CN114516791A - Method and system for recovering solid salt in production of isooctanoic acid - Google Patents
Method and system for recovering solid salt in production of isooctanoic acid Download PDFInfo
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- CN114516791A CN114516791A CN202210076634.XA CN202210076634A CN114516791A CN 114516791 A CN114516791 A CN 114516791A CN 202210076634 A CN202210076634 A CN 202210076634A CN 114516791 A CN114516791 A CN 114516791A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/295—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with inorganic bases, e.g. by alkali fusion
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/16—Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for recovering solid salt in the production of isooctanoic acid, which comprises the following steps: s1, preparing sodium isooctanoate, S2, carrying out primary acidification on the sodium isooctanoate, S3, recovering solid salt, S4, carrying out subsequent acidification on the sodium isooctanoate, S5, and repeating the steps S3 and S4; a system for recovering solid salt in the production of isooctanoic acid comprises a reaction kettle, a precipitation tank, a centrifuge and a water storage tank. The invention aims to solve or at least reduce the problems of high COD value, high energy consumption and low purity of recovered salt in the traditional acidification process of generating a large amount of wastewater and free acid, and alkali neutralization, and provides a method and a system for recovering solid salt in the production of isooctanoic acid.
Description
Technical Field
The invention relates to the technical field of production of isooctanoic acid, in particular to a method and a system for recovering solid salt in production of isooctanoic acid.
Background
Isooctanoic acid is a colorless, slightly odorous liquid and is useful as an intermediate for paints and coating siccatives, alkyd resin modifiers, production of peroxides as a catalyst for polymerization, and in lubricating oil esters and PVC stabilizers, among others.
In the prior art, when the ethylhexanol sodium hydroxide oxidation method is adopted for producing the isooctanoic acid, ethylhexanol and sodium hydroxide are dehydrogenated under the action of a catalyst to directly generate sodium isooctanoate, then clear water is used for dissolving the sodium isooctanoate, in order to completely convert the sodium isooctanoate into the isooctanoic acid, 20% of excessive acid is required to be added to form strong acid condition for acidification, so that a large amount of waste water and free acid are generated, the COD value is as high as tens of thousands, the direct discharge causes great pollution and damage to the environment, therefore, alkali neutralization is required to be adopted, and a two-effect or three-effect evaporator is used for evaporating water to recover solid salt. It has the following disadvantages: the energy consumption is large, and the caustic soda consumption is increased; the purity of the recovered salt is low, the utilization of the recovered salt is influenced, and the recovered salt needs to be purified and reprocessed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, solve or at least reduce the problems of high COD value, high energy consumption and low purity of recovered salt in the traditional acidification process of generating a large amount of wastewater and free acid, and alkali neutralization, and provide a method and a system for recovering solid salt in the production of isooctanoic acid.
The invention is realized by the following technical scheme:
a method for recovering solid salts in the production of isooctanoic acid comprising the steps of:
s1, preparing sodium isooctanoate, namely adding isooctanol and caustic soda flakes into a reaction kettle, adding a catalyst, stirring and heating, discharging hydrogen generated by reaction, and obtaining sodium isooctanoate in the reaction kettle when no hydrogen is generated as a reaction end point;
s2, carrying out primary acidification on sodium iso-octoate, dissolving the sodium iso-octoate obtained in the primary acidification in the step S1 in clear water, and adding 20% of excessive acid to carry out acidification reaction to obtain acidified sodium iso-octoate;
s3, recovering solid salt, standing the acidified sodium iso-octoate to separate an upper organic phase and a lower water phase, wherein the organic phase is iso-octoate, and performing solid-liquid separation on the lower water phase through a centrifugal machine to obtain solid salt and salt saturated liquid;
s4, subsequent acidification of sodium iso-octoate, dissolving sodium iso-octoate obtained in the step S1 in the salt saturated liquid obtained in the step S3, cooling, stirring and adding equimolar acid to obtain acidified sodium iso-octoate;
and S5, repeating, and repeating the step S3 and the step S4.
In order to further implement the present invention, the following technical solutions may be preferably selected:
preferably, the catalyst in step S1 is one or more of zinc acetate, zinc oxide, copper acetate, nickel oxide, and nickel acetate.
Preferably, the catalyst in step S1 is added in an amount of 0.05% to 0.2% of isooctanol.
Preferably, in the step S1, the temperature is raised to 145-150 ℃, and the pressure in the reaction kettle is 0.2-3 MPa when hydrogen is discharged.
Preferably, the acid in step S2 and step S4 is one of hydrochloric acid, sulfuric acid, nitric acid or acetic acid.
Preferably, the temperature of the aqueous phase in the solid-liquid separation in the centrifuge in the step S3 is not lower than 38 ℃ and not higher than 40 ℃.
The system for recovering the solid salt in the production of the isooctanoic acid comprises a reaction kettle, a precipitation tank, a centrifugal machine and a water storage tank, wherein the discharge end of the reaction kettle is communicated to one end of the precipitation tank, which is far away from the reaction kettle, is communicated to the feed end of the centrifugal machine, the liquid outlet end of the centrifugal machine is communicated to the water storage tank, and the water storage tank is communicated to the feed end of the reaction kettle through a pump.
Through the technical scheme, the invention has the beneficial effects that:
the invention utilizes the waste water discharged by acidification to directly dissolve the next sodium isooctanoate, and then adds acid to carry out acidification reaction, wherein the molar ratio of the added acid to the added alkali is 1: 1. all the salts generated in the reaction are separated out. By centrifugal separation, a salt by-product having high purity can be obtained. Saves energy, reduces raw material consumption and improves yield.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a method for recovering solid salts in the production of isooctanoic acid comprising the steps of:
s1, preparing sodium isooctanoate, namely adding isooctanol and caustic soda flakes into a reaction kettle, adding a catalyst, stirring and heating, discharging hydrogen generated by reaction, and obtaining sodium isooctanoate in the reaction kettle when no hydrogen is generated as a reaction end point;
s2, carrying out primary acidification on sodium iso-octoate, dissolving the sodium iso-octoate obtained in the primary acidification in the step S1 in clear water, and adding 20% of excessive acid to carry out acidification reaction to obtain acidified sodium iso-octoate;
s3, recovering solid salt, standing the acidified sodium iso-octoate to separate an upper organic phase and a lower water phase, wherein the organic phase is iso-octoate, and performing solid-liquid separation on the lower water phase through a centrifugal machine to obtain solid salt and salt saturated liquid;
s4, subsequent acidification of sodium iso-octoate, dissolving sodium iso-octoate obtained in the step S1 in the salt saturated liquid obtained in the step S3, cooling, stirring and adding equimolar acid to obtain acidified sodium iso-octoate;
and S5, repeating, and repeating the step S3 and the step S4.
In order to optimize the product structure, the catalyst in step S1 is one or more of zinc acetate, zinc oxide, copper acetate, nickel oxide or nickel acetate; the adding amount of the catalyst in the step S1 is 0.05-0.2% of that of isooctanol; in the step S1, the temperature is raised to 145-150 ℃, and the pressure in the reaction kettle is 0.2-3 MPa when hydrogen is discharged.
Preferably, the acid in step S2 and step S4 is one of hydrochloric acid, sulfuric acid, nitric acid or acetic acid.
The temperature of the water phase in the solid-liquid separation of the centrifuge in the step S3 is not lower than 38 ℃ and not higher than 40 ℃.
The system for recovering the solid salt in the production of the isooctanoic acid comprises a reaction kettle, a precipitation tank, a centrifugal machine and a water storage tank, wherein the discharge end of the reaction kettle is communicated to one end of the precipitation tank, which is far away from the reaction kettle, is communicated to the feed end of the centrifugal machine, the liquid outlet end of the centrifugal machine is communicated to the water storage tank, and the water storage tank is communicated to the feed end of the reaction kettle through a pump.
Example 2:
560g of isooctanol, 182g of flake caustic and 12g of zinc acetate are added into a reaction kettle. The temperature is raised to 140-145 ℃. Releasing hydrogen under the condition of pressure 3Mqa until no hydrogen is generated, namely the reaction end point, and then cooling for later use. The sodium isooctoate reacted above is dissolved in 490g of water, and under the condition of reducing the temperature, 276g of sulfuric acid (96% content) is added dropwise at the temperature controlled below 80 ℃, the acid is added and stirred for 30 minutes, the machine is stopped and kept stand for 40 minutes, and the lower aqueous phase containing sodium sulfate is separated. The upper layer is i.e. iso-octanoic acid according to phase, then a small amount of clear water is added for washing, and then the refined acid is obtained by distillation. When the temperature of the water phase is reduced to 40 ℃, a small amount of crystallized anhydrous sodium sulphate is separated out by a centrifuge. (the temperature of the mother liquor is not lower than 38 ℃). In the second reaction, the mother liquor (saturated aqueous sodium sulfate) of the previous batch was used to dissolve sodium isooctanoate in water, and a small amount of water was added to the mother liquor. The amount of sulfuric acid added dropwise was 230 g. All sodium sulfate produced in this reaction will be separated out with water. Separating with a centrifuge (temperature is not lower than 38 deg.C), and drying to obtain anhydrous sodium sulfate.
Example 3:
560g of isooctanol, 182g of flake caustic soda, 3g of zinc oxide, 3g of copper acetate and 1g of nickel acetate are added into a reaction kettle. The temperature is raised to 145-150 ℃, and the produced hydrogen is discharged under the pressure condition of 0.2 MPa. When no hydrogen is generated, the reaction is terminated. And (5) cooling for later use. The above reactant (sodium isooctanoate) was dissolved in 490g of clear water. Dripping 330g of glacial acetic acid under the condition of temperature reduction at the temperature of not higher than 80 ℃, stirring for 30 minutes, standing for 40 minutes, separating a lower layer of water (containing sodium acetate) phase, and taking an upper layer of organic phase as isooctanoic acid. During the next reaction, the sodium isooctanoate dissolved in the aqueous (sodium acetate-containing) phase separated from the batch. 275g of glacial acetic acid is added dropwise at a temperature of below 80 ℃. After the acid is added, stirring is carried out for 30 minutes, standing is carried out for 40 minutes, an aqueous solution containing solid sodium acetate is separated, and the sodium acetate is separated and dried. The solution is reused again, and sodium acetate generated in the reaction is fully supersaturated and separated out.
The invention is not limited to the production of isooctanoic acid by acidification of sodium isooctanoate, and is also suitable for the reaction of organic acid by acidification of sodium salt and potassium salt of organic acid.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.
Claims (7)
1. A method for recovering solid salt in the production of isooctanoic acid is characterized by comprising the following steps:
s1, preparing sodium isooctanoate, namely adding isooctanol and caustic soda flakes into a reaction kettle, adding a catalyst, stirring and heating, discharging hydrogen generated by reaction, and obtaining sodium isooctanoate in the reaction kettle when no hydrogen is generated as a reaction end point;
s2, carrying out primary acidification on sodium iso-octoate, dissolving the sodium iso-octoate obtained in the primary acidification in the step S1 in clear water, and adding 20% of excessive acid to carry out acidification reaction to obtain acidified sodium iso-octoate;
s3, recovering solid salt, standing the acidified sodium iso-octoate to separate an upper organic phase and a lower water phase, wherein the organic phase is iso-octoate, and performing solid-liquid separation on the lower water phase through a centrifugal machine to obtain solid salt and salt saturated liquid;
s4, subsequent acidification of sodium iso-octoate, dissolving sodium iso-octoate obtained in the step S1 in the salt saturated liquid obtained in the step S3, cooling, stirring and adding equimolar acid to obtain acidified sodium iso-octoate;
and S5, repeating, and repeating the step S3 and the step S4.
2. The method of claim 1, wherein the catalyst in step S1 is one or more selected from zinc acetate, zinc oxide, copper acetate, nickel oxide, and nickel acetate.
3. The method of claim 1, wherein the catalyst used in step S1 is added in an amount of 0.05% -0.2% of isooctanol.
4. The method of claim 1, wherein the temperature of step S1 is raised to 145-150 ℃, and the pressure in the reaction kettle when the hydrogen is discharged is 0.2-3 MPa.
5. The method of claim 1, wherein the acid used in steps S2 and S4 is one of hydrochloric acid, sulfuric acid, nitric acid, or acetic acid.
6. The method for recovering solid salt in the production of isooctanoic acid according to claim 1, wherein the temperature of the aqueous phase in the solid-liquid separation in the centrifuge of step S3 is not lower than 38 ℃ and not higher than 40 ℃.
7. The system for recovering the solid salt in the production of the isooctanoic acid is characterized by comprising a reaction kettle, a precipitation tank, a centrifugal machine and a water storage tank, wherein the discharge end of the reaction kettle is communicated to one end of the precipitation tank, which is far away from the reaction kettle, is communicated to the feed end of the centrifugal machine, the liquid outlet end of the centrifugal machine is communicated to the water storage tank, and the water storage tank is communicated to the feed end of the reaction kettle through a pump.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210076634.XA CN114516791A (en) | 2022-01-24 | 2022-01-24 | Method and system for recovering solid salt in production of isooctanoic acid |
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| CN202210076634.XA CN114516791A (en) | 2022-01-24 | 2022-01-24 | Method and system for recovering solid salt in production of isooctanoic acid |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249262A (en) * | 2011-04-29 | 2011-11-23 | 史永军 | Concentration and cold-precipitation separation method of sodium sulfate and ammonium sulfate from vanadium-precipitation mother liquor high-salt wastewater |
| CN103693660A (en) * | 2013-12-12 | 2014-04-02 | 中国中轻国际工程有限公司 | Process for producing sodium sulfate and sodium chloride from high-salinity nitrate aqueous solution by adopting circulation method |
| CN203602366U (en) * | 2013-11-25 | 2014-05-21 | 广州新普利节能环保科技有限公司 | Preparation system of anhydrous sodium sulphate |
| CN104672079A (en) * | 2015-02-05 | 2015-06-03 | 河北工业大学 | Process for recovering sodium isooctoate from pharmaceutical waste liquor |
| CN106278875A (en) * | 2015-06-12 | 2017-01-04 | 泰安汉威化工有限公司 | A kind of production method of isooctyl acid |
| CN111533142A (en) * | 2020-06-04 | 2020-08-14 | 新疆中泰化学阜康能源有限公司 | Circular production method for heating precipitated anhydrous sodium sulphate, cooling, crystallizing and concentrating |
-
2022
- 2022-01-24 CN CN202210076634.XA patent/CN114516791A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249262A (en) * | 2011-04-29 | 2011-11-23 | 史永军 | Concentration and cold-precipitation separation method of sodium sulfate and ammonium sulfate from vanadium-precipitation mother liquor high-salt wastewater |
| CN203602366U (en) * | 2013-11-25 | 2014-05-21 | 广州新普利节能环保科技有限公司 | Preparation system of anhydrous sodium sulphate |
| CN103693660A (en) * | 2013-12-12 | 2014-04-02 | 中国中轻国际工程有限公司 | Process for producing sodium sulfate and sodium chloride from high-salinity nitrate aqueous solution by adopting circulation method |
| CN104672079A (en) * | 2015-02-05 | 2015-06-03 | 河北工业大学 | Process for recovering sodium isooctoate from pharmaceutical waste liquor |
| CN106278875A (en) * | 2015-06-12 | 2017-01-04 | 泰安汉威化工有限公司 | A kind of production method of isooctyl acid |
| CN111533142A (en) * | 2020-06-04 | 2020-08-14 | 新疆中泰化学阜康能源有限公司 | Circular production method for heating precipitated anhydrous sodium sulphate, cooling, crystallizing and concentrating |
Non-Patent Citations (1)
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| 安家驹: "实用精细化工辞典", 北京：中国轻工业出版社, pages: 1057 * |
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