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脂肽类表面活性剂的合成及其在原油采收中的应用
Alternative TitleSynthesis of lipopeptide surfactant and its application in enhanced oil recovery
刘祥玉
Subtype硕士
Thesis Advisor张松平
2013-05-01
Degree Grantor中国科学院研究生院
Degree Discipline生物工程
Keyword表面活性剂驱   提高采收率   鱼鳞胶原蛋白   大豆分离蛋白   脂肽   表/界面张力   乳化指数   静态洗油   填砂管
Abstract在油田开采过程中,三元复合驱是一种新型提高采收率技术,选择优良的表面活性剂是这一技术的关键。由于传统的化学表面活性剂难以生物降解,给环境带来了巨大的危害。而生物表面活性剂具有环境友好、生物可降解、低毒、高乳化性和选择性等显著优点,在三次采油中展示了广阔的应用前景。但是生物表面活性剂目前主要采用发酵的方法进行生产,过程较繁琐,产量和纯度低,导致后续提纯的成本高。利用化学或酶催化法合成具有生物表面活性剂相似结构的表面活性物质是一个非常具有挑战性的课题。本论文着重探索以一些农业加工过程中产生的蛋白类副产物,如鱼鳞蛋白,大豆蛋白等为起始原料,通过酶催化水解制备多肽,并进一步通过酰化反应制备脂肽类表面活性剂,并将其应用于三次采油中。具体研究包括如下几个方面: (1)通过红外光谱(IR)、质谱(MOLDI-TOF)、核磁共振(NMR)等仪器对目前应用于三次采油比较有效的一种产品GreenZyme?结构进行分析,初步确定了GreenZyme?是以烷基萘磺酸盐表面活性剂为主要成分的复杂混合物,而非商品所宣称的生物酶驱油剂。 (2)利用碱性蛋白酶Protex 6L或6 mol/L HCl对鱼鳞胶原蛋白进行水解,获得水解度为0%、5%、10%和100%的多肽水解产物;然后分别用不同链长的烷基酰氯(包括油酰氯、月桂酰氯和癸酰氯)和苯甲酰氯对多肽进行酰化修饰,制备出16种具有不同亲水基和亲油基的脂肽表面活性剂。乳化指数测定结果表明,与常用于驱油的化学表面活性剂十二烷基苯磺酸钠(SDBS)乳化指数E24最大仅有20%相比,脂肽具有更好的乳化性能,其中500 mg/L的油酰脂肽-5%的E24达到60%以上。静态洗油实验结果显示,pH值11.0的油酰脂肽-10%和月桂酰脂肽-10%洗油能力最强,在40 oC,150 r/min转速下,20 min内可以将35%以上的原油从油砂上洗下来,远远高于SDBS(<10%)的洗油率。在填砂管驱油实验中,水驱采油后注入油酰脂肽-10%或月桂酰多肽-10%,可以显著提高原油的采收率,原油增产油率分别达到52.35%和41.18%。 (3)同样,以大豆分离蛋白为原料,经过水解获得水解度为5%、10%、15%和100%的多肽产物,然后酰化修饰制备脂肽表面活性剂。表界面性能测定显示,与化学表面活性剂相比,脂肽具有极低的CMC值,在100~300 mg/L之间;最低可以将水的表面张力由72 mN/m降低到28mN/m;在浓度(=40 mg/L)极低的情况下,脂肽可以将十二烷/水和原油/水的界面张力分别降低到5 mN/m和1 mN/m。乳化指数测定结果表明,大豆分离蛋白基脂肽具有更好的乳化性能,当浓度为2 g/L以上时,乳化指数都能达到70%左右。静态洗油实验结果显示,脂肽-15%的洗油能力最强,能将30%左右的原油从油砂上洗下来。 论文中制备出一种新型的脂肽类表面活性剂,其表界面和乳化性能都要远远优于驱油常用的化学表面活性剂。在静态洗油和动态驱油方面,脂肽表面活性剂也要优于其他表面活性剂,因而可以广泛应用于三次采油领域。
Other AbstractSynthesis of lipopeptide surfactant and its application in enhanced oil recovery LIU Xiang-yu(Biological Engineering) Directed by Professor ZHANG Song-ping Abstract Alkaline/Surfactant/Polymer (ASP) flooding is an efficient technology for enhanced oil recovery(EOR) in the exploration process of oilfield. Selecting proper surfactant is one of the key factors for successful ASP flooding. Conventional chemical surfactants are non-biodegradable, and are great harm to the environment. Biosurfactants have demonstrated broad application prospects for their characteristics including environmental friendly, biodegradable, low toxicity, high selectivity of emulsification and other significant advantages. However, biosurfactants are mainly produced by fermentation, a time consuming process with low yield, low purity and high cost. Synthesizing a new kind of surfactant with the similar structure of biosurfactants using chemical or enzymatic methods is of a great challenge. The aim of this study is to explore a novel method to synthesize lipopeptide surfactants for EOR. The starting materials are the byproducts of agricultural process such as fish scale collagen and soy protein isolates. The materials were hydrolyzed by enzyme to obtain peptides which were then acylated with acyl chlorides. The thesis includes the following three parts: (1) Structure of GreenZyme?, one of the most widely used commercial product for EOR, was analyzed by infrared spectroscopy (IR), mass spectrometry (MOLDI-TOF) and nuclear magnetic resonance (NMR). Its main component was speculated to be a kind of alkyl naphthalene sulfonate surfactants, instead of bioactive enzymes as claimed by the producer. (2) Fish scale collagen was hydrolyzed by alkaline protease Protex 6L or 6 mol/L HCl to obtain peptides with the degree of hydrolysis of 0%, 5%, 10% and 100%. The peptides were then acylated with oleoyl chloride, lauroyl chloride, decanoyl chloride or benzoyl chloride to prepare 16 lipopeptide surfactants with different hydrophilic groups and hydrophobic groups. Results of the emulsion index (E24) measurements showed that the synthesized lipopeptide surfactants had strong emulsifying capacity. The E24 of oleoyl peptide-5% reached to 60% at concentration of 500 mg/L, while the maximal E24 value of chemical surfactant sodium dodecyl benzene sulfonate (SDBS) was only about 20%. Lipopeptides also showed much higher crude oil removal capacity than SDBS. Oleoyl peptide-10% and lauroyl peptide-10% of pH 11.0 could wash about 35% of crude oil from oil sand within 20 min at 40 oC, 150 r/min shaking, while the oil removal rate of SDBS was less than 10%. Results of sand pack column experiments showed that injection of oleoyl peptide-10% or lauroyl peptide-10% after water flooding could significantly enhance oil recovery. The additional oil recovery rate after surfactant flooding reached to 52.4 % and 41.2 %. (3) Soy protein isolate was hydrolyzed by alkaline protease Protex 6L or 6 mol/L HCl to obtain peptides with the degree of hydrolysis of 5%, 10%, 15% and 100%. The peptides were then acylated to prepare lipopeptide surfactants. Results of surface/interfacial tension measurements showed that compared with chemical surfactants, synthesized lipopeptide surfactants had extreme low value of CMC about 100~300 mg/L; the surface tension of water can be lowered from 72 mN/m to 28 mN/m; the interfacial tension of dodecane/water and crude oil/water could be lowered to 5 mN/m and 1 mN/m separately at extremely low concentration of about 40 mg/L. Results of the emulsion index (E24) measurements showed that the synthesized lipopeptide surfactants had strong emulsifying capacity. The E24 of acylated peptide reached to 70% at concentration of 2 g/L. Acylated peptide-15% had the strongest capacity of oil sand washing which could wash about 30 % of the crude oil. Synthesized lipopeptide was superior to chemical surfactants for EOR in four aspects including surface/interface tension, emulsifying capacity, static oil washing and dynamic displacement. Therefore they could be widely used in enhanced oil recovery.
Pages95
Language中文
Document Type学位论文
Identifierhttp://ir.ipe.ac.cn/handle/122111/8373
Collection研究所(批量导入)
Recommended Citation
GB/T 7714
刘祥玉. 脂肽类表面活性剂的合成及其在原油采收中的应用[D]. 中国科学院研究生院,2013.
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