原油乳状液的稳定与破乳机理研究进展

综述了原油乳状液中天然表面活性物质 ,如沥青质、胶质、固体颗粒物以及石蜡对原油乳状液稳定性的影响。讨论了原油破乳机理和破乳剂组成、HLB值等物化性质、破乳剂用量、复配与原油破乳脱水的关系。同时介绍了目前国内使用较多的几个系列破乳剂。     

原油破乳剂研究进展与发展趋势

根据近几年国内外对破乳剂的研究,综述了原油破乳剂的研究进展。原油破乳剂按相对分子质量可分为:低分子量破乳剂、高分子量破乳剂和超高分子量破乳剂。分别介绍了各类型破乳剂的特点以及研究现状,提出在未来原油破乳剂向环境友好、高效脱水、低温破乳、价格低廉以及广普性较高的方向发展的趋势。     

聚醚型原油破乳剂结构与破乳性能关系的研究

以直链和支链结构的醇类、胺类以及稠环树脂为起始剂,通过烷氧基化反应合成了一系列嵌段聚醚型破乳剂。针对新疆塔河油田原油,讨论了聚醚破乳剂的起始剂类型、支化结构、起始剂含量、环氧乙烷与环氧丙烷质量比值[m(EO)/m(PO)]以及嵌段结构和方式对其脱水效果的影响。结果表明,针对新疆塔河油田原油,合成的多分枝型聚醚破乳剂脱水效果较好;聚醚破乳剂的起始剂质量比在0.3%～1.5%,HLB值在9.5～11.5,破乳脱水效果较好;末端为PEO嵌段的二嵌段聚醚破乳剂脱水速率快,脱水率最高;多嵌段结构聚醚破乳剂脱水速度较慢,但分离出的水色清,污水含油率低。     

稠油低温破乳剂研制与应用研究

胜利油田陈庄联合站原油属于稠油,原油黏度高、密度大、胶质和沥青质含量高,其原油乳状液稳定性强,破乳脱水很困难,脱水温度高达92℃,导致脱水热能耗高和原油处理成本高。在陈庄联现有工艺条件下,开展新型稠油低温破乳剂试验研究。现场应用结果表明：该低温破乳剂对陈庄联稠油具有显著的破乳脱水效果,在药剂用量降低5 kg/d条件下,破乳脱水温度可降低11℃,外输原油含水率为1.1%,满足外输油含水≤2.0%的规定要求。陈庄联合站由于大幅度降低脱水加热能耗,使原油综合处理成本降低27.3%,实现了节能降耗目的。     

原油破乳机理研究与破乳剂的发展

针对原油破乳剂的发展问题,本次研究首先对原油破乳的机理进行分析,在此基础上,对原油破乳剂的发展现状进行研究,为推动原油破乳剂的发展奠定基础。研究表明：原油破乳剂的发展经历了三个阶段,第一阶段的原油破乳剂主要是低分子量的阴离子表面活性剂,其破乳的效果相对较差,且使用过程中非常容易受到电解质的影响,第二阶段的原油破乳剂主要是聚氧乙烯醚非离子表面活性剂,使用该种类型的破乳剂,可以使得原油脱水效果大幅提升,原油破乳剂的使用量也相对较少,第三阶段的原油破乳剂以高分子量的聚醚型破乳剂为主,该种类型破乳剂的破乳效果相对较好。我国对于破乳剂的研究起步相对较晚,目前常用的破乳剂以环氧乙烷和环氧丙烷为主。     

原油破乳剂与添加剂复配的实验研究

用陕北地区有代表性的宝塔区、安塞和子长原油，对该地区目前正在使用的八种商品破乳剂用瓶试法进行破乳脱水试验，从中筛选出四种破乳脱水性能较好的破乳剂：GT-940、YT-100、SP-169和HQ96-l。将这四种破乳剂与OP乳化剂、洗衣粉等添加剂按不同比例进行破乳剂-添加剂复配，用瓶试法比较这些复配破乳剂的破乳脱水性能。在55℃，破乳剂总加量lOOmg／L，脱水时间为3h的条件下，发现只有GT-940与OP乳化剂和洗衣粉的复配破乳剂对宝塔区原油的破乳脱水性能得到改善。对宝塔区原油GT-940与OP乳化剂复配脱水率最高的配比是2：3；GT-940和洗衣粉的复配物脱水率最高的配比是2：3。     

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。     

安塞和子长原油破乳剂筛选研究--陕北原油破乳剂的筛选研究(Ⅱ)

本文对陕北安塞和子长原油用现有的不同破乳剂进行破乳脱水试验，筛选出对这些原油破乳脱水性能较好的破乳剂。     

志丹和川口原油破乳剂筛选研究--陕北原油破乳剂的筛选研究(Ⅰ)

本文对陕北志丹和川口原油用现有的不同破乳剂进行破乳脱水试验，筛选出对这些原油破乳脱水性能较好的破乳剂。     

破乳剂的RSN值与破乳脱水性能的关系

本文以壬基酚胺树脂(PAR)为起始剂与环氧乙烷(EO)、环氧丙烷(PO)聚合,合成一系列PPO、PEO含量不同的嵌段共聚物PAR-PPO-PEO,分别测定了他们的RSN值和破乳脱水效果。结果表明:当PPO数量固定时,RSN值与嵌段共聚物中PEO含量呈线性相关,当PEO含量固定时,RSN值随着PPO数量增加而减小。破乳结果表明:随着RSN值的增加,脱水效果先增加后降低,当PEO含量为30%时对应的RSN值处具有最佳脱水效果。     

Demulsification efficiency of some novel styrene/maleic anhydride ester copolymers

Four demulsifiers were prepared in three steps. In the first step, styrene and maleic anhydride were copolymerized. In the second step, a long‐chain alcohol (dodecanol) was reacted with the prepared copolymer to form the monoesterified copolymer. In the final step, the resulting product was further esterified with poly(propylene oxide) (PPO)–poly(ethylene oxide) (PEO) block copolymers of different molecular weights (1.1, 2.5, 3.0, 5.0, and 8.0 × 10³) and different PPO/PEO ratios. The demulsification efficiency of these demulsifiers was investigated with the bottle test (Sany glass). The effects of the molecular weight and ratio of the PPO–PEO block copolymers on the demulsification efficiency were studied. The demulsification efficiency could be enhanced from 66% by an individual demulsifier to 100% by demulsifier blends. The surface‐active and thermodynamic properties of the prepared demulsifiers were measured at 25, 35, and 45°C. The kinematics of the demulsification process were photographed with a binocular microscope. The demulsification mechanism was found to occur in three stages, that is, adsorption and flocculation, coalescence, and channel formation followed by separation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

一种新型低温破乳剂的研制

本文对丙烯酸与乙烯基硅油共聚物改性非离子破乳剂单体以制备新型低温破乳剂进行了研究。首先筛选出适合安塞原油的两类非离子破乳剂单体,然后进行了丙烯酸和丙烯酸与乙烯基硅油共聚物对两类非离子破乳剂的改性试验,最后以安塞原油为研究对象,详细考察了药剂成本相同、实验条件相同条件下两种非离子破乳剂单体的改性效果。当脱水温度为45℃时...     

获得（超）高分子量W／O型原油破乳剂的途径

本文综述了目前国内外获得（超）高分子量W/O型原油破乳剂的途径，并指出了国内原油破乳剂存在的不足及今后的发展方向。     

Dynamics in complex systems: Dendrimer-polymer blends in electric and mechanical fields

An investigation was carried out on the molecular dynamics of blends composed of poly(amidoamine) (PAMAM) dendrimers with ethylenediamine core and amino surface groups (generations 0 and 3) and three linear polymers: poly(propylene oxide) - PPO and two block copolymers, poly(propylene oxide)/poly(ethylene oxide) - PPO/PEO with different mole ratios: 29/6 (amorphous) and 10/31 (crystalline). The results were generated over a broad range of frequency and temperature by Dielectric Relaxation Spectroscopy (DRS) and Dynamic Mechanical Spectroscopy (DMS). Dielectric spectra of dendrimers in the PPO matrix reveal a decrease in the time scale of normal and segmental relaxation with increasing dendrimer concentration. In the amorphous blends with 29PPO/6PEO matrix, no effect of concentration on the time scale of normal and segmental processes was observed. But in the crystalline blends with 10PPO/31PEO matrix, relaxation time increases with increasing dendrimer concentration. Results acquired by DRS and DMS were contrasted and the obtained relaxation times were found to be in excellent agreement. A detailed analysis of the effect of generation and concentration of dendrimers, hydrophilicity and morphology of the polymer matrix and temperature on the molecular origin, the shape of the relaxation spectra, the dielectric relaxation strength and the frequency location for the maximum loss in dendrimer-polymer blends is provided.     

TA162824原油破乳剂的复配

以有机胺为起始剂、环氧乙烷和环氧丙烷为单体、氢氧化钾为催化剂,合成嵌段聚醚型破乳剂单剂TA162824,用TA162824分别与助剂TEAC和DMA按不同比例进行复配,用瓶试法分别对陕北油田的河庄坪和子长原油进行脱水实验。结果表明,对河庄坪原油,在55 ℃,破乳剂总用量100 mg/L,脱水时间6 h时,TA162824与TEAC以2∶3和3∶2、与DMA以4∶1的比例进行复配,脱水率最高,分别达到99.7%、97.8%;对子长原油,在65 ℃,破乳剂总用量200 mg/L,脱水时间6 h时,TA162824与TEAC以2∶3和1∶4、与DMA以4∶1的比例进行复配,脱水率最高,分别达到97.3%和99.3%。其中TA162824与TEAC以2∶3、与DMA以4∶1的复配物对这两种不同原油的脱水率等性能都好,适应性强。     

聚醚型破乳剂对陕北原油破乳脱水性能的试验研究

以多乙烯多胺为起始剂,环氧丙烷和环氧乙烷为单体,合成嵌段数和链节长度不等的6种嵌段聚醚型破乳剂:X2,X23,X3,Y33,PPEP1221,PPEP11344,用瓶试法对陕北油田有代表性的河庄坪和子长原油,进行破乳剂脱水性能测试,发现X2,X3两种破乳剂对河庄坪原油破乳脱水性能较好,所有破乳剂对子长原油破乳脱水性能较差。并运用电导法、染色法鉴别出河庄坪和子长原油乳状液类型为W/O型。     

利用Pluronic嵌段共聚物的增溶胶束超滤分离技术

增溶胶束超滤 (MEUF)是新型膜分离技术 ,但迄今仅利用普通烷烃链表面活性剂作为其胶束物质 ,由于这些表面活性剂单体相对分子质量低 ,形成的胶束较小 ,不仅难以有效增溶有机分子 ,还可能透过超滤膜造成对水体的二次污染。聚氧乙烯 -聚氧丙烯 -聚氧乙烯三嵌段共聚物 (Pluronics)是一类重要的功能高分子 ,在合适条件下 ,它们在水溶液中聚集生成具有很大内核的胶束 ,这种胶束能有效增溶水溶液中的有机污染物。其次 ,Pluronic共聚物分子单体的大相对分子质量使其容易被超滤膜隔离 ,加上Pluronic共聚物无毒无刺激性 ,因而这类新型功能高分子适合用于增溶胶束超滤方法 ,实现对水体有机污染物的分离。综述Pluronic嵌段共聚物的胶束化、胶束结构、胶束增溶以及在增溶胶束超滤分离技术中的应用     

BNT系列原油破乳剂的研究

本文介绍了用KOH作催化剂、伯胺为起始剂、环氧丙烷和环氧乙烷为单体,合成了嵌段数和聚合度不等的14种嵌段聚醚型破乳剂,用瓶试法对陕北油田有代表性的河庄坪、子长原油进行脱水性能测试,发现BNT46对河庄坪原油脱水性能较好。BNT43对子长原油破乳脱水性能较好。     

MPEG grafted quaternized carboxymethyl chitosan for demulsification of crude oil emulsions

Four novel environmentally friendly and highly branched crude oil demulsifiers were prepared by using different molecular weight (M_n = 350, 750, 1000, 1900 g/mol) of methoxy poly(ethylene glycol) to modify quaternized N,O‐carboxymethyl chitosan. Fourier transform infrared and ¹H‐nuclear magnetic resonance were employed to confirm the structure of the demulsifiers. The surface tension of demulsifies was determined and hydrophile–lipophile balance value was calculated at the critical micelle concentration. The demulsification performance was evaluated by the bottle test method against water‐in‐oil emulsions simulated in the laboratory and it was found that the dehydration rate of four demulsifiers can come to 74.2%–80.4%, which have better demulsification performance than the commercial demulsifier JL‐1. Demulsification mechanism was discussed, and it was encouraging to find that the tiny water droplets in the emulsion coalesced to form the water phase and separated with the water from the polarization microscope. Results show that methoxy poly(ethylene glycol) grafted quaternized carboxymethyl chitosan has a promising application as a demulsifiers for dealing with W/O crude oil emulsions. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45867.     

Binary blends of polyethers with fatty acids: A thermal characterization of the phase transitions

A series of binary blends of poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), and polytetrahydrofuran (PTHF), characterized by similar average molecular weights, with selected fatty acids (capric acid, lauric acid, myristic acid, palmitic acid, and stearic acid) were prepared by melt mixing. Differential scanning calorimetry was applied to characterize the phase transitions of melting and crystallization, and a synergistic effect was found to occur for PEO/fatty acid blends, as evidenced by the values of the enthalpy of the phase transition. This effect was probably due to hydrogen bonding between PEO and the fatty (carboxylic) acids, which facilitated the formation of crystalline structures; an analysis of IR spectroscopy data showed a shift in the absorption bands of OH groups. The morphology development of the PEO/carboxylic acid blends, as observed with polarizing light microscopy, could be described as spherulitic growth with spontaneous selection of the lamellar thickness. The textures of the individual fibrils, consisting of stacks of several tens of lamellae corresponding to PPO and PTHF, were less regular than the texture of PEO and showed large macroscopic heterogeneity. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 861–870, 2003