阅读说明：本技术 一种邻二醇化合物的提纯方法及提纯系统 (Purification method and purification system of vicinal diol compound ) 是由 滕文彬 王春梅 刘博闻 杜桂强 郝小军 宋世晶 于 2018-07-16 设计创作，主要内容包括：本发明提供了一种邻二醇化合物的提纯方法,包括：S1)将邻二醇粗产品经萃取精馏后,得到萃取精馏后的邻二醇；S2)将所述萃取精馏后的邻二醇与脱味剂混合进行反应精馏；所述脱味剂为含有氨基的化合物。与现有技术相比,本发明将萃取精馏与反应精馏相结合,通过萃取精馏将粗品中大量的有味杂质去除,再通过反应精馏借助添加化学脱味剂,将微量气味杂质去除,使所得产品纯度＞99.9％,澄清透明,无刺激性味,收率可以达到85％,提升了产品品质,得到的邻二醇化合物可以满足化妆品级别要求,极大地提高了产品的附加值,解决了高端原料长期依赖进口的局面。(The invention provides a method for purifying an o-diol compound, which comprises the following steps: s1) carrying out extraction and rectification on the o-diol crude product to obtain the o-diol after extraction and rectification; s2) mixing the extracted and rectified vicinal diol with a deodorizing agent for reactive rectification; the smell removing agent is a compound containing amino. Compared with the prior art, the method combines extractive distillation and reactive distillation, removes a large amount of odorous impurities in the crude product through the extractive distillation, removes trace odorous impurities through the reactive distillation by adding a chemical deodorant, ensures that the purity of the obtained product is more than 99.9 percent, is clear and transparent, has no pungent smell, has the yield of 85 percent, improves the product quality, can meet the requirement of the cosmetic grade by the obtained vicinal diol compound, greatly improves the added value of the product, and solves the problem that high-end raw materials depend on import for a long time.)

1. A method for purifying a vicinal diol compound, comprising:

s1) carrying out extraction and rectification on the o-diol crude product to obtain the o-diol after extraction and rectification;

s2) mixing the extracted and rectified vicinal diol with a deodorizing agent for reactive rectification; the smell removing agent is a compound containing amino.

2. The purification method according to claim 1, wherein the crude vicinal diol is a crude vicinal diol obtained by an olefin oxidation process; the smell removing agent is selected from one or more of alkylamine, hydroxylamine, hydrazine and 2, 4-dinitrophenylhydrazine.

3. The purification method according to claim 2, wherein the alkylamine is selected from trimethylamine and/or triethylamine.

4. The purification method according to claim 1, wherein the amount of the deodorizing agent added is 1 to 500ppm based on the mass of the vicinal diol after the extractive distillation.

5. The purification method according to claim 1, wherein the deodorizing agent is mixed with water and then with the ortho-diol after the extractive distillation, and the mixture is subjected to reactive distillation.

6. The purification method according to claim 5, wherein the mass ratio of the water to the ortho-diol after the extractive distillation is (1-4): 1.

7. the purification method according to claim 1, wherein the temperature of the reactive distillation is 100 ℃ to 160 ℃; the pressure of the reactive distillation is 0.03-0.08 MPa; the reflux ratio of the reactive distillation is 0.3-0.8; the reaction rectification time is 20-60 min.

8. The purification method according to claim 1, further comprising:

s3) refining the ortho-diol after the reaction and the rectification to obtain refined ortho-diol; the refining temperature is 100-200 ℃; the refining pressure is 5-15 kPa; the reflux ratio of the refining is 1.5-2.5.

9. A system for purifying a vicinal diol compound, comprising:

an extractive distillation column;

the reaction rectifying tower is communicated with the extraction rectifying tower;

the reaction rectifying tower is provided with a smell removing agent feeding port; the smell removing agent is a compound containing amino.

10. The purification system of claim 9, wherein the reactive distillation column comprises a rectifying section, a reactive section, and a stripping section; the rectifying section is a silk screen structured packing; the reaction section is a guide float valve tray; the stripping section is a guide float valve tray.

Technical Field

The invention belongs to the technical field of organic synthesis, and particularly relates to a purification method and a purification system of an o-diol compound.

Background

Vicinal diol compounds such as 1, 2-pentanediol, 1, 2-hexanediol, 1, 2-octanediol, and the like are important fine chemicals and are used in the fields of cosmetics, medicines, agricultural chemicals, surfactants, polyesters, inks, and the like. Particularly, the o-glycol compound has no corrosiveness, can dissolve various active ingredients, is widely used in various cosmetics such as skin cream, eye cream, skin lotion, infant care products, sunscreen products and the like, and has the effects of moisture preservation and corrosion prevention.

At present, the domestic synthetic routes of the vicinal diol compounds mainly comprise two routes: the method has the advantages that the method is a direct oxidation method taking olefin as a raw material, and although the method has simple steps, the needed catalyst has the factors of high price, toxicity, low product yield and the like which restrict the industrialized development; secondly, the epoxy compound is used as a raw material, and the o-diol compound is prepared by hydrolysis under acidic conditions, the synthetic route is easy to realize, but the required cost is quite high. The o-diol derived from olefin generally has the problems of high impurity content, poor chromaticity, odor and the like, cannot meet the use requirement of high-end cosmetic industry, and is very important for developing a method for purifying and deodorizing the o-diol compound by using an olefin oxidation method.

European patent No. EP1876162a1 studies that during the preparation of glycols by the olefin oxidation process, there are mainly three types of by-products produced: one is dioxane compound, and the content of the compound is controlled below 0.2 percent; one is ester compound, mainly is the product of the reaction of epoxide or dihydric alcohol and acid, should be controlled below 0.005%; the other is diol compound containing ether bond, and the content is controlled below 0.3%. Because these impurities are very close to the boiling point of the glycol product, conventional distillation is not satisfactory. The method is characterized in that the purification is carried out by reduced pressure azeotropic distillation, and takes octanediol as an example, and the specific implementation method comprises the following steps: adding 100 g of octanediol sample, 100 g of propylene glycol and 50 g of water into a 500 ml four-neck flask, and heating the mixture to 90-95 ℃ under the pressure of 1.33kPa to obtain pure octanediol.

Chinese patent publication No. CN103570493A discloses extracting a vicinal diol mixture with ethyl acetate, washing the extract with saturated brine for 2 times, drying and dehydrating the washed extract with anhydrous sodium sulfate, vacuum filtering, and distilling under reduced pressure to obtain vicinal diol. However, the refining process of the method is complicated and continuous production cannot be realized.

Therefore, it is of great importance to develop a purification and odor elimination method suitable for the preparation of vicinal diol compounds by the olefin oxidation process.

Disclosure of Invention

In view of the above, the present invention provides a method and a system for purifying a higher yield of an o-diol compound.

The invention provides a method for purifying an o-diol compound, which comprises the following steps:

s1) carrying out extraction and rectification on the o-diol crude product to obtain the o-diol after extraction and rectification;

s2) mixing the extracted and rectified vicinal diol with a deodorizing agent for reactive rectification; the smell removing agent is a compound containing amino.

Preferably, the crude vicinal diol is obtained by an olefin oxidation method; the smell removing agent is selected from one or more of alkylamine, hydroxylamine, hydrazine and 2, 4-dinitrophenylhydrazine.

Preferably, the alkylamine is selected from trimethylamine and/or triethylamine.

Preferably, the addition amount of the deodorant is 1-500 ppm of the mass of the vicinal diol after extraction and rectification.

Preferably, the deodorant is mixed with water and then with the o-glycol after extraction and rectification for reaction and rectification.

Preferably, the mass ratio of the water to the o-diol after the extractive distillation is (1-4): 1.

preferably, the temperature of the reactive distillation is 100-160 ℃; the pressure of the reactive distillation is 0.03-0.08 MPa; the reflux ratio of the reactive distillation is 0.3-0.8; the reaction rectification time is 20-60 min.

Preferably, the method further comprises the following steps:

s3) refining the ortho-diol after the reaction and the rectification to obtain refined ortho-diol; the refining temperature is 100-200 ℃; the refining pressure is 5-15 kPa; the reflux ratio of the refining is 1.5-2.5.

The present invention also provides a system for purifying a vicinal diol compound, comprising:

an extractive distillation column;

the reaction rectifying tower is communicated with the extraction rectifying tower;

the reaction rectifying tower is provided with a smell removing agent feeding port; the smell removing agent is a compound containing amino.

Preferably, the reactive distillation column comprises a rectifying section, a reaction section and a stripping section; the rectifying section is a silk screen structured packing; the reaction section is a guide float valve tray; the stripping section is a guide float valve tray.

The invention provides a method for purifying an o-diol compound, which comprises the following steps: s1) carrying out extraction and rectification on the o-diol crude product to obtain the o-diol after extraction and rectification; s2) mixing the extracted and rectified vicinal diol with a deodorizing agent for reactive rectification; the smell removing agent is a compound containing amino. Compared with the prior art, the method combines extractive distillation and reactive distillation, removes a large amount of odorous impurities in the crude product through the extractive distillation, removes trace odorous impurities through the reactive distillation by adding a chemical deodorant, ensures that the purity of the obtained product is more than 99.9 percent, is clear and transparent, has no pungent smell, has the yield of 85 percent, improves the product quality, can meet the requirement of the cosmetic grade by the obtained vicinal diol compound, greatly improves the added value of the product, and solves the problem that high-end raw materials depend on import for a long time.

Drawings

FIG. 1 is a schematic structural diagram of a vicinal diol compound purification system provided by the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.

The invention provides a method for purifying an o-diol compound, which comprises the following steps: s1) carrying out extraction and rectification on the o-diol crude product to obtain the o-diol after extraction and rectification; s2) mixing the extracted and rectified vicinal diol with a deodorizing agent for reactive rectification; the smell removing agent is a compound containing amino.

The sources of all raw materials are not particularly limited in the invention, and the raw materials can be either commercially available or self-made.

The crude vicinal diol may be any one known to those skilled in the art, and is not particularly limited, and in the present invention, it is preferably a crude vicinal diol obtained by an olefin oxidation process or a technical grade vicinal diol compound obtained by an olefin oxidation process.

Carrying out extractive distillation on the o-diol crude product to obtain the o-diol after the extractive distillation; the extractant used for the extractive distillation is an extractant well known to those skilled in the art, and is not particularly limited, and in the present invention, one or more of aromatic hydrocarbons, ketones, aliphatic hydrocarbons, esters, ethers and organic chlorides are preferred, and one or more of toluene, xylene, methyl isobutyl ketone, cyclohexane, heptane, ethyl acetate, butyl acetate, diethyl ether, butyl ether, dichloromethane and chloroform are more preferred; the mass ratio of the o-glycol crude product to the extracting agent is preferably (2-6): 1, more preferably (3-5): 1, more preferably 4: 1; the temperature of the extraction rectification is preferably 100-160 ℃, and can be correspondingly adjusted according to the selected extractant; the extractive distillation can be carried out under normal pressure or under reduced pressure; the reflux ratio of the extractive distillation is preferably 1-3, more preferably 1.5-2.5, and further preferably 2; the time for the extractive distillation is preferably 0.5-2 h, more preferably 0.5-1.5 h, and further preferably 1-1.5 h; the extractive distillation can adopt an extraction and distillation coupling process, can also be a continuous extractive distillation operation process, and is not particularly limited, the continuous extractive distillation process is preferred in the invention, and the continuous extractive distillation process is more preferred to be carried out in an extractive distillation tower; the pressure at the top of the extraction rectification tower is preferably 0.03-0.1 MPa, more preferably 0.03-0.08 MPa, still more preferably 0.04-0.06 MPa, and most preferably 0.05 MPa; the extractant at the top of the tower after extraction and rectification can be recycled and reused.

Mixing the extracted and rectified vicinal diol with a deodorizing agent for reactive rectification to obtain reactive rectified vicinal diol; the deodorizing agent is a compound containing an amino group, which is well known to those skilled in the art, and is not particularly limited, and in the present invention, one or more of alkylamine, hydroxylamine, hydrazine and 2, 4-dinitrophenylhydrazine are preferable; the alkylamine is any alkylamine known to those skilled in the art, and is not particularly limited, and in the present invention, trimethylamine and/or triethylamine are preferable; the dosage of the deodorant is preferably 1-500 ppm, more preferably 50-500 ppm, still more preferably 100-500 ppm, and most preferably 200-500 ppm of the mass of the o-diol after extraction and rectification; in the invention, the deodorant is preferably mixed with water and then mixed with the ortho-diol after extraction and rectification for reaction and rectification; the water is well known to those skilled in the art, and is not particularly limited, and in order to reduce the introduction of impurities, it is preferable to use demineralized water in the present invention; the mass ratio of the water to the o-diol after the extractive distillation is preferably (1-4): 1, more preferably (1.5 to 3): 1, and preferably (2-2.5): 1, most preferably 2: 1; the temperature of the reactive distillation is preferably 100-160 ℃, more preferably 120-140 ℃, and further preferably 130 ℃; the pressure of the reactive distillation is preferably 0.03-0.08 MPa, more preferably 0.04-0.07 MPa, still more preferably 0.04-0.06 MPa, and most preferably 0.05 MPa; the reflux ratio of the reactive distillation is preferably 0.3-0.8, more preferably 0.4-0.7, still more preferably 0.4-0.6, and most preferably 0.5; the reaction rectification time is preferably 20-60 min, more preferably 20-50 min, and still more preferably 30-40 min.

According to the invention, in order to increase the purity of the vicinal diols; preferably, the ortho-diol after the reaction rectification is further refined to obtain refined ortho-diol; the refining method is not particularly limited, and is static distillation known to those skilled in the art, and the refining temperature is preferably 100 ℃ to 200 ℃; the refining pressure is preferably 5-15 kPa; the reflux ratio of the refining is preferably 1.5-2.5; in the present invention, the refining is preferably carried out in a refining column; the temperature of the tower kettle of the refining tower is preferably 150-200 ℃; the temperature at the top of the refining tower is preferably less than the boiling point of the o-diol; the tower top pressure of the refining tower is preferably 5-15 kPa, more preferably 8-12 kPa, and further preferably 10 kPa; the whole tower operation pressure drop is preferably 2-7 kPa, more preferably 3-6 kPa, and further preferably 4-5 kPa; the water-containing crude vicinal diol can be obtained at the top of the refining tower and can be recycled, vicinal diol with the purity of more than 99.9 percent can be collected at the boiling point of the vicinal diol at the upper part of the refining tower, and the material in the tower bottom of the refining tower can be used as industrial vicinal diol or the purification process is carried out again.

The method combines extractive distillation and reactive distillation, removes a large amount of odorous impurities in a crude product through the extractive distillation, removes trace odorous impurities through the reactive distillation by adding a chemical deodorant, realizes continuous high-efficiency refining and deodorization of industrial-grade vicinal diol compounds, ensures that the purity of the obtained product is more than 99.9 percent, is clear and transparent, has no pungent taste, has the yield of 85 percent, improves the product quality, ensures that the obtained vicinal diol compounds can meet the requirements of cosmetic grade, greatly improves the added value of the product, and solves the situation that high-end raw materials depend on import for a long time.

The present invention also provides a system for purifying a vicinal diol compound, comprising: an extractive distillation column; the reaction rectifying tower is communicated with the extraction rectifying tower; the reaction rectifying tower is provided with a smell removing agent feeding port; the smell removing agent is a compound containing amino.

Referring to fig. 1, fig. 1 is a schematic structural view of a vicinal diol compound purification system provided by the present invention.

The extraction and rectification tower comprises an o-diol crude product feed port, an extractant feed port, an o-diol outlet and an extractant outlet after extraction and rectification; the feed inlet of the o-diol crude product is preferably positioned on a packing layer at the upper part of the extractive distillation tower; the extractant feed port is preferably positioned at the lower part of the extractive distillation column; the extraction agent outlet is preferably communicated with an extraction agent regeneration device, and the outlet of the extraction agent regeneration device is communicated with an extraction agent feed inlet of the extraction rectification tower, so that the used extraction agent can be recycled.

The outlet of the vicinal diol after the extraction and the rectification is communicated with the reaction and rectification tower; the reaction rectifying tower preferably comprises a rectifying section, a reaction section and a stripping section; the rectifying section is preferably a screen structured packing; the height of the silk screen specification filler is preferably 3-8 m, more preferably 3-7 m, further preferably 4-6 m, and most preferably 5 m; the reaction section is preferably a guide float valve tray; the number of the reaction section guide float valve trays is preferably 15-30, more preferably 15-25, further preferably 18-22, and most preferably 20; the stripping section is preferably a guide float valve tray; the number of the stripping section guide float valve trays is preferably 15-30, more preferably 15-25, further preferably 18-22, and most preferably 20; the outlet of the vicinal diol after the extractive distillation is preferably communicated with the reaction section of the reaction distillation tower, and more preferably communicated with the first tray of the reaction section; the deodouring agent feed inlet is preferably located in the reaction section of the reactive distillation column, more preferably located in the 3 rd to 8 th trays of the reaction section, still more preferably located in the 4 th to 6 th trays of the reaction section, and most preferably located in the 5 th tray of the reaction section.

According to the present invention, the purification system preferably further comprises a refining column in communication with the reactive distillation column. The refining tower preferably comprises a rectifying section and a stripping section; the stripping section is preferably structured packing; the height of the structured packing is preferably 3-8 m, more preferably 3-7 m, still more preferably 4-6 m, and most preferably 5 m; the rectifying section is preferably a tray; the number of the tower trays is preferably 40-60, more preferably 45-55, still more preferably 48-52, and most preferably 50; the discharge hole of the reaction rectifying tower is preferably communicated with the upper part of the stripping section of the refining tower; a water-containing crude vicinal diol product can be obtained at the top of the refining tower, and a product with the purity of more than 99.9 percent can be obtained at a rectifying section, preferably at a 25 th-27 th tower tray of the rectifying section; the material of the tower body and the internal tower internals of the refining tower is preferably stainless steel, and more preferably 304 stainless steel.

The purification system of the vicinal diol compound provided by the invention realizes continuous purification treatment.

In order to further illustrate the present invention, the following will describe in detail a method and a system for purifying a vicinal diol compound according to the present invention with reference to examples.

The reagents used in the following examples are all commercially available.