BEM系列原油流动性改进剂及其应用

扼要讨论了原油流动性改进剂（降凝剂）的作用机理，性能要求及生产技术关键。分别介绍了华冠石油化工公司生产的降凝剂BEM-3在输送胜利原油的长655.37km的鲁宁（临邑-仪征）线和长252km的东（营）黄（岛）老线，BEM-5P在输送中原原油的长282.55km的中洛（濮阳-洛阳）线和长241.9km的濮（阳）临（邑）线以及在大港油田长47.8km的一段集输干线，BEM-6N在输送南阳原油的长422.1km的魏（岗）荆（门）线和输送高凝高粘胜利原油的长约51.6km的河（口）沾（化）线，BEM-7H在顺序输送国内外多种原油的长201km的洪（湖）荆（门）线的应用工艺，降凝降粘效果及降低输量下的高效，经济，安全运转。在魏荆线上用BEM-6N所作的现场测试表明，在析蜡高峰期的过泵剪切和重复加热使加剂原油低温流动性显著恶化，在析蜡点以上的剪切和重复加热则影响不大。     

Carbon Distribution of n-Paraffins in Diesel and the Effects on the Sensitivity of Flow Improvers

Abstract

In this study, we analyze and describe the carbon distribution of n-paraffin in five kinds of diesel fuel, particularly using mathematical statistics. At the significance level α = 0.10, the distributions of all these diesel fuels submit to the normal distribution. The n-paraffin, with a lesser variance of σ², shows a weak sensitivity of flow improver. Statistic test quantity χ² reflects whether carbon distribution of n-paraffin fits the normal distribution. While the carbon distribution does not fit the normal law well, it will be difficult for this diesel to decrease the Cold Filter Plugging Point (CFPP).     

n-Alkane Distributions,Wax Settling Levels,and Responses to Flow Improvers in Diesel Distillations

The authors have statistically analyzed the relationship between the distributions of n-alkanes in diesels and the response of the diesel flow improver (DFI) to explore the reasons for the performance variation of DFIs. Diesel with a small n-alkane distribution variance showed a weak sensitivity to the DFI. The wax settling levels of the diesels were calculated at low temperature using a thermodynamic model and were found to increase as the n-alkane distribution variance decreased. Higher levels of settled crystals led to the poor performance of the DFI in the diesel with a small n-alkane distribution variance.     

Flow Enhancement of Medium-Viscosity Crude Oil

Abstract

This study investigated the different alternatives to enhance the flowability of crude oil with medium viscosity. These alternatives include the addition of water into crude oil to form water-in-oil emulsion, the addition of light petroleum product, the addition of flow improver, and a preheating technique. Temperature range of 10–50°C, water concentration range of 0–50% by volume, flow improver concentration range of 0–5000 ppm, and kerosene concentration range of 0–50% by volume were investigated in the flowability enhancement study of crude oil with medium viscosity. The flowability enhancement in terms of viscosity reduction was investigated using RheoStress RS100 from Haake. A cone–plate sensor was used with a cone angle of °4, cone diameter of 35 mm, and 0.137-mm gap at the cone tip. The addition of kerosene to crude oil improves the flowability much better than any other investigated technique.     

Flow Enhancement of Medium-Viscosity Crude Oil

This study investigated the different alternatives to enhance the flowability of crude oil with medium viscosity. These alternatives include the addition of water into crude oil to form water-in-oil emulsion, the addition of light petroleum product, the addition of flow improver, and a preheating technique. Temperature range of 10-50°C, water concentration range of 0-50% by volume, flow improver concentration range of 0-5000 ppm, and kerosene concentration range of 0-50% by volume were investigated in the flowability enhancement study of crude oil with medium viscosity. The flowability enhancement in terms of viscosity reduction was investigated using RheoStress RS100 from Haake. A cone-plate sensor was used with a cone angle of °4, cone diameter of 35 mm, and 0.137-mm gap at the cone tip. The addition of kerosene to crude oil improves the flowability much better than any other investigated technique.     

Synthesis and Evaluation of Some C14MC-MCNR2 Copolymers and C14MC-MA-MCNR2 Terpolymers as Cold Flow Improvers in the Diesel Fuels

In order to find efficient cold flow improvers for diesel fuels, a series of copolymers (C14MC-MCNR₂) derivated from long chain alkyl (i.e., tetradecyl) methacrylate C14MC and methacrylamide (MCNR₂) were prepared, and a series of terpolymers (C14MC-MA-MCNR₂) derivated from tetradecyl methacrylate C14MC, maleic anhydride (MA), and methacrylamide (MCNR₂) were also prepared. These copolymers and terpolymers were purified, and their structures were characterized by IR, ¹HNMR, and GPC. Their low temperature fluidities and filterability, such as solid point depression (ΔSP) and cold filter plugging point depression (ΔCFPP), used as cold flow improvers in two diesel fuels were evaluated. The results indicate that: (1) The C14MC-MCNR₂ copolymers possess good solid point depressing performance. (2) The C14MC-MA-MCNR₂ terpolymers exhibit dual function both as wax dispersants and flow improvers simultaneously, and they all possess very excellent solid point depressing performance, and can attain optimum effectiveness of CFPP depression when NR₂ is morpholine.     

Synthesis and Evaluation of Some C14MC-MCNR2 Copolymers and C14MC-MA-MCNR2 Terpolymers as Cold Flow Improvers in the Diesel Fuels

Abstract

In order to find efficient cold flow improvers for diesel fuels, a series of copolymers (C14MC-MCNR₂) derivated from long chain alkyl (i.e., tetradecyl) methacrylate C14MC and methacrylamide (MCNR₂) were prepared, and a series of terpolymers (C14MC-MA-MCNR₂) derivated from tetradecyl methacrylate C14MC, maleic anhydride (MA), and methacrylamide (MCNR₂) were also prepared. These copolymers and terpolymers were purified, and their structures were characterized by IR, ¹HNMR, and GPC. Their low temperature fluidities and filterability, such as solid point depression (ΔSP) and cold filter plugging point depression (ΔCFPP), used as cold flow improvers in two diesel fuels were evaluated. The results indicate that: (1) The C14MC-MCNR₂ copolymers possess good solid point depressing performance. (2) The C14MC-MA-MCNR₂ terpolymers exhibit dual function both as wax dispersants and flow improvers simultaneously, and they all possess very excellent solid point depressing performance, and can attain optimum effectiveness of CFPP depression when NR₂ is morpholine.     

生产润滑油基础油的原油优化选择

各炼厂采用不同的生产工艺对不同的原油进行加工生产基础油,得到的基础油产品性能存在一定的差异。文章将说明原油对基础油产品性能的影响,以及在采用不同生产工艺时原油对基础油产生的影响。溶剂精制工艺生产的基础油受原油性质影响较大,原油的选择尤为重要,VGO馏分为强石蜡基特性的原油更适合生产基础油产品。加氢及异构化等工艺受到原油限制小,对原油进行适当优化能显著提高炼厂的经济效益。     

Synthesis and Evaluation of Copolymers as Pour-point Depressants

Abstract

α-Olefin maleic anhydride copolymers were prepared by reacting C₈ or C₁₄ olefin with maleic anhydride, then esterified with dodecyl or NAFOL 1822B alcohol, purified and characterized through average molecular weight, polydispersity index, and infrared spectroscopy. A waxy crude oil (pour point = 21°C and wax content = 18.9 wt%) was treated with the four synthesized additives as pour-point depressants and determined using x-ray diffractometer. It is found that the x-ray diffraction patterns of waxes with additives are remarkably different from those without additives. The NAFOL 1822B ester of 1-tetradecene maleic anhydride copolymer also show stronger interaction with the wax than NAFOL 1822B ester of 1-octene copolymer, dodecyl ester of 1-tetradecene maleic anhydride copolymer, and dodecy ester of 1-octene maleic anhydride copolymer. These effects can be attributed to the chain length of side hydrocarbon. The wax solubilization is a function of copolymer.     

Synthesis of cyclohexanone-alcohol hemiketals and evaluation as flow improver for waxy crude oil

In this paper, four novel cyclohexanone-alcohol hemiketals (KL-1, KL-2, KL-3, KL-4) as waxy crude oil flow improver have been prepared by cyclohexanone and 1-pentanol, 1-Hexanol, 1-heptanol, 1-octanol. Evaluation results demonstrate the hemiketal compounds have obvious effect on the viscosity and pour point of Henan crude oil. DSC analysis showed that waxing point and waxing peak decreased to a certain degree in 0.05% hemiketal solutions. Wax crystal morphology analysis indicated the four hemiketals played a role of nucleation in the process of waxy crude oil decoagulation, and in that way acts as waxy crude oil flow improver.     

应对原油变化的装置腐蚀防护

针对常减压蒸馏装置加工原油性质的变化,装置的腐蚀现象也随之发生了变化。通过对腐蚀情况的汇总分析,指出应根据原油性质的变化及时调整"一脱三注"工艺、采取混炼措施保持原油性质相对稳定、选用耐蚀材料以及考虑增加三级脱盐等相应防护措施,可缓解装量的腐蚀,并为今后装置运行提供参考。     

原油流动改性剂在冀东油田的研究与应用

针对冀东油田的原油特性,研究开发了适用于冀东油田不同油品性质的原油流动改性剂产品.通过室内和现场实验,考察了原油流动改性剂对冀东油田不同物性原油的降黏、降凝情况.实验结果表明,使用改性剂后,降黏、降凝效果显著,提高了原油的流动性能,可以使系统在较低的温度下运行,药剂能够满足现场生产要求,达到了设计指标,取得了很好的效果,油区同期相比,单井集油温度平均降低20℃左右,部分区块实现了全年停炉,显著节约了生产成本.     

BEM-5P原油流动改进剂的应用研究

应用BEM－5P原油流动改进剂，在河沾输油线上进行了现场试验，结果表明，这种原油流动改进剂对河沾线原油具有较好的降凝，降粘效果，可降低运行温度，增加运行的安全性，而且经济效益明显。     

Characteristic Temperatures of Waxy Crude Oils

Gel point or pour point is widely used to evaluate the low temperature flowability of crude oil. However, it is not adequate to describe the gelling properties of waxy crude oils under flow conditions with gel point or pour point, since the rheological behavior of crude oils is dependent on shear history. Waxy crude oils tend to gel at a low temperature. Based on gelation theory, the characteristic temperature of waxy crude oil was determined by analyzing viscosity-temperature data. Two mathematical models were developed for calculating characteristic temperatures of virgin crude oils and pour point depressants (PPD) beneficiated crude oils, respectively. By using these two models, the characteristic temperatures of crude oils that have experienced shearing and thermal histories can be predicted. The model for predicting the characteristic temperature of virgin crude oils has an average relative deviation of 4.5%, and all predicted values have a deviation within 2 ℃. Tested by 42 sets of data, the prediction model for crude oil treated with PPD has a high accuracy, with an average relative deviation of 4.2%, and 95.2 percent of predicted values have a deviation within 2 ℃. These two models provide useful ways for predicting the flowability of crude oils in pipelines when only wax content, wax appearance point and gel point are available.     

A Study on Flow Characteristics of Heavy Crude Oil for Pipeline Transportation

In this work, the flow characteristics of heavy crude oil were investigated by using a rheometer and a lab scale flow loop, respectively. In the experiments of rheometer, there is an approximate linear relationship between the yield stress and the area of thixotropic loop independent to the system temperature and crude oil types. A comparison between the experimental data of yield stress versus start-up rate obtained in the pipe start-up flow with those measured in the rheometer reveals that the transport characteristics of heavy crude oil can be predicted well by the rheological measurements.     

Effects of Demulsifier Structure on Desalting Efficiency of Crude Oils

The desalting and dewatering of six crude oils with deferent properties have been studied. The contents of asphaltene and resin of #1, #2, and #4 crude oil are high; the demulsifiers with higher lipophilic values than others in the same series such as DA2, DB2, and DC2 can be easily absorbed on the interface of a water-oil emulsion and reveal better dewatering and desalting efficiency. The carbon atom number of alkyl on phenol core in nonyl-alkylphenol formaldehyde resin, which is the initiator of the DC series, is more than that of the DB series. DC was easier to diffuse into the interface of water in oil, and the dewatering efficiency increased. Because more multipoint adsorbed, their dewatering rate was slower, and the salts can dissolve in washing water and be removed with water. The density and viscosity of #3 crude oil are lower, and wax content is high. The hydrophilic group and lipophilic group in the molecular of DA4, DB4, and DC4 demulsifier can well be absorbed on the interface of water-oil emulsion of #3 crude oil, which have better efficiencies of desalting and dewatering than other demulsifiers of their same series. The density, viscosity, and wax content of #5 and #6 crude oils are lower; however, sulfur content is high. The self-made demulsifiers have excellent dewatering efficiency for #5 and #6 crude oil, but the desalting efficiency is unsatisfied, because the content of salts sulfate and sulfide in #5 and #6 crude oil is high as shown in the analysis of anion content before and after desalting. It can be improved by adding acid assistant TJ1, TJ2, and TJ3, thus indiffluent salts sulfate and sulfide transform into diffluent salts that can be removed, so the desalting efficiency obviously increases.     

Reaction Performance of FCC Catalyst for Cracking Inferior Crude Oils

Driven by the increasing supply of heavy oils with deteriorating quality,a high nickel-resistant catalyst for catalytic cracking of inferior crude oils was developed by the Research Institute of Petroleum Processing(RIPP).Catalyst performance was evaluated in a laboratory fixed fluidized bed reactor.The test results showed that the high nickel resistance catalyst exhibited good bottoms crackability,good nickel resistance,and good adaptability to changes in operating parameters,which had no adverse effect on the product distribution,indicating to a most promising prospect for application of this catalyst in catalytic cracking of inferior crude oil.     

含蜡原油流动性改进机理实验研究

将配方组分在100℃搅拌1小时，由25号变压器油，50号、60号粗晶蜡或80号微晶蜡(单种蜡或混合蜡)及60号道路沥青(只用在个别配方中)配成了一系列模拟含蜡原油及其加剂油，加剂量400mg／kg，药荆为以聚丙烯酸高碳醇酯为主的商品降凝剂GY1。测定了空白和加剂模拟油的相关特性，考察了20℃下析出的蜡晶在偏光显微镜下的形态结构，讨论了化学剂改进含蜡原油流动性的机理。加入GY1使模拟油浊点(析蜡点)只下降0～2℃，使30℃时析蜡量增加10％～35％，因此这两点都不是使流动性改进的因素。GY1的降凝效果随模拟油中蜡的标号增大、含量减小而增大，降凝效果较好时，在接近凝点温度下的屈服值降低率和降粘率也较大。降凝、降粘的共同切入点是抑制蜡晶形成网状结构或拆散蜡晶网状结构。化学剂改进含蜡原油流动性的机理是改变蜡晶表面性质。促使蜡晶长大，形成形状对称性高的蜡晶聚集体。图12表3参6。     

高酸原油的加工方法研究进展

随着石油资源的日益减少,高酸值原油的产量逐年增加。在加工过程中对设备的腐蚀问题已引起国内外的广泛关注。综述了近年来国内外高酸原油的加工方法,并对碱中和、抽提、吸附、化学转化、加氢、热分解等脱酸方法及其技术路线进行了比较,指出加氢脱酸是较为彻底且无公害的方法,但投资较高;热加工法由于方便可行且成本较低,越来越受到更多的关注。