational modulus, and enhances the structure of the interfacial film. This contributes to the formation of small droplets and improves emulsion stability to a certain extent. At 15 ℃, by contrast, increasing the liquid paraffin content promotes the development of a more structured wax crystals network, which significantly enhances emulsion stability by binding water droplets. Additionally, it is also found that a wax crystal interfacial film could be formed at the surface of the emulsified drops, which improves further the interfacial film strength and emulsion stability. Based on the above findings, an influencing mechanism model is presented concerning the synergistic stabilization of model oil emulsion containing asphaltene and paraffin wax.

, correspAuthors=Chuan-xian LI, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, authorCompany=null, fund=null, authors=null, authorsList=Zhen LIU, Chuan-xian LI), CN=ArticleExt(id=1156949449781105051, articleId=1156949366956184156, tenantId=1146029695717560320, journalId=1146123166801305609, language=CN, title=油相组成及相态变化对含蜡油包水乳状液稳定性的影响, columnId=1156262729603207500, journalTitle=科学技术与工程, columnName=论文·石油、天然气工业, runingTitle=null, highlight=null, articleAbstract=

在油田开发过程中,原油与水极易形成乳状液,增大了原油处理难度,而原油组成尤其是原油中石蜡的析出对乳状液稳定性的影响显著。从油相组成影响相态变化进而改变乳状液稳定性的独特角度出发,通过乳状液稳定性测试、油水界面特性测试、析蜡特性测试、沥青质分散稳定性测试、显微观察等方法开展系统研究。研究发现,随着油相中液体石蜡含量的增大,蜡晶的形貌从细小颗粒变为较大的团聚蜡晶,沥青质的分散稳定性也随之下降。测量温度显著影响乳状液稳定性:测量温度为30 ℃时,增大液体石蜡含量可以降低界面张力、提高扩张模量,这有助于液滴保持分散,在一定程度上提高乳状液的稳定性;测量温度为15 ℃时,增大液体石蜡含量促进结构更强的蜡晶网络形成,通过束缚水滴大幅提高乳状液稳定性。此外,研究还发现,在乳化水滴表面析出的蜡晶可形成一层蜡晶界面膜,从而进一步提高界面膜强度和乳状液稳定性。基于上述研究,首次提出油相组成对沥青质与石蜡协同稳定模拟原油乳状液的影响机理模型。

, correspAuthors=李传宪, authorNote=null, correspAuthorsNote=
*李传宪(1963—),男,汉族,山东菏泽人,博士,教授。研究方向:原油乳化与破乳技术。E-mail:
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刘真(1972—),女,汉族,江苏武进人,硕士,高级工程师。研究方向:海洋平台油气及海底管线工艺设计。E-mail:

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刘真(1972—),女,汉族,江苏武进人,硕士,高级工程师。研究方向:海洋平台油气及海底管线工艺设计。E-mail:

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刘真(1972—),女,汉族,江苏武进人,硕士,高级工程师。研究方向:海洋平台油气及海底管线工艺设计。E-mail:

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油相组成及相态变化对含蜡油包水乳状液稳定性的影响
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刘真 1 , 李传宪 2, *
科学技术与工程 | 论文·石油、天然气工业 2025,25(4): 1428-1437
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科学技术与工程 | 论文·石油、天然气工业 2025, 25(4): 1428-1437
油相组成及相态变化对含蜡油包水乳状液稳定性的影响
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刘真1 , 李传宪2, *
作者信息
  • 1 中石化石油工程设计有限公司, 东营 257029
  • 2 中国石油大学(华东)储运与建筑工程学院, 青岛 266580
  • 刘真(1972—),女,汉族,江苏武进人,硕士,高级工程师。研究方向:海洋平台油气及海底管线工艺设计。E-mail:

通讯作者:

*李传宪(1963—),男,汉族,山东菏泽人,博士,教授。研究方向:原油乳化与破乳技术。E-mail:
Effects of Oil Composition and Phase Change on the Stability of Water-in-waxy Model Oil Emulsions
Zhen LIU1 , Chuan-xian LI2, *
Affiliations
  • 1 Sinopec Petroleum Engineering Corporation, Dongying 257029, China
  • 2 College of Pipeline and Civil Engineering, China University of Petroleum (East China), Qingdao 266580, China
出版时间: 2025-02-08 doi: 10.12404/j.issn.1671-1815.2308634
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在油田开发过程中,原油与水极易形成乳状液,增大了原油处理难度,而原油组成尤其是原油中石蜡的析出对乳状液稳定性的影响显著。从油相组成影响相态变化进而改变乳状液稳定性的独特角度出发,通过乳状液稳定性测试、油水界面特性测试、析蜡特性测试、沥青质分散稳定性测试、显微观察等方法开展系统研究。研究发现,随着油相中液体石蜡含量的增大,蜡晶的形貌从细小颗粒变为较大的团聚蜡晶,沥青质的分散稳定性也随之下降。测量温度显著影响乳状液稳定性:测量温度为30 ℃时,增大液体石蜡含量可以降低界面张力、提高扩张模量,这有助于液滴保持分散,在一定程度上提高乳状液的稳定性;测量温度为15 ℃时,增大液体石蜡含量促进结构更强的蜡晶网络形成,通过束缚水滴大幅提高乳状液稳定性。此外,研究还发现,在乳化水滴表面析出的蜡晶可形成一层蜡晶界面膜,从而进一步提高界面膜强度和乳状液稳定性。基于上述研究,首次提出油相组成对沥青质与石蜡协同稳定模拟原油乳状液的影响机理模型。

油包水乳状液  /  油相组成  /  石蜡  /  油水界面  /  稳定性

In the process of oilfield development, the formation of emulsion between crude oil and water is quite common, which increases the difficulty of crude oil treatment. The composition of crude oil, especially the precipitation of paraffin wax, has significant influence on the stability of the emulsion. From the unique perspective that the oil composition affects the phase change and then further determines the emulsion stability, a systematic study was carried out with the methods of emulsion stability test, oil-water interfacial characteristic test, wax precipitation test, asphaltene dispersion stability test, and microscopic observation. It is observed that increasing the amount of liquid paraffin in the solvents leads to a change in the form of wax crystals from fine particles to larger agglomerated wax crystals, and the asphaltenes dispersion stability decreases along with it. Test temperature can significantly affect emulsion stability. At 30 ℃, increasing the percentage of liquid paraffin reduces the interfacial tension, increases the interfacial dilatational modulus, and enhances the structure of the interfacial film. This contributes to the formation of small droplets and improves emulsion stability to a certain extent. At 15 ℃, by contrast, increasing the liquid paraffin content promotes the development of a more structured wax crystals network, which significantly enhances emulsion stability by binding water droplets. Additionally, it is also found that a wax crystal interfacial film could be formed at the surface of the emulsified drops, which improves further the interfacial film strength and emulsion stability. Based on the above findings, an influencing mechanism model is presented concerning the synergistic stabilization of model oil emulsion containing asphaltene and paraffin wax.

water-in-oil emulsion  /  solvent composition  /  paraffin wax  /  oil-water interface  /  stability
刘真, 李传宪. 油相组成及相态变化对含蜡油包水乳状液稳定性的影响. 科学技术与工程, 2025 , 25 (4) : 1428 -1437 . DOI: 10.12404/j.issn.1671-1815.2308634
Zhen LIU, Chuan-xian LI. Effects of Oil Composition and Phase Change on the Stability of Water-in-waxy Model Oil Emulsions[J]. Science Technology and Engineering, 2025 , 25 (4) : 1428 -1437 . DOI: 10.12404/j.issn.1671-1815.2308634
在油田开发过程中,原油与地层水会在油藏深部的孔隙介质、近井地带和井筒处受到剪切作用,常会形成W/O型原油乳状液[1-2],而原油中的胶质、沥青质、有机酸、油湿性固体颗粒等界面活性物质能够作为天然乳化剂起到稳定乳状液的作用[3-5]。在原油生产过程中,石蜡分子由于过饱和而在较高温度下结晶析出,这会显著恶化原油低温流变性[6-7],并且还会影响乳状液的稳定性。稳定的乳状液给原油生产带来诸多问题,如原油黏度增大,处理困难[8],原油管道的停输再启动困难[9],管道安全性降低[10-11]等。为有效指导原油的破乳脱水,有必要充分了解影响W/O型原油乳状液稳定性的机理。
中外学者对W/O型原油乳状液的稳定机理开展了大量研究工作[12]。目前,普遍接受的为界面膜稳定机理和立体稳定机理。即油相黏度和密度显著影响乳状液稳定性(立体稳定机理),但由胶质、沥青质、油湿性固体颗粒等活性物质形成的界面吸附膜才是稳定乳状液的关键(界面膜稳定机理),其中沥青质是主要的界面吸附物质,对原油乳状液稳定性的贡献最为显著[13]。此外,本团队前期研究表明,除沥青质外,石蜡对原油乳状液的稳定性也有重要影响[14]。在低于析蜡点温度下,石蜡会结晶析出[15],析出的蜡晶颗粒必然参与稳定过程。
目前,人们已针对沥青质的界面吸附动力学和界面吸附膜结构开展了大量研究工作[16-18],深入考察了蜡含量、胶质含量、沥青质分散状态、水相驱油用剂(碱、表面活性剂与聚合物)对沥青质界面吸附膜和原油乳状液稳定性的影响[19-21],揭示了界面吸附膜特性与乳状液稳定性的内在相关性。研究表明,原油中界面活性物质是影响原油乳状液稳定性的主要因素[1-5,22]。沥青质分子能在油-水界面上构成具有一定厚度的黏弹性膜,阻碍水滴间的聚并,而界面膜强度、界面流变性等因素则决定了乳状液的稳定性[23]
研究表明,沥青质的分散状态在乳状液的稳定方面起重要的作用,而影响沥青质分散状态的因素有表面活性剂、胶质[24]、油相组成等。其中,学者们对表面活性剂、胶质等已经开展了大量的研究,但是,针对油相组成影响原油乳状液稳定性的相关研究十分有限,目前的研究内容大多限于油相组成的变化会影响含蜡原油的析蜡特性及低温流变性,进而影响所形成的W/O型原油乳状液的稳定性。既然油相组成能够显著改变沥青质在油相中的分散状态,油相组成也将显著影响所形成的W/O型原油乳状液的稳定性,但相关研究报道较少。
鉴于此,配置不同油相组成的含沥青质和石蜡的模拟原油,并在30 ℃(高于析蜡点)和15 ℃(低于析蜡点)下研究油相组成与测量温度对乳状液稳定性的影响,通过沥青质分散稳定性测量、模拟原油及其乳状液析蜡特性测量、模拟原油流变性测量、稀释模拟原油-模拟地层水的界面膜特性测量、乳状液稳定性测量与微观观察等研究方法,探究油相组成与测量温度对模拟原油乳状液沉降/聚结稳定性的影响规律,并提出相应的机理模型。研究成果有助于进一步理解含蜡原油采出液的稳定机理,为油田实现高效破乳提供理论指导和技术支持。
含0.05 mol/L NaCl的蒸馏水用作模拟地层水;二甲苯纯度大于99%,用作油溶剂;液体石蜡,相对密度为0.84~0.86,通过Agilent 7890B气相色谱仪分析了液体石蜡的组成,发现液体石蜡主要由C16~C26的异构烷烃构成[25]。如图1所示,在60~-20 ℃的降温过程中,液体石蜡单位质量热流量呈线性减小的趋势,没有吸放热峰,证明液体石蜡作为溶剂不会对切片石蜡的结晶特性产生影响;切片石蜡,正构烷烃质量分数大于95%,石蜡的碳数分布很宽(C20~C42),主峰区碳数为C29,与真实含蜡原油中石蜡的碳数分布相近。所用沥青质通过正庚烷沉淀法从塔河稠油中提取。
模型原油中沥青质量分数保持0.5%不变,石蜡质量分数保持10%不变,二甲苯与液体石蜡按质量比1∶0、4∶1、2∶1和1∶1混合,分别记为溶剂1~溶剂4。
具体制备步骤:将定量的石蜡、沥青质、二甲苯、液体石蜡密封于玻璃瓶中并加热至80 ℃,然后在磁力搅拌条件下恒温12 h,以保证沥青质充分分散和石蜡充分溶解;再将一定量的模拟原油控温至30 ℃,并加入相同温度的模拟地层水;利用均质机乳化,即得模拟原油乳状液。均质机转速为18 000 r/min,模拟地层水和模型原油的体积比为7∶3,总的油水体积为60 mL,乳化时间10 min。乳化温度为30 ℃,远高于析蜡点。
使用DSC 821e差示扫描量热仪分析模型原油的析蜡特性。令温度从60 ℃以10 ℃/min的速率降温至-20 ℃。基于基于差示扫描量热(differential scanning calorimetry,DSC)曲线,可以得到模型原油的析蜡点和累积析蜡量[26]。通过带冷热台的Olympus BX53M偏光显微镜观察模型原油中析出蜡晶的形貌。首先将一滴模型原油置于载玻片,并在60 ℃下保持20 min。然后,以0.5 ℃/min的冷却速度将油样从60 ℃冷却至15 ℃。之后,拍摄并记录模型含蜡原油中在15 ℃下沉淀的蜡晶体。
微观分散状态观察:将含蜡与沥青质的模拟原油置于60 ℃水浴中热处理30 min;然后取少量油样置于Olympus BX53M光学显微镜的冷热台中,并以1 ℃/min的降温速率降至30 ℃(高于析蜡点,无蜡晶析出);恒温5 min后,通过显微镜的常光光源观察沥青质在油相中的分散状态。
粒度分析:利用二甲苯对含蜡+沥青质模拟油进行稀释处理,使油相中沥青质的质量分数降至0.05%,然后在30 ℃下通过Mastersize 3000激光粒度仪测量模拟油中沥青质的粒度及粒度分布情况。
利用Tracker-H悬滴界面张力仪测量模型原油-模拟地层水界面张力和界面扩张模量随时间的变化。令油滴-水体系在30 ℃下恒温,以观测沥青质在油水界面的等温吸附行为;然后以1 ℃/min的降温速率从30 ℃降至0 ℃,以评估降温和析蜡对界面特性的影响。
乳化结束后,立刻将乳状液倒入两个比色管中。一个比色管置于30 ℃水浴中,另一个置于15 ℃水浴中,观测24 h内乳状液的宏观稳定性。在宏观观察过程中,未发现分出水相,进而通过对比初始时刻和24 h后乳状液显微照片中水滴的粒度,定性评价乳状液的聚结稳定性。此外,通过BX53M偏光显微镜观测15 ℃下乳状液中析出蜡晶的形貌,以明确水滴是否能够参与析蜡过程。
油相组成对模拟原油析蜡放热特性的影响如图2(a)所示。沥青质通过成核效应和共晶效应与蜡分子相互作用已被广泛接受。成核效应会增加油相的析蜡点(wax appearance temperature,WAT),但共晶效应会降低WAT。油相最终WAT是这两种效应竞争的结果。在溶剂4中的沥青质与蜡显示出更强的成核效应,因此WAT略微高1 ℃。
基于DSC曲线,得到不同温度下模拟原油的累积析蜡量,如图2(a)所示。随着溶剂中液体石蜡含量的增大(溶剂1→溶剂4),溶剂对石蜡分子的溶解性增强,-20 ℃下的累积析蜡量有所降低,这也间接证明,与二甲苯相比较,液体石蜡是石蜡组分更优良的溶剂。
图3为油相组成在15 ℃下对模拟原油蜡晶形貌的影响。在溶剂1[图3(a)]中,沥青质可以起到成核作用形成大量的细小蜡晶颗粒(几个微米)。随着溶剂中液体石蜡含量的提高(溶剂2→溶剂4),可分辨的蜡晶数量增多,蜡晶颗粒显著变大,但实际数量减少。
油相组成对模拟原油中沥青质分散状态的影响如图4所示。随着溶剂中液体石蜡含量的增大(溶剂1→溶剂4),模拟原油中沥青质的分散稳定性减弱,缔合沥青质胶粒尺寸有所增大。
油相组成对模拟原油中沥青质的粒度分布的影响如图5所示。根据相似相溶规则,具有稠合芳环结构的沥青质在二甲苯中分散性良好,但在液体石蜡中分散性较差。因此,随着溶剂中二甲苯含量减少和液体石蜡含量的增大(溶剂1→溶剂4),沥青质的分散性变差,缔合度增加,缔合胶粒的粒度增大。
在恒温(30 ℃)和冷却(从30 ℃降温至0 ℃)过程中,油相组成和测试温度对含0.05%沥青质+1.0%石蜡稀释模拟原油-水界面张力和扩张模量的影响分别如图6(a)图6(a)所示。
在恒温过程中,由于沥青质在油水界面的持续吸附,界面张力不断下降,但界面扩张模量不断增大。沥青质的界面吸附可分为扩散控制、反应控制和老化3个阶段[27],接近20 min时沥青质的等温界面吸附已进入老化阶段,此时沥青质界面吸附量不再增加,但由于老化作用吸附膜的结构不断增强,因而界面张力变化较缓慢而界面模量仍显著增大。在冷却降温过程中,稀释模拟原油-水界面张力和扩张模量随时间的延长逐渐增大。研究表明,油水界面张力随温度的升高而降低,这与实验结果相符[28-29]。随着温度的降低,吸附于油水界面的沥青质颗粒稳定性变差、相互作用增强,这增强了界面吸附膜的结构强度,因此界面扩张模量不断增大。
随着溶剂中液体石蜡含量的增大(溶剂1→溶剂4),稀释模拟原油-水界面张力明显降低但扩张模量显著变大。这是由于随着液体石蜡含量的增大,溶剂中沥青质的分散稳定性降低,更多沥青质可吸附于油水界面的缘故。
此外,在低于析蜡点(图6中圆圈标出)的温度下,一些石蜡分子可能在油水界面结晶并影响界面特性。然而,在析蜡点以下,界面张力和扩张模量的变化趋势几乎无变化。因此,仅根据油水界面张力和扩张模量无法确定石蜡是否在油水界面上结晶并对界面特性产生影响。
油相组成对模拟原油乳状液30 ℃下沉降稳定性的影响如图7(a)图7(a)所示。在乳化结束后,立刻通过显微镜观察了乳状液的微观结构,如图8所示,通过对图8的处理得到水滴的粒度及粒度分布,如图9所示。可以看出,随着溶剂中液体石蜡含量的增大,乳状液中水滴粒度有减小的趋势。可能的原因是,随着溶剂中液体石蜡含量的增大,沥青质在溶剂中的分散稳定性变差,这促进了沥青质在油-水界面的吸附,进而导致乳状液中水滴粒度的逐渐减小。随着水滴粒度的减小,一方面水滴的重力沉降作用减弱;另一方面,水滴间作用力增强,乳状液的黏度增大,这两方面因素均使得乳状液的稳定性逐渐提高。
油相组成对模拟原油乳状液15 ℃下沉降稳定性的影响如图7(a)图7(a)所示。可见,乳状液在15 ℃下的沉降稳定性得到了大幅提高,并且随着溶剂中液体石蜡含量的增大(溶剂1→溶剂4),沉降稳定性也得到明显改善。在15 ℃测量温度下,模拟原油的黏度远高于30 ℃下的黏度,这有助于提高乳状液的沉降稳定性;但是,随着溶剂中液体石蜡含量的增大,模拟原油黏度显著减小,这将降低乳状液沉降稳定性,与图7中的实验结果不符。由此可见,15 ℃下乳状液的沉降稳定性受乳状液中水滴粒度的影响更大。
图7(a)可以看出,将试瓶上部分出的油相去除之后水平放置试瓶,底部的浓乳状液相并不流动,这表明浓乳状液中水滴间的相互作用增强,使浓乳状液呈凝胶态,从而抑制乳状液的进一步沉降。
综上所述,油相组成和测试温度均显著影响乳状液的沉降稳定性。
图10为油相组成对乳液聚结稳定性的影响。可见,油相组成和测量温度均显著影响乳状液的聚结稳定性。溶剂1时[图10(a)],30 ℃下静置24 h后,乳状液中水滴粒度有一定增大趋势,但总体来看乳状液的聚结稳定性相对较好。可能的原因是此时所形成的乳状液液滴尺寸小、数量多,相互作用强,这增强了乳状液体系的结构强度,进而抑制水滴聚结。15 ℃下静置24 h后水滴粒度增幅较小,聚结稳定性进一步提高。溶剂1时,15 ℃下模拟原油所形成的蜡晶网络结构最强,这显著抑制了水滴的聚结,因而15 ℃下乳状液的聚结稳定性较好。
溶剂4时[图10(a)],与图10(a)相比较,30 ℃下乳状液的聚结稳定性又有一定程度的提高。由于溶剂4中液体石蜡含量大,沥青质的分散稳定性变差,这促进了沥青质的界面吸附,降低了乳滴粒度,提高了沥青质吸附膜的结构,因而聚结稳定性有所提高。然而,与30 ℃测试温度相比较,15 ℃下乳状液的聚结稳定性并没有明显提高;可能的原因是,溶剂4时,15 ℃下模拟原油中虽有蜡晶析出,但所形成的蜡晶网络结构最弱,这不利于提高乳液聚结稳定性。
为明确石蜡分子能否在乳化水滴表面结晶析出并形成蜡晶界面膜,对15 ℃下模拟原油乳状液中析出蜡晶的形貌进行了观测,结果如图11所示。通过与图3对比可知,溶剂1~溶剂3时,由于模拟原油中析出的蜡晶和乳状液中析出的蜡晶均非常细小,难以分辨两者之间的差异。然而,溶剂4时,乳状液中和模拟原油中析出蜡晶的形貌出现了显著变化:由模拟原油中较大的蜡晶颗粒(10 μm)转变为乳状液中非常细小的点状蜡晶。这表明乳状液中尺寸小、数量多的水滴能够有效起到蜡晶成核剂的作用,使蜡晶数量变多、尺寸变细小,进而引发石蜡分子在水滴表面结晶析出并形成一层蜡晶界面膜,这进一步提高乳状液的宏观稳定性。
通过上述研究,揭示了油相组成对0.5%沥青质+10%石蜡协同稳定乳状液作用的影响机理。当溶剂仅为二甲苯时,沥青质的分散稳定性良好,油水界面吸附的沥青质较少,油水界面张力高、界面膜强度弱,所形成的乳化水滴较大,不利于乳状液的稳定。但此时析出的蜡晶颗粒细小,低温下(15 ℃)形成的蜡晶网络结构较强,这有助于提高乳状液的低温稳定性。乳状液的宏观稳定性是上述两种作用的综合体现。
随着溶剂中液体石蜡含量的增大,沥青质的分散稳定性变差,油水界面吸附的沥青质增多,界面张力低,界面膜强度高,所形成的乳化水滴粒径减小,这有利于乳状液的稳定;尺寸小、数量多的水滴作为有效的蜡晶成核剂,能够促进大量细小蜡晶的形成(15 ℃),同时在水滴表面形成蜡晶界面膜,这提高了乳状液的宏观结构强度和水滴界面膜的强度,进而深度提高乳状液的低温(15 ℃)稳定性。
通过油品物性测量、油水界面膜特性测量、乳状液稳定性测量与微观观察等手段,系统性研究了油相组成和相态变化对W/O乳状液稳定性的影响规律,揭示了油相组成对油水界面膜结构的影响机理。得出如下结论。
(1)油相组成显著影响模拟原油的物性。随着溶剂中液体石蜡含量的增大(溶剂1→溶剂4),WAT变化较小,累积析蜡量减少,沥青质在油相中的分散稳定性降低。
(2)油相组成和测量温度对乳状液的稳定性有显著影响。随着溶剂中液体石蜡含量的增大,界面稳定性不断提高,有助于小水滴的形成,15 ℃时乳化水滴的粒度比30 ℃时更小,因此乳状液的稳定性更高。15 ℃时,增大液体石蜡含量能够形成结构更强的蜡晶网络,抑制了水滴的运移,在乳滴表面还会形成蜡晶界面膜,从而大幅提高乳状液稳定性。
(3)提出了油相组成对沥青质-石蜡协同稳定模拟原油乳状液的影响机理模型。增大溶剂中液体石蜡的含量能够促进沥青质的吸附,提高界面稳定性,减小乳化水滴的粒度,还能促进石蜡分子在乳滴表面形成蜡晶界面膜。因此乳状液的稳定性不断提高。
  • 山东省自然科学基金面上项目(ZR2022ME115)
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doi: 10.12404/j.issn.1671-1815.2308634
  • 接收时间:2023-11-04
  • 首发时间:2025-07-29
  • 出版时间:2025-02-08
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  • 收稿日期:2023-11-04
  • 修回日期:2024-11-05
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山东省自然科学基金面上项目(ZR2022ME115)
作者信息
    1 中石化石油工程设计有限公司, 东营 257029
    2 中国石油大学(华东)储运与建筑工程学院, 青岛 266580

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*李传宪(1963—),男,汉族,山东菏泽人,博士,教授。研究方向:原油乳化与破乳技术。E-mail:
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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
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