加氢基础油的发展和市场前景

本文论述了全球９０年代润滑油中加氢基础油的发展态势和下世纪初对加氢基础的市场需求。并从新一代ＰＣＭＯ和ＡＴＦ对基础油的要求说明加氢基础油得以迅猛发展的必然趋势。     

加氢法生产高质量润滑油基础油

加氢裂化未转化油和／或加氢精制过的溶剂脱蜡油经催化脱蜡工艺生产高质量润滑油基础油。该基础油料具有很好的低温流动性能，且对添加剂感受性好，硫、氮含量低，饱和烃含量高，可以调合中、高档润滑油。经补充精制或深度精制，可使该基础油芳烃饱和并深度脱氧、脱硫、脱氮，使杂环化合物分解，改善基础油的颜色，提高光安定性。     

加氢油作为液压油基础油的性能考察

本文按液压油基础油的要求，对加氢油的基础性能，加氢油对添加剂和复合剂的感受性做了考察，并对用加氢油加入LAN3008复合剂调制的L－HM46高级抗磨液压油进行了质量评定。     

用加氢工艺制取高质量润滑油基础油

叙述了用环烷基、中间基及石蜡基原油，在现有的润滑油基础油生产工艺中引入加氢精制技术，采用润滑油馏分加氢脱酸、临氢降凝工艺和润滑油加氢处理工艺、润滑油溶剂萃取－中压加氢处理组合工艺，以及由蜡膏异构等项技术，制取ＬＶＩ、ＬＶＩＷ、ＨＶＩ、ＶＨＶＩ、ＵＨＶＩ各种基础油的研究结果。     

加氢基础油生产高粘度白油技术

针对国内润滑油加氢技术应用特点，石油化工科学研究院研制了贵金属型精制催化剂RLF-10W，开发了以加氢基础油为原料经加氢精制(一段法)生产优质白油技术。经固定床加氢中型装置试验和一年来的实际应用，结果表明．该技术具有流程简单，适应性强等特点，特别适合于生产高粘度与很高粘度优质白油。     

加氢基础油的特点

用柴油清洗发动机润滑油道虽然能够去除发动机内的一些污垢，但在不拆检的情况下，对于一些长期形成的结胶和漆膜却不是短时间能够清洗干净的。由于柴油的粘度与发动机润滑油相比要小很多，又不含抗磨损的添加剂，在不拆检清洗的情况下会对发动机摩擦付造成磨损。另外，柴油的闪点有的仅在40～50℃，在清洗过程中也有一定的安全隐患。     

石蜡基原料油加氢异构脱蜡制润滑油基础油催化剂的研制

以AEL分子筛为载体,制备出一种贵金属异构脱蜡催化剂;以n-C12为模型物,以大庆炼化加氢预精制后的650SN糠醛精制油为实际原料考察该催化剂的加氢异构化催化性能。试验结果表明,所制备的异构脱蜡催化剂对n-C12以及650SN糠醛精制油均具有良好的异构化活性和选择性,其性能优于国外同类参比剂,加工650SN糠醛精制油时,可高收率地生产出优质API Ⅲ类润滑油基础油,目标产品倾点为－21 ℃,比采用参比剂时低6 ℃,重质基础油收率为62.79%,比采用参比剂时高5.55百分点。     

加氢润滑油基础油氧化稳定性国内外研究现状

油品组成和外界条件、使用状况两方面是加氢润滑油氧化稳定性的影响因素，烃类组成对其氧化稳定性的影响机理目前已被公认为自由基反应，国内外解决加氢基础油氧化稳定性的手段包括，改进加工工艺和加入抗氧剂、光稳定剂两种方法。     

润滑油基础油酸值、中和值与精制深度相关性研究

针对兰州石化公司润滑油基础油靠标试生产中基础油的“酸值”合格而“中和值、不合格问题进行了相关性研究,结果认为中和值比酸值更能科学、准确、严格地反映润滑油基础油的精制深度及内在质量,为润滑油基础油生产提供了可靠的依据。     

3673润滑油加氢补充精制催化剂器内再生

对锦西炼油化工总厂润滑油加氢补充精制装置３６７３催化剂器内再生的过程以及再生后催化剂的评价和使用情况做了介绍。工业应用表明３６７３催化剂再生后的活性和选择性稳定，能满足生产要求，产品质量符合标准，３６７３催化剂再生是成功的。     

USE OF UV SPECTROSCOPY TO PREDICT THE DAYLIGHT STABILITY OF HYDROCRACKED BASE STOCKS

Some hydrocracked base stocks are not stable to ultraviolet (UV) light and form a flocculant precipitate upon prolonged exposure. To understand the reason for their daylight instability, their aromatic and polar contents were analyzed. Selected hydrocracked base stocks were found to show a similar UV absorbance in the range of 260-340 nm with the max absorption peak in the range of 270-280 nm. The FTIR analysis indicated a presence of oxidized aromatic compounds in the form of acids, esters and ketones. The hydrofining process was found effective in improving the daylight stability of hydrocracked base stocks and in eliminating their UV absorbance in the range of 260-340 nm. The remaining absorption at 310 nm indicated a trace content of polyaromatic molecules. The results showed that the presence of polyaromatic compounds, coronenes, found in some hydrocracked base stocks does not affect their daylight stability. The UV absorbance data in the range of 260-285 nm were found to correlate with the daylight stability of hydrocracked base stocks. Independent of their processing and the storage conditions, base stocks showing a high absorbance, above 2 units, were found to have a poor daylight stability of 5 days or less. The hydrocracked base stocks showing a low absorbance, below 0.4 unit, were found to have an excellent daylight stability of 44 days or longer.     

USE OF UV SPECTROSCOPY TO PREDICT THE DAYLIGHT STABILITY OF HYDROCRACKED BASE STOCKS

Some hydrocracked base stocks are not stable to ultraviolet (UV) light and form a flocculant precipitate upon prolonged exposure. To understand the reason for their daylight instability, their aromatic and polar contents were analyzed. Selected hydrocracked base stocks were found to show a similar UV absorbance in the range of 260–340 nm with the max absorption peak in the range of 270–280 nm. The FTIR analysis indicated a presence of oxidized aromatic compounds in the form of acids, esters and ketones. The hydrofining process was found effective in improving the daylight stability of hydrocracked base stocks and in eliminating their UV absorbance in the range of 260–340 nm. The remaining absorption at 310 nm indicated a trace content of polyaromatic molecules. The results showed that the presence of polyaromatic compounds, coronenes, found in some hydrocracked base stocks does not affect their daylight stability. The UV absorbance data in the range of 260–285 nm were found to correlate with the daylight stability of hydrocracked base stocks. Independent of their processing and the storage conditions, base stocks showing a high absorbance, above 2 units, were found to have a poor daylight stability of 5 days or less. The hydrocracked base stocks showing a low absorbance, below 0.4 unit, were found to have an excellent daylight stability of 44 days or longer.     

溶剂脱氮-白土精制组合工艺提高润滑油基础油氧化安定性的研究

针对目前我国润滑油基础油的质量状况，开发了新型脱氮剂和溶剂脱氮-白土精制组合工艺，进行了润滑油基础油的脱氮研究，考察了脱氮工艺条件对脱氮率及精制油理化性质的影响。结果表明：溶剂脱氮-白土精制组合工艺可以选择性地脱除基础油中的含氮化合物，显著提高油品的氧化安定性。脱氮精制油的硫含量和其它理化性质脱氮前后变化不大。     

用于不同类别基础油的抗氧剂研究

润滑油的氧化安定性由基础油和抗氧剂两方面决定,是评价润滑油质量的一项重要指标。在API基础油分类中,从Ⅰ类油过渡到Ⅳ类油,基础油中饱和烃含量逐渐增加,不加抗氧剂时API前四类油的氧化安定性并无明显差别,而且Ⅰ类油略还好于后三类油;加入抗氧剂后,从Ⅰ类油到Ⅳ类油的氧化安定性逐渐增强,其中Ⅰ类和Ⅱ类油对酚类抗氧剂的感受性强于胺类,而Ⅲ类和Ⅳ类油对胺类的感受性远强于酚类,两类抗氧剂结合在一起使用能获得更好的抗氧效果。     

USE OF MASS SPECTROMETRY TO STUDY THE EFFECT OF HYDROCRACKING ON THE COMPOSITION OF BASE STOCKS

ABSTRACT

Mass spectrometry (MS) was used to study the compositional changes taking place during the hydrocracking process and the effect of composition on viscosity index (VI) of base stocks. The determination of compound types by MS required a separation of the petroleum samples into aromatic and nonaromatic fractions. After the hydrotreating of the feed, an increase in 1–ring naphthenes was observed. The value of an average ring number per mole did not change indicating the absence of ring–opening reactions. After the hydrocracking step, the MS analysis of the nonaromatic fraction showed a significant decrease in 1–6 ring naphthenes. A decrease in average ring number from 0.4 to 0.2 per mole indicated that the ring-opening reactions were taking place. The MS analysis of different hydrocracked base stocks, having a VI in the range from 143 to 148, showed no significant effect of paraffins/isoparaffins, 1-ring naphthenes and the condensed naphthenes on VI. The hydrocracked base stocks, having a VI of 143–144, were found to have an average ring number of 0.3 per mole. The hydrocracked base stocks, having a higher VI of 146–148, were found to have a lower average ring number of 0.2 per mole. The MS results indicated that the severity of hydrocracking and the extension of the ring-opening reactions were better described by an average ring number per mole rather than the contents of different chemistry hydrocarbons.     

USE OF MASS SPECTROMETRY TO STUDY THE EFFECT OF HYDROCRACKING ON THE COMPOSITION OF BASE STOCKS

Mass spectrometry (MS) was used to study the compositional changes taking place during the hydrocracking process and the effect of composition on viscosity index (VI) of base stocks. The determination of compound types by MS required a separation of the petroleum samples into aromatic and nonaromatic fractions. After the hydrotreating of the feed, an increase in 1-ring naphthenes was observed. The value of an average ring number per mole did not change indicating the absence of ring-opening reactions. After the hydrocracking step, the MS analysis of the nonaromatic fraction showed a significant decrease in 1-6 ring naphthenes. A decrease in average ring number from 0.4 to 0.2 per mole indicated that the ring-opening reactions were taking place. The MS analysis of different hydrocracked base stocks, having a VI in the range from 143 to 148, showed no significant effect of paraffins/isoparaffins, 1-ring naphthenes and the condensed naphthenes on VI. The hydrocracked base stocks, having a VI of 143-144, were found to have an average ring number of 0.3 per mole. The hydrocracked base stocks, having a higher VI of 146-148, were found to have a lower average ring number of 0.2 per mole. The MS results indicated that the severity of hydrocracking and the extension of the ring-opening reactions were better described by an average ring number per mole rather than the contents of different chemistry hydrocarbons.     

USE OF DSC TO STUDY THE FLOW PROPERTIES OF HYDROCRACKED BASE STOCKS AND LUBRICATING OILS

The differential scanning calorimetry (DSC) technique was found useful in assessing the effect of different processing conditions on the wax content and the wax-type of hydrocracked base stocks. The DSC thermograms showed a wide crystallization peak, in the range from -40 to -20°C, indicating the presence of paraffinic wax molecules. The second, narrow crystallization peak at about -75°C, indicated the presence of lower melting isoparaffinic or branched-type wax molecules. The DSC technique was used to study the onset wax crystallization temperature and the wax formation in hydrocracked base stocks containing different chemistry pour point depressants. The fumarate-vinylacetate (FVA) pour point depressant was not as effective as polymethacrylate (PMA) type chemistry. A decrease in depressed pour points of hydrocracked base stocks was found to follow a decrease in the onset wax crystallization temperature. In engine oil formulations containing hydrocracked base stocks, a decrease in depressed pour point was also found to follow a decrease in the onset wax crystallization temperature. For pour point depressants used in lubricating oils, the mechanism of decreasing the onset wax crystallization was found to be more important than the mechanism of suppressing the wax formation.     

SOLUBILISED WAXES AND THEIR INFLUENCE ON THE FLOW PROPERTIES OF LUBE OIL BASE STOCKS

The physico-chemical properties of Lubricating oil base stocks (LOBS) are generally influenced by the type/nature and concentration of solubilised waxes present in them. Detailed composition of the solubilised waxes, saturates and aromatics present in LOBS and its distillate fractions has been sludied. Further the influence of these solubilised waxes and as well of saturates/aromatics on the flow properties particularly pour point, viscosity and viscosity temperature relationship of LOBS sample and its distillate fractions have been investigated. The response of a commercial pour point depressant additive with varying composition of solubilised waxes in lube oil base stock sample has also been studied.