CN100375739C - Process of eliminating and recovering naphthenic acid from oil product - Google Patents
Process of eliminating and recovering naphthenic acid from oil product Download PDFInfo
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- CN100375739C CN100375739C CNB2006100113804A CN200610011380A CN100375739C CN 100375739 C CN100375739 C CN 100375739C CN B2006100113804 A CNB2006100113804 A CN B2006100113804A CN 200610011380 A CN200610011380 A CN 200610011380A CN 100375739 C CN100375739 C CN 100375739C
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- acid
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- imidazole
- naphthenic acid
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Abstract
The present invention relates to a method of eliminating and recovering naphthenic acid from oil products, which selects one kind of similar imidazole derivants or 5 to 60% of alcoholic solution as a deacidifying agent; under the condition with 20 to 90 DEG C, the deacidifying agent reacts and mixes with oil products according to 1/1 to 1/15 catalyst-oil ratio. The naphthenic acid in the oil product reacts with similar imidazole derivants to generate ionic liquid; after the reaction is over, the oil product phase with reduced acid value and the ionic liquid phase are fast and effectively separated by utilizing the characteristic that the ionic liquid has great differences with the oil product. The formed ionic liquid can be decomposed by adopting a heating method or adding a small amount of volatile acid, and the deacidifying agent and the naphthenic acid can be recovered with high efficiency. The present invention has the advantages of more than 85% of deacidifying rate, no large amounts of water introduction, no emulsification problem, high solvent recovery rate and continuous operation.
Description
Invention field: the present invention relates to removing and reclaiming of naphthenic acid in the petrochemical industry oil product.
Background of invention:
Naphthenic acid is a kind of mixture of carboxylic acids that has five yuan or six-ring, and its molecular weight is many between 200～700, is a kind of more difficult evaporable thick liquid.The existence of naphthenic acid has caused the refining of distillate and processing and has seriously influenced, as: when the oil product acid number surpassed 2mg/g, rectifiying plate, interchanger and pipeline had the danger of the perforation of being corroded at any time, and made the increase of unplanned shutdown number of times, and production efficiency is low; Make distillate refining and following process complexity, the following process catalyst life is too short.Therefore, in the course of processing, naphthenic acid removed and be very important.On the other hand, naphthenic acid is an important chemical material, has many uses, and is worth very high.The cobalt of naphthenic acid, manganese, calcium, iron, barium, magnesium salts and cycloalkanes acid esters all are the great Chemicals of economic implications.China's oil product output surpasses hundred million tons, and wherein contained naphthenic acid is above 200,000 tons.But China's naphthenic acid output has only 0.6～0.8 ten thousand ton, and 97% naphthenic acid resource loss is not recycled.Therefore, the recovery of naphthenic acid also is vital.
The removing process of naphthenic acid mainly contains at present: caustic washing electric refining acid neutralisation, hydrofining method, ammonia alcohol method etc.These technologies all exist certain shortcoming and limitation, as: adopt the emulsification of caustic washing electric refining acid neutralisation serious, generate a large amount of alkaline residues, naphthenic acid reclaims difficulty; Adopt hydrofining method severe reaction conditions, life of catalyst is very short, and naphthenic acid can not become product, the cost height; Adopt the emulsification of ammonia alcohol method serious, need emulsion splitter, influential to oil quality, and water to carry the oil product loss secretly big etc.Therefore develop a kind of mild condition, lower, the eco-friendly oil product depickling of cost novel environment-friendly process is very necessary.
Summary of the invention
The objective of the invention is to develop a kind of mild condition, can effective elimination again can the high efficiente callback naphthenic acid, and all kinds of SOLVENTS can both obtain the novel environment-friendly process of recycle.
Concrete grammar of the present invention is: choose N-Methylimidazole, glyoxal ethyline, 4-methylimidazole, 1, the mixture of one or more in 2-methylimidazole, N-ethyl imidazol(e), 2-ethyl imidazol(e), N-propyl imidazole, 2-propyl imidazole, N-isopropylimdazole, 2 isopropyl imidazole, 1-vinyl imidazole, N-butyl imidazole, benzoglyoxaline, the 1-acetyl imidazole, separately or be made into one or several the alcoholic solution of mixture in 5%～60% methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol as de-acidying agent.According to agent-oil ratio is 1: 1～1: 15, following at 20～90 ℃ with crude oil or by the various distillate hybrid reactions normal, that underpressure distillation obtains, naphthenic acid in the oil product just can generate ionic liquid with imidazole derivative generation neutralization reaction, wherein ion liquid positively charged ion is the formed imidazole ring positively charged ion of imdazole derivatives, and negatively charged ion is the formed carboxylate anion of naphthenic acid.Reaction utilizes ionic liquid and the big characteristics of oil product polarity difference after finishing, and realizes the oil product phase of acid number reduction and rapidly and efficiently separating of ionic liquid phase.The ionic liquid that forms can adopt and be heated to 80～230 ℃ or the method that adds volatile acids such as small amount of hydrochloric acid, hydrofluoric acid, nitric acid, formic acid, acetate and decomposed, thereby de-acidying agent and naphthenic acid can be reclaimed expeditiously.This method acid removal rate can reach more than 85%, has avoided the introducing of big water gaging, does not have emulsification problem; And the solvent recovering yield height, cyclical operation continuously.
Embodiment:
The present invention illustrates with following example, but the present invention is not limited to following embodiment, under the scope of described aim, changes and implements to be included in the technical scope of the present invention before and after not breaking away from.
Embodiment 1
Get certain refinery second line of distillation distillate, its acid number is 2.37mgKOH/g, and de-acidying agent adopts the N-Methylimidazole.By agent-oil ratio is mixing in 1: 5,60 ℃ of following thorough mixing reactions.After reaction finished, insulation was left standstill under 60 ℃.Oil product after the depickling and the ionic liquid layering of reacting the back generation.Recording its acid number is 0.21mgKOH/g, and acid removal rate is 91.1%.The ionic liquid of lower floor is added to 2mol/LHCl, and naphthenic acid is just separated out mutually from ionic liquid.Leave standstill the back and separate, naphthenic acid is made with extra care, and the heating ionic liquid is then recyclable N-Methylimidazole and HC1 (absorbing with water) mutually.N-Methylimidazole and HCl be recycle in addition.
Embodiment 2
Get certain refinery and subtract three-way distillate, its acid number is 2.93mgKOH/g, and the 2-ethyl imidazol(e) is made into 30% ethanolic soln as de-acidying agent under 55 ℃.By agent-oil ratio is 1: 1, abundant stirring reaction under 70 ℃.After reaction finished, insulation was left standstill under 60 ℃.The upper strata is the oil product after the depickling, and recording its acid number is 0.39mgKOH/g, and acid removal rate is 86.7%.Lower floor's solution heating also keeps 80 ℃, reclaims used ethanol.Continue to be warmed up to 230 ℃, naphthenic acid is just separated out from lower floor's solution.Separate while hot after leaving standstill, naphthenic acid is made with extra care.The recycle in addition of 2-ethyl imidazol(e).
Embodiment 3
The ketone benzene of getting certain refinery second line of distillation takes off cured oil, and its acid number is 0.47mgKOH/g, and de-acidying agent adopts the N-Methylimidazole.By agent-oil ratio is 1: 6,50 ℃ of reactions down.Reaction is left standstill after finishing.Oil product after the depickling and the ionic liquid layering mutually of reacting the back generation, recording its acid number is 0.05mgKOH/g, acid removal rate is 89.4%.The ionic liquid of lower floor is added to 1mol/LHNO
3, naphthenic acid is just separated out mutually from ionic liquid.Leave standstill the back and separate, naphthenic acid is made with extra care, and the heating ionic liquid is then recyclable N-Methylimidazole and HNO mutually
3(absorbing) with water.N-Methylimidazole and HCl be recycle in addition.
Embodiment 4
Get certain refinery and subtract three-way benzol-kentone dewaxing oil, its acid number is 0.64mgKOH/g, and the N-propyl imidazole is made into 40% butanol solution as de-acidying agent.By agent-oil ratio is 1: 2,85 ℃ of reactions down.Reaction is left standstill under 85 ℃ after finishing.The upper strata is the oil product after the depickling, and recording its acid number is 0.05mgKOH/g, and acid removal rate is 92.2%.Lower floor's solution heating also keeps 165 ℃, reclaims used propyl carbinol.Keep 165 ℃ and underpressure distillation, reclaim N-propyl imidazole and naphthenic acid respectively.
Embodiment 5
Get certain refinery and subtract four line benzol-kentone dewaxing oil, its acid number is 0.79mgKOH/g, and de-acidying agent adopts 2-ethyl-4-methylimidazole.By agent-oil ratio is 1: 10,80 ℃ of reactions down.Reaction is left standstill under the room temperature after finishing.The upper strata is the oil product after the depickling, and recording acid number is 0.11mgKOH/g, and acid removal rate is 86.1%.The ionic liquid of lower floor is added to 2mol/LCH
3COOH, naphthenic acid just separate out mutually from ionic liquid.Leave standstill the back and separate, naphthenic acid is made with extra care, and the heating ionic liquid is then recyclable 2-ethyl-4-methylimidazole and CH mutually
3COOH (absorbing) with water.2-ethyl-4-methylimidazole and CH
3COOH is recycle in addition.
Claims (9)
1. method that from oil product, removes and reclaim naphthenic acid, it is characterized in that choosing a kind of or alcoholic solution and the reaction of the naphthenic acid in the oil product in the imidazole derivative, after reaction finishes, because polarity difference is bigger, oil phase and ionic liquid that layering is good are separated, the ionic liquid that obtains oil product that acid number reduces and reaction generation mutually, add volatile acid to ionic liquid in mutually, naphthenic acid is separated mutually from ionic liquid, by heating, reclaim imdazole derivatives or its alcoholic solution and volatile acid respectively again.
2. method according to claim 1, wherein the temperature range of imdazole derivatives or its alcoholic solution and oil product hybrid reaction is 20～90 ℃.
3. method according to claim 1, wherein imdazole derivatives or its alcoholic solution are 1: 1～1: 15 with the oil volume ratio.
4. according to one of them described method of claim 1～3, wherein imdazole derivatives is selected from N-Methylimidazole, glyoxal ethyline, 4-methylimidazole, 1,2-methylimidazole, N-ethyl imidazol(e), 2-ethyl imidazol(e), N-propyl imidazole, 2-propyl imidazole, N-isopropylimdazole, 2 isopropyl imidazole, 1-vinyl imidazole, N-butyl imidazole, benzoglyoxaline, 1-acetyl imidazole, alcohol is selected from methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, and alcoholic solution is 5%～60% a alcoholic solution of imdazole derivatives.
5. according to one of them described method of claim 1～3, wherein oil product is meant crude oil or by the various distillates normal, that underpressure distillation obtains.
6. method according to claim 1, wherein the generation of ionic liquid phase is formed by naphthenic acid generation neutralization reaction in imidazole derivative and the oil product.
7. method according to claim 6, wherein ion liquid positively charged ion are the formed imidazole ring positively charged ion of imdazole derivatives, and negatively charged ion is the formed carboxylate anion of naphthenic acid.
8. method according to claim 1, wherein in order to reclaim naphthenic acid, the volatile acid that adds in mutually to ionic liquid is selected from hydrochloric acid, hydrofluoric acid, nitric acid, formic acid, acetate.
9. method according to claim 1, wherein for reclaim ionic liquid mutually in imdazole derivatives or its alcoholic solution and volatile acid, the method for being taked is with ionic liquid heat phase to 80～230 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100113804A CN100375739C (en) | 2006-02-28 | 2006-02-28 | Process of eliminating and recovering naphthenic acid from oil product |
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| CNB2006100113804A CN100375739C (en) | 2006-02-28 | 2006-02-28 | Process of eliminating and recovering naphthenic acid from oil product |
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| CN1810757A CN1810757A (en) | 2006-08-02 |
| CN100375739C true CN100375739C (en) | 2008-03-19 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100506949C (en) * | 2006-04-18 | 2009-07-01 | 中国海洋石油总公司 | Method of eliminating naphthenic acid from crude oil or fraction oil |
| NO331987B1 (en) * | 2009-06-22 | 2012-05-21 | Statoil Asa | Process for the isolation and quantification of naphthenic acids (ARN acids) in crude oil. |
| CN111548270A (en) * | 2020-05-09 | 2020-08-18 | 上海早苗食品有限公司 | Molecular distillation glycerin monostearate emulsifier and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1123825A (en) * | 1995-09-05 | 1996-06-05 | 新疆石油管理局克拉玛依炼油厂 | Deacidifying process for petroleum cut fraction with amino-alcohol |
| US6627069B2 (en) * | 2000-04-18 | 2003-09-30 | Exxonmobil Research And Engineering Company | Method for reducing the naphthenic acid content of crude oil and its fractions |
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2006
- 2006-02-28 CN CNB2006100113804A patent/CN100375739C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1123825A (en) * | 1995-09-05 | 1996-06-05 | 新疆石油管理局克拉玛依炼油厂 | Deacidifying process for petroleum cut fraction with amino-alcohol |
| US6627069B2 (en) * | 2000-04-18 | 2003-09-30 | Exxonmobil Research And Engineering Company | Method for reducing the naphthenic acid content of crude oil and its fractions |
Non-Patent Citations (1)
| Title |
|---|
| 石油中环烷酸的脱除与精制工艺. 苏联娟等.河南石油，第19卷第1期. 2005 * |
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