CN1065858A - The separation method of unsaponifiables in the organic acid - Google Patents
The separation method of unsaponifiables in the organic acid Download PDFInfo
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- CN1065858A CN1065858A CN 91106670 CN91106670A CN1065858A CN 1065858 A CN1065858 A CN 1065858A CN 91106670 CN91106670 CN 91106670 CN 91106670 A CN91106670 A CN 91106670A CN 1065858 A CN1065858 A CN 1065858A
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Abstract
The invention discloses the method for unsaponifiables in a kind of separating organic acid, be particularly useful for the by product of petroleum refinement---the separation of unsaponifiables in the crude naphthenic acid.
Feature of the present invention is to adopt in organic acid soap metering to feed the method for water vapor, the unsaponifiables that the component distillation that reduces pressure separation is contained, again through acidifying, wash pure organic acid.This method technological temperature is low, the thermolysis of organic acid soap is few, acidificatoin time is short, and the pure organic acid content of gained is up to more than 95% (weight), and acid number surpasses 200mgKOH/g, and the organic acid yield is greater than 90%.
The present invention can handle under the normal pressure boiling point at the organic acid below 420 ℃, especially naphthenic acid and normal chain alkyl lipid acid.
Description
The present invention relates to the separation method of unsaponifiables in a kind of organic acid.
Be R(COOH generally at general formula) organic acid (n=1-3 in the formula of n, R is H, cycloalkyl, positive isomery chain alkylene) in, contain a certain amount of unsaponifiables, contain 10-55%(weight in the by product-crude naphthenic acid as refining of petroleum) unsaponifiables, influence its use properties.Therefore, must take measures to remove wherein contained unsaponifiables, to improve its use properties.
In the prior art, adopt the unsaponifiables in tube oven method and extraction process separating organic acid such as the naphthenic acid usually, these class methods are the flow process complexity often, cost height and etching apparatus.
The contriver is among the CN90105528X at number of patent application, to adopt direct underpressure distillation to divide dried up and unsaponifiables after the crude naphthenic acid saponification, the naphthenic soap that separated unsaponifiables adds acidification adjuvant again and carries out acidifying under 100-250 ℃ temperature, obtain highly purified naphthenic acid.Adopt this technical point higher from the required temperature of unsaponifiables, in carrying out acidifying under the high temperature in the stainless steel still, thereby material easily decomposes and causes equipment corrosion easily.
The present invention aim to provide a kind of technological temperature low, be difficult for causing equipment corrosion and obtain high purity organic acid separation method.
For achieving the above object, the present invention adopts following technical scheme: with thick organic acid through saponification separates water outlet and part unsaponifiables with underpressure distillation after, measure the feeding water vapor in the organic acid soap of gained, the component distillation that directly reduces pressure on still separates unsaponifiables wherein.When acidifying, the organic acid soap imported under molten state in the acidproof still that is added with acid in advance carry out acidifying, again acidizing fluid is promptly got highly purified organic acid through washing.
Implement the present invention, can earlier thick organic acid be added in the stainless steel still, under agitation add alkaline solution and heating, adopt direct underpressure distillation to separate saponification water and part unsaponifiables.When the still temperature is 150-350 ℃, in soap, measure the feeding water vapor again, on still, directly carry out azeotropic underpressure distillation, the unsaponifiables in the separating organic acid soap.The used alkali of saponification can be one or more of sodium hydroxide, potassium hydroxide or their carbonate, and the thick organic acid alkali of saponification consumption should be than the high 0-3%(weight of theoretical amount), with the isolating unsaponifiables acid number of this proportioning less than 0.02mgKOH/g.The vacuum tightness of organic acid direct underpressure distillation after saponification is preferably lower than the 10000Pa(absolute pressure), the vacuum tightness of water vapor azeotropic underpressure distillation can be the 500-20000Pa(absolute pressure), the water vapor add-on reduces with the minimizing that separates the unsaponifiables amount, can be in the 100%(of unsaponifiables fractional dose weight) in change, water vapor is fed simultaneously by the bottom of still or bottom and side.When the quantity of distillate of unsaponifiables reduces and during near theoretical fractional dose, the operation that separates unsaponifiables can stop gradually.Adopt this technology to compare with the unsaponifiables technology in the direct underpressure distillation separating organic acid soap, the still temperature can reduce below 50 ℃.
Implement the present invention, can also be after stopping to separate the operation of unsaponifiables, soap temperature drop in the still is molten mass to 250-300 ℃ after, it is imported acidifying still carries out acidifying.The acidifying still should be acidproof still such as glass-lined kettle, and the acidifying still has reflux exchanger, stirring and cooling jacket.Before the soap molten mass is imported into the acidifying still, in still, add quantitative acid earlier, added acid can be sulfuric acid, hydrochloric acid or their mixture, acid concentration is a 18-23%(weight), the add-on of acid is the 100-103%(weight of theoretical amount), souring temperature is below 105 ℃, need to open stir in the acidization and toward the logical water coolant of chuck, acidificatoin time be 50 minutes to below 120 minutes.
Implement the present invention, acidizing fluid being washed to pH value is that 6-7(generally need wash about secondary again), promptly get smart organic acid, sour yield is greater than 90%.
Implement the present invention, the smart organic acid production of gained, acid content is higher than 95%(weight), color and luster is 6-8 number (iron-cobalt colorimetric).
It is thick organic acid below 420 ℃ that the present invention can handle boiling point under the normal pressure, as naphthenic acid, contain or do not contain unsaturated link(age) just, monoprotic acid, diprotic acid and triprotic acid or its mixture of isomery chain alkylene, be particularly useful for handling naphthenic acid and normal chain alkyl lipid acid.
The present invention has following tangible advantage:
1, with reduce pressure unsaponifiables in the component distillation separating organic acid soap of water vapor, with the technology of unsaponifiables in the direct underpressure distillation separating organic acid soap relatively, can reduce in 50 ℃ of the temperature, not only reduced the thermolysis of organic acid soap, also saved energy;
2, adopt this processing method, the organic acid soap is added acidifying in the acidproof still under molten state, not only avoided equipment corrosion, do not produced boiling explosion phenomenon, also simplified technological process, shortened acidificatoin time greatly;
3, the organic acid content of this separation method gained can reach more than 95%, and product color reaches (iron-cobalt colorimetric) 6-8 number, thereby has product purity height, coloury advantage.
Below be specific embodiments of the invention:
Embodiment 1:
Adding thick acid number in stainless steel cauldron is 155mgKOH/g, pure acid number is 210mgKOH/g, moisture 0.5%, atmospheric boiling point is less than 538 parts of (weight of crude naphthenic acid of 420 ℃, as follows), stir that to add concentration under the unlatching situation be 50%(weight) 120 parts of aqueous sodium hydroxide solutions, carry out underpressure distillation, when the still temperature reaches 210 ℃, feed water vapor by metering at the bottom of the still, component distillation reduces pressure, when the still temperature reaches 330 ℃, vacuum tightness reaches the 10600Pa(absolute pressure) time, the unsaponifiables quantity of distillate is few, be cooled to 280 ℃, it imported the acidifying still carry out acidifying.Be added with concentration in the acidifying still in advance and be 323 parts in 23% sulfuric acid, temperature is 23 ℃, stirring under the situation of opening, 250 ℃ naphthenic soaps is carried out acidifying, and under 100 ℃, stirred 20 minutes, be cooled to 60 ℃ of layerings then, naphthenic acid washing secondary to water lotion pH value is 6-7, acid content is 395 parts of 97.67% naphthenic acid, its thick acid number is 210mgKOH/g, pure acid number is 215mgKOH/g, and color and luster is No. 7 (iron-cobalt colorimetric), the acid number rate of recovery 99.47%.The soap thing is not 133 parts, acid number 0.005mgKOH/g.
The best result layer temperature of unsaponifiables is 330 ℃ in the said process, and in the underpressure distillation of water vapor azeotropic, the weight ratio of unsaponifiables and water vapor is 1.4: 1, acidificatoin time meter 90 minutes.
Embodiment 2:
Adding thick acid number in the stainless steel still is 181mgKOH/g, pure acid number is 230mgKOH/g, water content 1%, and boiling point is lower than 400 ℃ 600 parts of crude naphthenic acids under the normal pressure, under the situation of stir opening, add concentration and be 260.7 parts of 30% aqueous sodium hydroxide solutions, carry out underpressure distillation.When the still temperature reaches 250 ℃, feed water vapor in still bottom and side, the component distillation that reduces pressure, when the still temperature reaches 300 ℃, vacuum tightness is the 8KPa(absolute pressure) time, unsaponifiables promptly no longer distillates, and is cooled to 250 ℃, it is imported acidifying still carry out acidifying.Be added with concentration in the acidifying still in advance and be 421 parts in 23% sulfuric acid, souring temperature is 102 ℃, washing of use-case 1 same procedure and layering, acid content is 470 parts of 98.5% smart naphthenic acid, its thick acid number is 230mgKOH/g, pure acid number is 233.5mgKOH/g, and color and luster is No. 6 (iron-cobalt colorimetric), and the acid number rate of recovery reaches 99.5%.
Embodiment 3:
Adding thick acid number in the stainless steel still is 151mgKOH/g, pure acid number is 205mgKOH/g, water content 0.8%, boiling point is lower than 400 ℃ 550 parts of thick positive structure naphthenic acid under the normal pressure, under the situation of stir opening, add concentration and be 149.5 parts of 40% aqueous sodium hydroxide solutions, separate unsaponifiables with the technology identical with example 2, be 278 parts of 20% hydrochloric acid with concentration again, carry out acidifying and washing with same method, acid content is 387 parts of 98.94% smart normal fatty acids, its thick acid number is 205.8mgKOH/g, pure acid number is 210mgKOH/g, color and luster is No. 7 (iron-cobalt colorimetric), and the acid number rate of recovery is 95.9%.
Claims (2)
1, a kind of molecular formula is the separation method of unsaponifiables in the organic acid of R (COOH) n, comprise processes such as saponification, fractionation by distillation and acidifying, n=1-3 in the formula, R are one or more of H, cycloalkyl, positive isomery chain alkylene, or their mixture, it is characterized in that:
(a) measure the feeding water vapor in the organic acid soap that separated water and part unsaponifiables gained, the component distillation that directly reduces pressure in still separates wherein remaining unsaponifiables;
(b) during acidifying, the organic acid soap imported under molten state in the acidproof still that is added with acid in advance carry out acidifying;
(c) acidizing fluid through wash pure organic acid.
2, separation method according to claim 1, one or more of employing sodium hydroxide, potassium hydroxide or their carbonate, after thick organic acid saponification, directly underpressure distillation divides dried up and the part unsaponifiables, metering feeds water vapor again, component distillation directly reduces pressure on still, unsaponifiables in the further separating organic acid soap, the sulfuric acid or the hcl acidifying that add theoretical amount 100-103% in the organic acid soap that separated unsaponifiables, wash with water again and promptly get smart organic acid production, the invention is characterized in:
(a) feed the water vapor component distillation that on still, directly reduces pressure, water vapor feeds simultaneously from the bottom of still or from bottom and side, the water vapor add-on is the 100%(weight of unsaponifiable matter content in the organic acid soap) below, the temperature of soap is 150-350 ℃, and vacuum tightness is the 500-20000Pa(absolute pressure);
(b) in the acidization, the organic acid soap that will separate unsaponifiables earlier is cooled to 250-300 ℃, import then to have reflux exchanger, stirring and cooling jacket and be added with in advance in the sour acidifying still and carry out acidifying, souring temperature is below 105 ℃, and acidificatoin time is below 50-120 minute;
(c) acidizing fluid is 6-7 through being washed to pH value, promptly gets smart organic acid, and its purity reaches 95%(weight) more than, color and luster is 6-8 number (iron-cobalt colorimetric).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91106670 CN1031993C (en) | 1991-04-13 | 1991-04-13 | Method for separating unsaponifiables from organic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91106670 CN1031993C (en) | 1991-04-13 | 1991-04-13 | Method for separating unsaponifiables from organic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1065858A true CN1065858A (en) | 1992-11-04 |
| CN1031993C CN1031993C (en) | 1996-06-12 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91106670 Expired - Fee Related CN1031993C (en) | 1991-04-13 | 1991-04-13 | Method for separating unsaponifiables from organic acid |
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| Country | Link |
|---|---|
| CN (1) | CN1031993C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102648271A (en) * | 2009-10-23 | 2012-08-22 | 普瓦图-夏朗德瓦拉格罗可再生碳公司 | Method for extracting unsaponifiables from renewable raw materials |
| CN113121332A (en) * | 2021-03-29 | 2021-07-16 | 湖南万象生物科技有限公司 | Method for reducing content of unsaponifiable matters in high-purity oleic acid |
| CN113384911A (en) * | 2021-08-06 | 2021-09-14 | 鞍山昊旻稀土科技有限公司 | Grease-decomposing distillation process for aged naphthenic acid extractant |
-
1991
- 1991-04-13 CN CN 91106670 patent/CN1031993C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102648271A (en) * | 2009-10-23 | 2012-08-22 | 普瓦图-夏朗德瓦拉格罗可再生碳公司 | Method for extracting unsaponifiables from renewable raw materials |
| CN102648271B (en) * | 2009-10-23 | 2015-03-11 | 普瓦图-夏朗德瓦拉格罗可再生碳公司 | Method for extracting unsaponifiables from renewable raw materials |
| CN113121332A (en) * | 2021-03-29 | 2021-07-16 | 湖南万象生物科技有限公司 | Method for reducing content of unsaponifiable matters in high-purity oleic acid |
| CN113384911A (en) * | 2021-08-06 | 2021-09-14 | 鞍山昊旻稀土科技有限公司 | Grease-decomposing distillation process for aged naphthenic acid extractant |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1031993C (en) | 1996-06-12 |
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