【作者】 康寿兴；

【导师】 吴伟；

【作者基本信息】 中国石油大学 ， 化学， 2010， 硕士

【摘要】 压裂液是油田开发压裂施工的工作液,其性能的优劣对施工效果起着关键性的作用。目前以粘弹性表面活性剂为增稠剂的压裂液体系主要使用季铵盐型表面活性剂,存在成本较高,抗温能力差的缺点。本文探索分别以动植物油脂和N-胺丙基吗啉为基础原料构造粘弹性表面活性剂的憎水基和亲水基,合成具有一定耐温能力的粘弹性表面活性剂压裂液体系。首先采用气相色谱法测定动植物油脂中脂肪酸的组成和分布。以脂肪酸、甲醇为原料,对甲苯磺酸为催化剂,制备系列高级脂肪酸甲酯样品。然后将动植物油脂转化成混合高级脂肪酸甲酯,经比对分析得出动植物油脂中脂肪酸的组成和分布情况。以单一高级脂肪酸为原料分别合成了酰胺叔胺盐型、Gemini型、甜菜碱型和非离子型四种粘弹性表面活性剂。考察了影响体系粘度的因素,如主剂浓度、盐加量、盐类型、脂肪酸类型等。结果表明:(1)Gemini型表面活性剂耐温性能差,而酰胺叔胺盐型、甜菜碱型、非离子型粘弹性表面活性剂均具有良好的耐温性能。(2)高级脂肪酸类型对粘弹性表面活性剂压裂液体系性能影响较大。相同条件下(表面活性剂浓度为5 wt%,n(酰胺叔胺):n(H2SO4)=2:1, 2 wt%NaCl,温度98℃),硬脂酸系列酰胺叔胺体系的其粘度达到173 mPa·s,耐温性能明显优于油酸和棕榈酸系列。在表面活性剂浓度为5 wt%,温度98℃条件下,硬脂酸、油酸、棕榈酸系列甜菜碱型压裂液体系的粘度分别为117 mPa·s,21 mPa·s和198 mPa·s,以棕榈酸系最好。对于非离子型表面活性剂压裂液体系,在表面活性剂浓度为5 wt%,温度95℃条件下,剪切粘度分别为210 mPa·s、243 mPa·s和348 mPa·s,以棕榈酸系最好。以大豆油、花生油、棉油、菜籽油、棕榈油、葵花籽油等油脂为原料分别合成了酰胺叔胺胺盐型、甜菜碱型、非离子型表面活性剂。结果表明:(1)以花生油和大豆油制备的酰胺叔胺型表面活性剂体系的耐温性能较差,低于90℃。(2)以花生油制备的甜菜碱型粘弹性表面活性剂浓度为4 wt%的压裂液体系的耐温能力可达90℃。(3)在表面活性剂浓度为5 wt%,温度95℃条件下,棕榈油、花生油、棉油、葵花籽油、大豆油、菜籽油系列非离子粘弹性表面活性剂压裂液体系的粘度依次为306 mPa·s、255 mPa·s、219 mPa·s、198 mPa·s、90 mPa·s和78 mPa·s。本文探索了酸化油、地沟油等废旧油脂的利用新途径。以酸化油和地沟油为原料制备的表面活性剂在与与其它油脂系表面活性剂系列以及助剂复配后,体系具有良好的耐温性能。浓度为5 wt%的酸化油-棕榈油(1:1)复合体系在95℃下的粘度达到180 mPa·s,而酸化油-棕榈酸基-硬脂酸基(2:1:1)复合体系在95℃下的粘度达到171 mPa·s,地沟油-棕榈油(1:1)复合体系在95℃下的粘度达到102 mPa·s,均能满足地层温度100℃下的压裂施工。更多还原

【Abstract】 Fracturing fluids is one of the working liquids in fracturing operation. Its performance plays an important role to the effectiveness of fracturing operation. Most of the viscoelastic surfactant-based fracturing fluids consist of a quaternary ammonium salt surfactant, showing low high-temperature stability and high cost.In this thesis, a novel series of viscoelastic surfactants (VES) were prepared by using of vegetale oil and N-aminopropylmorpholine as the hydrophobic and hydrophilic groups, respectively.The composition and distribution of fatty acid in vegetable/animal oil were investigated by GC analysis. A series of fatty acid methyl ester (FAME) samples were systhesized from free fatty acids in the presence of p-toluenesulfonic acid. Vegetable/animal oils were transformed into their corresponding mixed FAMEs. The acid composition and distribution in each of the vegetal/animal oil were obtained through comparison of the mixed FAMEs with individual free fatty acid FAME.Four types of VES, including amide-amine salt, Gemini, betaine and non-ionic VES were prepared from free fatty acids. Main factors that influence the system viscosity, such as concentration of VES, the type and the amount of inorganic salt additives and the type of fatty acids, were investigated. The following results were concluded: (1) Amideamine salt-type, betaine-type and non-ionic surfactant-type VES show satisfactory high-temperature performance, while Gemini-type VES exhibits poor high-temperature stability. (2) The type of fatty acids show considerable effects to the properties of VES fluids. Under the same condition (concentration 5%, molar ratio n(amideamine):n(H2SO4)=2:1, 2 wt% NaCl and 98℃), the viscosity of steric acid series VES reaches upto 173 mPa·s, better than oleic acid and palmitic acid series. For betaine-type VES at concentration of 5% and 98℃, the fluid viscosities are 117 mPa·s, 21 mPa·s and 198 mPa·s, for steric, oleic and palmitic acid series, respectively. Among them palmitic acid series is the best. For non-ionic type VES, the viscosities for the above three acid series are 210 mPa·s, 243 mPa·s and 348 mPa·s, again palmitic acid shows the best results under the same condition.Sterting from vegetable oils, including soybean oil, peanut oil, cotton seed oil, rapeseed oil, palm oil and sunflower oil etc, three types of VES (amide-amine salt, betaine, non-ionic) were prepared. Results show that: (1) Amideamine salts VES made from peanut oil and soybean oil exhibit poor high-temperature performance(lower than 90℃). (2) Betaine-type VES made from peanut oil can be used up to 90℃at concentration of 4%. (3) At concentration of 5% and 95℃, the viscosities for VES fluids, in the order of palm, peanut, cotton, sunflower, soybean ans rapeseed oil, are as follows: 306 mPa·s, 255 mPa·s,219 mPa·s, 198 mPa·s, 90 mPa·s and 78 mPa·s.In addition, as a novel application for waste or used oils, VES from acidified oil and cooked oil were prepared and utilized as fracturing fluid thickening reagents. When mixed with other series VES and certain additives, the fluid system showed satisfactory high-temperature properties. For example, the viscosity for 5% VES fluid from acidified oil and palm oil(1:1) can reach to 180 mPa·s at 95℃, while the number for an acidified oil-palmitic acid-steric acid VES fluid mixture is 171 mPa·s. The viscosity for a cooked oil-palm oil VES mixed system is 102 mPa·s at 95℃. The aforementioned results indicate that both acidified oil and cooked waste oil can be used to make VES for fracturing fluids.更多还原