江汉原油降凝剂的制备及其性能研究

利用溶液聚合反应合成了一系列丙烯酸酯类高蜡原油降凝剂,并对其降凝效果进行研究。研究结果表明：采用摩尔配比为6：3：1的丙烯酸十八酯,马来酸酐和醋酸乙烯酯组成的混合单体制备的三元聚合物高蜡原油降凝剂MVA-3对江汉原油具有明显的降凝效果,在加剂量为1000mg／kg时,可以使江汉原油的凝点降低12℃。高蜡原油降凝剂MVA-3能够同原油中的胶质和沥青质有效结合,可以降低原油中固有的胶质一沥青质聚集体在原油中的析出温度,改变原油中蜡的结晶方式,降低蜡结晶析出温度和蜡结晶析出速度,并能减少原油中蜡的析出总量。     

Effect of drag reducer and pour point depressant on the wax deposition of crude oil pipeline

In this paper, the data of wax precipitation before and after the addition of the additives showed that the addition of the drag reducing agent (DRA) and the pour point depressant (PPD) cannot change the wax appearance temperature (WAT) of crude oil. When the dosage of DRA is small, the DRA cannot increase, stop, or slow down the precipitation of wax crystals. The addition of PPDs has no influence on the amount of precipitated wax crystals. From the GPC analysis, the molecular weight of the wax deposit samples in Linpu pipeline is from 500 to 76,800, which indicates that there is no enrichment of DRA in wax deposit samples. The results of IR show that the C?O group was not detected in the wax deposit sample of the Wei Jing pipeline, which indicates that there is no enrichment of the PPDs in wax deposit samples. The results showed that the DRA and PPD have no obvious effect on crude oil pipeline wax deposition.     

高凝原油降凝剂的制备及其降凝机理研究

 由丙烯酸十八酯、马来酸酐和醋酸乙烯酯三元共聚物的胺解改性物（MAVA）和乙烯-醋酸乙烯酯的共聚物（EVA）为原料,通过复配制备了一种高凝原油降凝剂(PPD),并对其降凝效果和降凝机理进行了研究。结果表明,所制备的高凝原油降凝剂对凝点为43℃的胜利原油具有明显的降凝效果,在加剂量为400?g/g时,原油的凝点降低了11℃;由原油中的沥青质和胶质所形成的聚集体结构是原油的蜡晶成核剂,降凝剂可以同原油中的沥青质和胶质结合形成新的沥青质-降凝剂-胶质聚集体结构,该聚集体结构作为加剂原油的蜡晶成核剂,可以改变蜡的结晶方式,延缓蜡晶的析出速率,大幅地降低了原油的凝点。     

潍北高凝点原油降凝降黏剂的研制

实验室自制的三元共聚物AMV-22与EVA复配,添加SLA-107作助剂,制备适用于胜利油田潍北区块高凝点原油的降凝剂AMVES。实验考察了该降凝剂对原油的降凝降黏效果。DSC热分析结果表明,AMVES加量为1000 mg/L时,可使原油凝点从48℃降低到37℃,析蜡点降低2℃。流变性曲线表明原油的剪切稀释作用随温度升高显著增强,当剪切速率大于100 s^-1后黏度基本不变,降凝剂可以大幅降低启动原油的屈服应力。偏光显微镜图显示原油温度越低,蜡晶网状结构越致密,交联度强,黏度大,流动性差;加AMVES之后原油中蜡晶变为团簇状颗粒,原油的流动性增强。由此可见降凝剂AMVES作用于蜡晶使其三维网状结构破坏,从而有效降低原油凝点和黏度。     

Wax deposition during production of waxy crude oil and its remediation

In the current paper, fundamental aspects of wax deposition problems in pipeline are defined, and characterization of paraffin and their solubility tendencies have been discussed. Wax deposition depends on flow rate, the temperature differential between crude and pipe surface, the cooling rate, and surface properties. The physico-chemical characterization of crude oil is determined. The experiments were carried out in “Cold Finger Apparatus.” Best pour point depressant for the selected crude oil has been found out as Lubrizol-6682 among different chemicals available that reduces the pour point from 36° to 12°. The deposition of paraffin wax, its dispersion, and inhibition were studied with available chemicals and by the optimization of suitable additives for particular well. Kinetics of crude oil in terms of time and differential temperature has also been studied and effective dispersion times are observed for particular oil. It is found that dispersion is effective within 30–60 min of starting. Kinetic study of oil with respect to differential temperature is done in two ways either by varying ambient/surface temperature or pumping/reservoir temperature. The tendencies of wax deposition on different sample with neat and treated crude are observed and ideal differential temperature for particular oil to flow is determined.     

The Effect of Commercial Additives as Pour Point Depressants for Fuel Oils

When the crude oil temperature goes below the pour point value wax crystals will come out of solution and tend to plug lines and filters. Additionally, the wax deposited in tanks decreases the storage capacity. In general, wax deposition can cause problems in production, storage, transportation, and consumption. Pretreatment of the crude oil with flow improver or pour point depressants has received the greatest acceptance due to its simplicity and economy. Four commercial additives were evaluated as pour point depressant for fuel oils. The structures of the commercial additives were confirmed by FTIR spectra. The results indicate that the n-alkanes carbon distributions display an obvious normal distribution in fuel oils. The distributions of high carbon n-alkanes are all broad so that wax crystals not precipitate in fuel oil at low temperatures is good. These commercial additives were tested as pour point depressants for fuel oil. The obtained data revealed that the prepared compounds depress the pour point of the fuel oil successfully. Comparison of structures of wax crystals in untreated and treated fuel oil was also done by photomicrographic analysis.     

阴离子聚合物St-OMA的合成和应用

采用阴离子聚合法合成苯乙烯（Styrene）-甲基丙烯酸十八酯（Octadecyl methyl acrylate）的二元共聚物St-OMA,评价了不同聚合条件下的聚合物对苏丹原油的降凝效果。通过偏光显微镜和图片处理软件对加剂前后原油中的蜡晶形态和分布进行微观分析,原油中蜡晶由大量片状、针状形态改变为颗粒状,蜡晶尺寸较小,蜡晶间也密实,分散得更细更匀称。这表明降凝剂的加入确实改变了原油中蜡的结晶形态,使析出的蜡晶尺寸变小变密,从而改善了原油的流动性,降低了原油的凝点。     

Correlations Between the Pour Point/Gel Point and the Amount of Precipitated Wax for Waxy Crudes

The amount of precipitated wax is one of the key factors that governs the flow properties of waxy crudes. Experimental results of 24 crudes have shown that approximately 2 wt% precipitated wax is sufficient to cause a virgin waxy crude gelling. Accordingly, a correlation between the pour point and the temperature at which 2 wt% of wax has precipitated out from a crude oil; i.e., T_c(2 wt%), and a correlation between the gel point and T_c(2 wt%) have been developed. The proposed correlation of the pour point is in accordance with the correlation developed by Letoffe et al. (1995) on the basis of 14 crudes from eight countries. The development of the gel point correlation and further verification of the pour point correlation indicate that there is a relationship between the gelling of virgin waxy crudes and the amount of precipitated wax. According to these correlations and the amount of precipitated wax, which can be determined only with a little sample by thermodynamic models or Differential Scanning Calorimetry (DSC) experiment, the gel point and pour point of virgin waxy crude can be predicted even if the oil sample is very limited. Heat treatment and chemical treatment can greatly improve flow behavior of waxy crudes, and more precipitated wax is present when the beneficiated (thermally beneficiated or PPD-beneficiated) crude oils gel. Experimental results showed that approximately two or three times the amount of precipitated wax presents at the gelling temperature when the oils were in their beneficiated (thermally beneficiated or PPD-beneficiated) conditions.     

锦州高含蜡原油降凝剂的筛选及现场应用

锦州原油高含蜡量高,凝点普遍在20℃以上,低温流动性差。为了保证冬季的安全输送,对实验室内开发研制的G5系列降凝剂进行了筛选,得到降凝效果最好的G51,并对影响其降凝效果因素进行了分析研究。实验结果表明,最佳加剂温度为60℃,合理的加剂浓度为400mg／L,可使原油的凝点由原来的22℃降至13℃,并且降凝剂具有良好的静态稳定性和配伍性,能保证管道的安全运行。     

一种新型原油降凝剂的研究

由乙烯、醋酸乙烯酯和乙烯醇聚醚组成的三元共聚物(WHP)是一种新型高分子表面活性剂型原油降凝剂.这种原油降凝剂既具有聚合物的特点,又有一定的表面活性,与某些常用的降凝剂,如EVA、聚丙烯酸高碳醇酯等相比,这种降凝剂无论对含高碳蜡(C₃₇-C₆₃)的吐哈原油和新疆混合原油,还是含一般蜡的江汉原油、鲁宁线原油和中洛线原油均表现出良好的降凝效果.例如,对吐哈原油在加药量为50mg/l时,一般原油降凝剂没有降凝效果,而WHP可以将原油凝固点从17℃降至10℃;而对新疆混合原油,当加药量为20mg/l时,WHP可以将原油凝固点从11℃降至-15℃而一般最好的降凝剂只能降至-8℃,即使对凝固点比较高的江汉原油,当加药量为100mg/l时,一般降凝剂只能将原油凝固点从34℃降至22℃,而WHP则可降至14℃.此外,WHP对鲁宁线原油还有一定的降粘效果,在加药量为40mg/l时,在30℃测定的降粘幅度为25.2%,而一般降凝剂最大的降粘幅度为14%.在室内模拟鲁宁线原油流动的情况下,原油加入WHP后依次经过多次慢速(80r/min)和快速(1500r/min)搅拌剪切后,原油凝固点回升幅度有较大的降低,且粘度的回升幅度也有所改善.     

一种高效防蜡降凝剂的研制与应用

姬塬油田部分区块原油蜡质、胶质含量高,油井结蜡严重,现有防蜡技术在该区块应用效果不佳,针对上述问题利用蜡晶晶格扭曲机理和微乳液机理,将蜡晶改进剂以纳米颗粒的形式均匀分布在水中,制备出一种不易燃烧、防蜡降黏效果好、密度较大、冬季可方便使用的高效防蜡降凝剂.研究结果表明,在最佳的合成工艺条件下制备出的高效防蜡降凝剂,纳米粒...     

Evaluation of Effect of Polymeric Pour Point Depressant Additives on Indian Waxy Crude Oil

Abstract

Wax deposition in oil production constitutes a critical and difficult-to-control problem in terms of productivity and production operation costs going from the reservoir to surface facilities. In the present work, four polymeric additives were prepared and used as pour point depressants (PPD) for Limbodara (Indian) crude oil via polymerization of different undecylenates with maleic anhydride with a further reaction with amine. The results are encouraging and show that prepared additives function both as wax dispersants and flow improvers due to the presence of polar groups in the structure. Cross–polarizing microscopic studies were performed to study changes in morphology of wax crystals in crude oil with and without additive. A zero-friction advanced rheometer AR-500 was used to determine the viscosity by applying Bingham plastic-flow model.     

Transportation technology with pour point depressant and wax deposition in a crude oil pipeline

The authors systematically studied transportation technology with pour point depressant and wax deposition in an industrial crude oil pipeline. Experiment results manifest that beneficiated oil acquires obvious modification effect and the reheating temperature of intermediate heat stations should be above 55°C to avoid effect deterioration. Heating schemes are made with lower heating temperature and wider output range. Moreover, an applicable wax deposition model is established to predict wax deposition distribution along the pipeline under various operating conditions. Wax deposition rate varies severely along the pipeline and it is necessary to consider its non-uniformity in production.     

Evaluations of the effect of selected wax inhibitive chemicals on wax deposition in crude oil flow in sub-sea pipe-lines

Comparative studies were made on the effect of different wax inhibitive chemicals on the wax deposition volume during crude oils flow in pipeline. Two crude oils from Ovhor and Jisike oil fields in the southern part of Nigeria were used in the study. The four identified chemicals: Alkyl sulphonates (wax dispersant), polyethylene (wax inhibitors/crystal modifier), acrylate ester copolymer (pour point depressant, PPD) and xylene (wax solvents) inhibit wax deposition to varying degree of between 14.6–44.9% for crude oil A, and between 21.6–41.4% for crude oil B when 1500 ppm of each chemical was mixed with the crude oil sample. The optimal wax inhibition formulation of polyethylene, xylene, acrylate ester polymer and alkyl sulphonate contains 40.4, 19.2, 27.6, 12.8% and 36.3, 21.5, 25.8, 16.4% for crude oil A and B respectively. Applications of the optimal formulated mixtures of the above chemicals inhibit wax deposition by 58.9% and 62.4% for crude oil A and B respectively.     

甲基丙烯酸十八酯-顺丁烯二酸酐-醋酸乙烯酯-苯乙烯降凝剂对原油蜡晶形态的影响

用偏光显微镜(PLM)观察甲基丙烯酸十八酯-顺丁烯二酸酐-醋酸乙烯酯-苯乙烯(OMVS)降凝剂添加量对原油蜡晶形态的影响。实验结果表明,随OMVS降凝剂添加量的增加,蜡晶由不规则的棒状和片状逐渐变为粒径小、分散均匀的近似球状的蜡晶;PLM表征结果显示,加入OMVS降凝剂的非洲原油和国产原油的蜡晶颗粒数均由不到100个增至大于1300个和1700个,原先占主导地位的表面积较大(非洲原油150～250μm2和国产原油100～200μm2)的蜡晶个数由超过60%降至1%以内,表面积较小(5～50μm2)的蜡晶个数由不到10%增至90%以上。通过指数回归可确定OMVS降凝剂添加量-蜡晶平均表面积-降凝幅度的内在关系,计算结果与实验结果吻合。     

Studies of Wax Deposition Onset in the Case of Indian Crude Oil

Abstract

Before taking any decision regarding strategies for prevention and remediation of wax deposition problems in the production tubing, pipeline, and process equipment, it is essential to identify the conditions of wax deposition and to predict wax deposition rates. In this article a study on the prediction of wax deposition, different factors affecting the deposition, and the practical applications of laboratory results obtained for characterization of the Indian crude oils have been presented. The waxy crude characterization study was performed on both stock tank crude oil and recombined integrated crude oil. The results of it exemplify the influence of composition, temperature, and pressure on the solid behavior of Indian paraffinic crudes.     

普适性结蜡模型研究

根据原油在管道内流动特性及析蜡规律,提出了有效析蜡量的计算方法.利用F检验法筛选了原油结蜡的主要影响因素,包括原油黏度、管壁处剪切应力、温度梯度及管壁处蜡晶溶解度系数.利用9种原油室内环道结蜡实验数据,按照逐步线性回归的方法,得到了含蜡原油的普适性结蜡模型.该模型不需进行结蜡模拟实验,只需根据原油的黏度、析蜡特性及密度等物性参数就可预测原油的结蜡规律.在未进行室内结蜡模拟实验的情况下,利用普适性结蜡模型预测了中宁-银川输油管道不同工况下沿线结蜡分布,并和现场运行参数进行了对比,平均误差为6.32%,最大误差为20%,预测结果为现场清管作业提供了依据.     

胺解聚合物型原油降凝剂的合成及应用

通过丙烯酸高碳酯与马来酸酐、醋酸乙烯酯、苯乙烯共聚后进行不同系列胺解得到一系列新型高蜡原油降凝剂。考察了该类降凝剂对大庆高蜡原油和尼尔阿曼混合原油的降凝效果。结果表明，胺解聚合物型原油降凝剂具有较好的原油降凝性能，降凝幅度最高达到27℃；同时，测定了加剂温度对降凝剂降凝效果的影响，结果发现，当加剂温度高于原油析蜡温度时，降凝剂的降凝效果才能充分显现出来。     

大庆原油蜡沉积规律研究

在理论分析及室内试验的基础上,系统研究了油温、流速、管壁处温度梯度等参数对大庆原油蜡沉积的影响.在原油与管壁温差相同时,不同温度段蜡沉积速率并不相同,存在蜡沉积高峰区.在壁温相同时,随油温升高,蜡沉积速率逐渐增加.在油温、壁温相同的条件下,随流速增加,蜡沉积速率下降.建立了大庆原油蜡沉积模型,并利用该模型预测了铁岭-秦皇岛输油管线不同季节、不同时间沿线蜡沉积分布.铁-秦线冬季存在蜡沉积高峰区;春、秋季出站时蜡沉积最严重,下一站进站时蜡沉积最轻;夏季蜡沉积速率更小,且沿线变化不大.     

Prediction of Wax Deposition in an Insulation Crude Oil Pipeline

This study establishes an insulation crude oil pipeline wax deposition experimental device and describes the experimental method for insulation crude oil pipeline wax deposition. The experimental program is based on the operational plan of Tieling–Huludao insulation crude oil pipeline. The data are analyzed according to the effect of varying oil temperature, insulation thickness, and flow on wax deposition. Using SPSS software, a Daqing crude oil wax deposition rate model is derived from the linear regression. The use of the wax deposition rate model forecasts the wax deposition of the Tieling–Huludao insulation crude oil pipeline during different seasons.