超支化聚酰胺-胺的合成及其在O/W型乳状液的破乳应用

采用“一锅法”,通过Michael加成法以及逐步升温缩聚法,调节起始剂和丙烯酸甲酯的比例,合成了一系列超支化聚酰胺-胺（h-PAMAM）破乳剂,并应用数字化技术控制产品质量更加稳定,考察了添加量、破乳温度及沉降时间对破乳性能的影响,并探究界面张力和破乳过程中乳状液透射率与粒径的变化,分析其破乳机理。结果表明,在60℃、沉降时间为30min、破乳剂的添加量为40mg/L时,其脱油率达到95%。与商用破乳剂相比,超支化聚酰胺-胺因具有独特的超支化多位点以及酰胺基团和伯胺基团结构,用作破乳剂时界面活性高、沉降时间短。     

超支化聚合物破乳剂HPO-1在强乳化含油污水处理中的应用

为了提高强乳化含油污水的破乳处理效率,以超支化聚乙烯亚胺（HPEI）和复合脂肪酸单体FO-1为主要原料制备了一种超支化聚合物破乳剂HPO-1,采用红外光谱图和核磁1HNMR谱图对其结构进行了表征,评价了其界面活性,考察了破乳剂投加量、温度、沉降时间和污水矿化度对HPO-1破乳效果的影响,并与现场用破乳剂XCP-16S的性能进行了对比。结果表明：HPO-1的界面活性和破乳性能均明显优于XCP-16S,当HPO-1投加量为50 mg/L,温度为30℃,沉降时间为30 min,污水矿化度为8 350 mg/L时,其脱油效率可以达到90.8%,破乳处理后水相中HPO-1的残留量小于0.5 mg/L。HPO-1对海上A油田某采油平台强乳化含油污水的现场破乳处理效果较好,沉降时间大于30 min后,脱油效率即可以达到90%以上。研究结果表明HPO-1能够满足强乳化含油污水快速高效破乳处理的需求。     

疏水缔合聚合物驱乳状液破乳规律研究

本文采用瓶试法考察了直链型、支链型及超支化型聚醚破乳剂及其与阳离子反相破乳剂协同作用对乳状液破乳效果的影响。结果表明,超支化聚酰胺-胺聚醚破乳剂与阳离子反相破乳剂协同作用对模拟疏水缔合聚合物驱乳状液有良好的破乳效果,随着聚醚破乳剂分子结构中环氧乙烷(EO)数增加,破乳效果增强,破乳剂最佳的EO/PO质量比为1/1。聚酰胺-胺聚醚破乳剂能显著降低油水之间的界面张力和界面扩张模量,表明该破乳剂分子易于在油水界面吸附,并破坏原乳状液界面膜的强度,从而有利于破乳。     

几种聚电解质对含HPAM污水的反相破乳研究

采用模拟含油污水,研究了3种结构聚电解质：超支化聚酰胺胺（PAMAM）、阳离子聚丙烯酰胺（CPAM）和聚醚破乳剂SP-169对污水的破乳除油效果,及部分水解聚丙烯酰胺（HPAM）和无机盐对破乳的影响规律。结果表明：随HPAM质量浓度增大,破乳效果变差。聚合物和盐的相互作用是影响含聚污水处理效果的重要原因。ρ（HPAM）=100mg/L时,NaCl对CPAM破乳有利。当ρ（HPAM）=400mg/L时,NaCl不利于PAMAM和CPAM破乳。二价盐CaCl2使PAMAM失去破乳作用,但对CPAM破乳有利。     

酯交换法合成聚甘油丙烯酸酯

以聚甘油、丙烯酸甲酯为原料，利用酯交换法，以硫酸为催化剂，对苯二酚为阻聚剂，无溶剂，在共沸温度下，合成了一种水溶性聚甘油丙烯酸酯破乳剂。考察了催化剂用量、阻聚剂用量、反应时间、聚甘油中羟基与丙烯酸甲酯之摩尔比、不同聚合度聚甘油合成的聚甘油丙烯酸酯对原油乳状液脱水率的影响。实验表明，考察的影响条件均存在最佳值，即在催化剂用量占反应物总量的2％（w），阻聚剂用量占丙烯酸用量的2％（w），反应时间16h，聚甘油中羟基与丙烯酸甲酯之摩尔比为2．6：1，聚甘油聚合度为6．3，在破乳剂用量为300mg／L时，破乳脱水率达69％。     

有机硅改性破乳剂破乳脱水工艺研究

针对三次采油脱水困难,目前的大多数破乳剂遇到瓶颈,将有机硅改性破乳剂与其他4种聚醚破乳剂进行破乳性能考察,比较得出经过硅改性破乳剂用量为50 mg/L,破乳温度为65℃,破乳时间为30 min时的破乳效果都优于其他聚醚类破乳剂,经过硅改性的破乳剂在用量、破乳温度等方面有较明显的优点,适合对三次采油进行破乳。通过复配破乳剂189和硅改性破乳剂在加剂量分别为100 mg/L和50 mg/L时,破乳脱水后的三次采油油水界面齐整,脱出的水质清澈,达到生产中破乳脱水效果的要求。     

有机硅改性破乳剂破乳脱水工艺研究

针对三次采油脱水困难,目前的大多数破乳剂遇到瓶颈,将有机硅改性破乳剂与其他4种聚醚破乳剂进行破乳性能考察,比较得出经过硅改性破乳剂用量为50 mg/L,破乳温度为65℃,破乳时间为30 min时的破乳效果都优于其他聚醚类破乳剂,经过硅改性的破乳剂在用量、破乳温度等方面有较明显的优点,适合对三次采油进行破乳。通过复配破乳剂189和硅改性破乳剂在加剂量分别为100 mg/L和50 mg/L时,破乳脱水后的三次采油油水界面齐整,脱出的水质清澈,达到生产中破乳脱水效果的要求。     

脱除催化裂化油浆中催化剂粉末的实验研究

文章采用破乳-絮凝沉降分离工艺处理高桥催化裂化油浆,在实验室考察了破乳剂和絮凝剂类型及加量、水相pH、沉降温度及沉降时间对催化裂化油浆中催化剂粉末脱除的影响。选择PR-3复配物为破乳剂,添加量100μg.g-1,聚丙烯酰胺为絮凝剂,用量1000μg.g-1,加入质量浓度30%的葡萄糖水溶液,水溶液pH为7,沉降温度90℃,时间12 h,可以有效地脱出油浆中催化剂粉末,油浆灰分含量可降低到100μg.g-1以下。     

聚醚破乳剂结构对二元驱乳状液破乳性能的影响

本文考察了破乳剂结构对模拟二元复合驱石油采出液破乳效果。结果表明:随着破乳剂支链化程度升高,破乳性能增强,具有超支化结构的聚酰胺-胺聚醚破乳剂的析水率最高,达到90%,但脱出水浑浊且存在较厚乳化中间层。聚酰胺-胺聚醚破乳剂与反相破乳剂协同作用提升破乳性能,最佳条件下析水率接近100%。     

二元聚合物的合成及在稠油破乳中的应用

采用丙烯酸（AA）与自制丙烯酸壬基酚聚醚酯（NPEAA）为原料,在偶氮二异丁腈（AIBN）为引发剂,甲苯为溶剂的条件下,引发聚合制备了二元共聚物稠油破乳剂,采用FTIR、1HNMR对产物结构进行了确证,GPC测试了分子量;采用荧光光谱仪与表面张力仪测得其临界胶束浓度(CMC)为0.5g/L,表面张力为25.684mN/m。并以脱水率和脱出污水含油量为衡量指标,探讨了不同因素下聚合物破乳剂对陈庄稠油W/O乳液的破乳脱水性能,确定最佳破乳条件：温度55?C,时间2h,用量0.5g/L时,脱水率为88.5%,脱出水中含油量为198.4mg/L。研究了聚合物破乳剂对乳状液表观粘度、体系稳定性、油水界面的影响以及微观破乳过程,探讨分析得出聚合物破乳剂在油水界面更易润湿扩散,脱水速率快,破乳效果好。     

Interfacial and Demulsifying Behavior of Novel Fluorinated Hyperbranched Polymers

In our previous study, a series of novel hyperbranched fluoropolymers with polyglycerol as the core and poly(hexafluorobutyl acrylate) as hydrophobic arms were synthesized. As potential demulsifier for lubricants, the demulsification behavior, dynamic interfacial tension, and dilational rheological properties of the fluorinated polymers were investigated in this paper. The influence of polymer concentration and molecular structure on the interfacial properties was analyzed. We conclude that the diffusion rate of the polymers and the viscoelastic properties of the water–oil interface are critical factors in determining the demulsification performance. The longer hydrophobic chains of the fluorinated polymers leads to a faster and more effective interfacial adsorption, which is favorable to improve demulsification efficiency. In contrast, the longer hydrophobic chain also enhances the elastic property of interface due to its entangled structure, which is unfavorable to demulsification. As a result, the polymer with medium hydrophobic chain length show the best demulsification performance.     

Demulsification of oil-in-water emulsions using hyperbranched poly(amido amine) demulsifiers with 4,4-diaminodiphenyl methane as initial cores

Hyperbranched poly(amido amine) demulsifier (PDDM) was synthesized by a modified “one-pot” method with 4,4-diaminodiphenyl methane as the central core and ethylenediamine as the interior branches. The structure of the demulsifier was confirmed by proton nuclear magnetic resonance and Fourier transform infrared. The effects of the temperature and PDDM concentration on the demulsification performance were investigated, and PDDM performance was compared to that of the hyperbranched demulsifier with 1,3-propanediamine as the central core. When the emulsions were treated with the demulsifier concentration of 50 mg L⁻¹ at 60 °C for 120 min, the light transmittance and removed total organic content of the aqueous phase reached 87.4 and 99.72%, respectively. At the optimal demulsification temperature of 60 °C, the surface tension reduction and the critical micelle concentration were 27.38 mN m⁻¹ and 1.30 × 10⁻³ mol L⁻¹, respectively. The combination of surface tension and interfacial tension measurements and the analysis of micrographs and particles sizes provide evidence for the possible demulsification mechanism. The excellent demulsification performance of the hyperbranched demulsifier indicates that it has great potential for use in the demulsification of oil-in-water emulsions. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48846.     

一类非聚醚破乳剂的破乳效果与油水界面膜强度的关系

以甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸、丙烯酸为原料,采用乳液法合成了一系列亲水、疏水基团比例不同的四元共聚物破乳剂。主要考察了合成的LG系列非聚醚破乳剂及其与工业聚醚破乳剂LP复配的破乳性能,以及破乳性能与油水界面膜强度的关系,并分析了温度对界面膜强度的影响,而且对产物进行了傅里叶变换红外光谱检测。结果表明,在85℃,LG系列破乳剂中LG2的破乳效果相对较好,加量120mg/L时脱水率达80.36%,当LP与LG2按V(LP)∶V(LG2)=1∶1复配后破乳效果最好,脱水率达93.33%,高于LP单剂的脱水率90.91%,2种破乳剂产生了协同增效作用。破乳剂和温度是影响界面膜强度的重要因素,破乳剂降低界面膜强度的能力越强,破乳效果越好。同种破乳剂相同破乳时间内,温度越高,界面膜强度越低,越有利于破乳。     

胜利孤岛注聚原油破乳剂的筛选与性能评价

以研究孤岛注聚原油乳状液破乳为目的,通过瓶试法和界面性质的测定,筛选了多种类型的原油破乳剂,考察了破乳剂质量浓度、聚合物和原油组分对破乳效果的影响,探讨了原油乳状液的破乳机理。结果表明,破乳剂BF-069质量浓度在100mg/L,50℃条件下,脱水率达到70%以上,现场温度稍微升高,脱水率达到85%左右,破乳剂BF-069已在胜利油田应用,现场使用效果良好;聚合物质量浓度在50mg/L时,原油乳状液最难破乳;原油中不同组分对破乳效果的影响不同,油水界面性质的测定表明,胶质和沥青质是影响原油破乳的主要因素。     

Study on Demulsification of Crude Oil Emulsions by Microwave Chemical Method

Abstract

The demulsifying and separating experiments of crude oil emulsion were performed by using the heating method, the thermal chemical method, the microwave radiating method, and the microwave chemical method separately. The water content of this emulsion was 78 v/v%, and the type was water‐in‐oil (w/o). The influence tendencies of the key factors on demulsification effect were explored by changing the heating temperature, the demulsifier amount used and the microwave radiating time in this paper. With the microwave chemical experiments on the self‐made emulsions of different water content, the demulsification rate and separation efficiency were explored. The type of these emulsions were oil‐in‐water (o/w), water‐in‐oil (w/o) and the multiple type, related to the water content scopes which were less than 30 v/v%, more than 70 v/v% and between them, respectively. The separation effect by the microwave chemical method for the high water content crude oil emulsion was better than that of emulsion with lower water content. For the crude oil used in this experiment, the result could be obtained that the separation efficiency was about 95 v/v% under the conditions of 50 ppm of demulsifier, 10 seconds radiation time, and 1 minute settling time for the microwave chemical method.     

纺丝油剂废水处理工艺研究

纺丝油剂废水是高浓度的O/W型乳状液,具有相当的稳定性。采用“破乳-反渗透”处理工艺得到了良好的实验结果。以自配的DEMUL-B1作为破乳剂,试验并分析了破乳剂的用量、水样的pH值、加热温度和加热时间等因素对破乳效果的影响。以OSMONICS公司的SE反渗透膜对破乳后的水样进一步处理。结果表明,经“破乳-反渗透”处理净化后的水质,其COD的去除率达到99.96%,含油量和浊度的去除率均为100%,达到了污水综合排放一级标准(GB8978-1996),可以直接排放或回用。     

Synthesis of a novel reverse demulsifier with the characteristics of polyacrylate and polycation and its demulsification performance

As the development of oilfield exploitation, more and more oil in water (O/W) emulsion was produced, thus efficient reverse demulsifier becomes increasingly important. In this paper, a series of novel reverse demulsifiers (R-PED1 ~ 4) with the characteristics of polyacrylate and polycation were prepared. The structure of the product was verified by IR specter and ¹H NMR. The thermal stability was studied with TGA and the molecular weight was obtained by GPC. Field evaluation results showed that the oil content in produced liquid after R-PED4 treatment can be reduced from 1550 to 81 mg/L at R-PED4 dosage was 50 mg/L. Furthermore, the demulsification mechanism of R-PED was discussed. The R-PED has good surface/interfacial activity. It can effectively reduce the oil–water interfacial film strength and reduce the zeta potential of oil droplets, which is beneficial for the coalescence of oil droplets. Especially, the interaction force between oil droplets was measured by the optical tweezers. R-PED4 can increase the attraction force between oil droplets. Consequently, the contact time of oil droplets during the demulsification process can be prolonged and the coalescence of oil droplets also can be effectively promoted. The novel reverse demulsifier offers a new option for the oilfield produced liquid treatment.     

微波化学法原油破乳脱水工艺的优化

对原油乳状液分别采用热化学法及微波热化学法进行了破乳脱水实验。对于本实验所用含水量为78%的1#原油乳状液,采用热化学方法时,破乳剂的用量为100 mg/L,加热温度为65℃,加热9 min后,可脱水约为96.2%;而采用微波化学法时,破乳剂的用量为50 mg/L,辐射时间为10 s,沉降时间为2 min,可脱水约为94.9%。提出了原油乳状液脱水的工艺为对原油乳状液采用二次脱水处理,首先采用微波化学法,再对一次脱水后的上层原油乳状液采用加热法。对1#原油乳状液,一次微波辐射脱水后,上层油的含水量在18%左右;对上层油进行加热二次脱水后,原油的含水率小于0.3%,可得到合格原油。