CN1461795A - Method of crude oil and fraction oil deacidification and naphthenic acid refining method - Google Patents
Method of crude oil and fraction oil deacidification and naphthenic acid refining method Download PDFInfo
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- CN1461795A CN1461795A CN 02119496 CN02119496A CN1461795A CN 1461795 A CN1461795 A CN 1461795A CN 02119496 CN02119496 CN 02119496 CN 02119496 A CN02119496 A CN 02119496A CN 1461795 A CN1461795 A CN 1461795A
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- naphthenic acid
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- acidying agent
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- lighter hydrocarbons
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Abstract
A process for deacidifying crude oil and fractional oil includes such steps as preparing the deacidifying agent which is the ammonia solution of a solvent consisting of two components, mixing it with raw oil, depositing separation to obtain deacidified oil and the mixture of deacidifying agent and naphthenic acid, extracting neutral oil from the mixture by light hydrocarbon, thermal decomposition to recover nath thenic acid and deacidifying agen, and refining naphthenic acid by water washing. Its advantages are high deacidifying rate (90% or more) and high purity of naphthenic acid (90% or more).
Description
Technical field
The invention belongs to oil and petroleum fractions field of refinement thereof, relate to removing of oil or petroleum fractions middle acid substance and making with extra care of petroleum acid.International Classification of Patents belongs to C10G 19/00.
Background technology
Contain some acidic substance in oil and the cut thereof, be called for short petroleum acid, the main composition of these acidic substance is naphthenic acid, and the existence of naphthenic acid is etching apparatus not only, and influence the color and the stability of petroleum products, therefore when refining of petroleum, naphthenic acid should be removed.Therefore naphthenic acid is a kind of good industrial chemicals and additive, has good market outlook, removes naphthenic acid and refining naphthenic acid has great importance.The method that removes naphthenic acid at present has a variety of, as hydrofining method, alkali wash, ethanol-ammonia process, Virahol-ammonia process etc., these methods all have its use range and limitation: the hydrofining method need consume hydrogen, facility investment height, process cost are also high, can not obtain naphthenic acid; Alkali wash need consume a large amount of alkali, and contaminate environment forms emulsification easily; Ethanol-ammonia process and Virahol-ammonia process solvent recuperation expense is too high, and industrial being difficult to bears.
Summary of the invention
The objective of the invention is to find a kind of cheap, reliable, effective acid stripping method, make the solvent depickling overcome the limitation of original acid stripping method, remove naphthenic acid and obtain the high naphthenic acid of acid content.Method of the present invention is as follows:
1. the ammonia solution that uses a kind of solvent is about to ammonia and is dissolved in this solvent as de-acidying agent.The composition of solvent comprises A, B two portions, and A is an alcoholic solvent, comprises one-component or its mixtures such as ethylene glycol, Diethylene Glycol, glycerol; B is water, methyl alcohol, ethanol or its mixture.A accounts for 50%～100% (weight) of solvent, and B accounts for 0～50% (weight) of solvent, and ammonia accounts for 1%～20% (weight) of de-acidying agent.
2. with de-acidying agent that obtains in 1 and the stock oil mixing and stirring (ratio of de-acidying agent and stock oil is 3～60% (weights)) for the treatment of depickling, after reacting 2～120 minutes under 20～70 ℃, naphthenic acid just with de-acidying agent in ammonia generation chemical reaction, form naphthenic acid ammonia, and be dissolved in the de-acidying agent, then at 20～90 ℃ of following standing demix, de-acidying agent carries naphthenic acid at bottom, oil after the depickling (being called for short depickling oil) is on the upper strata, lower floor's de-acidying agent and upper strata depickling oil content are opened, and then the most of naphthenic acid in the stock oil just is removed.Acid removal rate can reach more than 90%.
3. the lower floor's de-acidying agent that obtains in 2 is mixed with the part lighter hydrocarbons, then 60～80 ℃ settlement separate down, can adopt also that electric field is settlement separate, centrifugal settling separation or wet cyclone separate the weight component.Be divided into two-layerly up and down after settlement separate, the upper strata light constituent mainly is that lighter hydrocarbons dissolve a small amount of neutral oil, and lighter hydrocarbons are steamed recyclable recycling behind the solvent, and neutral oil can be got back in the stock oil; Lower floor's heavy constituent mainly are that de-acidying agent adds naphthenic acid.The lighter hydrocarbons consumption is 30～200% (volume %) of de-acidying agent consumption, and suitable consumption is 50～150% (volume %).Lighter hydrocarbons are boiling spread at 40～150 ℃ lighter hydrocarbons, comprise alkane in this scope of petroleum naphtha, sherwood oil, various boiling point, aromatic hydrocarbons etc.
4. the de-acidying agent layer that obtains in 2 or 3 is heated to 80～170 ℃, then the naphthenic acid ammonia in the de-acidying agent decomposes, be decomposed into ammonia and naphthenic acid, the ammonia useable solvents absorbs the back to be reused, and naphthenic acid is insoluble in the solvent, swim in the solvent upper strata, so just naphthenic acid and solvent are separated, solvent is reusable after absorbing ammonia, need not like this solvent is reclaimed in solvent evaporation, so the energy consumption of solvent recuperation reduces greatly, process cost is also low.
5. the naphthenic acid that obtains in 4 is added the part lighter hydrocarbons, add a part of water mixing, washing after the dissolving again, then standing demix, telling the upper strata is naphthenic acid and lighter hydrocarbons, lighter hydrocarbons are recycled after evaporating, and remaining is naphthenic acid, and the content of naphthenic acid can reach more than 90%.Lower floor is the mixture of water and depickling solvent, and just obtaining the depickling solvent after water is steamed can reuse.The consumption of water is 10～200% (weights) of naphthenic acid amount, and is many with unrestricted.
Use the method that present patent application adopted, can make the decreasing ratio of naphthenic acid be higher than 90%, the purity of naphthenic acid is greater than 90%, and do not contain de-acidying agent in the depickling oil substantially, so need not be with depickling oil heating evaporation de-acidying agent wherein, therefore make the energy consumption of depickling reduce greatly, the rate of recovery of de-acidying agent is also very high, can reach more than 99.9%, and de-acidying agent is reusable, so the energy consumption of whole process and process cost are all very low, help industrial application.
Embodiment
Further specify technology of the present invention below in conjunction with embodiment.
Embodiment 1:
Stock oil is certain refinery second line of distillation distillate, its acid number is 3.79mgKOH/g, de-acidying agent consists of: ethylene glycol 90%, glycerol 5%, water 2%, ammonia 3% (weight), the de-acidying agent consumption is 30% (weight) that accounts for stock oil, 50 ℃ of following stirrings 20 minutes, be heated to 70 ℃ of following and sedimentation layerings in 2 hours under this temperature then, tell two-layer up and down, the upper strata is a depickling oil, acid number 0.35mgKOH/g, acid removal rate 90.8%, lower floor's de-acidying agent are heated to 90 ℃ and kept 1 hour, naphthenic acid ammonia in the de-acidying agent decomposes, resolve into naphthenic acid and ammonia, the ammonia volatilization absorbs and can reuse with de-acidying agent, and naphthenic acid is separated out and swum in the de-acidying agent upper strata, separate with separating funnel, record the pure acid number 154mgKOH/g of naphthenic acid, thick acid number 105mgKOH/g, purity 68.6%.
Embodiment 2:
Embodiment 1 gained lower floor de-acidying agent is mixed with sherwood oil (60～90 ℃ of boiling points) with volume, and settlement separate then, the upper strata is a petroleum ether layer, obtain neutral oil after steaming sherwood oil, lower floor is the de-acidying agent that removes behind the neutral oil, and this de-acidying agent is heated to 90 ℃, decomposites ammonia, ammonia absorbs with de-acidying agent, naphthenic acid and de-acidying agent are immiscible, swim in the de-acidying agent upper strata, separate with separating funnel, the thick acid number that records this naphthenic acid is 132mgKOH/g, purity 85.7%; The sherwood oil that in this naphthenic acid, adds equivalent, the dissolving back adds the water of two volumes, mix back sedimentation layering, lower floor is a water, the upper strata is naphthenic acid and sherwood oil, obtain naphthenic acid after upper strata naphthenic acid layer heating evaporation fallen sherwood oil, the acid number that records this naphthenic acid is 147mgKOH/g, purity 95.5%.
Embodiment 3:
Stock oil is certain refinery three-way distillate that reduces pressure, acid number 3.51mgKOH/g, use the de-acidying agent identical with example 1, the de-acidying agent consumption is 30% (weight) that accounts for stock oil, stirred 20 minutes down at 55 ℃, 70 ℃ of following sedimentations 1 hour, tell upper strata depickling oil and lower floor's de-acidying agent layer, depickling oleic acid value 0.32mgKOH/g, acid removal rate 90.8%, add sherwood oil downwards in the layer de-acidying agent with volume, mix back sedimentation layering, the upper strata is a petroleum ether layer, obtain neutral oil after steaming sherwood oil, lower floor is the de-acidying agent that removes neutral oil, is heated to 90 ℃ and keeps 1 hour, then naphthenic acid ammonia is decomposed into ammonia and naphthenic acid, ammonia absorbs with de-acidying agent, and naphthenic acid and de-acidying agent are immiscible, swims in the de-acidying agent upper strata, separate with separating funnel, the sherwood oil that in this naphthenic acid, adds equivalent, the dissolving back adds the water of two volumes, mixes back sedimentation layering, lower floor is a water, the upper strata is naphthenic acid and sherwood oil, obtains naphthenic acid after upper strata naphthenic acid layer heating evaporation fallen sherwood oil, and the thick acid number that records this naphthenic acid is 128mgKOH/g, pure acid number 140mgKOH/g, purity 91.4%.
Claims (10)
1. the method for crude oil and fraction oil deacidification, it is characterized in that de-acidying agent and stock oil hybrid reaction, settlement separate then, obtain depickling oil and the de-acidying agent that contains naphthenic acid after the separation, the de-acidying agent that contains naphthenic acid can remove a small amount of neutral oil of dissolved in the de-acidying agent with the lighter hydrocarbons extraction process, to improve the purity of gained naphthenic acid, contain the de-acidying agent of naphthenic acid or can reclaim naphthenic acid and de-acidying agent with the method for thermal degradation through the de-acidying agent that extraction process removes neutral oil.
2. method according to claim 1 is characterized in that used de-acidying agent is a kind of ammonia solution of solvent, and the composition of this solvent comprises A, B two portions, and A is an alcoholic solvent, comprises one-component or its mixtures such as ethylene glycol, Diethylene Glycol, glycerol; B is water, methyl alcohol, ethanol or its mixture; A accounts for 50%～100% (weight) of solvent, and B accounts for 0～50% (weight) of solvent, and ammonia accounts for 1%～20% (weight) of de-acidying agent.
3. method according to claim 1, it is characterized in that for improving the purity of naphthenic acid, employing lighter hydrocarbons method of extraction removes the neutral oil in the de-acidying agent, with standing demix behind an amount of lighter hydrocarbons and the de-acidying agent mixing certain hour that contains naphthenic acid, then lighter hydrocarbons have dissolved behind the neutral oil and the de-acidying agent layering, and lighter hydrocarbons are on the upper strata, and de-acidying agent is in lower floor, the upper strata lighter hydrocarbons obtain neutral oil through evaporating recyclable lighter hydrocarbons; The de-acidying agent that lower floor removes behind the neutral oil can reclaim naphthenic acid with the method for thermal degradation.
4. according to claim 1 and 3 described methods, adopt the method for heating when it is characterized in that reclaiming the de-acidying agent that contains naphthenic acid, de-acidying agent is heated to 80～170 ℃, then the naphthenic acid ammonia that generates can be decomposed into ammonia and naphthenic acid, ammonia can be used depickling solvent (i.e. alleged solvent in 2, as follows) recycling of absorption back, the solubleness of naphthenic acid in the depickling solvent is very little, with the depickling demixing of solvents, swim in depickling solvent upper strata, available conventional separation method separates, the recyclable utilization of depickling solvent that obtains.
5. according to the described method of claim 1, the temperature that it is characterized in that de-acidying agent and stock oil hybrid reaction is 20～70 ℃.
6. according to the described method of claim 1, after it is characterized in that the reaction of de-acidying agent and stock oil finishes, 20～90 ℃ of following sedimentation layerings, settling time is 1～200 minute, settling time is long more, depickling oil separates good more with de-acidying agent, but considers the convenience of industrial realization, and it is good being no more than 200 minutes with the settling time.
7. according to the described method of claim 1, it is characterized in that the indication distillate is meant the cut that crude oil obtains by distillation, its boiling spread is at 200～550 ℃ that part or a certain narrow fraction of boiling spread in 200～550 ℃ of scopes.
8. method according to claim 3, it is characterized in that the lighter hydrocarbons consumption is 30～200% (volume %) of de-acidying agent consumption, extraction temperature is 20～120 ℃, lighter hydrocarbons are boiling spread at 40～150 ℃ lighter hydrocarbons, comprise alkane in this scope of petroleum naphtha, sherwood oil, solvent oil, various boiling point, aromatic hydrocarbons etc.
9. according to the described method of claim 6, it is characterized in that 60～80 ℃ of settling temperature, 20～120 minutes settling times.
10. according to the described method of claim 4, when it is characterized in that heating the de-acidying agent that contains naphthenic acid, the temperature of heating is 90～150 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02119496 CN1219854C (en) | 2002-05-28 | 2002-05-28 | Method of crude oil and fraction oil deacidification and naphthenic acid refining method |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 02119496 CN1219854C (en) | 2002-05-28 | 2002-05-28 | Method of crude oil and fraction oil deacidification and naphthenic acid refining method |
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| CN1461795A true CN1461795A (en) | 2003-12-17 |
| CN1219854C CN1219854C (en) | 2005-09-21 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100497537C (en) * | 2006-05-10 | 2009-06-10 | 中国科学院过程工程研究所 | Removal of naphthenic acid in oil using composite deacidifying agent |
| CN102311775A (en) * | 2010-07-05 | 2012-01-11 | 中国石油化工股份有限公司 | Method for recovering naphthenic acid from hydrocarbon oil and device thereof |
| 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 |
| CN114133953A (en) * | 2021-11-25 | 2022-03-04 | 中国石油大学(华东) | Method and equipment for continuous deep deacidification of petroleum distillate oil |
-
2002
- 2002-05-28 CN CN 02119496 patent/CN1219854C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100497537C (en) * | 2006-05-10 | 2009-06-10 | 中国科学院过程工程研究所 | Removal of naphthenic acid in oil using composite deacidifying agent |
| CN102311775A (en) * | 2010-07-05 | 2012-01-11 | 中国石油化工股份有限公司 | Method for recovering naphthenic acid from hydrocarbon oil and device thereof |
| 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 |
| CN114133953A (en) * | 2021-11-25 | 2022-03-04 | 中国石油大学(华东) | Method and equipment for continuous deep deacidification of petroleum distillate oil |
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| Publication number | Publication date |
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| CN1219854C (en) | 2005-09-21 |
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Granted publication date: 20050921 Termination date: 20110528 |