CN1245160A - Process for separating and recovering naphthenic acid from fractional oil of petroleum - Google Patents
Process for separating and recovering naphthenic acid from fractional oil of petroleum Download PDFInfo
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- CN1245160A CN1245160A CN 98117282 CN98117282A CN1245160A CN 1245160 A CN1245160 A CN 1245160A CN 98117282 CN98117282 CN 98117282 CN 98117282 A CN98117282 A CN 98117282A CN 1245160 A CN1245160 A CN 1245160A
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- naphthenic acid
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Abstract
A process for separating and recovering naphthenic acid from fractional oil of petroleum includes preparing the deacidifying solvent with 5-45% of aalcohol concentration and 1-8 wt.% of sodium hydroxide concentration from the mixture of one or two or more of those chosen from C1-C3 alphatic alcohols, sodium hydroxide and water, mixing it with said fractional oil at 20-90 deg.c, laying asie, separating oil phase from water phase, and recovering naphthenic acid. Its advantages are high deacidifying rate up to over 95 wt.%, high purity of naphthenic acid up to over 90 wt.%, and no colour change of deacidified oil on the whole.
Description
The invention belongs to the method for hydrocarbon oil refining, exactly, is the method for separating, reclaim naphthenic acid from fraction oil of petroleum.
Contain a considerable amount of naphthenic acid in oil and the distillate thereof, the existence of naphthenic acid is unfavorable for the processing of oil, also influences the use properties of product, thereby need remove.But then, naphthenic acid has important use and is worth, thereby needs to reclaim.The quality of naphthenic acid and grade depend primarily on the purity of naphthenic acid, and for example, the purity of No. 85 acid of China's regulation is not less than 85 weight %, and the purity of No. 55 acid is not less than 55 weight %.Purity is high more, and quality is good more, and price is high more.
At present, mainly adopt aqueous sodium hydroxide washes to wash the depickling that distillate is realized distillate, make oil-soluble naphthenic acid be converted into water miscible sodium napthionate and enter water, again aqueous phase as acidified is obtained naphthenic acid.Because sodium napthionate has stronger surfactivity, usually cause the emulsification of oil and water in the fraction oil of petroleum alkaline cleaning procedure, the water that obtains is muddy attitude (the industrial alkaline residue that is commonly called as), when emulsification is serious even cause oil phase and water to be difficult to separate.The existence of big gauging not only influences the yield of depickling oil product in the alkaline residue, also can cause the reduction of reclaiming naphthenic acid purity.In addition, even eliminated emulsification fully, because sodium napthionate has the intensive solublization to distillate, aqueous phase still is dissolved with the appreciable distillate of quantity.Adopt traditional aqueous sodium hydroxide solution alkali cleaning acid stripping method, although the acid removal rate of stock oil can reach more than the 95 weight %, because the existence of emulsification and solubilising phenomenon is reclaimed the purity of naphthenic acid and had only 50～60 heavy % usually from alkaline residue.
At the existing many methods of the improvement of traditional aqueous sodium hydroxide solution alkali cleaning depickling technology.Adopt the method that in sodium hydroxide lye, adds an amount of inorganic salt as CN1047882, can suppress the emulsification problem in the alkali cleaning deacidification to a certain extent, but this method does not fully take into account the solublization of sodium napthionate to distillate, and is difficult to fundamentally eliminate emulsification problem.
US4634519 is with the naphthenic acid in the mixed-solvent extraction fraction oil of petroleum of methyl alcohol, ammonia, water, and acid removal rate can reach 95 heavy %.But this method is separated the time long, reclaim naphthenic acid purity and can only reach 85 heavy %, and, depickling oil color is obviously deepened owing to added ammoniacal liquor.
CN1070182 improves US4636519, naphthenic acid in the mixed-solvent extraction heavy distillate of employing ethanol, ammonia, water, acid removal rate also reaches about 95 heavy %, reclaiming naphthenic acid purity can reach about 80 heavy %, accelerated phase separation speed, but the purity of the acid removal rate of distillate and recovery naphthenic acid is subjected to the effects of operation conditions such as composition of temperature and depickling solvent bigger, and still has the problem of depickling oil color burn.
The object of the present invention is to provide a kind of method of separating from fraction oil of petroleum, reclaiming naphthenic acid, this method not only can improve the purity that reclaims naphthenic acid, and acid removal rate and recovery naphthenic acid purity influences not quite by operational condition, and the oily color of depickling is constant substantially.
The method of separation provided by the invention, recovery naphthenic acid is with C
1～C
3It is 5～45% that two or more mixture, sodium hydroxide and water of a kind of in the Fatty Alcohol(C12-C14 and C12-C18) or its is made into determining alcohol, naoh concentration is the depickling solvent of 1～8 heavy %, under 20～90 ℃ the depickling solvent is mixed with distillate, leaves standstill, separate oil phase and water then, reclaim naphthenic acid.
Specifically, separation provided by the invention, recovery method can be implemented as follows: with C
1～C
3Fatty Alcohol(C12-C14 and C12-C18), as methyl alcohol, ethanol, Virahol, propyl alcohol, or their mixture is dissolved in the aqueous sodium hydroxide solution, being made into determining alcohol is 5～45%, preferred 10～35 heavy %, naoh concentration is 1～8 heavy %, the depickling solvent of preferred 1.5～5 heavy %, at 20～90 ℃, under preferred 30～70 ℃ of temperature, press sodium hydroxide to naphthenic acid in the distillate stoichiometric 98～120%, preferred 100～105%, above-mentioned depickling solvent is mixed with the distillate for the treatment of depickling, leave standstill sedimentation layering in 1～10 minute, obtain as clear as crystal oil phase and water, separate two-phase, with water be heated to alcohol boiling point more than 10～20 ℃, after reclaiming alcohols, at stoichiometric industrial sulphuric acids such as aqueous phase adding and above-mentioned sodium hydroxide, Separation and Recovery upper strata naphthenic acid.According to specification of quality to depickling oil, also can distill recovery to little fat alcohol residual in the oil phase, recycle with the alcohols merging of reclaiming from aqueous phase.
The method of from fraction oil of petroleum, separating, reclaiming naphthenic acid provided by the invention, owing to eliminated emulsification and solubilising phenomenon, the acid removal rate of distillate is reached more than the 95 heavy %, the purity that reclaims naphthenic acid reaches more than the 90 heavy %, and the purity of the acid removal rate of distillate and recovery naphthenic acid is subjected to effects of operation conditions little.Owing to do not add ammoniacal liquor, the color of depickling oil is unaffected substantially in addition.
The invention will be further described below by embodiment.Example 1
In 100 gram concentration is to add 22 gram methyl alcohol in 1.8% the sodium hydroxide solution, being made into naoh concentration is 1.5 heavy %, and determining alcohol is the depickling solvent of 18 heavy %, gets this depickling solvent 7.2ml and joins in the diesel oil distillate oil of the 100ml Liaohe River, mixed 2 minutes down at 40 ℃, standing sedimentation is 2 minutes then, tells water, is heated to 90 ℃, steam methyl alcohol, adding 0.15 gram concentration at aqueous phase is 98% industrial sulphuric acid, and branch vibration layer reclaims the upper strata naphthenic acid.
Adopt the ASTMD2887 method to measure the stock oil boiling range, stock oil character sees Table 1.
Adopt the GB264 method to measure the acid number of depickling oil, acid removal rate=(1-depickling oleic acid value) * 100%.
Adopt the SH/T0092-91 method to measure and reclaim thick acid number of naphthenic acid and purity, naphthenic acid purity=(reclaiming the pure acid number of the thick acid number/naphthenic acid of naphthenic acid) * 100, separating resulting sees Table 2.Example 2
In 100 gram concentration is to add 11 gram ethanol in 3.2% the sodium hydroxide solution, being made into naoh concentration is 2.8 heavy %, and determining alcohol is the depickling solvent of 10 heavy %, gets this depickling solvent 3.9ml and joins in the diesel oil distillate oil of the 100ml Liaohe River, mixed 2 minutes down at 55 ℃, standing sedimentation is 4 minutes then, tells pure water, is heated to 95 ℃, steam ethanol, adding 0.15 gram concentration at aqueous phase is 98% industrial sulphuric acid, and branch vibration layer reclaims the upper strata naphthenic acid.Separating resulting sees Table 2.Example 3
In 100 gram concentration is to add 8 gram ethanol and 8 gram Virahols in 1.9% the sodium hydroxide solution, being made into naoh concentration is 1.6%, and ethanol and isopropyl alcohol concentration are the depickling solvent of 7 heavy %, gets this depickling solvent 8.4ml and joins in normal two distillates of 100ml crow petrochemical industry, mixed 2 minutes down at 70 ℃, standing sedimentation is 7 minutes then, tells pure water, is heated to 95 ℃, steam alcohols, adding 0.2 gram concentration at aqueous phase is 98% industrial sulphuric acid, and branch vibration layer reclaims the upper strata naphthenic acid.Separating resulting sees Table 2.Example 4
In 100 gram concentration is to add 42 gram Virahols in 4.4% the sodium hydroxide solution, being made into naoh concentration is 3.1 heavy %, and determining alcohol is the depickling solvent of 30 heavy %, gets this depickling solvent 4.4ml and joins in normal two distillates of 100ml crow petrochemical industry, mixed 2 minutes down at 60 ℃, standing sedimentation is 4 minutes then, tells pure water, is heated to 95 ℃, steam Virahol, adding 0.18 gram concentration at aqueous phase is 98% industrial sulphuric acid, and branch vibration layer reclaims the upper strata naphthenic acid.Separating resulting sees Table 2.Example 5
In 100 gram concentration is to add 25 gram ethanol in 1.9% the sodium hydroxide solution, being made into naoh concentration is 1.5 heavy %, and determining alcohol is the depickling solvent of 20 heavy %, gets this depickling solvent 21ml and joins in normal three distillates of 100ml gram refining, mixed 2 minutes down at 70 ℃, standing sedimentation is 6 minutes then, tells pure water, is heated to 95 ℃, steam ethanol, adding 0.42 gram concentration at aqueous phase is 98% industrial sulphuric acid, and branch vibration layer reclaims the upper strata naphthenic acid.Separating resulting sees Table 2.Example 6
In 100 gram concentration is to add 50 gram ethanol in 5.1% the sodium hydroxide solution, being made into naoh concentration is 3.4 heavy %, determining alcohol is the depickling solvent of 33 heavy %, get this depickling solvent 9.3ml and join in normal three distillates of 100ml gram refining, mixed 2 minutes down at 55 ℃, standing sedimentation is 4 minutes then, tell pure water, adding 0.42 gram concentration at pure aqueous phase is 98% industrial sulphuric acid, and branch vibration layer reclaims the upper strata naphthenic acid.Separating resulting sees Table 2.
Table 1
| The stock oil source | Liaohe River diesel oil distillate oil | Normal two distillates of crow petrochemical industry | Normal three distillates of gram refining |
| Stock oil boiling range (10%～90%), ℃ | 270～340 | 275～362 | 270～351 |
| The stock oil acid number, mgKOHg -1 | 1.62 | 2.12 | 4.65 |
| Stock oil density, mgm -3 | 901.9 | 850.0 | 884.8 |
| The pure acid number of naphthenic acid, mgKOHg -1 | 212.0 | 177.1 | 190.1 |
Table 2
| Example | 1 | 2 | 3 | 4 | 5 | 6 |
| Depickling oleic acid value, mgKOHg -1 | 0.06 | 0.05 | 0.09 | 0.1 | 0.15 | 0.13 |
| Acid removal rate, weight % | 95.5 | 96.9 | 95.8 | 95.3 | 96.8 | 97.2 |
| Reclaim the thick acid number of naphthenic acid, mgKOHg -1 | 202.5 | 195.2 | 156.4 | 161.2 | 174.0 | 169.0 |
| Reclaim naphthenic acid purity, weight % | 95.5 | 94.6 | 91.3 | 92.2 | 91.5 | 90.9 |
Claims (6)
1. the method for separating from fraction oil of petroleum, reclaiming naphthenic acid is characterized in that, will be selected from C
1～C
3It is 5～45 heavy % that two or more mixture, sodium hydroxide and water of a kind of in the Fatty Alcohol(C12-C14 and C12-C18) or its is made into determining alcohol, naoh concentration is the depickling solvent of 1～8 heavy %, under 20～90 ℃ the depickling solvent is mixed with distillate, leaves standstill, separate oil phase and water, reclaim naphthenic acid.
2. according to the described separation of claim 1, recovery method, it is characterized in that determining alcohol is 10～35 heavy % in the depickling solvent.
3. according to the described separation of claim 1, recovery method, it is characterized in that naoh concentration is 1.5～5 heavy % in the depickling solvent.
4. according to the described separation of claim 1, recovery method, it is characterized in that the depickling temperature is 35～70 ℃.
5. according to the described separation of claim 1, recovery method, it is characterized in that naphthenic acid in the distillate stoichiometric 98～120% being mixed the depickling solvent with distillate by sodium hydroxide.
6. according to claim 1 or 5 described separation, recovery method, it is characterized in that naphthenic acid in the distillate stoichiometric 100～105% being mixed the depickling solvent with distillate by sodium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98117282A CN1072641C (en) | 1998-08-14 | 1998-08-14 | Process for separating and recovering naphthenic acid from fractional oil of petroleum |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98117282A CN1072641C (en) | 1998-08-14 | 1998-08-14 | Process for separating and recovering naphthenic acid from fractional oil of petroleum |
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| CN1245160A true CN1245160A (en) | 2000-02-23 |
| CN1072641C CN1072641C (en) | 2001-10-10 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1200538A4 (en) * | 1999-05-11 | 2003-04-16 | Exxonmobil Res & Eng Co | Process for treatment of petroleum acids |
| CN101058745B (en) * | 2007-05-16 | 2011-09-07 | 中国科学院过程工程研究所 | Removal and recovery of naphthenic acid in oil based on ion switch principle |
| CN103265972A (en) * | 2013-05-20 | 2013-08-28 | 宁波市蓝润石化有限公司 | Deep refining process of asphalt-based non-standard base oil |
| CN105368574A (en) * | 2014-08-13 | 2016-03-02 | 石家庄搏澳增塑材料科技有限公司 | Deacidifying agent decreasing acid value of liquid organic mixtures and preparation technology |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3806437A (en) * | 1973-03-22 | 1974-04-23 | Petrolite Corp | Treatment of petroleum distillates containing naphthenic acids |
| CN1019129B (en) * | 1990-07-27 | 1992-11-18 | 中国石油化工总公司武汉石油化工厂 | Inhibiting emulsification in alkali wash process of straight-run oils by adding additives |
| CN1032060C (en) * | 1992-09-25 | 1996-06-19 | 新疆石油管理局重油加工研究所 | Method for separating naphthenic acid from heavy lubricating oil fraction |
| CN1032749C (en) * | 1993-02-26 | 1996-09-11 | 中国石化广州石油化工总厂 | Oil-removing purifying of crude naphthenic acid by amination |
-
1998
- 1998-08-14 CN CN98117282A patent/CN1072641C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1200538A4 (en) * | 1999-05-11 | 2003-04-16 | Exxonmobil Res & Eng Co | Process for treatment of petroleum acids |
| US6767452B1 (en) | 1999-05-11 | 2004-07-27 | Exxonmobil Research And Engineering Company | Process for treatment of petroleum acids |
| CN101058745B (en) * | 2007-05-16 | 2011-09-07 | 中国科学院过程工程研究所 | Removal and recovery of naphthenic acid in oil based on ion switch principle |
| CN103265972A (en) * | 2013-05-20 | 2013-08-28 | 宁波市蓝润石化有限公司 | Deep refining process of asphalt-based non-standard base oil |
| CN105368574A (en) * | 2014-08-13 | 2016-03-02 | 石家庄搏澳增塑材料科技有限公司 | Deacidifying agent decreasing acid value of liquid organic mixtures and preparation technology |
| CN105368574B (en) * | 2014-08-13 | 2020-04-07 | 石家庄搏澳增塑材料科技有限公司 | Method for reducing acid value of liquid organic mixture |
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| Publication number | Publication date |
|---|---|
| CN1072641C (en) | 2001-10-10 |
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Granted publication date: 20011010 |