纤维膜法分离馏分油中石油酸盐的工艺研究
摘要
本文主要以高酸值的减二线馏分油为研究对象,将馏分油加入过量碱液使其中石油酸完全转变成盐类,采用纤维膜分离与间歇萃取分离工艺分离馏分油中的石油酸盐,以油相与剂相的pH值和含水量为指标考察其分离效果,以油相的pH值和含水量随时间的变化考察其静态沉降效果,计算石油酸盐的脱除率和粗石油酸回收率考察其脱除效果和石油酸回收效果。
研究结果表明:与未稀释的油样相比,稀释的油样在进行纤维膜水洗分离试验时,其石油酸盐脱除率和粗石油酸回收率有明显的提高,油相中的含水量与水相的含油量都有所降低,但是乳化现象严重,油品回收率较低。而使用复合溶剂分离石油酸盐,乳化现象减轻,石油酸盐脱除率和粗石油酸回收率有明显的提高;采用不同复合溶剂比进行纤维膜分离试验,发现提高复合溶剂比有利于石油酸的回收,二级分离比一级分离更有利于降低馏分油的酸值,提高石油酸盐脱除率;不论使用纤维膜水洗分离还是纤维膜复合溶剂分离石油酸盐,其油相的pH值和含水量都随静态沉降时间的延长而降低;纤维膜复合溶剂脱除石油酸盐较合适的工艺条件为:油样稀释比0.3:1、复合溶剂比1:1、剂油比1:1进行两级纤维膜分离;此工艺条件下石油酸盐脱除率可达98.6%,粗石油酸回收率为81.7%。
对浓缩油进行复合溶剂间歇萃取分离石油酸盐试验,确定合适的工艺条件为:浓缩比60%、复合溶剂比1:1、剂油比1:1,在此条件下,石油酸盐脱除率和石油酸的回收率均达到了97%以上,同时在此工艺条件下,进行二次萃取分离,分离后油样酸值降低至0.086mgKOH/g,石油酸盐脱除率达到99.12%。
This paper mainly discussed the deacidification of Suizhong36-1 VGO with high acid number by fibre membrance. Adding superfluous alkali lye into the VGO, the petroleum acid can be changed into naphthenate. After that, the naphthenate can be separated from VGO by means of fibre membrance or intermittent extraction separation. The separation effect can be valued by the pH and water content of the oil phase and solvent phase.The static sedimentation effect can be valued by the pH and water content of the oil phase. And the ratio of removing naphthenate and recycling petroleum acid can value the effect of removing naphthenate and recycling petroleum acid.
The results show that: compared with the non-diluted oil, the ratio of removing naphthenate and recycling petroleum acid in diluted oil was greatly improved with water as extraction agent by fibre membrane. But the emulsification was very serious and the ratio of recycling oil was quite low. However, in the test of separation naphthenate by fibre membrane with multiple solvents as extraction agent, the emulsification was lightened and the ratio of removing naphthenate and recycling petroleum acid was greatly improved. With the improvement of the rate of the multiple solvents, the ratio of recycling petroleum acid also can be improved. Meanwhile, compared with single-stage extraction, the acid number of oil in the couple-stage extraction can be lowered and the ratio of removing acid can be improved. The pH and water content of the oil phase can be decreased according to the static sedimentation time with water or multiple solvents to separate naphthenate by fiber membrane. A better process conditions is dilution ratio 0.3:1, the ratio of multiple solvents1:1, solvent-oil ratio 1:1,at couple-stage extraction, Under this condition, the ratio of removing naphthenate is 98.6% and the ratio of recycling petroleum acid is 81.7%.
According to the test of removing enriched naphthenate with multiple solvents, a better process conditions is concentration factor 60%, the ratio of multiple solvents 1:1, solvent-oil ratio 1:1. Under this condition, the ratio of removing naphthenate and recycling petroleum acid can be both increased to 97%in the single-stage extraction, and under the same condition, the acid number can be lowered to 0.086mgKOH/g and the ratio of removing acid can be increasd to 99.12% in couple-stage extraction.
研究结果表明:与未稀释的油样相比,稀释的油样在进行纤维膜水洗分离试验时,其石油酸盐脱除率和粗石油酸回收率有明显的提高,油相中的含水量与水相的含油量都有所降低,但是乳化现象严重,油品回收率较低。而使用复合溶剂分离石油酸盐,乳化现象减轻,石油酸盐脱除率和粗石油酸回收率有明显的提高;采用不同复合溶剂比进行纤维膜分离试验,发现提高复合溶剂比有利于石油酸的回收,二级分离比一级分离更有利于降低馏分油的酸值,提高石油酸盐脱除率;不论使用纤维膜水洗分离还是纤维膜复合溶剂分离石油酸盐,其油相的pH值和含水量都随静态沉降时间的延长而降低;纤维膜复合溶剂脱除石油酸盐较合适的工艺条件为:油样稀释比0.3:1、复合溶剂比1:1、剂油比1:1进行两级纤维膜分离;此工艺条件下石油酸盐脱除率可达98.6%,粗石油酸回收率为81.7%。
对浓缩油进行复合溶剂间歇萃取分离石油酸盐试验,确定合适的工艺条件为:浓缩比60%、复合溶剂比1:1、剂油比1:1,在此条件下,石油酸盐脱除率和石油酸的回收率均达到了97%以上,同时在此工艺条件下,进行二次萃取分离,分离后油样酸值降低至0.086mgKOH/g,石油酸盐脱除率达到99.12%。
This paper mainly discussed the deacidification of Suizhong36-1 VGO with high acid number by fibre membrance. Adding superfluous alkali lye into the VGO, the petroleum acid can be changed into naphthenate. After that, the naphthenate can be separated from VGO by means of fibre membrance or intermittent extraction separation. The separation effect can be valued by the pH and water content of the oil phase and solvent phase.The static sedimentation effect can be valued by the pH and water content of the oil phase. And the ratio of removing naphthenate and recycling petroleum acid can value the effect of removing naphthenate and recycling petroleum acid.
The results show that: compared with the non-diluted oil, the ratio of removing naphthenate and recycling petroleum acid in diluted oil was greatly improved with water as extraction agent by fibre membrane. But the emulsification was very serious and the ratio of recycling oil was quite low. However, in the test of separation naphthenate by fibre membrane with multiple solvents as extraction agent, the emulsification was lightened and the ratio of removing naphthenate and recycling petroleum acid was greatly improved. With the improvement of the rate of the multiple solvents, the ratio of recycling petroleum acid also can be improved. Meanwhile, compared with single-stage extraction, the acid number of oil in the couple-stage extraction can be lowered and the ratio of removing acid can be improved. The pH and water content of the oil phase can be decreased according to the static sedimentation time with water or multiple solvents to separate naphthenate by fiber membrane. A better process conditions is dilution ratio 0.3:1, the ratio of multiple solvents1:1, solvent-oil ratio 1:1,at couple-stage extraction, Under this condition, the ratio of removing naphthenate is 98.6% and the ratio of recycling petroleum acid is 81.7%.
According to the test of removing enriched naphthenate with multiple solvents, a better process conditions is concentration factor 60%, the ratio of multiple solvents 1:1, solvent-oil ratio 1:1. Under this condition, the ratio of removing naphthenate and recycling petroleum acid can be both increased to 97%in the single-stage extraction, and under the same condition, the acid number can be lowered to 0.086mgKOH/g and the ratio of removing acid can be increasd to 99.12% in couple-stage extraction.
引文
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[15] RichardA.Frank,Richard Kavanagh,B.Kentburnison,etal.Diethylaminoethcellulose clean-up of a large volume naphthenic acid extract[J]. Chemosphere. 2006, (64): 1346-1352
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[18] Aihua Zhang,Qisheng Ma,Kangshi Wang,etal.Naphthenic acid removal from crude oil through catalytic decarboxylation on magnesium oxide [J].Applied CatalysisA. 2006,(303):103-109
[19]王会东,韩志群,王仁安等.加氢处理润滑油基础油光照沉淀的研究[J].石油学报(石油加工),2003,19(3):72-77
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[21] Grande K ,et al.A Process for RemovM Essentially Naphthenie Acids from a Hydrocarbon oil. W 09606899
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[23] Trachte, Angelo etal. Catalytic reduction of acidity of crude oils in the absence of hydrogen[P].US 5871636,1999,2
[24] Trachte,Kenneth L.,Robbins etal.Process for selectively removing lower molecular weight naphthenic acids from acdic crudes[P].US 5897769,1999,4
[25] Lazar A .eta1. Process of Treating Hydrocarbon Oils.USP1953353. l934
[26]申海平,王玉章,李锐.高酸原油热处理脱酸的研究[J].石油炼制与化工,2004,35(2):32-35
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