CN101665716B - Composite deacidification agent and method for recovering naphthenic acid from oil - Google Patents
Composite deacidification agent and method for recovering naphthenic acid from oil Download PDFInfo
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- CN101665716B CN101665716B CN 200910272193 CN200910272193A CN101665716B CN 101665716 B CN101665716 B CN 101665716B CN 200910272193 CN200910272193 CN 200910272193 CN 200910272193 A CN200910272193 A CN 200910272193A CN 101665716 B CN101665716 B CN 101665716B
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- naphthenic acid
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Abstract
The invention relates to a composite deacidification agent and a method for recovering a naphthenic acid from oil. The composite deacidification agent is formed by the mixing of cyclohexylamine dissolving in organic alcohol, wherein the weight percentage of the cyclohexylamine is 0.1wt percent to 50wt percent. By adding the composite deacidification agent to the oil, the naphthenic acid can be effectively separated. Compared with the prior art, the method has good naphthenic acid removal effect with the acid removal rate of up to 80 percent, does not have emulsification problem nor secondary pollution as no water is introduced in the whole reaction, has simple operation and mild condition in the whole technological process, leads the deacidification agent to be capable of being recycled, can efficiently recover the naphthenic acid, and has broad application prospect.
Description
Technical field
The present invention relates to a kind of oil product depickling treatment agent and acid stripping method, specifically a kind of composite deacidifying agent reaches the method that reclaims naphthenic acid from oil product.
Technical background
Generally contain the organic acids such as naphthenic acid in the crude oil.The crude oil of total acid value (acid number be in and the milligram number of the required potassium hydroxide of 1g oil sample) greater than 1 is commonly referred to high-acid crude oil.At present, the output of high-acid crude oil accounts for about 5% of global crude oil ultimate production every year on world's Crude Oil Market, and with 0.3% speed increment, the acid number of crude oil in China is improving constantly, and the kind of acid-containing raw oil and quantity are also in rising trend.In general, will in 210～420 ℃ of temperature ranges naphthenic acid corrosion appear when crude oil neutralization value or total acid value surpass 0.5.And when rate of flow of fluid height or fluid impact equipment surface, such as transfer line, return bend and confined area etc., all can cause the heavy corrosion at these positions.Simultaneously, naphthenic acid is important industrial chemicals, and purposes is wide, value is high.The cobalt of naphthenic acid, manganese, calcium, iron, barium and magnesium salts also can be widely used in the fields such as paint drier, plant growth substances, sanitas, catalyzer and petroleum additive.Naphthenic acid esters can be used as the softening agent of plastics and rubber, the fatting agent in the leather processing industry etc.
At present, the technology that removes of naphthenic acid mainly contains two kinds of methods in the oil product: destructiveness removes the method and the method for separating and recycle naphthenic acid of naphthenic acid.The method that destructiveness removes naphthenic acid comprises: hydrogenation deacidification, non-hydrogen catalytic deacidification, non-hydrogen pyrolysis depickling.Oil product depickling route, the especially hydrogenation deacidification of these class methods, effect is best, but the price of catalyst system therefor, hydrogen is higher, and operation and investment cost are also very high, and valuable naphthenic acid resource is destroyed.
The method of separation and recycling naphthenic acid comprises from oil product: acid-base neutralisation method, ammonia alcohol method, adsorption method of separation, complexing abstraction, membrane separation process, solvent oil formulation etc.These class methods are low for the removal efficiency of naphthenic acid, and energy consumption is higher, and exist emulsification serious, have the problem of secondary pollution.For a long time, remove naphthenic acid and mainly contain two kinds of methods from crude oil, a kind of is solvent-extracted method, employing adds the organic bases solution depicklings such as thanomin in crude oil, then acidifying extracts with low boiler cut, removal effect is bad, is difficult to large-scale industrial production.Another kind method is for destroying the organic acid in the crude oil by the way of thermolysis.US Patent No. 5891325 discloses a kind of organic acid processing method of destroying under the sufficient temp condition, the shortcoming of this method is higher for the temperature that needs, and energy consumption is high and cause easily and the decomposition of other components in the crude oil lose utility value after naphthenic acid is destroyed.
From diesel oil and light ends oil, remove at present the existing many processing methodes of sour composition, for example US4752381 proposed a kind of in and in oil and the petroleum fractions organic acid to obtain neutralization value less than 1.0 method; The method comprises: process petroleum fractions with monoethanolamine, heat at a certain temperature the sufficiently long time to form acid amides.These amine can not obtain simple naphthenic acid product as the present invention.US4634519 discloses with methyl alcohol-ammoniacal liquor double solvents and has removed the method for the sour composition in the distillate.Because solvent for use lacks security, and the final step in deacidification, be white emulsion to occur in the useless double solvents process of heating recovery, make the yield of petroleum acid be lower than 50%, this mainly is because after failing to resolve the petroleum acid ammonium salt and decomposing due to the problem of emulsification.
Chinese patent ZL 01135182.9 discloses with the aqueous solution of sodium hydroxide and relevant auxiliary agent and has carried out depickling, and emulsification is serious; Although neutralized naphthenic acid, most of sodium napthionate is still in crude oil.Chinese patent CN1847366A discloses the method with the ionic liquid depickling, but the method is complicated, and the depickling time is long.Chinese patent CN101134907A discloses and has used ammonia to be dissolved in the method for carrying out the reaction, extraction depickling in the alcohol, wherein the dissolving of ammonia needs high-tension apparatus, simultaneously, the organic ammonium salt that remains in the crude oil can cause the incrustation of crude oil atmospheric vacuum distillation equipment and affect technological process; In addition, not high for its acid removal rate of oil product of high acid value, because the solubleness of ammonia in alcoholic solvent is difficult to improve.
Summary of the invention
Purpose of the present invention is exactly the defective that removes naphthenic acid technology in the oil product for existing, and a kind of composite deacidifying agent reaches the method that reclaims naphthenic acid from oil product.The method mild condition can efficiently remove naphthenic acid in the oil product, improves oil quality, can guarantee that again de-acidying agent is able to recycle.
Technical scheme of the present invention is achieved in that it is dissolved in the Organic Alcohol by hexahydroaniline and mixes that wherein the weight percentage of hexahydroaniline is 0.1wt%-50wt%.
The present invention preferably technical scheme is: described Organic Alcohol is C
1-C
3Organic Alcohol.
The better technical scheme of the present invention is: described organic solvent is selected from one or more in methyl alcohol, ethanol, ethylene glycol, propyl alcohol, 1,3-PD or the glycerol.
A kind of method that from oil product, removes naphthenic acid, it may further comprise the steps:
(1), hexahydroaniline be dissolved in be mixed into composite deacidifying agent in the Organic Alcohol, wherein the weight percentage of hexahydroaniline is 0.1wt%-50wt%.
(2), in sour oil product, add composite deacidifying agent, fully leave standstill after the hybrid reaction, obtain the two-phase of layering, the oil product phase that acid number reduces and the organic solvent of naphthenic acid enrichment are mutually.
(3), separate two-phase and namely from oil product, removed naphthenic acid.
Reasonable technical scheme be also be included in-pressure condition of 0.09～0MPa under, distillation organic solvent phase is distilled out of composite deacidifying agent under 150～230 ℃ the temperature condition, separates obtaining naphthenic acid and composite deacidifying agent.
Wherein said organic solvent is selected from one or more in methyl alcohol, ethanol, ethylene glycol, propyl alcohol, 1,3-PD or the glycerol.The volumetric usage of described composite deacidifying agent is 3%～50% of oil volume.The temperature of hybrid reaction is-10 to 95 ℃, and the reaction times is 5-50 minute.
The present invention forms a kind of well behaved composite deacidifying agent by the suitable organic solvent of screening with hexahydroaniline.Compared with prior art, the present invention removes the effective of naphthenic acid, and acid removal rate can reach more than 80%; Owing in whole reaction, do not introduce water, there is not emulsification problem, there is not secondary pollution; Simple to operate, the mild condition of whole technical process, de-acidying agent can recycles, can also the high efficiente callback naphthenic acid, have broad application prospects.
Embodiment
The present invention is illustrated by the following examples, but the present invention is not limited to subordinate embodiment, and under the scope of described aim, change is included in the technical scope of the present invention before and after not breaking away from.
Embodiment 1
Getting initial acid value is that the depickling oil product is treated in the conduct of 1.13mgKOH/g oil fraction oil, selects ethylene glycol as the required organic solvent of reaction, extraction, and the weight percentage of hexahydroaniline is 0.1wt% in the composite deacidifying agent.
Then, composite deacidifying agent is mixed with treating the depickling oil product, the composite deacidifying agent consumption is to treat 50% of depickling oil volume, hybrid reaction 5min under-10 ℃ temperature condition.After reaction finished, under normal temperature, normal pressure, standing demix 15min just obtained the good two-phase of layering: the oil product phase that acid number reduces and the organic solvent of naphthenic acid enrichment are mutually.Measure the acid number of refined oil phase, its acid removal rate is 82%.
In the reduced pressure of-0.09MPa, under 180 ℃ the temperature condition organic solvent is distilled mutually the naphthenic acid that is recycled and composite deacidifying agent.Composite deacidifying agent can be done circulation, and yield is 98.0%.Naphthenic acid further exquisiteness obtains high purity product.
Embodiment 2
Getting initial acid value is that the depickling oil product is treated in the conduct of 1.17mgKOH/g oil fraction oil, selects methyl alcohol as the required organic solvent of reaction, extraction, and the weight percentage of hexahydroaniline is 50wt% in the composite deacidifying agent.
Then, composite deacidifying agent is mixed with treating the depickling oil product, the consumption of composite deacidifying agent is for treating depickling oil volume 3%, hybrid reaction 50min under 10 ℃ temperature condition.After reaction finished, under normal temperature, normal pressure, standing demix 10min just obtained the good two-phase of layering: the oil product phase that acid number reduces and the organic solvent of naphthenic acid enrichment are mutually.Measure the acid number of refined oil phase, its acid removal rate is 89%.
In the reduced pressure of-0.02MPa, under 150 ℃ the temperature condition organic solvent is distilled mutually the naphthenic acid that is recycled and composite deacidifying agent.Composite deacidifying agent can be done circulation, and yield is 99.0%.Naphthenic acid further exquisiteness obtains high purity product.
Embodiment 3
Getting initial acid value is that the depickling oil product is treated in the conduct of 3.96mgKOH/g oil fraction oil, selects glycerol as the required organic solvent of reaction, extraction, and the weight percentage of hexahydroaniline is 20wt% in the composite deacidifying agent.
Then, composite deacidifying agent is mixed with treating the depickling oil product, the consumption of composite deacidifying agent is to treat 20% of depickling oil volume, hybrid reaction 20min under 95 ℃ temperature condition.After reaction finished, under normal temperature, normal pressure, standing demix 20min just obtained the good two-phase of layering: the oil product phase that acid number reduces and the organic solvent of naphthenic acid enrichment are mutually.Measure the acid number of refined oil phase, its acid removal rate is 87.5%.
In the reduced pressure of-0.09MPa, under 230 ℃ the temperature condition organic solvent is distilled mutually the naphthenic acid that is recycled and composite deacidifying agent.Composite deacidifying agent can be done circulation, and yield is 99.2%.Naphthenic acid further exquisiteness obtains high purity product.
Embodiment 4
Getting initial acid value is that the depickling oil product is treated in the conduct of 1.47mgKOH/g oil fraction oil, selects ethanol as the required organic solvent of reaction, extraction, and the weight percentage of hexahydroaniline is 40wt% in the composite deacidifying agent.
Then, composite deacidifying agent is mixed with treating the depickling oil product, the consumption of composite deacidifying agent is to treat 5% of depickling oil volume, hybrid reaction 30min under 10 ℃ temperature condition.After reaction finished, under normal temperature, normal pressure, standing demix 15min just obtained the good two-phase of layering: the oil product phase that acid number reduces and the organic solvent of naphthenic acid enrichment are mutually.Measure the acid number of refined oil phase, its acid removal rate is 89%.
In the reduced pressure of-0.06MPa, under 170 ℃ the temperature condition organic solvent is distilled mutually the naphthenic acid that is recycled and composite deacidifying agent.Composite deacidifying agent can be done circulation, and yield is 99.1%.Naphthenic acid further exquisiteness obtains high purity product.
Embodiment 5
Getting initial acid value is that the depickling oil product is treated in the conduct of 4.15mgKOH/g oil fraction oil, selects 1,3-PD as the required organic solvent of reaction, extraction, and the weight percentage of hexahydroaniline is 25wt% in the composite deacidifying agent.
Then, composite deacidifying agent is mixed with treating the depickling oil product, the consumption of composite deacidifying agent is to treat 15% of depickling oil volume, hybrid reaction 20min under 60 ℃ temperature condition.After reaction finished, under normal temperature, normal pressure, standing demix 20min just obtained the good two-phase of layering: the oil product phase that acid number reduces and the organic solvent of naphthenic acid enrichment are mutually.Measure the acid number of refined oil phase, its acid removal rate is 86.5%.
In the reduced pressure of-0.06MPa, under 210 ℃ the temperature condition organic solvent is distilled mutually the naphthenic acid that is recycled and composite deacidifying agent.Composite deacidifying agent can be done circulation, and yield is 99.4%.Naphthenic acid further exquisiteness obtains high purity product.
Embodiment 6
Getting initial acid value is that the depickling oil product is treated in the conduct of 1.46mgKOH/g oil fraction oil, selects ethylene glycol and Virahol as the required organic solvent of reaction, extraction, and the two volume ratio is 3: 1, and the weight percentage of hexahydroaniline is 25wt% in the composite deacidifying agent.
Then, composite deacidifying agent is mixed with treating the depickling oil product, the consumption of composite deacidifying agent is to treat 8% of depickling oil volume, hybrid reaction 25min under 30 ℃ temperature condition.After reaction finished, under normal temperature, normal pressure, standing demix 15min just obtained the good two-phase of layering: the oil product phase that acid number reduces and the organic solvent of naphthenic acid enrichment are mutually.Measure the acid number of refined oil phase, its acid removal rate is 92%.
In the reduced pressure of-0.06MPa, under 190 ℃ the temperature condition organic solvent is distilled mutually the naphthenic acid that is recycled and composite deacidifying agent.Composite deacidifying agent can be done circulation, and yield is 99.0%.Naphthenic acid further exquisiteness obtains high purity product.
Claims (7)
1. composite deacidifying agent, it is dissolved in the Organic Alcohol by hexahydroaniline and mixes, and wherein the weight percentage of hexahydroaniline is 0.1wt%-50wt%, and described Organic Alcohol is C
1-C
3Organic Alcohol.
2. a kind of composite deacidifying agent according to claim 1, wherein said Organic Alcohol is selected from one or more in methyl alcohol, ethanol, ethylene glycol, propyl alcohol, 1,3-PD or the glycerol.
3. method that from oil product, removes naphthenic acid, it may further comprise the steps:
(1), hexahydroaniline be dissolved in be mixed into composite deacidifying agent in the Organic Alcohol, wherein the weight percentage of hexahydroaniline is 0.1wt%-50wt%, described Organic Alcohol is C
1-C
3Organic Alcohol;
(2), in sour oil product, add composite deacidifying agent, fully leave standstill after the hybrid reaction, obtain the two-phase of layering, the oil product phase that acid number reduces and the organic solvent of naphthenic acid enrichment are mutually;
(3), separate two-phase and namely from oil product, removed naphthenic acid.
4. a kind of method that from oil product, removes naphthenic acid according to claim 3, it is included in-pressure condition of 0.09～0MPa under, distillation organic solvent phase is distilled out of composite deacidifying agent under 150～230 ℃ the temperature condition, separates obtaining naphthenic acid and composite deacidifying agent.
5. a kind of method that removes naphthenic acid from oil product according to claim 3, wherein said organic solvent is selected from one or more in methyl alcohol, ethanol, ethylene glycol, propyl alcohol, 1,3-PD or the glycerol.
6. a kind of method that removes naphthenic acid from oil product according to claim 3, the volumetric usage of wherein said composite deacidifying agent is 3%～50% of oil volume.
7. a kind of method that from oil product, removes naphthenic acid according to claim 3, wherein the temperature of hybrid reaction is-10 to 95 ℃, the reaction times is 5-50 minute.
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| CN 200910272193 CN101665716B (en) | 2009-09-22 | 2009-09-22 | Composite deacidification agent and method for recovering naphthenic acid from oil |
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| CN 200910272193 CN101665716B (en) | 2009-09-22 | 2009-09-22 | Composite deacidification agent and method for recovering naphthenic acid from oil |
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| CN101665716B true CN101665716B (en) | 2013-03-13 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103305264A (en) * | 2013-07-01 | 2013-09-18 | 烟台市牟平区留德润滑油销售有限公司 | Method for deacidifying lubricating oil distillate oil by using cyclohexane |
| CN105419863A (en) * | 2015-12-10 | 2016-03-23 | 广东石油化工学院 | Process method for deacidifying high acid thickened oil |
| CN110577843A (en) * | 2019-10-08 | 2019-12-17 | 磁悬浮润滑油(苏州)有限公司 | Method for deacidifying oil product by using low-molecular mixed alcohol |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4752381A (en) * | 1987-05-18 | 1988-06-21 | Nalco Chemical Company | Upgrading petroleum and petroleum fractions |
| US6258258B1 (en) * | 1998-10-06 | 2001-07-10 | Exxon Research And Engineering Company | Process for treatment of petroleum acids with ammonia |
| CN1850947A (en) * | 2006-05-10 | 2006-10-25 | 中国科学院过程工程研究所 | Removal of naphthenic acid in oil using composite deacidifying agent |
| CN101016477A (en) * | 2007-03-05 | 2007-08-15 | 中国石油化工集团公司 | Method of reducing acid value for crude oil |
-
2009
- 2009-09-22 CN CN 200910272193 patent/CN101665716B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4752381A (en) * | 1987-05-18 | 1988-06-21 | Nalco Chemical Company | Upgrading petroleum and petroleum fractions |
| US6258258B1 (en) * | 1998-10-06 | 2001-07-10 | Exxon Research And Engineering Company | Process for treatment of petroleum acids with ammonia |
| CN1850947A (en) * | 2006-05-10 | 2006-10-25 | 中国科学院过程工程研究所 | Removal of naphthenic acid in oil using composite deacidifying agent |
| CN101016477A (en) * | 2007-03-05 | 2007-08-15 | 中国石油化工集团公司 | Method of reducing acid value for crude oil |
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