1、在70 ,加量为1.4 mL的实验条件下,对辛三站原油乳状液的脱水率可达82%,而单纯的2031仅为67%;另外,2072的改性产品,在55 ,加量为1.4 mL的实验条件下,对永一站原油乳状液的脱水率由79%提高到92%;在70 ,加量为1.4 mL的实验条件下,对辛三站原油乳状液的脱水率可达80%,而单纯的2072仅为62%;2131的改性产品,在55 ,加量为1.4 mL的实验条件下,对永一站原油乳状液的脱水率由73%提高到92%;在70 ,加量为1.6 mL的实验条件下,对辛三站原油乳状液的脱水率可达58%,而单纯的2031为50%。该结果表明,采用适当条件对常规破乳剂改性,可以明显提
2、高其破乳性能。关键词:聚醚,破乳剂,改性,脱水率,破乳性能AbstractIn order to demulsify the production fluid effectively, polyether demulsifier was modified to synthetise a new kind of demulsifier.In this paper, allyl chloride and 2072, a kind of polyether demulsifier, as selected to synthetise propylene glycol polyether modifi
3、ed demulsifier. The reaction included two steps: etherification and polymerization, and the reaction conditions were probed. Based on these studies, another two modified demulsifiers, named by glycerin polyether demulsifier 2031 demusifiers and glycerin polyether anddimethyl carbonate crosslinkings
4、products 2131 demusifiers, were synthetised by one pot reaction of allyl chloride and 2031, allyl chloride and 2131, respectively.We select six preferable demulsifiers by the bottle testing method with the oil of yong-1 station and xin-3 station. The effects of demulsification temperature, demulsifi
5、er dosage, demulsification time on the demulsification performance are studied. The evaluation indicated that such demulsifier showed excellent performance of demulsification for oils from yong-1 station and xin-3 station in shengli oil field. For oil from yong-1, the final dehydration rate of modif
6、ied 2031 demulsifier was up to 92% within mass concentration of 1.4 mL at 55 , while for 2031, the raw material, it was only 75% at the same conditions, used for oil of xin-3, the final dehydration rate of modified 2031 demulsifier was up to 82% within mass concentration of 1.4 mL at 70 , while it w
7、as only 67% with 2031; For oil from yong-1, the final dehydration rate of modified 2072 demulsifier was up to 92% within mass concentration of 1.4mL at 55 , while for 2072, the raw material, it was only 79% at the same conditions, used for oil of xin-3, the final dehydration rate of modified 2031 de
8、mulsifier was up to 82% within mass concentration of 1.4 mL at 80 , while it was only 62% with 2072; For oil from yong-1, the final dehydration rate of modified 2131 demulsifier was up to 92% within mass concentration of 1.4 mL at 55 , while for 2131, the raw material, it was only 73% at the same co
9、nditions, used for oil of xin-3, the final dehydration rate of modified 2131 demulsifier was up to 58% within mass concentration of 1.6 mL at 70 , while it was only 50% with 2131. The results confirmed that, to improve performance conventional demulsifier can be modified into another structure polym
10、er by adequate means.Key words: Polyether,Demulsifier,Modify,Dehydration rate,Demulsification performance第一章 绪论原油自地下采出是以油水乳状液状态出现的。据了解,现在国内陆上多数油田原油综合含水率已达80%以上,如果不及时脱水,会增加泵、管线和贮罐负荷,引起金属表面腐蚀和结垢;而排放水中含有的油也会造成环境污染和原油浪费,因此无论从经济角度,还是从环境保护角度,均需对原油进行破乳脱水。基于化学破乳剂具有活性高、见效快等优点,投加破乳剂就成了目前最常用的破乳方法。随着各大油田相继进入高含水
11、期和特高含水期开发阶段,原油中胶质、沥青质的含量不断增加,以及各种增产措施的相应应用,特别是三次采油中使用了表面活性剂/聚合物/碱驱方式,造成油井采出液油/水乳化严重,油/水分离难度加大,造成目前的常规破乳剂对这种采出液的脱水不理想,如脱水率下降、破乳剂用量大、破乳温度高、脱出水含油率高等。针对上述问题,人们对破乳剂质量的要求不断提高,迫切需要研制出适应性强、生产成本低、效率高、多功能以及无污染的新产品。尤其是近几年,破乳剂的研究有了很大进展,新型低温高效破乳剂不断被开发出来,而根据不同情况选择适用于不同性质原油的破乳剂显得极为重要1,2。1.1 乳状液的定义乳状液是一个多相分散体系,其中至少
12、有一种液体以液珠的形式不均匀地分散在另一种与它不相混溶的液体中,分散液珠的直径通常大于0.1微米,属于热力学不稳定体系,但具有一定的动力稳定性。我们把乳状液以液滴形式存在的一相称为分散相(不连续相),另一相称为分散介质(连续相)。此种体系有一个最低的稳定度。乳化剂的加入可明显增加其稳定性,液珠与介质间存在很大的相界面,体系的界面能很大,属于热力学不稳定体系。小液珠合并成大液珠是一种自发趋势,由此可降低体系的界面能量,使乳状液更加稳定。油田采出液中含有的大量水分中只有极少量的水以游离态形式存在,绝大部分是以极其微小的颗粒分散在原油中3。以原油作为分散介质或分散相的乳状液称之为原油乳状液4,大部分
13、学者5-7,认为原油乳状液是在原油开采过程中形成的。1.2 乳状液的生成及成膜物质1.2.1 乳状液的生成条件对于纯水和纯油无论怎样搅拌它们绝不会形成乳状液,因为这种液体彼此强烈地排斥。要想制备乳状液,必须满足下述三个条件,缺一不可:(1) 存在着互不相溶的两相,如水相和油相。(2) 存在有乳化剂一类的表面活性剂,其作用是降低体系的界面张力,在其微液珠的表面上形成薄膜或双电层阻止微液珠的相互聚结,增大乳状液的稳定性。(3) 具备强烈的搅拌条件,增加体系的能量,以使油水混合物中一种液体充分中。1.2.2 乳状液的成膜物质原油乳状液之所以比较稳定,主要是由于原油中含有胶质、沥青质、环烷酸酯类等天然
14、乳化剂以及微晶蜡、细沙、粘土等微细分散的固体物质。这些物质在油水界面形成较牢固的保护膜,使乳状液处于稳定状态。原油中的成膜物质主要是以下几类:(1) 沥青质沥青质通常是指原油中不溶于小分子正构烷烃(如正戊烷、正庚烷等)而溶于苯的物质,它对原油乳状液的稳定作用是最为重要的。沥青质微粒是由沥青质分子通过键、氢键或脂肪烃链堆积起来的。沥青质除了充当天然乳化剂外,还可以把水润湿性的微粒转变成油润湿性的微粒,它如果以分子或胶束状态完全分散在油相中,或以大的颗粒形式分散在油相中,起不到乳化作用,其必须以微粒形式充分分散在油相中时才会有强的乳化作用,这就要求在沥青质微粒中,沥青质的平面结构要恰当地堆积起来,
15、而且需要大量的官能团使微粒之间具有足够的吸引力,使沥青质颗粒紧密堆积在一起。在油/水界面中,由沥青质形成的油/水界面膜强度越大,界面粘度就越高,所形成的乳状液就越稳定8。(2) 胶质胶质也是原油乳状液稳定存在的一个重要因素。就界面膜的强度而言,胶质形成的界面膜强度较小,这是由于胶质相对分子质量比沥青质小,为弱的有机酸,形成的界面膜为液体流动膜9。一般认为,胶质和沥青质具有很强的协同乳化作用。这是由于胶质可被沥青质吸附,并对沥青质有溶解作用,从而改变沥青质的胶束状态。这样一来,吸附了胶质的沥青质微粒可充分分散在原油中,防止了沥青质的沉淀8。(3) 蜡和固体颗粒蜡吸附在油/水界面上,能够促进乳状液的稳定性。蜡在较低的温度下,可在油中形成细小的蜡晶和网状结构,提高原油的粘度。蜡
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