Base Oil Production. Part II: Dewaxing, Finishing, and Blending

Three feedstocks supplied by Alexandria Petroleum Company were adjusted to bench scale extraction as a first step in refining using N-methyl pyrrolidone (NMP) and NMP containing 10% ethanolamine at the most suitable extraction conditions. The raffinates were solvent-dewaxed under constant dewaxing conditions. Then the dewaxed oils were treated with adsorption technique or with oleum treatment followed by adsorption technique to produce finished base oils. Eight formulated blends were prepared by blending selective base oils. The base oils and blended ones were evaluated according to the standard specifications of the Egyptian Organization for Standardization (EOS) and Mobil velocite oil.     

The Improvement of the Quality of Raffinate Obtained from Solvent Extraction of Lubricating Oils

Abstract

Vacuum distillates of an Egyptian crude oil were subjected to solvent extraction process applying N-methyl-2-pyrrolidone (NMP) and furfural as dearomatization solvents. The study shows that the extraction solvent together with the temperature and solvent-to-oil ratio have a significant effect on the yield and quality of produced lubricating oils. The optimum temperature for extracting light waxy distillates with NMP is 55°C at the solvent-to-feed ratio 2:1. These conditions are appropriate to remove the major portion of aromatics from the raffinate. The apparent activation energy (Ea), enthalpy (ΔH*), entropy (ΔS*), and free energy of activation (ΔG*) were calculated for the solvent dearomatization process.     

Clarified Oil from Fluid Catalytic Cracking as an Additional Source of Group II Base Oil Components

Abstract

Clarified oil (CLO) from a commercial fluid catalytic cracking unit was subjected to solvent extraction followed by solvent dewaxing and adsorption chromatography to analyze its various components for different end-use applications. The clarified oil was first solvent extracted using N-methyl pyrrolidone (NMP) to produce paraffinic rich raffinate (68.9 wt% yield). The raffinate thus obtained was dewaxed using methyl isobutyl ketone (MIBK) to get an oil of pour point 0°C. This dewaxed oil was then subjected to adsorption chromatography to determine group II base oil potential through yield v/s viscosity index (VI) curve. The results revealed that clarified oil has an actual potential of around 27.1 wt% of group II base oil components, suggesting that clarified oil can be used as an additional source of feed for production of group II base oil. This article also describes the potential of other components in clarified oil such as slack wax (24.2 wt%), aromatics (31.1 wt%), and low VI oil (17.6 wt%).     

Novel Impact of Wet Dosages of NMP in Extraction for Production of High BMCI Carbon Black Feedstocks

Abstract

In separation sciences, “Solvent Extraction” is one of the most important unit operations, a very widely used process, next only to distillation. In the petroleum refining industry, solvent extraction is commonly widely applied to produce a number of specialty products such as BTX, lube base oils, waxes, etc. There are many solvents used in various separation processes, like sulfolane, phenol, furfural, ketones, and N-methyl pyrollidone (NMP). NMP in particular is an environmentally benign, new generation solvent, which can be tailored for specific separations by using it in conjunction with small doses of water. In recent years, researchers are re-looking at the separation processes and their modifications to exploit these for producing high-value industrial products from low-value refinery streams. The present study deals with the production of high-quality carbon black feedstocks (CBFS) from clarified oils. The study shows the beneficial effect of using NMP in combination with different dosages of water as extraction solvent to extract low-value clarified oil, a cracked material from the FCC unit of an operating Indian refinery. In the present study, water ranging from 0.3 wt% to 10 wt% was used with NMP to produce aromatic extract of BMCI (Bureau of Mines Correlation Index) up to 146 through liquid-liquid equilibrium and mass transfer studies on clarified oil (CLO). The effect of solvent-to-feed ratio at constant temperature on solvent extraction was also studied. The addition of water in NMP alters the “selectivity” of solvent, which can be exploited for producing aromatic extracts of a wide range of BMCI for different end-use applications. The major users of such high BMCI extracts are carbon black and electrode pitch manufacturers. Regression analysis was also done to develop correlations between water percentage in NMP and targeted BMCI of aromatic extract. Presently, CLO is blended with fuel oil and sold as a very low value product in refinery. Since the demand of CBFS is increasing continuously and current short-fall in India is met through imports from China, Korea, and Japan, it is desirable that such studies are undertaken and will lead to production of high-value CBFS from low-value refinery streams through separation processes.     

Deep Desulfurization of Diesel Fuel by Extraction with Task-Specific Ionic Liquids

Abstract

Extraction of S-compounds from diesel oil by task-specific ionic liquids has been investigated. The influences of different ionic liquids, extraction time, extraction temperature, different S-compounds, the amount, and the recycling of ionic liquid were studied. This process is capable of removing up to 56% of dibenzothiophene in model diesel oil under optimum extraction conditions. At the same time, this process was applied to the real predesulfurized diesel oils. The results indicate that such a process could be an alternative to common hydrodesulfurization for deep desulfurization.     

Light hydrocarbon geochemistry of crude oils from Eastern Niger Delta

Abstract

Geochemical evaluation of oil samples from the eastern part of the Niger Delta divided into western, eastern, and central sections of the study area was carried out for the characterization of their light hydrocarbons content in order to correlate oils from different parts. The hydrocarbons in the oil samples were determined using gas chromatographic (GC) technique. The results obtained showed that CPI, Pr/Ph, Pr/nC₁₇, and Ph/nC₁₈ ratios ranged from 0.99–1.55, 2.19–4.79, 0.92–2.35, and 0.27–0.47, respectively. The Pr/nC₁₇ versus Ph/nC₁₈ plot showed that the oils were derived from terrestrial organic materials that were deposited under oxic to suboxic conditions. They are moderately matured with minimal effect of biodegradation on most of the oil samples although two of the oils showed relatively higher degradation. Both bivariate and multivariate plots of the light hydrocarbon ratios differentiated the western and central oils from the eastern oils. The classification of the oils into families was not based on origin but rather on post generative alterations that include reservoir conditions and possibly migration effects. The light hydrocarbon parameters identified can be used in the correlation tools.     

BOILING RANGE DISTRIBUTIONS OF VARIOUS SHALE OILS AND INFLUENCE OF CARBON DIOXIDE RETORTING

Abstract

The boiling range distributions of seven different shale oils from the United States and Australia which were retorted in the same retort under identical conditions were obtained and compared. These data are important in forming an engineering data base for shale oils.

Also, the effects of carbon dioxide retorting versus nitrogen retorting on oil quality were investigated. Through the study of the initial and final boiling points and the boiling range distribution it was found that carbon dioxide retorting increased the yield of low to mid-distillate fractions in the shale oil, thus enhancing the oil quality.     

Recycling of used motor oil as an alternative method for production feedstock for the conversion processes

Abstract

Used lubricating motor oil is a high pollutant material that requires responsible management. It may cause damage to the environment when dumped into the ground or into water streams including sewers. This may result in groundwater and soil contamination. Recycling of such contaminated materials will be beneficial in reducing lubricating motor oil costs. In addition, it will have a significant positive impact on the environment.

Used oil can be refined to yield base oils that are blended into lubricating products, thus reducing the consumption of virgin oils and it can be used as a feedstock for hydro conversion for production fuels and fuel oil.

This work investigates refining of used lubricating motor oil using solvent extraction method. The laboratory experiment was based on a full factorial design and two categorical factors with two levels were nominated which were solvent to used oil ratio and solvent type (2-Propanol and n-Butanol, MEK and blended the solvents with gazoline).

The type of solvent used and the mixing ratio applied for different runs has shown significant effects on the yield of recovered oil. The yield with bisolvent type MEK+gasoline was higher than the other solvents. The yield of treated oil with butanol mixed with gasoline is 87.5% and it is so close to the yield when we used the butanol alone which is 88.6%.     

重质原料高压加氢裂化尾油生产HVIW基础油的工艺研究

对以重质VGO为原料的高压加氢裂化尾油进行溶剂脱蜡-糠醛精制-白土补充精制，生产HVIW润滑油基础油，低凝轻质基础油的综合收率达30%，重质基础油的综合收率约为10%，考察了不同转化率的尾油生产HVIW基础油的性质及糠醛精制工艺对产品光安定性的影响，结果表明糠醛精制可以明显改善加氢基础油的光安定性。     

伊朗原油生产润滑油基础油的工业试验

进行了伊朗原油减二、减三线、减四线及脱沥青油采用糠醛精制、酮苯脱蜡和白土精制传统加工工艺生产润滑油基础油的工业放大试验。结果表明,伊朗减二线及脱沥青油基础的粘度指数大于９０,与ＨＶ１１５０及ＨＶ１１５０ＢＳ基础油的具体指标有一定差距,其它质量指标分别达到ＨＶ１１５０和ＨＶ１１５０ＢＳ基础油的技术要求;伊朗减三线、减四线基础油的粘度指数小于９０,其它质量指标分别达到ＨＶ１４００和ＨＶ１６５０基础油的     

Production of Low Metal Content Re-refined Lubricating Oil

Abstract

A number of metals are found in used lubricating oil. In this article, performance of solvent extraction followed by adsorption on magnesite has been studied for removal of metals from used oil. The suggested process is one of the efficient methods to remove not only sludge, but also the metals either present in the lubricating oil as additives or picked up by the oil during its working life. The re-refined oil has metal content comparable with base oil. In some cases, even lower metal content has been observed.     

润滑油精制中NMP对石油酸抽提规律的研究

NMP(N-甲基吡咯烷酮)润滑油精制是国外近年发展起来的一种性能较优的精制工艺。以减三线油为原料,系统地研究了NMP作为溶剂对石油酸的抽提能力,包括温度、乙醇胺和水的加入对抽提能力的影响。实验结果表明,NMP对石油酸具有相当高的抽提能力;但随着原料油酸值的升高,现有的工艺条件下抽提能力仍嫌不足;在溶剂中加入适量的乙醇胺和水对于石油酸的抽提有较大的改进。     

Removal of the Polycyclic Aromatic to Produce Eco-friendly Aromatic-rich Rubber Extender Oils

Abstract

Polycyclic aromatic (PCA) hydrocarbon-rich extender oils were to be banned by December 2009, which gave rise to challenges for the oil and rubber industries. In the present work, removal PCA from distillate aromatic extracts (DAE) by absorption and solvent extraction were studied. When the ratio of solvent-sample was 8:1, 81.2% PCA in DAE was removed by three-stage countercurrent extraction using dimethyl sulfoxide as the extractant, which simulated industrial continuous flowsheet. Using the extraction-absorption processing, the content of PCA in DAE was further decreased to 2.93%. The properties of the oil sample after removal PCA accorded with the requirements of eco-friendly aromatic-rich rubber extender oil.     

润滑油基础油生产技术的新进展

对中国石化石油化工科学研究院开发的系列润滑油基础生产技术进行了介绍,其中包括环烷基原油润滑油馏分临氢降凝,中东原油或中间基原油采用溶剂精制与中压加氢组合工艺及中东原油采用异构脱蜡等。这些润滑技术的开发,有利于提高我国润滑油基础油的质量及技术水平。     

SUPERCRITICAL FLUID EXTRACTION OF TURKISH LIGNITES AND OIL SHALE WITH TOLUENE MIXTURES

Abstract

Supercritical -Fluid extraction (SFE) of two Turkish lignites and oil shale with toluene mixtures were investigated. Experiments were performed in a batch autoclave at 623 K. Extracts recovered from SFE were fractionated into oils, asphaltenes and preasphal-tenes by solvent extraction.

The conversion of lignites decreased with increasing n-pentane content in the mixture. The extraction yield and the products (oils, AS, PAS) increased with increasing n-pentane content in its range below 15 %

The conversion and the extract yield obtained from Cöynük ail shale is higher with toluene mixture than toluene.     

加氢基础油对添加剂溶解性能和极压抗磨性能影响的研究

研究了加氢基础油对添加剂的溶解性能和极压抗磨性能的影响, 并与溶剂精制基础油进行了比较。结果表明：加氢基础油对丁二酰亚胺无灰分散剂、高碱值硫化烷基酚钙、二烷基二硫代磷酸锌具有较好的溶解性能,对研究的高碱值磺酸钙的溶解性较差;基础油中的芳烃含量影响极压抗磨剂在摩擦表面的吸附,在芳烃含量低的基础油中,极压抗磨剂有更好的使用性能。     

The Demetallization of Residual Fuel Oil and Petroleum Residue

Abstract

Heavy residual fractions were treated to remove metal contaminants by nonconventional methods, such as centrifugation, solvent extraction, and contacting the material with various chemicals and chelating agents. The centrifugal method was found to be effective in reducing water-soluble metal salts and the Na/V mass ratio was reduced from about 0.5 to about 0.1. The extraction method using polar solvent (ethyl acetate) was found to be very effective for removal of oil-soluble metals from heavy residual fractions. Among the acids used in the chemical treatment method, sulfuric acid showed the most promising results. Although sulfuric acid effectively removed sulfur and metals along with the resinous and asphaltic substances from petroleum, the formation of an emulsion was always a serious problem; when broken it yielded darkened oil and a lot of acid sludge. Most of the chemical agents appeared to be effective for the demetallization of heavy oils and residue. The contact of heavy residual fractions with aqueous solutions of FeCl₃ and SnCl₄ (0.1–0.5 M range) in acidic solution appeared to be effective. A pretreatment step before the traditional hydroprocessing methods is recommended for the upgrading of heavy oils.     

Extractive dearomatization,denitrification and desulfurization of gas oil fractions by a mixed extractant of N,N-methylpyrrolidone,N,N-dimethylformamide and ethylene glycol via microwave radiations

In an attempt to develop alternative process that meet the prescribed levels and green-technology criteria in gas-oil refining, N,N-methylpyrrolidone (NMP), dimethylformamide (DMF) mixed solvents under microwave-radiations (MW) were tested for the gas-oil desulfurization (EDS), denitrification (EDN) and dearomatization (EDA). In optimal conditions the gas-oil EDS-efficiency via MW can reach as high as 99.1% within 5?min at 500?W in three stages, which is much higher than EDS without MW (88.5% within 15?min) or than those of ionic liquids. The NMP/DMF/EG can be reused for multi-cycles before being regenerated by adsorption method. This study will provide useful information for future industrial application.     

辽河稠油生产低凝点润滑油基础油

介绍辽河稠油生产低凝点润滑油的组合工艺,重点报道在不适合选用传统溶剂脱蜡工艺的情况下,利用石油化工科学研究院开发的临氢降凝技术,在工业装置上采用临氢降凝,加氢补充精制串联,氢气一次通过流程,分别以RDW－1和RN－1为催化剂处理辽河稠常二,常三,减二线糠醛精制油,可降低润滑油凝点20℃以上,完善了辽河稠油以加氢脱酸－糠醛精制－临氢降凝－加氢或白土后精制的工艺流程生产低凝润滑油的加工过程,可生产出符合工艺指标的各种低凝点润滑油基础油产品。     

Optimizing the Process Conditions for the Production of Lube Base Oil From Heavy Distillate

In order to meet the increasing process demand of heavy crude, the deep processing of heavy oils, especially the vacuum residue, may be a best choice. The authors selected ketone-benzol dewaxing, furfural refining, clay finishing (AFC); and furfural refining, ketone-benzol dewaxing, clay finishing (FAC) were selected to process base oils. Elemental analysis, n-d-M method, and ¹H nuclear magnetic resonance were used to investigate the structure characteristics of base oils. Experimental data show that the FAC process conditions are more rigorous than AFC process, the yield of AFC process is higher than that of FAC process, but their base oils have their advantages and disadvantages.