用于高含蜡原油的双聚合物降凝剂的研制

通过在有机溶剂中进行的引发聚合 ,由摩尔比 2∶3∶3的马来酸酐、丙烯酸十八酯、醋酸乙烯酯合成了共聚物降凝剂A ,由摩尔比 1∶2∶3的苯乙烯、马来酸酐、丙烯酸十八酯合成了共聚物降凝剂B。A和B均为质量分数 30 %的溶液。简介了合成方法。A +B组合实验和组合物加量实验结果表明 ,对于密度 86 8.9kg m3、含蜡量 2 6 .6 %的辽河曙光原油 ,质量比 3∶1的A +B的降凝降粘效果最好 ,加入量为 0 .5 %时原油凝点由 2 9℃降至 2 1℃ ,80℃、15 0s- 1下的粘度由 2 0 0 0mPa·s降至 95 0mPa·s,降粘率达 5 2 .5 % ;对于密度 886 .7kg m3、含蜡量 18.9%的吉林新民渣油(原油减压蒸馏釜底残液 ) ,质量比 1∶2的A +B的降凝降粘效果最好 ,加入量为 0 .4 %时渣油凝点由 13℃降至 1.0℃ ,80℃、15 0s- 1 下的粘度由 95 0mPa·s降至 2 6 0mPa·s,降粘率达 72 .6 %。降凝剂A +B加量增大时 ,原油和渣油的凝点、粘度均降低。表 3参 8。     

水性降凝剂BEM-6N-W的研制

使用固体颗粒状原油降凝剂需要有复杂的溶解、注入装置.将固体颗粒降凝剂BEM-6N在90℃溶于混合溶剂中,配成30%～50%溶液(油相),在60～90℃下其黏度均在103mPa·s数量级.使用用量3%～8%的复配乳化剂及适量杀菌剂,将上述油相乳化在水中,制成15%的水性降凝剂BEM-6N-W.取加量为50 mg/L,对不同剂型的BEM-6N进行了评价.油性降凝剂(1%柴油溶液)、15%水性降凝剂及稀释至1%的水性降凝剂在加剂热处理温度为70℃时,均可使青海原油凝点由28℃降至10℃;在加剂热处理温度为55℃时,只有油性降凝剂对大庆原油有降凝效果,使凝点由35℃降至24℃,当加剂热处理温度提高至60℃时,水性降凝剂对大庆原油也有同样降凝效果.从水性降凝剂在原油中的破乳、分散、溶解出发,解释了以上实验结果.15%水性降凝剂BEM-6N-W于2007年10月在输送青海原油的花格线、2008年10月在输送大庆原油的秦京线试验获得成功.     

管输原油降凝剂的研究进展

总结了石蜡结晶机理及其影响因素,并对国内外含蜡原油降凝剂的发展过程、作用机理、常用降凝剂的种类以及影响降凝剂作用效果的各种因素进行了介绍;指出了降凝剂在研究和应用中存在的问题,对降凝技术的发展进行了客观评价和展望。     

锦州原油降凝剂的研究

锦州原油为高蜡质原油,本研究针对该原油的特性,优选合成了多种羧酸酯共聚物型降凝剂LF一04,并对试验结果和影响加剂效果的因素进行了分析。锦州原油最佳热处理温度在50℃以上,最优加剂浓度为400mg／L,其原油凝点值由原来的21℃降至9℃,反常点降至40℃,比空白原油反常点降低了5℃。在原油温度25℃,剪速为16s-1下加入400mg／L的降凝剂LF－04,原油表观粘度由原来1150mPa·s降至339mPa·s,降粘率为70．5％。     

前南高蜡原油降凝剂的研究

文章选择了几种不同的单体进行聚合反应,得到了两种三元聚合物,并分别和EVA进行复配。依次考察了两种复配型降凝剂在不同加剂量和不同温度下对前南原油的降凝效果。实验结果表明:在加剂温度为70℃时,AMS-EVA复配降凝剂的最佳加剂量为0.03%,可使前南原油凝点降低9℃;AVS-EVA复配降凝剂的最佳加剂量为0.1%,可使前南原油凝点降低10℃。这两种复配型降凝剂均可以降低前南原油的黏度,改善其低温流变性。     

加剂低凝柴油的研制及工业生产

通过对柴油降凝剂的筛选评价和对不同降凝剂冷滤点感受性的考察,选择出性能优良的柴油降凝剂。在组分优化的基础上,研制出－10号、－20号、－35号低凝柴油的调合配方,并投入工业生产,为企业创造了良好的经济效益。     

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.     

高凝原油降凝剂使用效果及性能

对一种新型液体原油降凝剂KYJN-1进行了室内模拟试验,考察了该降凝剂在实际运行环境下的使用性能及存放条件.试验结果表明,在加剂量为50 mg/L,热处理温度为75℃的最佳条件下,该降凝剂能降低原油凝固点8～13℃,现场生产运行环境对降凝效果没有影响,降凝剂现场存放温度为40～45℃.     

苏丹混合原油复配型降凝剂研制

苏丹三七区各油田所产原油高蜡、高胶质、高黏、高凝.外输油采用加剂加热处理工艺,经φ181.3 mm、长1367 km 管道输送至苏丹港.加剂量大,降凝降黏效果不佳.实验外输油烷烃碳数分布范围C6～C36,C26和C17～C16处有2个峰值,在DSC曲线上有2组析蜡点和析蜡峰59℃和56℃,42℃和35℃.从八大类商品降凝剂中未筛选出可用的剂种.研制了由2种EVA、一种高分子量聚丙烯酸高级醇酯、一种具强极性基的三元共聚物及胶质沥青质改性剂组成的复配降凝剂SL2.加剂量1.0 g/L的该荆使实验外输油凝点由39℃降至30℃.35℃、13 1/s黏度降至843 mPa·s,35℃稠度系数降至40.0 Pa·sn,流动指教接近1(1.156).DSC分析及显微研究表明该剂不改变原油析蜡点和析蜡峰温,可使析出的蜡晶变细小.按现场管榆工艺,考察三次加剂(1.0、1.0、0.5 g/L)的降凝降黏效果,认为接转站和中心处理站热处理温度可由105℃降为95℃,在4号泵站则由65℃升至80℃.对于加剂原油的凝点和流变性,管流剪切影响较小,过泵剪切影响很大,温度越低则影响越大.图6表5参2.     

小型炼油装置在海上原油主电站低闪点燃料解决方案中的应用研究

以南海X-2海上油气田项目为例,分析了原油燃料对海洋平台主电站的影响因素,指出低闪点原油会影响主电站的正常运行和安全,同时是第三方的强制要求。提出利用小型炼油装置提高低闪点原油的闪点,并对提高原油闪点的处理流程以及操作参数进行模拟计算,得到了该生产系统的压力、温度、设备负荷以及尺寸等参数。对油田油样进行了初步实验,实验结果表明此处理流程可行。对设备的工业应用进行了调研。研究结论表明,利用小型炼油装置将原油提高到要求的闪点是可行的,而且相对于传统的外购原油方案,节省了大量的费用和能源消耗,在海上油气田开发中具有重要意义。     

A Study on the Interaction of Crude Oil Waxes With Polyacrylate Pour Point Depressants by Monte Carlo Simulation

The interaction of crude oil waxes with polyacrylate pour point depressants (PPDs) bearing different structures was investigated in detail by Monte Carlo simulation, using n-hexadecane as representative component of wax crystal. It was demonstrated that during wax precipitation the mixed energy was low when the side chain length of polyacrylate was close to that of n-hexadecane. Meanwhile, the mixed energy between polyacrylate PPDs and n-hexadecane was shown to be closely related with the polarity of building blocks of polyacrylate. Our results indicated that it is easier for polyacrylate polymers with polar building blocks to interact with n-alkanes, which would effectively inhibit wax-crystal precipitation and improve crude oil low-temperature fluidity. The simulation results provide with some knowledge for guiding the molecular design and synthesis of polyacrylate PPDs.     

The Formation of Waxy Crude Oil-in-water Emulsions for the Reduction of Pour Point and Viscosity

Waxy crude oil is characterized by high pour point and poor flow properties, which bring great difficulty to the oil exploitation and transportation. In this study, the fluidity of waxy crude oil with the pour point of 47°C was highly improved by emulsification with synthetic formation water used as aqueous phase. It was found that the combination of CAO-35 and sodium oleate was an effective emulsifier mixture to form stable waxy crude oil-in-water emulsion and when the mass ratio of oil to water was 7:3, the optimum composition of emulsifying additives with respect to the total mass of the emulsion was obtained as follows: emulsifier mixture (the mass ratio of CAO-35 to sodium oleate was 8:2) 0.4% (w/w), sodium triphosphate 0.028% (w/w), NaOH 0.05% (w/w), and polyacrylamide 0.15% (w/w). Diverse factors affecting the pour point of the formed emulsion were also studied. It was found that the pour point of emulsion increased as oil content increased and the optimum mixing speed and cooling rate were 600 rpm and 0.5°C/min, respectively. Under the optimum emulsifying conditions, when mixing speeds were 250 and 600 rpm, respectively, by forming O/W emulsions with the oil content of 70%, the pour point reductions were 20 and 25°C, respectively, and the corresponding viscosity reductions were 89.79% and 97.46% (40°C), respectively. Thus the pour point and viscosity of waxy crude oil are obviously reduced by forming oil-in-water emulsion, which is highly promising for the exploitation and transportation of waxy crude oil.     

Comparison of the Performance of Empirical Models Used for the Prediction of the PVT Properties of Crude Oils of the Niger Delta

A review of the literature has revealed the lack of a formal analysis of the performance of empirical methods for the prediction of pressure volume temperature (PVT) properties of Niger delta crude oils. This study presents an assessment of the predictive accuracy of five bubble-point pressure (P_b) correlations and five bubble-point oil formation volume factor (B_ob) correlations against a large measured PVT data bank from Niger Delta crude oils. Statistical analysis techniques were used to evaluate the performance and the accuracy of the commonly used empirical models for estimating PVT properties of Niger crude oil in order to guide designers and operators in selecting the best correlations for their particular applications. Agreement between calculated and measured P_b and B_ob values for the various models was very poor. The model predictions of P_b and B_ob can be different from the measured values by 56% and 242%, respectively. Development of improved models for predicting the PVT properties of Niger delta crude oils is urgently required.     

Evaluation of Trace Metals and Physical Properties of Nigerian Crude Oil Saturate Fraction

Analyses of trace elements and physical properties of the saturate fraction of Nigerian crude oil were done in order to establish the characteristics that may aid the developmental processes of the natural resources. Crude oil samples were collected from three different oil fields in Niger-Delta area of Nigeria. The saturate fractions were eluted by column chromatography using n-hexane. The saturate fractions were investigated for functional groups using Fourier transform infrared spectrometry (FT–IR); the elemental concentrations were determined using Atomic absorption spectrometry, while the physical properties (flash point, ash content, refractive index, and color) were determined using standard analytical methods. The results revealed that the infrared spectra of the saturate fraction of the Nigerian crude oil showed mainly the presence of C-H(CH₃) and C-H(CH₂) functional groups, indicating high purity of the samples. The concentrations of the analyzed elements (Mn, Cu, Co, Zn, Fe, V, Cr, and Ni) in the saturate fraction were generally low compared to other fractions of Nigerian crude oil. This study revealed that Co has the highest mean concentration of 1.81 ± 0.36 mg/L, while Mn has the lowest mean concentration of 0.04 ± 0.02 mg/L. The t test values for the comparison of the elemental concentrations of Nigerian crude oil /saturate fraction and crude oil asphaltene/saturate fraction showed significant difference (except Mn) with respect to Nigerian crude oil /saturate fraction. The cluster analysis for the elements showed two groups, which are fairly well correlated indicating similar source and similar chemical affinity. The cross-plot analysis of the Nigerian crude oil and its saturate using elemental concentrations as the variables showed a strong positive inter element correlation since (R² = 0.71), establishing a relationship between the Nigerian crude oil and the saturate fraction. The color of the saturate fraction ranged from off-white to colorless. The results of analysis provide useful information on its conversion mechanism and environmental implications of the development of the fossil fuel deposit.     

原油酸值测定方法的对比分析

目前国内原油酸值的标准分析方法主要有GB/T 7304-2000《石油产品和润滑剂酸值测定法(电位滴定法)》和GB/T 264-1983《石油产品酸值测定法》。讨论了两种方法分析对胜利油田分公司高硫高酸原油所测酸值数据的差异。认为造成结果差异的原因主要有两种:一是滴定溶剂对原油的溶解性及对原油中酸性物质的抽出能力不同;二是终点判断的方式不同。通过分析发现,原油(尤其是重质高酸原油)的酸值宜采用GB/T 7304-2000方法进行分析,采用GB/T 264-1983测定原油酸值有一定的局限性,会存在测定结果偏低的问题。     

一种简单的混合原油性质估算方法

为了估计混合原油的性质,提出一种简单、快速的计算方法.该方法的计算结果和PIMS的计算结果几乎相同,说明了该方法的可行性.     

A Method of Testing the Pour Point of Petroleum Products on a Refrigerated Sloping Surface

The method of testing pour points of pure substances and multicomponent hydrocarbon mixtures basing on the analyses of the path lengths of passing of equal volumes of substances along the tracking grooves on the refrigerated sloping metallic panel has been presented. Repeatability of the method makes up ±0.3°C, which surpasses the repeatability of testing pour points by the known international standards (ASTM D5853-95, ASTM D97-09, ISO 3016, GOST 20287-91) 5–7 times. Operability of the method has been shown on the example of testing pour points of hexadecane, octadecane, and paraffinic oil. It has been established that experimental curve plotted in coordinates (length of sample passing path ? temperature), can be presented by the sum of two terms, the first of which is described by hyperbola with asymptote at temperature, equal to the pour point of the sample, which actually corresponds to the flow regime, and the second term is described by the parabola of variable exponent and the contribution to drop rolling regime. Drop rolling has a greater contribution into the experimental curve with the increase of the panel slope angle, and with the greater difference between the temperature of the panel and the pour point of the sample.     

原油降凝降粘剂的合成与性能评价

以十八醇和丙烯酸为原料,在不加带水剂的条件下合成了丙烯酸十八酯（ODA）,其合成条件为：十八醇108g,n（十八醇）：n（丙烯酸）=1．0：1．2,对甲苯磺酸1．0％（催化剂,以醇酸总质量计）,对苯二酚0．7％（阻聚剂,以醇酸总质量计）,反应温度135℃,反应时间6h。然后再用实验合成的丙烯酸十八酯、顺丁烯二酸酐（MA）和醋酸乙烯酯（VA）3种单体为原料,采用自由基溶液聚合反应合成了原油降凝剂AMV。通过实验确定了最佳合成条件：nODA：nMA：nVA=8：1：1,引发剂为偶氮二异丁腈（AIBN）,用量0．5％（w））;聚合温度90℃;聚合时间6h。在原油中加入质量分数为0．5％的AMV可以使原油的凝固点降低10℃。50℃时的粘度由148．2mPa·s下降到40mPa·s,降粘率迭73％。     

不同原油对常减压蒸馏装置的腐蚀及防护措施

文章对常减压蒸馏装置加工高含硫含酸原油过程中存在的腐蚀问题以及加工劣质化原油现状进行了分析,并对其现行的一系列防止设备腐蚀的有效措施进行了概述。针对该装置所加工原油性质,提出了一系列防范措施：定期进行原油腐蚀性能评定;原油电脱盐工艺防腐蚀（脱盐后盐的质量浓度小于3 mg/L）;＂三顶＂工艺防腐蚀;加强腐蚀在线监测;现有设备及管道材质升级等措施。通过这一系列措施的实施,常减压蒸馏装置每年发现并处理隐患约16处,提高了装置运行的安全系数,减缓了设备的腐蚀,实现了装置长周期运行。并提出了目前存在的不足及后续改进建议。     

质子交换膜燃料电池用氢气的质量控制

简要介绍了化石燃料制氢、工业副产氢、电解水制氢以及光解水和生物质等新型制氢的方法,叙述了冷凝-低温吸附、低温吸收-吸附、变压吸附、钯膜扩散、金属氢化物分离五种氢气提纯方法,对质子交换膜燃料电池用氢气所依据的相关标准进行了比较分析,指出了氢气中总硫、一氧化碳、甲醛与甲酸、总卤化物、氨气、二氧化碳、水、总烃、氧气、颗粒物、...