POLYMER SOLUBILITY THEORY PREDICTS EFFICIENCY OF RESIDUAL OIL EXTRACTION BY POLAR SOLVENTS

ABSTRACT

Light paraffinic solvents (C2 to C7) have traditionally been utilized by the petroleum refining industry to extract oils from crude distillation residua. Extracted oils constitute feedstock to lubricants manufacture and, to a lesser extent, additional cracking stock. More recent literature reveals a growing interest in polar, non-hydrocarbon partially oil-soluble solvents such as alcohols, ketones, and esters of lower carboxylic acids. In this work, articles and patents which report the separation of residua into asphalt and extracted oil by means of polar solvents are briefly reviewed, and the separation performance of same of those solvents is correlated to the solute-solvent interaction parameter (?) in the Flory-Huggins theory of polymer solubility. The three dimensional solubility parameter (δ) approach is followed to estimate ? for the solvents of interest at the appropriate operating conditions. The saturate, aromatic, and polar compounds fractions of a bitumen are characterized by solubility parameters equal to the values of δ of the solvents or mixtures thereof used by the standard ASTM D-2007 chromatographic fractionation of the deasphaltenated oil (DAO). A mean value of ? is found for every DAO-solvent pair, treatment ratio and temperature. For each solvent considered, yields of extracted oil at varying operating conditions (temperature, pressure, solvent /feed ratio) are found to be well correlated to ?, in according with theoretical predictions that the lower a value of ? a solvent has for a given solute, the better it dissolves the solute and the higher the yield.

It is suggested that this type of approach could supply criteria to select solvents and operating conditions for applications requiring high yields (to produce additional cracking stock) or lower yields but high rejection of metals and heteroatoms (e.g. for lube oil bases extraction).     

Deasphalting of crude oils using supercritical fluids

A crude oil has four main SARA constituents: saturates, aromatics, resins, and asphaltenes. The asphaltenes in crude oil are the most complex and heavy organic compounds. The asphaltenes contain highly polar substituents and are insoluble in an excess of n-heptane (or n-pentane). The classic definition of asphaltenes is based on the solution properties of petroleum residuum in various solvents. Asphaltenes are a solubility range that is soluble in light aromatics such as benzene and toluene, but is insoluble in lighter paraffins. The particular paraffins, such as n-pentane and n-heptane, are used to precipitate asphaltenes from crude oil. The effects of four different solvents (water, carbon dioxide, propane, and ethanol) on the deasphalting process under the supercritical conditions were reviewed. Supercritical water is an excellent solvent for removing of high molecular weight organic compounds such as asphaltenes from crude oils under the supercritical conditions.     

油基钻井液用有机土胶体率的影响因素分析

针对不同生产工艺、不同类型的有机土在不同基础油中的胶体率差异较大的问题,分别对两个不同厂家的有机土（1#和2#有机土）进行胶体率实验。考察了不同类型的基础油、不同的极性溶剂（激活剂）和浓度、不同的搅拌速率、不同的搅拌时间对有机土胶体率的影响。结果显示:1#有机土在0#柴油中的胶体率100%,而在5#白油中的胶体率为20%,加入不同的极性溶剂胶体率达到100%;2#有机土在0#柴油、3#白油、5#白油中的胶体率均不足10%,加入极性溶剂后胶体率有不同程度的提高。此外,搅拌速率从3000 r/min增加至13 000 r/min,有机土胶体率从18%增加至29%;搅拌时间由5 min延长至40 min,有机土胶体率从22%增加至40%。通过实验数据分析,揭示了激活剂对有机土胶体率的作用机理,并对有机土胶体率性能指标的评价提出了建议,应明确测试条件,比如搅拌时间、搅拌速率、测试温度等,这些因素对有机土胶体率有一定的影响。      

采用组合工艺提高辽河减压渣油轻油收率

以辽河减压渣油为原料,采用C5为溶剂,在压力4.0~7.0 MPa、剂油质量比4:1及温度160/180 ℃的条件下进行深度溶剂脱沥青试验,残炭降低率50%左右,90%以上的沥青质得到脱除,并富集到脱油沥青中。采用溶剂脱沥青-脱沥青油催化裂化-沥青残渣焦化组合工艺加工辽河减压渣油的研究结果表明：随溶剂脱沥青压力的提高,脱沥青油的收率增加,压力为7.0 MPa时,总脱沥青油收率达到74.22%,沥青残渣收率明显降低;轻、重脱沥青油催化裂化的平均液化气＋轻油收率分别为25.74%及12.72%,沥青残渣焦化的液化气＋轻油收率均值为7.17%。采用组合工艺技术,辽河减压渣油的液化气＋轻油收率较减压渣油直接焦化提高了4.06 百分点。     

LIQUEFACTION OF ELB�STAN AND YATAĞAN LIGNITES I N CARBON MONOXIDE/HYDROGEN GAS MIXTURES

Thc effects of experimental parameters on the liquefaction yields of Elbistan and Yatagan lignites vcre investigated by using different solvents, guses and catalysts.

In hydroliquefaction of Elbistan lignite with anthracene and creosote oils, higher oil yields were obtained with anthracene oil. Based on this result, anthracene oil was chosen as solvent for further work done with Elbistan lignite. First the effect of moisture in lignite samples vas observed with synthesis gas as medium gas: then, the effect of carbon monoxide/ hydrogen ratio in liquefaction gas mixture was determined using moist lignite samples. The highest oil yield was obtained with moist lignite sample in 3CO/IH₂gas mixture and it was 57.3 % (daf).

The hydroliquefaction oil yields of Yatagan lignite obtained with creosote oil were higher than those obtained in anthracene ail. On Further work done with Yatagan lignite, creosote oil was chosen as solvent. First, the effects of CoMo and red mud catalysts, then in catalyzed medium, the effects of moisture in lignite samples and at last, using moist lignite samples and red mud catalyst. the effects o f carbon monaxide/hydrogen in synthesis gas medium and also, the increase in the oil yield a s an effect of catalyst presence, increased further: the 3CO/lH, ratio in gas medium was suitable for obtaining higher oil yields; and also for obtaining high oil yields, 440°c could be taken a s the most suitable temperature value and the pressure should be increased a s much as technical and economical conditions permit.     

四碳醇溶剂精制再生废润滑油的研究

针对溶剂精制再生废润滑油环保、经济、高效的特点,应用四碳醇极性溶剂为萃取剂、聚丙烯酰胺为絮凝剂进行再生废润滑油研究,采用单因素实验方法考察工艺条件的影响,得到的最佳工艺条件为：萃取溶剂为异丁醇、精制时间15 min、精制温度25 ℃（室温）、剂油质量比5/1、絮凝剂用量1.0%。该工艺下再生油产率达82.1%,再生油理化指标得到明显改善,黏温指数达130以上、闪点超过200 ℃、酸值为0.01 mg KOH/g、残炭含量降低到0.01%以下,表明采用该精制工艺再生废润滑油是可行的,有广阔的应用前景。     

LIQUEFACTION OF ELBI˙STAN AND YATAĞAN LIGNITES I N CARBON MONOXIDE/HYDROGEN GAS MIXTURES

Abstract

Thc effects of experimental parameters on the liquefaction yields of Elbistan and Yatagan lignites vcre investigated by using different solvents, guses and catalysts.

In hydroliquefaction of Elbistan lignite with anthracene and creosote oils, higher oil yields were obtained with anthracene oil. Based on this result, anthracene oil was chosen as solvent for further work done with Elbistan lignite. First the effect of moisture in lignite samples vas observed with synthesis gas as medium gas: then, the effect of carbon monoxide/ hydrogen ratio in liquefaction gas mixture was determined using moist lignite samples. The highest oil yield was obtained with moist lignite sample in 3CO/IH₂gas mixture and it was 57.3 % (daf).

The hydroliquefaction oil yields of Yatagan lignite obtained with creosote oil were higher than those obtained in anthracene ail. On Further work done with Yatagan lignite, creosote oil was chosen as solvent. First, the effects of CoMo and red mud catalysts, then in catalyzed medium, the effects of moisture in lignite samples and at last, using moist lignite samples and red mud catalyst. the effects o f carbon monaxide/hydrogen in synthesis gas medium and also, the increase in the oil yield a s an effect of catalyst presence, increased further: the 3CO/lH, ratio in gas medium was suitable for obtaining higher oil yields; and also for obtaining high oil yields, 440°c could be taken a s the most suitable temperature value and the pressure should be increased a s much as technical and economical conditions permit.     

SOLVENT REFINING OF WASTE LOCOMOTIVE OIL

The potential of ten solvent in the refining of waste locomotive oil have been examined and evaluated The solvents studied were butanone, methyl-isobutyl ketone (MIBK), methyl normal - propyl ketone (MNPK), methyl ethyl ketone (MEK), butyl alcohol, sec-butyl alcohol, pentanol, hexanol, hexane and n-heptane. The solvents were evaluated on the basis of the percent sludge removal, sludge settling rate, oil recovery (yield) and their physico - chemical properties. The optimum settling time and solvent to waste oil ratio were determined to be 24 hours and 5:1 respectively. On the basis of sludge removal potential butyl alcohol ranks first followed by sec-butyl alcohol, butanone, pentanol, hexanol, MEK, MNPK, MIBK, hexane and n-heptane in that order. All the solvents gave very high yields of the refined oils. The physico-chemical properties of the re-refined oils are within acceptable limits. Generally, the properties remained approximately constant regardless of the solvent used for extraction.     

DISSOLUTION OF COALS NEAR CRITICAL CONDITIONS

Two lignites and one bituminous coal were extracted with benzene, toluene and pyridine at both sub and overcritical conditions in a specially designed experimental system which enabled easy solid-liquid separation. Extract yields increased somewhat at overcritical conditions due to more thermal decomposition. The differences between the power of the solvents were not apparent for the lignites, whereas the solubility in pyridine of the bituminous coal was very much higher than those in benzene and toluene. The amounts of oils, asphaltenes and preasphaltenes in the extracts depended on the type of coal and the solvent.     

吸附富集裂解原料中的正构烷烃蒸汽裂解制乙烯效果研究

研究了直馏石脑油、加氢焦化石脑油和天然气凝析油三种裂解制乙烯原料及其通过分子筛吸附分离后相应的富含正构烷烃脱附油的裂解乙烯收率,并考察了裂解反应条件对不同裂解原料的裂解性能的影响。在工业装置典型操作条件下,直馏石脑油及其吸附分离吸余油和脱附油的乙烯收率分别为29.9%,23.0%,41.1%,脱附油的乙烯收率比直馏石脑油增加11.2个百分点,脱附油的三烯总收率比石脑油增加8.6个百分点;对于加氢焦化石脑油和凝析油,其相应脱附油的裂解乙烯收率分别提高11.1和6.5个百分点。石脑油和脱附油裂解乙烯收率和丁二烯收率均随裂解出口温度的升高而增加,丙烯收率基本不随裂解出口温度的变化而改变。     

脱沥青油及其糠醛抽余油的催化裂化性能研究

采用提升管催化裂化装置,考察脱沥青油（DAO）以及抽提条件分别为剂油质量比2:1、抽提温度80℃;剂油质量比2:1、抽提温度85℃两种工况下对DAO进行糠醛抽提所得到的抽余油A与B等三种催化裂化原料的裂化性能。实验结果表明：DAO经过糠醛抽提后所得抽余油的催化裂化转化率较高,轻质油收率较高,重油和焦炭产率较低,其催化裂化性能和裂化产品的性质均优于DAO。     

蜡下油资源在润滑油加氢装置的应用

蜡下油是溶剂脱蜡工艺生产润滑油基础油的副产物,一般用作催化裂化原料。文章介绍了如何通过在润滑油加氢装置原料中掺入一定比例的蜡下油,来优化原料性质、提高产品质量,并重点对基础油质量、收率的变化及装置能耗等的影响进行了分析。结果表明:通过对掺炼量、反应温度等操作条件的调整,生产出了高品质的APIⅢ类基础油产品。     

炼油厂重质馏分油作蒸汽裂解装置原料的研究

应用小型蒸汽裂解模拟试验装置对加氢尾油、常二线油、常三线油、减一线油、减二线油等重质馏分油的裂解性能进行评价，考察水油质量比为0.8时裂解温度对产品收率的影响。结果表明：随着裂解温度的升高，乙烯收率逐渐增大，丙烯收率逐渐减小，双烯（乙烯+丙烯）收率和三烯（乙烯+丙烯+丁二烯）收率先增大后减小，在810 ℃时达到最大；加氢尾油的目的产物（乙烯、丙烯、丁二烯）收率最高，裂解性能最好，常二线油、常三线油次之，减一线油和减二线油最差。     

炼油厂重质馏分油作蒸汽裂解装置原料的研究

应用小型蒸汽裂解模拟试验装置对加氢尾油、常二线油、常三线油、减一线油、减二线油等重质馏分油的裂解性能进行评价,考察水油质量比为0.8时裂解温度对产品收率的影响。结果表明：随着裂解温度的升高,乙烯收率逐渐增大,丙烯收率逐渐减小,双烯（乙烯+丙烯）收率和三烯（乙烯+丙烯+丁二烯）收率先增大后减小,在810 ℃时达到最大;加氢尾油的目的产物（乙烯、丙烯、丁二烯）收率最高,裂解性能最好,常二线油、常三线油次之,减一线油和减二线油最差。     

COAL LIQUEFACTION WITH ANTHRACENE OIL. INFLUENCE OF SOLVENT PRETREATMENT, TEMPERATURE, CATALYST AND PRESSURE

The effect of solvent pretreatment, temperature, a CoMo/Al₂O₃ catalyst and pressure on coal liquefaction with anthracene oil has been evaluated. The experiments were conducted in a 500 ml autoclave with 10 g of a Spanish subbituminous A coal. 30 g of solvent, 1 hour reaction time and 400 rpm stirring speed. The liquefaction products were fractionated into oils, asphaltenes and preasphaltenes using pentane, toluene and THF as extractive solvents. The behaviour of anthracene oil as coal liquefaction solvent is very much enhanced by prehydrogenating it and by the addition ot an active catalyst. The influence of temperature depends on the operating conditions such as solvent pretreatment, catalyst, pressure etc. The addition of an active catalyst greatly improves conversion and the quality of the liquefaction products and diminishes repotimerization reactions. Hydrogen pressure is essential for coal liquefaction with anthracene oil, although over 16 MPa no further increase in coal conversion is observed.     

DISSOLUTION OF COALS NEAR CRITICAL CONDITIONS

ABSTRACT

Two lignites and one bituminous coal were extracted with benzene, toluene and pyridine at both sub and overcritical conditions in a specially designed experimental system which enabled easy solid-liquid separation. Extract yields increased somewhat at overcritical conditions due to more thermal decomposition. The differences between the power of the solvents were not apparent for the lignites, whereas the solubility in pyridine of the bituminous coal was very much higher than those in benzene and toluene. The amounts of oils, asphaltenes and preasphaltenes in the extracts depended on the type of coal and the solvent.     

Optimization of vacuum resid solvent deasphalting to produce bright stock and hard asphalt

To prepare bright stock (BS) and 30# hard asphalt simultaneously, propane solvent deasphalting (SDA) of Oman vacuum residue was optimized. Result showed the optimal process conditions were as follows: extraction tower top temperature of 64°C, settling tower top temperature of 74°C, extraction pressure of 3.35 MPa, solvent ratio of 5. Compared with SDA of Oman VR to prepare bright stock and 70# asphalt, the yields of light deasphalted oil (LDAO) and heavy deasphalted oil (HDAO) were 26.8% and 24.7%, and increased by 1.7% and 5.2% respectively; carbon residue of LDAO was less than 1.2%, conformed to the feed requirement of furfural refining to produce bright stock. The yield of DOA was 48.5%, and DOA could be directly used to produce 30# hard asphalt. The PG grade of 30# asphalt was PG 76–22 and the 30# asphalt mixture had high rut dynamic stability and water resistant stability. HDAO could be used as feedstock of catalytic cracking and light yield oil (gasoline and diesel) was 65.99%.     

COAL LIQUEFACTION WITH ANTHRACENE OIL. INFLUENCE OF SOLVENT PRETREATMENT,TEMPERATURE, CATALYST AND PRESSURE

ABSTRACT

The effect of solvent pretreatment, temperature, a CoMo/Al₂O₃ catalyst and pressure on coal liquefaction with anthracene oil has been evaluated. The experiments were conducted in a 500 ml autoclave with 10 g of a Spanish subbituminous A coal. 30 g of solvent, 1 hour reaction time and 400 rpm stirring speed. The liquefaction products were fractionated into oils, asphaltenes and preasphaltenes using pentane, toluene and THF as extractive solvents. The behaviour of anthracene oil as coal liquefaction solvent is very much enhanced by prehydrogenating it and by the addition ot an active catalyst. The influence of temperature depends on the operating conditions such as solvent pretreatment, catalyst, pressure etc. The addition of an active catalyst greatly improves conversion and the quality of the liquefaction products and diminishes repotimerization reactions. Hydrogen pressure is essential for coal liquefaction with anthracene oil, although over 16 MPa no further increase in coal conversion is observed.     

DIRECT HYDROGENATION OF A SPANISH LOW RANK COAL. THE EFFECT OF PROCESS VARIABLES

The effect of operating conditions on the liquefaction behaviour of a Spanish lignite was studied using a 250 ml stirred autoclave, and the following operating conditions (except otherwise specified): 400 °C, 1 hour, 3.5 MPa initial (cold) H₂ pressure, 400 rpm and 40 g/10 g tetralin/coal charge. The liquefaction products were fractionated into oils, asphaltenes, preasphaltenes and solid residue using pentane, toluene and THF as extractive solvents

The influence of temperature was explored in the 300-475 °C range, observing little further improvement in liquefaction yields over 400 °C, and retrogressive reactions over 450 °C. The effect of time was studied from 0 to 180 minutes and was concluded that 1 hour is an appropriate period for liquefying a black lignite, since there is little further conversion for longer times. The influence of pressure and gas type was studied using 0, 3.5 and 7.0 MPa initial (cold) pressure of H₂ and of N₂, and the effect of stirring using 0 and 400 rpm. Little influence of these variables was observed, which is attributed to the strong H-donor solvent, high solvent/coal ratio and long reaction time used.     

基于三碳醇溶剂精制再生废润滑油

 溶剂精制再生废润滑油具有环保、经济、高效的特点,采用单因素实验方法,以三碳醇(异丙醇、正丙醇)极性溶剂为萃取剂、乙二胺为絮凝剂组合精制再生废润滑油。最佳工艺条件：萃取溶剂异丙醇、精制时间25 min、精制温度40℃、剂/油质量比9、絮凝剂质量分数1.2%。在该精制工艺条件下,再生油的性能指标得到明显改善,黏温指数达130以上、闪点超过210℃、酸值为0.05 mg KOH/g、灰分降至0.01%以下、重金属元素含量显著下降,再生油产率为76.8%,基本上符合HVI150基础油指标,表明该精制工艺再生废润滑油可行,具有广阔的应用前景。