Crude Oil Emulsions- A State-Of-The-Art Review

四丁基溴化铵水合物的生成-分解特性丁垚;宫敬;彭宇【摘要】对四丁基溴化铵(TBAB)水溶液与柴油形成的油包水乳状液中的水合物生成-分解特性进行实验研究,考察水合物的悬浮液混输.结果表明:四丁基溴化铵水溶液分散到柴油中形成油包水乳状液以后,相对于TBAB+水体系,生成水合物所需的温度降低,反应时间延长,能形成较稳定的水合物悬浮液；在相同的剪切速率下,TBAB水合物悬浮液的表观黏度明显大于对应的油包水乳状液的表观黏度,并且TBAB水合物颗粒体积分数越大,悬浮液的表观黏度越大,非牛顿流体的特性越明显；温度升高时,TBAB水合物在油包水乳状液中迅速分解,由固体颗粒融化成为液体,在此过程中对油包水乳状液具有明显的破乳作用,导致TBAB水合物在柴油中的悬浮液与水滴在柴油中形成的油包水乳状液的复合体系稳定性下降.%Based on die investigation of hydrate suspension multiphase transportation technology, experiments on TBAB hy-dtate formation-dissociation characteristics in invert emulsions formed by TBAB solution and diesel were carried out. The following results were obtained; The formation of TBAB hydrate in invert emulsions requires lower temperature and longer induction time compared with that in TBAB aqueous solutions. The apparent viscosity of TBAB hydrate suspension is higher than that of corresponding invert emulsion signifieantly at the same shear rate. The non-Newtonian phenomenon of TBAB hydrate suspension is more obvious and the apparent viscosity of TBAB hydrate suspension increases with the rise of TBAB hydrate particle volume fraction. When the temperature increases, TBAB hydrate dissociates rapidly in invert emulsions, transforming fromsolid particles to liquid. This phenomenon has obvious demulsificatkm effect as invert emulsions, which induces instability of the complex system containing TBAB hydrate suspension and water/diead e-riaion【期刊名称】《中国石油大学学报（自然科学版）》【年(卷),期】2011(035)004【总页数】4页(P150-153)【关键词】四丁基溴化铵水合物;生成特性;分解特性;油包水乳状液【作者】丁垚;宫敬;彭宇【作者单位】中国石油大学城市油气输配技术北京市重点实验室,北京102249;中国石油大学城市油气输配技术北京市重点实验室,北京102249;中国石油大学城市油气输配技术北京市重点实验室,北京102249【正文语种】中文【中图分类】TE832.332在深海中小型凝析气田的开发过程中，生产井产出的油、天然气、水经管道输送到集中处理平台进行处理。

微波破乳法原油脱水技术研究丁洋;熊祥祖;魏世辕;秦帆;王隆军【摘要】对原油乳状液分别进行了热化学法和微波破乳法脱水实验,采用含水质量分数为58.88%的3#原油乳状液,根据本实验原油的特点,通过改变温度、微波震荡时间、脱水剂用量研究了影响原油脱水的相关因素以及趋势,依据实验结果提出新的工艺路线;结果证明:此工艺具有脱水速度快,脱出水清澈的特点.【期刊名称】《武汉工程大学学报》【年(卷),期】2010(032)005【总页数】4页(P15-18)【关键词】原油脱水;乳状液;脱水剂【作者】丁洋;熊祥祖;魏世辕;秦帆;王隆军【作者单位】武汉工程大学化工与制药学院,绿色化工过程省部共建教育部重点实验室,湖北省新型反应器与绿色化学工艺重点实验室,湖北,武汉,430074;武汉工程大学化工与制药学院,绿色化工过程省部共建教育部重点实验室,湖北省新型反应器与绿色化学工艺重点实验室,湖北,武汉,430074;武汉工程大学化工与制药学院,绿色化工过程省部共建教育部重点实验室,湖北省新型反应器与绿色化学工艺重点实验室,湖北,武汉,430074;武汉工程大学化工与制药学院,绿色化工过程省部共建教育部重点实验室,湖北省新型反应器与绿色化学工艺重点实验室,湖北,武汉,430074;武汉工程大学化工与制药学院,绿色化工过程省部共建教育部重点实验室,湖北省新型反应器与绿色化学工艺重点实验室,湖北,武汉,430074【正文语种】中文【中图分类】TE8680 引言石油是重要的工业原料和战略资源，随着国民经济和工业化的迅猛发展，石油的需求量越来越大.如何提高石油的采收率，充分利用有限的石油资源，意义十分重大.在石油采收过程中，原油的破乳对原油开采，集输和加工都极其重要；而传统的热化学法和电化学法破乳存在着耗能大、破乳剂用量多、易产生二次污染等问题.本实验依据原油破乳的发展趋势以及存在的问题，研究影响原油脱水效果的主要因素，并在此基础上提出了新的工艺路线.1 实验部分1.1 原理及其改进水在原油中以游离水和乳化水两种形式存在，游离水可通过简单的沉降措施从原油中分离出来，乳化水却不能[1].乳化水需要通过加热，破乳[2]，或者震荡等使小油珠和水珠聚集成大油珠和大水珠，由于重力差异，大油珠上浮，大水珠下沉，从而达到油水分离的目的[3-8].热化学脱水由于成本低廉，工艺简单，目前在国际上得到广泛的应用.然而单纯的热化学脱水往往无法使原油的脱水量到达合格的要求.因此对影响原油脱水的主要因素作综合分析后，建立了集加热破乳微波震荡为一体的原油脱水研究方案.采用微波破乳的同时利用震荡强化类聚过程，加快类聚速度提高油水分聚的效果，然后再将已成熟的热化学脱水法与之简约集合.经热脱水，化学脱水剂脱水，微波震荡类聚的方法集约在一起，发挥溶合脱水的合力作用，以期达到缩短脱水工艺过程、节约能耗和运输成本并提高脱水效率的目的.1.2 仪器及材料加热套，冷凝回流管，蒸馏烧瓶(1 000 mL)，分水器，干燥器，若干烧杯，温度计；电子天平[EL204，梅特勒—托利多仪器(上海)有限公司]，数显鼓风干燥箱(101A型，吴江市同里镇田库工业开发区)，恒温水浴箱(ZZ17-20L型，北京中西泰安技术服务有限公司)，微波震荡器(JP-C50A型，广州市吉普超声波电子设备有限公司)；1#，2#，3#，5#原油(安陆石油化工厂)，2#脱水剂(破乳剂SP169，北京大田丰拓化学技术有限公司).1.3 测定方法根据中华人民共和国国家标准(GB/T 8929-88)原油水含量的测定蒸馏法对原油含水量进行测定.1.4 实验步骤a.全部仪器用铬酸清洗一遍，除去粘附在仪器内表面上表面膜和有机残渣.b.标定接收器：用能读准至0.01 mL的精密微量移液管，以0.05 mL的增量逐次加入蒸馏水来接收器上刻度标线的准确度.c.空白试验：把足够的二甲苯加到烧瓶中，使二甲苯的总体积达到400 mL(为了减少暴沸，可加入适量的沸石).d.用量程为200 mL的量筒量取流动的原油.缓慢地把原油倒入烧杯中，避免空气进入，把液面调到要求的刻度.再把烧杯中的油倒入蒸馏烧瓶中，用至少200 mL 二甲苯以每次40 mL分5次洗涤烧杯，倒入烧瓶，要把烧杯中的试样完全倒净.把足够的二甲苯加到烧瓶中，使二甲苯的总体积达到400 mL.e.搭建好装配仪器，要保证全部接头的气密性和液封性.把装有显色干燥剂的干燥管插到冷凝器上端，防止空气中的水分在冷凝器内部冷凝.通过冷凝器夹套的循环冷却水采用常温自来水.f.加热蒸馏烧瓶.在蒸馏的初始阶段缓慢加热(约0.5 h)，防止暴沸和系统中可能存在的水分损失(不能让冷凝液上升到高于冷凝器内管的3/4处，为了使冷凝液容易洗下来，冷凝液应尽可能的保持在冷凝器冷却水入口处).初始加热后，调整沸腾速度，使冷凝液不超过冷凝器内管长度的3/4.馏出物应以大约每秒钟2至5滴的速度滴进接受器.继续蒸馏，直到除接受器外仪器的任何部分都没有可见水，接受器中水的体积至少保持恒定5 min.如果在冷凝器内管中有水滴持久积聚，就用二甲苯冲洗.冲洗后，要缓慢加热，防止暴沸，再蒸馏至少5 min(冲洗前，必须停止加热至少15 min，以防止暴沸)，重复这个操作，直到冷凝器中没有可见水和接受器中水的体积保持恒定至少5 min(如果这个操作不能除掉水时，使用聚四氟乙烯刮具把水刮进接受器中).g.水的移入完成后，把接受器和它的内含物冷却到室温，用聚四氟乙烯制的刮具把粘附在接受器壁上的水滴移到水层里.读出接受器中水的体积.2 结果与讨论2.1 原油的含水量的测定根据1.4实验步骤，测定原油的含水量.结果如表1所示.表1 1#，2#，3#，5#原油的含水量记录Table 1 1 #, 2 #, 3 #, 5 # crude oil moisture content records取样量/g收集水量/g原油含水量/%平均含水质量分数/%1#20.9110.9252.2251.299.754.9150.362#12.296.5353.1353.3312.936.925 3.523#16.189.5258.8458.8811.316.5557.915#11.222.4722.0122.067.681.712 2.2712.962.8421.912.2 热脱水温度对原油脱水的影响在不同温度下对原油进行破乳实验.取3#原油60 mL于5个相同的小烧杯中，分别在几个不同温度下恒温水浴箱中水浴加热30 min，静置片刻.分别取烧杯中上层成品油适量，测含水质量分数.结果如表2所示.表2 不同温度下成品油含水量Table 2 Measured beaker refined oil moisture content at different temperatures温度/℃取样量/g收集水量/g成品油含水质量分数/%406.321.4222.47509.782.1021.47608.271.6820.31709.412.0121.36 2.3 2#脱水剂用量对3#原油脱水的影响在不同脱水剂用量下对原油进行破乳实验.在原油中分别加入不同含量的破乳剂充分震荡混合，震荡50 min，静置片刻，分别取烧杯中上层油适量，测含水质量分数.结果如表3所示.表3 脱水剂不同用量下成品油含水量Table 3 Measured beaker refined oil moisture content under different content of dehydrating agent脱水剂/d取样量/g收集水量/g成品含水质量分数/%震荡时间/min终温/℃37.201.0214.17504659.841.4114.33504657.651.1014.38504669.311.3114. 075050810.201.6115.7850501611.752.0217.195046实验结果表明，震荡50 min原油脱水效果最佳.2.4 微波破乳震荡时间对3#原油脱水的影响在不同微波破乳震荡时间下对原油进行破乳实验.原油在不同的微波震荡时间下进行破乳，静置片刻，分别取烧杯中上层成品油适量，测含水质量分数.结果如表4所示.表4 不同震荡时间下成品油含水量Table 4 Measured beaker refined oil moisture content when concussion time is different震荡时间/min取样量/g 收集水量/g成品油含水质量分数/%3013.523.4225.305023.745.8124.477012.232.4319.879012.222.3018.8211 014.682.8419.352.5 脱水剂用量、微波破乳震荡时间对3#原油脱水量的影响保持震荡时间恒定，改变脱水剂用量对原油进行破乳实验，从上述实验中每组分别选取3个最佳实验数据，得到含水量最低的数据对应温度的脱水剂用量、微波破乳时间进行破乳实验.结果如表5所示.表5 震荡时间一定时，不同用量脱水剂下成品油的含水量Table 5 Measured refined oil moisture content under different content of dehydrating agent when vibration test time is constant取样量/g震荡时间/min脱水剂/d收集水量/g成品含水质量分数/%112.145042.2118.2029.275041.5016.1839.695041.3013.4149.765041.411 4.4558.185050.9111.1267.895051.0112.8078.115051.0012.34注：6，7组震荡时原油放在振荡器边缘.2.6 附加实验2.6.1 原油不搅动、静置对原油脱水的影响实验结果表明，静置不震荡对结果影响不大，但静置后震荡的结果比无静置的好.表6 静置对原油脱水的影响Table 6 The impact of crude oil dehydration in the static duration取样量/g震荡时间/min2#脱水剂量/d收集水量/g含水质量分数/%备注6.42001.1117.29静置8 h6.575000.9013.70静置8 h 后震荡9.08001.2113.32静置8 h6.735021.0215.16静置8 h后震荡2.6.2 静置与震荡对5#原油脱水的影响实验结果表明，静置后再震荡的脱水效果较好，而静置的最佳时间为12 h.表7 静置与震荡对原油脱水的影响Table 7 The impact of crude oil dehydration in the static duration and vibration取样量/g震荡时间/min脱水剂量/d收集水量/g含水质量分数/%备注6.645020.9013.567.075020.8111.46震荡前静置30 min6.565020.8212.506.855041.1116.206.14021.2320.03静置30 min而无震荡7.745020.9211.89震荡前静置30 min8.25021.6119.52静置4 h7.03021.4220.20静置8 h7.15021.4119.72静置12 h7.645020.709.16静置12 h后震荡6.44021.3220.50静置16 h6.555020.7110.84静置16 h后震荡综上所述，先加入2滴脱水剂(sp169)，再搅匀，静置12 h进行一次破乳，取一次破乳后的上层原油乳状液采用微波震荡二次破乳，震荡破乳50 min得到成品油的工艺流程，可使原油的含水量降低到9.16%，脱水效果最好.2.7 原油脱水的分析2.7.1 影响原油脱水的因素通过分别测定原油在不同温度的恒温水浴箱中加热30 min后的含水质量分数的实验，可知：温度的变化会影响乳状液的稳定性，温度升高，乳状液稳定性下降；同时使连续相的粘度降低，水分子在重力场作用下沉降加快[9]；在原油中加入一定含量的破乳剂，破乳剂分子的极性部分具有亲水性而浸没水中，非极性部分浸入油中.上述实验结果表明，破乳剂的用量也有最佳值.在低浓度时，油水界面张力随破乳剂浓度增加下降明显，脱水率增大，当超过最佳值后界面吸附趋于平衡，破乳剂分子易聚集形成胶束[10]，使界面张力回升，脱水率反而下降.微波震荡会产生热学、电学、和化学等效应，作用于液体时产生激烈而快速变化的机械运动，震动能量被媒介吸收转变为热能使自身温度升高，在液体中产生空穴或气泡.震荡时间在达到最佳值之前，破乳效果随震荡时间的增大而提高，超过最佳值以后，破乳效果几乎不发生变化.因此，选择合理的温度，微波震荡时间，破乳剂的用量是十分必要的.2.7.2 原油脱水工艺的探讨通过以上实验，单一的热化学脱水，微波震荡破乳，加入脱水剂破乳脱水效果有限.因此，采用多种方式联合破乳，进一步降低原油的含水量.根据实验数据知选取震荡时间为50 min时，温度50 ℃下，不同脱水剂浓度下实验，原油含水量降低明显.在适当的温度，震荡时间，脱水剂浓度下原油脱水效果明显，联合破乳效果远远优于单一的破乳效果.3 结语a.温度是影响热化学法和微波震荡法破乳的因素之一.原油破乳温度存在一最佳值.针对本文所采用原油，实验结果表明最佳破乳温度为50 ℃.b.对于同种原油，实验结果表明微波震荡破乳效果比热化学法破乳效果好.c.超声波震荡破乳实验过程中，震荡时间存在一最佳范围.实验结果表明，微波震荡破乳时间应控制在50 min左右.d.微波震荡破乳实验表明在温度适宜时，震荡时间，破乳剂用量对破乳影响十分明显.温度、震荡时间、破乳剂用量联合破乳存在一最佳范围.对于本实验所用原油，当温度为50 ℃，震荡时间为50 min时，破乳剂滴数为2滴时，原油脱水率最高，破乳效果显著.e.根据实验结果的分析，提出原油乳状液脱水工艺为：先加入2滴脱水剂(sp-169)，再搅匀，静置12 h进行一次破乳，取一次破乳后的上层原油乳状液采用微波震荡二次破乳，震荡破乳50 min得到成品油的工艺流程，可使原油的含水量降低到9.16%，脱水效果最好.参考文献：[1]杨小刚,谭蔚,谭晓飞. 高含水原油的热化学破乳方法[J]. 化学工业与工程, 2007,24 (3):36-239.[2]安秀林,李庆忠.乳状液稳定性的影响因素和表达[J].张家口农专学报,2003,19(3):29-31.[3]刘晓艳,楚伟华,李清波,等. 微波技术及微波破乳实验[J].大庆石油学报,2005,29(3):96-98.[4]王明宪.不同引发剂作用下PO-EO嵌段共聚物破乳性能的研究[J].油田地面工程，1993,12(4):38-42.[5]傅大放,吴海锁. 微波辐射破乳的实验研究[J].中国给水排水,1998,14:4-6.[6]李英,赵德智,袁秋菊.超声波在石油化工中的应用及研究进展[J].石油化工,2005,34(2):176-180.[7]Tan W,Yang X G,Tan X F.Study on demulsification of crude oil emulsions by microwave chemical method[J]. Separation Science and Technology,2007,42:1367-1377.[8]赵安康. 微波辐射在油/水乳状液分离中的应用[J].上海科技大学学报,1993,5(1):83-85.[9]李扬,朱建华,武本成,等. 格尔木混合原油中金属元素的赋存状态研究[J].武汉工程大学学报, 2009，31(1):1-4.[10]丁得磐,孙在春,杨国华,等.原油乳状液的稳定与破乳[J].油田化学,1998,15(1):82-86.。

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The power ends are equipped with a bridge for centering of long stuffing boxes.The new generation of the P-series has a crankshaft with multiple slide bearings and features three power groups with 3, 5 and 7 plungers.4Stuffing boxesDue to the wide-range of appli-cations for our plunger pumps,stuffing boxes and seals aredesigned to meet the requisites ofthe respective liquid. Easy-to-handleliquids, such as water, emulsionsor similar, can be controlled withsimple seals.URACA will provide the bestpossible design to match the liquidyou handle.With fluids it is necessary, forexample, to take special measuresto reduce dead space or to installplunger guide bushes that are self-lubricating. The more demandingthe liquid is, the more extensivethe back up systems integrated inthe stuffing boxes. Consequently,heating, cooling, synchronousinjection, flushing or interlockingcomponents can be installed.Valve blocksThe design of the valve blocksdepends to a high degree on theproperties of the respective liquid.Cone, plate and ball valves areavailable. What they have incommon is high efficiency, lowwear and tear and outstandinglyeasy maintenance.5Leak-free handlingHeightened environmental awareness requires both the pump manufacturer and the operator to consider leak-free handling when designing and selecting the pumping equipment.URACA diaphragm pumps offer aunique solution in the handling ofdangerous fluids. They help in parti-cular to increase the operatingsafety of production plants and toimprove the working conditions ofthe operatives. Hermetically sealedplunger pumps are mainly used fortoxic, explosive, aggressive, foul-smelling, environmentally harmfulor abrasive fluids. URACA diaphragm pumps offer the advantages of a piston sealing that is virtually free of wear and tear as well as abso- lutely leak-free handling.URAC A diaphragm pump heads operate at a pressure range of up to 350 bar, while the temperatures of the fluid handled can be from -40 to +150° C . The PTFE-dia- phragm, which is resistant to virtu- ally all fluids, hermetically seals the fluid chamber. The selection ofmaterials for the parts touchedby the fluid as well as the designof the self-acting valves andthe stroke frequency of the pumpdepend on the respective fluid.Integrated monitoring systems pre-vent any overload of the unitand signal any diaphragmfailures immediately.URAC A diaphragm pumps are available in a power range of up to 250 kW. Operating pressure may be350 bar, capacity up to 850 l /min.URAC A diaphragm pumpsfeature the following specific advantages:■ Economy ■ High operatingsafety■ High service quality■ Space-saving design■ Flexibility of drive6▲▲Consistent URACA quality – the basis of a mutually beneficial relationshipProduct research and develop- ment at modern 3D-C AD-work- places to meet customer s’ needs and wants.Precision machining guarantees failure-free service lifeMeticulous assembly work by a highly trained and committed workforceA trial run lasting several hours on the test bed as well as comprehen- sive test programs are a demon- stration of guaranteed excellence.Many years of service life at the customer – the basis of a mutually beneficial relationship.7VP.e5.6L+S High Pressure –State of the Art Technology –WorldwideU RA CA Pumpenfabrik GmbH& Co. K GSirchinger Straße 15D-72574 B ad U rach, GermanyPhone +49 (71 25) 133 - 0Fax +49 (71 25) 133 - 202*************w ww.uraca.deCertified acc. to:■DI N EN IS O 9001:2000 by LRQ A■VGB KTA 1401■GostURACA is a leading manufacturer ofhigh pressure plunger pumps andhigh pressure water jettingtechnology equipment. Since 1893the company has been a globalleader in the development of thistechnology.URAC A‘s core competency lies inthe development, design,and manufacture of high pressureplunger pumps, pump units, andaccessories for almost all industrialfields.URACA offers leading technologicalknow-how in the field of fullyautomated and process-integratedsystem technology.The key focus is on two marketsegments:■High-performance pumpsolutions for the CPI sectorsand heavy industry.■ A universal and modularcomplete programme for high-pressure water jettingtechnology, especially for highlyautomated plants.The German domestic marketis covered by URAC A sales centersand a network of service centers.Internationally, URAC A hassubsidiaries and agencies.Additionally numerous representa-tives underline the company’spresence around the globe.A high standard of research anddevelopment, plus a modernmanufacturing facility stand forunsurpassed product quality.Ongoing market research and closeattention to current marketneeds safeguards the company’stechnological l eadership.Each URAC A cu stomer profits fromthis comprehensive experienceand technology and will find thatURACA is a highly competentpartner in the solution of theircleaning problems.。

Abstract A properly understanding of how oil mixtures behaves as they flows in a pipeline is a key factor for piping design. Facilities engineers from oil companies currently use commercial pipeline simulators in order to perform pressure and temperature gradients predictions. Nearly all the simulators apply the general mixing rule when they need to calculate the viscosity of a certain oil mixture. As viscosity depends both on molecular characteristics and molecular interaction, and oil is a complex mixture of components, it is not surprising that this rule gives poor results. Besides, non-Newtonian behavior makes things more complex. This paper discusses experimental results of mixing at lab several different oils and measuring their viscosity. Each oil had its own composition and rheological behavior. Some mixtures were prepared in order to reproduce real situations. Once the mixtures viscosities were obtained they were introduced as input data in a commercial pipeline network and nodal analysis software. Then, pressure and temperature gradients were calculated a) Using the experimental mixture viscosity b) Using the general mixing rule viscosity estimated by the software Results showed, in some cases, dramatic differences between the two alternatives. Higher deviations were obtained where the mixtures were composed of crudes of different properties. In order to improve the accuracy other mixing rules were tried and some of , Society of Petroleum Engineers Inc. This paper was prepared for presentation at the SPE Latin American and Caribbean Petroleum Engineering Conference held in Buenos Aires, Argentina, 25–28 March 2001. This paper was selected for presentation by an SPE Program Committee following review of information contained in an abstract submitted by the author(s). Contents of the paper, as presented, have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material, as presented, does not necessarily reflect any position of the Society of Petroleum Engineers, its officers, or members. Papers presented at SPE meetings are subject to publication review by Editorial Committees of the Society of Petroleum Engineers. Electronic reproduction, distribution, or storage of any part of this paper for commercial purposes without the written consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of where and by whom the paper was presented. Write Librarian, SPE, P.O. Box 833836, Richardson, TX 75083-3836, U.S.A., fax 01-972-952-9435.