CN1032060C - Method for separating naphthenic acid from heavy lubricating-oil distillation - Google Patents
Method for separating naphthenic acid from heavy lubricating-oil distillation Download PDFInfo
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- CN1032060C CN1032060C CN 92110945 CN92110945A CN1032060C CN 1032060 C CN1032060 C CN 1032060C CN 92110945 CN92110945 CN 92110945 CN 92110945 A CN92110945 A CN 92110945A CN 1032060 C CN1032060 C CN 1032060C
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Abstract
The present invention belongs to the field of liquid-liquid extraction in the petroleum refining process, and particularly relates to a method for separating naphthenic acid of heavy lubrication oil fractions in an extraction tower filled with filling material through taking ammonia and ethanol water as extraction agents. The present invention overcomes the defects that the device is bulky due to long stay time or the energy consumption for recovering extraction agents and naphthenic acids is high; the solves is harmful to human bodies, etc. existing in the prior art. The extraction agent with convenient and easy acquirement, no harm to human bodies and circular use is used, the heavy lubrication oil fractions which are suitable for industrial production are refined, and the naphthenic acids in the heavy lubrication oil fractions are separated.
Description
The invention belongs to liquid-liquid extraction field in the petroleum refining process, specially referring to and adopting ammonia, aqueous ethanolic solution is extraction agent method of naphthenic acid in the separation of heavy lube cut in the counter-current extraction tower of filling filler.
At present, remove the existing many processing methodes of naphthenic acid from diesel oil or light lubricating oil fraction oil, depickling also has certain methods now for high acid value heavy grease fraction oil, but mostly rests on laboratory conditions, does not also have the industrialization of success.As the disclosed a kind of anhydrous ammonia, methanol solution of adopting of US2850435 as extraction agent method of naphthenic acid in the extracting fraction oil in a counter-current extraction tower, its acid removal rate can reach 98 weight %, but fraction oil and extraction agent flow slowly in tower, and the residence time is very long, can not be in industrial realization; And for example US4634519 discloses to adopt and has contained methyl alcohol, ammonia, the aqueous solution as the naphthenic acid in the extraction agent extracting fraction oil, and this method need be used underpressure distillation, and power consumption is big, and methyl alcohol is to environment and human body harmful.
It is long thereby cause equipment huge or reclaim extraction agent and the naphthenic acid energy consumption is too high and defective such as human body harmful to the present invention seeks to overcome in the existing method residence time, use a kind ofly conveniently be easy to get, harmless, the extraction agent that can recycle, refining industrial heavy grease fraction, the method for naphthenic acid in the separation of heavy lube cut of adapting to.
A kind of from the heavy grease fraction method of separating naphthenic acid, technological process comprises:
A. stock oil with carry out reaction, extraction as ammonia and alcoholic acid aqueous solution counter current contact in extraction tower A of extraction agent;
B. enter destructive distillation tower B from the effusive extraction liquid that contains the naphthenic acid ammonium of extracting cat head through heating, naphthenic acid ammonium decomposes discharges ammonia and naphthenic acid therein, and ammonia and solvent steam from destructive distillation tower B top together, and naphthenic acid is discharged at the bottom of destructive distillation tower B;
C. effusive depickling oil enters through heating and takes off agent tower C at the bottom of the extraction tower A, and the entrained a small amount of extraction agent of depickling oil steams from tower C top, takes off agent oil and discharges at the bottom of tower C;
D. from destructive distillation tower B top with take off extraction agent that agent tower C top steams and return extraction tower A and recycle.
Contain in the above-mentioned extraction agent as the ammonia of neutralizing agent with as the second alcohol and water of solvent, proportioning is:
The concentration of neutralizing agent ammonia in extraction agent is 1～7 weight %; The better concentration of neutralizing agent ammonia in extraction agent is 2～4 weight %; Alcohol concn is 45～95 weight % in the extraction agent; All the other compositions are water in the extraction agent.
Extraction agent is 20～200 weight % with respect to the raw material consumption.
The present invention adopts the counter-current extraction tower of extraction tower A for filling Mellapak packing or other kind fillers, and service temperature is 30～75 ℃ at the bottom of the tower, and the Mellapak packing height is a 1-5 rice.It is flashing tower or general distillation tower that extraction liquid destructive distillation tower B and depickling oil take off agent tower C, establishes reboiler at the bottom of the tower.Extraction liquid destructive distillation tower B and depickling oil take off agent tower C tower top temperature and are all 75～85 ℃, and column bottom temperature is all 110～130 ℃.Stock oil and extraction agent are 3～25 minutes in the residence time of extraction tower A extraction section, and the full tower residence time is 20～40 minutes.
The present invention adopts ammonia, aqueous ethanolic solution as extraction agent, and wherein ammonia plays neutralizing effect, and ethanol plays breakdown of emulsion and solublization.The alcoholic acid latent heat of vaporization is little, boiling point is low, help energy-conservation, convenient extraction agent and the naphthenic acid of from extraction liquid, reclaiming.Higher alcohol concn had both been accelerated the phase separation speed of extraction process, had eliminated emulsification problem, had improved extraction efficiency, and used extraction agent is to human body toxicological harmless, three-waste free discharge.The counter-current extraction tower that adopts the filling Mellapak packing is as extraction equipment, and fraction oil and extraction agent are in only 3～25 minutes residence time of extraction section, and acid removal rate can reach 95 weight %, adapts to industrialness production.Reclaim extraction agent and naphthenic acid in the destructive distillation tower simultaneously, the rate of recovery of extraction agent can reach 99 weight %, and naphthenic acid purity can reach 85 weight %, has simplified technological process, has reduced energy consumption.
The present invention is applicable to that various acid numbers can reach 10mgKOH/g, and the heavy grease fraction that 40 ℃ of kinematic viscosity can reach 1000 centistokes is sloughed naphthenic acid.
Fig. 1 is a process flow diagram of the present invention.
Description of drawings of the present invention is as follows: extraction tower A, and destructive distillation tower B takes off agent tower C, stock oil 1, extracting extraction agent 2, extraction liquid 3, the fraction oil 4 behind the decylization alkanoic acid, the extraction agent 579 of recovery, naphthenic acid 6 takes off the depickling oil 8 after the agent, replenishes extraction agent 10.
Embodiment 1: further specify processing method of the present invention below in conjunction with accompanying drawing.
Stock oil (fraction oil) 1 is dissolved in the extraction tower A the ethanol water solvent and leaves fraction oil with entering from the upper and lower import of counter-current extraction tower A respectively as the ammonia of extraction agent 2 and the alcoholic acid aqueous solution, the extraction liquid 3 that has dissolved the naphthenic acid ammonium flows out from tower A top through heating and enters destructive distillation tower B middle part, naphthenic acid ammonium decomposes discharges naphthenic acid and ammonia, and ammonia and solvent steam from destructive distillation tower B top together; The product naphthenic acid is discharged from destructive distillation tower B bottom.The fraction oil 4 that has removed naphthenic acid flows out from extraction tower A bottom to enter through heating and takes off agent tower C middle part, and a small amount of extraction agent 7 that carries in the oil steams from taking off agent tower C top, and the extraction agent 5 that steams with destructive distillation tower B top is combined into 9 and returns and recycle.The depickling oil 8 that takes off after the agent is discharged from taking off agent tower C bottom.The loss of extraction agent in the extraction agent 10 replenishment cycles processes.How much acidiferous according to fraction oil, extraction agent used in the present invention can be 20～200 weight % of stock oil, is preferably 50～75 weight %.Load material among the extraction tower A and be Mellapak packing, 1～5 meter of packing section height.Pressure in the extraction tower A is 0.1-0.6MPa, and the extracting column bottom temperature is 30-75 ℃, and destructive distillation tower B and the temperature of taking off agent tower C are 75～85 ℃ of cats head, at the bottom of the tower 110～130 ℃, and destructive distillation tower B and take off agent tower C top dress part rectangular saddle ring filler and play brokenly the foam effect.
Embodiment 2: the stock oil acid number is 8.64mgKOH/g, and 40 ℃ of kinematic viscosity are 84 centistokes, and the extraction agent consumption is 50 weight % of raw material, and extraction agent contains ethanol 77.5 weight %, contains ammonia 3.75 weight %, and all the other are water.Extraction tower A is the filling Mellapak packing, 3 meters of packing section height, and the extraction section residence time is 13 minutes, extraction tower A temperature is 40～55 ℃; 78 ℃ of the tower top temperatures of destructive distillation tower B; 115 ℃ of the column bottom temperatures of destructive distillation tower B; Take off 78 ℃ of the tower top temperatures of agent tower C; Take off 115 ℃ of the column bottom temperatures of agent tower C; Depickling oleic acid value is 0.43mgKOH/g, and acid removal rate is 95 weight %, and reclaiming the thick acid number of naphthenic acid that obtains is 119mgkoH/g, and naphthenic acid purity is 76.0 weight %.
Embodiment 3: the stock oil acid number is 9.14mgKOH/g, and 40 ℃ of kinematic viscosity are 402 centistokes, and the extraction agent consumption is 50 weight % of raw material.Extraction agent contains ethanol 70.3 weight %, and ammonia 2.55 weight %, all the other are water.Extraction tower A is the filling Mellapak packing, 3 meters of packing section height, and the extraction section residence time is 21 minutes, extraction tower A temperature is 50～65 ℃, 80 ℃ of destructive distillation tower B tower top temperatures; 120 ℃ of the column bottom temperatures of destructive distillation tower B; Take off agent tower C 80 ℃ of tower top temperatures; Take off 117 ℃ of the column bottom temperatures of agent tower C; Depickling oleic acid value is 0.93mgKOH/g, and acid removal rate is 89.8 weight %, and naphthenic acid purity is 71.5 weight %.
Table one second line of distillation and the result who subtracts naphthenic acid in the three-way separation of heavy lube cut
| Second line of distillation | Subtract three-way | |
| Extraction agent: stock oil w/w | 0.5 0.5 0.5 | 1.0 1.0 1.0 |
| Packing section height rice | 2.5 1.5 1.0 | 2.5 2.0 1.5 |
| Packing section temperature ℃ | 60 60 60 | 55 55 55 |
| Distillation tower B tower top temperature ℃ | 75 83 85 | 80 78 85 |
| Distillation tower B column bottom temperature ℃ | 115 120 125 | 125 120 130 |
| Take off agent tower C tower top temperature ℃ | 80 80 81 | 80 82 80 |
| Take off agent tower C column bottom temperature ℃ | 114 115 120 | 125 120 125 |
| Packing section residence time branch | 22 13 9 | 18 14 11 |
| Depickling oleic acid value mgkoH/g | 0.43 0.87 1.26 | 0.67 0.72 1.13 |
| Acid removal rate weight % | 95.0 89.9 85.4 | 92.7 92.0 87.6 |
| The thick acid number mgkoH/g of naphthenic acid | 117 125 125 | 103 106 109 |
| Naphthenic acid purity weight % | 74 79 79 | 71.5 73.6 75.7 |
| It is ammonia 3 weight % that extraction agent is formed, ethanol 75 weight %, and all the other are water. | ||
Table two stock oil character
| Stock oil character | Density | Kinematic viscosity | Acid number | Boiling range | |
| g/cm 2 | mm 2/s 40℃ 100℃ | mgkoH/g | ℃ | ||
| Second line of distillation | 0.9195 | 84.22 | 7.05 | 8.64 | 268.0-450.9 |
| Subtract three-way | 0.9280 | 402.54 | 15.54 | 9.14 | 349.4-518.1 |
Table three second line of distillation depickling test
| 1 | 2 | 3 | 4 | |
| Ethanol weight % | 45 | 55 | 65 | 75 |
| Ammonia weight % | 3 | 1 | 7 | 3 |
| Extraction agent: stock oil w/w | 0.50 | 0.50 | 0.50 | 0.75 |
| Temperature ℃ | 40 | 50 | 30 | 30 |
| The time branch | 3 | 10 | 5 | 10 |
| Depickling oleic acid value mgkoH/g | 0.23 | 0.67 | 0.34 | 0.23 |
| Acid removal rate weight % | 97.7 | 93.2 | 96.5 | 97.7 |
| The thick acid number mgkoH/g of naphthenic acid | 122 | 137 | 133 | 129 |
| Naphthenic acid purity weight % | 77 | 87 | 84 | 82 |
Claims (6)
1. the method for a separating naphthenic acid from the heavy grease fraction, it is characterized in that: technological process comprises:
A. stock oil with carry out reaction, extraction as ammonia and alcoholic acid aqueous solution counter current contact in extraction tower A of extraction agent;
B. enter destructive distillation tower B from the effusive extraction liquid that contains the naphthenic acid ammonium of extracting cat head through heating, naphthenic acid ammonium decomposes discharges ammonia and naphthenic acid therein, and ammonia and solvent steam from destructive distillation tower B top together, and naphthenic acid is discharged at the bottom of destructive distillation tower B;
C. effusive depickling oil enters through heating and takes off agent tower C at the bottom of the extraction tower A, and the entrained a small amount of extraction agent of depickling oil steams from taking off agent tower C top, takes off agent oil and discharges at the bottom of taking off agent tower C;
D. from destructive distillation tower B top with take off extraction agent that agent tower C top steams and return extraction tower A and recycle.
2. according to claim 1 a kind of from the heavy grease fraction method of separating naphthenic acid, it is characterized in that containing in the extraction agent as the ammonia of neutralizing agent with as the second alcohol and water of solvent, proportioning is:
The concentration of neutralizing agent ammonia in extraction agent is 1-7 weight %;
Alcohol concn is 45～95 weight % in the extraction agent;
All the other compositions are water in the extraction agent.
3. according to claim 1 and 2 a kind of from the heavy grease fraction method of separating naphthenic acid, it is characterized in that extraction agent is 20～200 weight % with respect to the raw material consumption.
4. according to claim 1 a kind of from the heavy grease fraction method of separating naphthenic acid, it is characterized in that the extraction tower A that adopts extraction tower for the filling Mellapak packing.
According to claim 1 or 4 described a kind of from the heavy grease fraction method of separating naphthenic acid; It is characterized in that the service temperature at the bottom of the extraction tower A tower is 30～75 ℃.
6. according to claim 1 a kind of from the heavy grease fraction method of separating naphthenic acid, it is characterized in that it is flashing tower or general distillation tower that extraction liquid destructive distillation tower B and depickling oil take off agent tower C, can establish reboiler at the bottom of the tower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92110945 CN1032060C (en) | 1992-09-25 | 1992-09-25 | Method for separating naphthenic acid from heavy lubricating-oil distillation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92110945 CN1032060C (en) | 1992-09-25 | 1992-09-25 | Method for separating naphthenic acid from heavy lubricating-oil distillation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1070182A CN1070182A (en) | 1993-03-24 |
| CN1032060C true CN1032060C (en) | 1996-06-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92110945 Expired - Lifetime CN1032060C (en) | 1992-09-25 | 1992-09-25 | Method for separating naphthenic acid from heavy lubricating-oil distillation |
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| Country | Link |
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| CN (1) | CN1032060C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063741C (en) * | 1995-07-21 | 2001-03-28 | 中国石化兰州炼油化工总厂 | Method for recovery of petroleum acids from mixed extract of isopropyl alcohol-ammonia water |
| CN1072641C (en) * | 1998-08-14 | 2001-10-10 | 中国石油化工集团公司 | Process for separating and recovering naphthenic acid from fractional oil of petroleum |
| GB9902518D0 (en) * | 1999-02-04 | 1999-03-24 | Bp Exploration Operating | A process for deacidifying a crude oil system |
| CN101914386B (en) * | 2010-07-30 | 2013-02-20 | 大连工业大学 | Composite method for removing and reclaiming naphthenic acid from fraction oil |
| CN105419863A (en) * | 2015-12-10 | 2016-03-23 | 广东石油化工学院 | Process method for deacidifying high acid thickened oil |
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1992
- 1992-09-25 CN CN 92110945 patent/CN1032060C/en not_active Expired - Lifetime
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| Publication number | Publication date |
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| CN1070182A (en) | 1993-03-24 |
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| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
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Expiration termination date: 20120925 Granted publication date: 19960619 |