分散剂对沥青质稳定性与稠油稳定性的改善效果

为了更加客观、准确地评价分散剂对稠油稳定性的改善效果,研究了5种分散剂对孤岛稠油和馆陶稠油沥青质和稠油稳定性的改善效果,包括含磺酸基的阴离子型分散剂AA、斯盘系列分散剂NA1、油酸、月桂酸、棕榈酸。结果表明,分散剂对沥青质和稠油的稳定性均具有一定的改善效果,其中AA和NA1可明显降低沥青质的聚集程度,对沥青质的稳定分散作用最强;分散剂对沥青质稳定性的改善效果普遍优于对稠油整体稳定性的改善效果。分散剂对沥青质稳定性的改善效果随分散剂浓度增大而增大,沥青质完全裸露在体系中易与分散剂作用;分散剂对稠油整体稳定性的改善效果随分散剂加量增大先增大后降低,分散剂对稠油稳定性改善用量存在最佳值。沥青质稳定性的提高对于稠油整体稳定性的提高具有重要影响,但稠油稳定性的改善还受到胶质、芳香分和饱和分等的影响。图12表3参20     

稠油油藏胶质沥青质分散技术

为解决稠油开采过程中胶质沥青质析出堵塞储层的问题,进行了稠油油藏胶质沥青质分散解堵技术研究,研制成功了稠油油藏胶质沥青质分散解堵剂.该分散剂具有极强的溶解、分散稠油中的胶质沥青质及杂环芳烃能力和抗凝固防沉降能力,在10℃低温下系统仍不会分层.注汽过程中能防止胶质沥青质沉积,疏通液体流动通道,大幅度降低注汽压力;同时可有效降低稠油黏度,提高原油在低温下的流动性,改善稠油、超稠油在井筒的举升能力及地面的集输效果.     

沥青质分散剂与阻聚剂研究进展

沥青质作为石油中极性最大、最重的组分,极容易发生絮凝沉降,给石油的开采、储运及加工带来困难,而添加化学添加剂是阻止和解决沥青质絮凝沉积的最有效方式之一。从化学添加剂的分类、结构特征、作用机理及效果等方面综述了近十年来沥青质化学添加剂的研究进展,并分析了影响沥青质化学添加剂作用效果的因素,对沥青质化学添加剂的选用及合成提出了一些建议。     

稠油沥青分散剂的筛选及效果研究

为解决我国西部某油田稠油开采过程中胶质、沥青质析出堵塞井筒问题,考察了沥青分散MCS,WD-06,JX-108,CL-5,XJ-2的溶解和分散性能,筛选出对堵塞物溶解效果最好的分散剂XJ-2。并考察了分散剂XJ-2对石蜡的溶解效果、热处理温度对分散剂溶解速率的影响、分散剂的最大溶解量及对稠油黏度的影响。结果表明,分散剂XJ-2具有良好的溶解蜡质堵塞物和抑制其析出的能力;当热处理温度为90℃时,溶解速率达1.713 2 mg/(m L·min);当其加量为1 000 mg/L时,原油黏度大幅下降。现场应用表明,该分散剂可有效防治胶质、沥青质沉积造成的堵塞。     

新型油溶性沥青质分散剂抑制重质原油沥青质沉积的研究

针对新疆重质原油沥青质沉积严重的问题,以聚异丁烯丁二酸酐、苯胺和对氨基苯酚为原料合成了尾部基团为高度枝链化的聚异丁烯基,头部基团分别为苯基及酚羟基的新型油溶性沥青质分散剂PA1和PA2。采用分光光度法与显微镜法评价了所合成分散剂对沥青质沉积的抑制效果。实验结果表明,分散剂PA2抑制沥青质沉积作用效果优于PA1。通过对分散剂PA2抑制沥青质沉积作用效果的评价,确定了最佳合成条件：对氨基苯酚与聚异丁烯丁二酸酐摩尔比为1.2,反应温度为120 ℃,反应时间为6 h。在分散剂PA2加入量为200 mg/L的条件下可以将新疆重质原油的初始絮凝点由-19.87提高到8.63,显著改善了新疆重质原油稳定性。     

塔河油田沥青质稠油成因分析及防治技术

塔河油田TK235、TK305等井陆续出现沥青质稠油沉积堵塞油管造成停产,对生产造成了严重影响。针对此类问题,文中对塔河油田原油中沥青质的沉积问题进行了综合研究,形成了有效的沥青质稠油沉积堵塞防治技术。通过对塔河油田沥青质原油组分进行分析,结合沥青质沉积堵塞物成分的分析,发现沥青质沉积主要是由于原油组分在举升过程中的环境条件变化所导致,从而开发了掺稠油、掺改性稠油（稠油＋沥青分散稳定剂）等治理工艺．试验结果表明：这些工艺较好地解决了沥青质沉积堵塞油管的问题,实现了油井的正常生产,并在现场应用中取得了良好的效果。     

沥青质分散剂评价方法改进与新型高效分散剂合成

为了更加高效准确地评价沥青质分散剂,首次利用测定掺稀后黏度变化的实验方法取代现有沉淀评价方法,结合对现有市售分散剂的评价结果,分析了原有方法的缺点与不足。利用新方法探索了不同基团、链长、结构对分散剂分散性能的影响。结果表明,在用沉淀法测定时,强极性的烷基苯磺酸和长链离子液体分散剂出现增稠现象。针对塔河某掺稀井最为合适的沥青质分散剂应是具有C18烷基链长、含有2~4个极性头基团的多胺类非离子型表面活性剂。在此基础上,以油酸和二乙烯三胺合成了新型的长链烷基酰胺二胺型沥青质分散剂。通过掺稀黏度法测得,新合成的分散剂与沥青混合液在30、60℃下的平均黏度为890和277 mPa·s,比常用的Span80多元醇类分散剂分别提高27%和46%。     

塔河油田稠油沥青质解堵技术研究与应用

塔河油田油藏原油高含沥青质,随着油井生产,油藏、井筒压力、温度场的变化,井筒堵塞现象时有发生.采用X射线荧光光谱、组分分析、溶剂萃取等方法分析了堵塞物成分.结果表明,堵塞物90%以上是有机物,有机物中沥青质含量大于38%.针对堵塞物主要组分,研制了新型沥青解堵剂,对其性能进行了评价.60 ℃时溶解速率最高可达到2.956 mg/(mL·min),胶体不稳定指数大于0.9的原油中加入质量分数1%新型沥青解堵剂,可有效抑制沥青质沉积.     

委内瑞拉稠油沥青质的XPS研究

以委内瑞拉稠油沥青质为原料,采用X射线光电子能谱（XPS）定性和定量分析了沥青质表面含碳、氧、氮、硫官能团结构和含量。结果表明,委内瑞拉稠油沥青质表面的碳原子主要以C-C和C-H形式存在,约5%的碳原子与氧原子结合;含氧官能团中羰基为主要含氧结构,其氧原子数量占氧原子总数量的44%左右,C-O和COO的氧原子数量分别占氧原子总数量的29%和27%;含氮官能团中,约59%的氮为弱碱性或非碱性的吡咯类氮,剩余为强碱性的吡啶类氮;含硫官能团中,脂肪类硫约占57%,其余为噻吩类硫。从委内瑞拉稠油沥青质表面杂原子官能团摩尔数量来看,羰基摩尔分数最多(>1%),其次是吡咯氮和脂肪硫(均约1%),C-O基、羧基、吡啶氮和噻吩硫摩尔分数基本相同（均约0.7%）。     

环烷酸对高沥青质含量稠油乳状液稳定性的影响

以高沥青质塔河稠油为研究对象,从中分离出沥青质,配制成模型油乳状液;从辽河、苏丹原油中分离出天然羧酸,考察原油中天然羧酸对塔河沥青质模型油乳状液稳定性的影响。 结果表明,天然羧酸可以起到类似于胶质的作用,通过对沥青质的分散作用,降低沥青质模型油乳状液的稳定性。 有机羧酸和烷基芳磺酸可以起到与天然羧酸类似的作用,而且烷基芳磺酸降低模型油乳状液稳定性的能力更强。     

Design of Synthetic Dispersants for Asphaltenes

Synthetic dispersants can greatly increase the solubility of asphaltenes in crude oils at low concentrations. They have one or more head groups that complex with the polynuclear aromatic structures in asphaltenes and long paraffinic tails that promote solubility in the rest of the oil. As a result, synthetic dispersants can be much more effective than the natural dispersants in the oil, the resins. At high concentrations, synthetic dispersants can even make all the asphaltenes soluble in n-heptane and thereby convert asphaltenes to resins. Asphaltene dispersants were optimized according to their ability to reduce the toluene equivalence of 05a crude oil. By synthesizing families of prospective dispersants, one sulfonic acid group was determined to be the most effective head attached to a two ring aromatic structure. As previously reported, a straight chain paraffinic tail is not effective above 16 carbons. We discovered that this was because of decreased solubility in the oil caused by crystallization with other tails and with waxes in the oil. In addition, not previously reported, n-alkyl-aromatic sulfonic acids lose their ability to disperse asphaltenes with time. Both of these problems were solved by using two branched tails of varying length proportions between the two tails. As a result, the effectiveness of the dispersant increases with total tail length, well above 30 carbons and it remains effective with time.     

Design of Synthetic Dispersants for Asphaltenes

Abstract

Synthetic dispersants can greatly increase the solubility of asphaltenes in crude oils at low concentrations. They have one or more head groups that complex with the polynuclear aromatic structures in asphaltenes and long paraffinic tails that promote solubility in the rest of the oil. As a result, synthetic dispersants can be much more effective than the natural dispersants in the oil, the resins. At high concentrations, synthetic dispersants can even make all the asphaltenes soluble in n-heptane and thereby convert asphaltenes to resins. Asphaltene dispersants were optimized according to their ability to reduce the toluene equivalence of 05a crude oil. By synthesizing families of prospective dispersants, one sulfonic acid group was determined to be the most effective head attached to a two ring aromatic structure. As previously reported, a straight chain paraffinic tail is not effective above 16 carbons. We discovered that this was because of decreased solubility in the oil caused by crystallization with other tails and with waxes in the oil. In addition, not previously reported, n-alkyl-aromatic sulfonic acids lose their ability to disperse asphaltenes with time. Both of these problems were solved by using two branched tails of varying length proportions between the two tails. As a result, the effectiveness of the dispersant increases with total tail length, well above 30 carbons and it remains effective with time.     

稠油沥青质水热裂解供氢催化及地质协同作用研究

探讨了辽河稠油中沥青质在注蒸汽热采条件下供氢催化水热裂解反应行为,以及油藏矿物对沥青质水热裂解的强化作用,结果表明,油藏矿物与硫酸镍、甲酸供氢剂可协同催化沥青质水热裂解反应,最终可使沥青质降解率达到49.2%;供氢催化反应前后稠油中沥青质红外谱图说明稠油中沥青质在供氢催化改质降粘反应时所发生的化学结构的变化,反映了沥青质在反应过程中经历了侧链断裂、环烷脱氢芳构化以及芳香结构进一步缩合等反应;对沥青质水热裂解反应产物中轻组分进行气相色谱全烃分析,证实了在注蒸汽热采条件下沥青质可以实现部分催化降解。     

石英砂对稠油乳状液的破乳作用机理

由于稠油乳状液不透明,无法直观认识砂粒对稠油乳状液稳定性的影响过程.曾有学者通过傅里叶红外光谱检测到矿物颗粒表面吸附的沥青质,推测这些颗粒因吸附油水界面膜上的沥青质破坏了油水界面膜强度,促进了水滴聚团沉降,从而实现稠油乳状液破乳分层.但这种认识无法解释笔者实验中的一些现象.针对这种情况,通过杯式分水、流变性测试和润湿性...     

Effect of Biological and Chemical Dispersants on Oil Spills

The aim of this work is to study the effect of different types of chemical and biological dispersants used for crude oil spill treatment. The dispersing efficiency of the different dispersants on the crude oil was determined for selecting the most effective one. The basic properties of crude oil participating in the efficiency of dispersion process as viscosity, pour point, wax content, asphaltene content, resin content, etc. were determined. Also the nature of the different dispersants on the dispersing process, studied by FT-IR analysis, showed the presence of the same effective functional groups but in different ratios. The hydrocarbons types distribution of crude oil undispersed and undispersed parts were used as a marker for the degree of dispersion and/or biodegradation. The lowest values of undispersed saturate indicate the highest degree of dispersion or biodegradation. The lower normal alkanes are much more dispersed than the higher ones. The enzyme showed a moderate efficiency for dispersing crude oil, and this efficiency increased by increasing the time of contact with oil which lead to the dispersion of higher molecular weight normal alkanes.     

稠油活化剂降黏机理及驱油效果研究

稠油降黏冷采是海上油田开发的主要方式,为深入认识稠油活化剂的降黏机理及其在原油黏度为150～1 000 mPa·s的稠油油藏中的应用效果,通过室内物理模拟实验和耗散粒子动力学模拟技术,研究了稠油活化剂对稠油的降黏机理及驱油效果。结果表明,稠油活化剂可提高水相黏度、降低油水界面张力,能有效降低常规可流动稠油的黏度。分子尺度上的研究结果显示,稠油活化剂分子对沥青质聚集体有明显的阻聚-分散效果,其活性基团能增大沥青质芳香盘的层间距和链间距,减小沥青质聚集体堆积高度和堆积层数,削弱沥青质间的相互作用,破坏稠油重质组分聚集结构,分散稠油,从而增强原油流动能力。稠油活化剂的多种机理协同作用使其在室内岩心驱替实验和矿场应用中,均可起到良好的降水增油效果。该研究从分子层面明确了活化剂降低稠油黏度机理,为稠油活化剂现场应用提供理论指导。     

Structural Studies on Residual Fuel Oil Asphaltenes by RICO Method

Structural characterization of asphaltenes isolated from Saudi Arabian heavy and medium crude oils was undertaken by using ruthenium ion catalyzed oxidation (RICO) method. The RICO method was capable to convert aromatic carbons selectively into carbon dioxide and carboxylic acids and esters group while leaving aliphatic and naphthenic structures of asphaltenes essentially unaffected. Detailed analyses of RICO products of both Arab heavy and Arab medium asphaltenes were conducted using FT-IR, ¹³C-NMR, IC, GPC, and GC-MS techniques. These analyses indicate that the aqueous phase fraction (water-soluble products) obtained from RICO reaction of asphaltenes consists of aliphatic dicarboxylic acids and aromatic poly carboxylic acids with longer alkyl chains. The ¹³C-NMR and GC-MS analyses of organic phase products of asphaltenes indicate that this fraction contains large amount of aliphatic carboxylic acids with longer alkyl groups. The oxidation products of both Arab heavy and Arab medium asphaltenes were found to be dominated by a homologous series of straight chain monocarboxylic acids suggesting that the normal alkyl chains are major and important constituents of the chemical structure of both asphaltenes.     

Structural Studies on Residual Fuel Oil Asphaltenes by RICO Method

Abstract

Structural characterization of asphaltenes isolated from Saudi Arabian heavy and medium crude oils was undertaken by using ruthenium ion catalyzed oxidation (RICO) method. The RICO method was capable to convert aromatic carbons selectively into carbon dioxide and carboxylic acids and esters group while leaving aliphatic and naphthenic structures of asphaltenes essentially unaffected. Detailed analyses of RICO products of both Arab heavy and Arab medium asphaltenes were conducted using FT-IR, ¹³C-NMR, IC, GPC, and GC-MS techniques. These analyses indicate that the aqueous phase fraction (water-soluble products) obtained from RICO reaction of asphaltenes consists of aliphatic dicarboxylic acids and aromatic poly carboxylic acids with longer alkyl chains. The ¹³C-NMR and GC-MS analyses of organic phase products of asphaltenes indicate that this fraction contains large amount of aliphatic carboxylic acids with longer alkyl groups. The oxidation products of both Arab heavy and Arab medium asphaltenes were found to be dominated by a homologous series of straight chain monocarboxylic acids suggesting that the normal alkyl chains are major and important constituents of the chemical structure of both asphaltenes.