CN113788751B - Purification method of byproduct acetic acid in linalyl acetate production - Google Patents
Purification method of byproduct acetic acid in linalyl acetate production Download PDFInfo
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Abstract
The invention provides a purification method of byproduct acetic acid in linalyl acetate production, which comprises the steps of adding organic nitrogen-containing substances into the byproduct acetic acid to be purified obtained in linalyl acetate production, and then obtaining acetic acid through decompression hypergravity rectification to complete separation and purification. The invention changes the relative volatility of unsaturated olefin in the azeotropic system by adding organic nitrogen-containing substances, improves the stability of the unsaturated olefin, and realizes the separation of the unsaturated olefin and acetic acid by mass transfer strengthening effect of the hypergravity rectification, thereby obtaining high-purity acetic acid byproducts, and the purity of the purified acetic acid can reach more than 99.5 percent.
Description
Technical Field
The invention belongs to the technical field of linalyl acetate preparation, and relates to a purification method of acetic acid as a byproduct in linalyl acetate production.
Background
Linalyl acetate naturally exists in essential oils of plants such as lavender and bergamot, and has elegant lavender fragrance. The main synthesis of linalyl acetate is obtained by esterification of linalool with acetic anhydride, and the preparation of linalyl acetate using trioctyl ammonia and DMAP as catalysts is reported in US patent 7355066 (B1). The reaction equation is as follows:
due to the crowded spatial structure of the hydroxyl in the linalool, a small amount of linalool can be used for removing a molecule of water to generate myrcene in the reaction process, and then the myrcene is cyclized to generate alpha-terpinene and limonene. The reaction formula is as follows:
the main byproduct in the linalyl acetate production process is acetic acid, and the acetic acid contains myrcene, alpha-terpinene, limonene and other substances, wherein the mass content of the substances is usually 1-5%, and the substances need to be purified. In addition, myrcene, alpha-terpinene and limonene are important spice products or intermediates, have economic values, and can be separated and recovered from acetic acid to improve the economic added value.
Laurene, alpha-terpinene and limonene are collectively called as unsaturated olefins below, and because of the azeotropic phenomenon of the unsaturated olefins and acetic acid, the ideal separation effect cannot be achieved through a conventional rectification mode, the purity of the acetic acid after reduced pressure rectification can only reach about 98%, the acetic acid with the specification is difficult to sell out, and only harmless treatment or low-price sales can be realized, so that the resource waste is caused.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a purification method of by-product acetic acid in linalyl acetate production, which aims at solving the problem that unsaturated alkene and acetic acid generated in linalyl acetate preparation process are difficult to separate due to azeotropic phenomenon.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a purification method of byproduct acetic acid in linalyl acetate production, which comprises the steps of adding organic nitrogen-containing substances into the byproduct acetic acid to be purified obtained in linalyl acetate production, and then obtaining acetic acid through decompression hypergravity rectification to complete separation and purification.
In the method of the invention, the linalyl acetate can be prepared by adopting the processes of esterification of linalool and acetic anhydride, esterification of linalool and ketene and the like;
preferably, the linalyl acetate is prepared by reacting linalool serving as a raw material with acetic anhydride under the catalysis of trioctyl ammonia and/or 4-dimethylaminopyridine serving as catalysts;
preferably, the acetic acid to be purified obtained by the linalyl acetate production process is obtained by separating linalool generated in the linalool esterification step after rectification operation, and comprises the following components in percentage by mass: 95-99 wt% of acetic acid and 1-5 wt% of unsaturated alkene; wherein the unsaturated alkene comprises 0.5 to 4 weight percent of myrcene, 0.1 to 3 weight percent of alpha-terpinene, 0.1 to 3 weight percent of limonene and trace amounts of other unsaturated alkene, and the other unsaturated alkene comprises terpinene, ocimene and the like; the sum of the mass contents of the components is within 100 percent;
more preferably, the acetic acid to be purified is a byproduct, which comprises the following components in percentage by mass: 97 to 99 weight percent of acetic acid and 1 to 3 weight percent of unsaturated alkene; wherein the unsaturated alkene comprises myrcene 0.5-2wt%, alpha-terpinene 0.1-1wt% and limonene 0.1-1wt%.
In the method of the invention, the organic nitrogen-containing substance is selected from any one or a combination of at least two of hydroxylammonium salt, ammonium halide and alcohol amine, wherein the hydroxylammonium salt is selected from mono (2-hydroxyethyl) ammonium formate, di (2-hydroxyethyl) ammonium acetate, tri (2-hydroxyethyl) ammonium formate and 2-hydroxybenzoic acid monoammonium salt, the ammonium halide is selected from caprolactam-tetrabutylammonium chloride, caprolactam-tetrabutylammonium fluoride, caprolactam-tetraethylammonium chloride and tetraethylammonium chloride, and the alcohol amine is selected from N, N-di-tert-butyl alcohol amine, triethanolamine, butyl alcohol amine and diglycolamine;
preferably, the organic nitrogen-containing substance is selected from any one or a combination of at least two of mono (2-hydroxyethyl) ammonium formate, di (2-hydroxyethyl) ammonium acetate, tri (2-hydroxyethyl) ammonium formate, caprolactam-tetrabutylammonium chloride, caprolactam-tetrabutylammonium fluoride, N-di-tert-butyl alcohol amine, more preferably caprolactam-tetrabutylammonium fluoride and/or N, N-di-tert-butyl alcohol amine;
preferably, the addition amount of the organic nitrogen-containing substance is 0.1-5%, preferably 0.5-2% of the mass of the byproduct acetic acid to be purified.
In the method of the invention, the vacuum degree (absolute pressure) is 0.1 to 100KPa, preferably 0.5 to 20KPa; the rotation speed is 200-3000 rpm, preferably 500-2500 rpm; the temperature is 40-110 ℃, preferably 45-90 ℃;
the reflux ratio in the rectification process is 1:5-10:1, preferably 1:2-2:1.
In the method, the decompression hypergravity rectification is completed by a hypergravity rectification machine, the hypergravity rectification machine is a multi-stage hypergravity rectification machine, the number of stages is 1-3, preferably, the hypergravity rectification machine device disclosed in patent CN200920247008.2 can be adopted, and other similar multi-stage hypergravity rectification machine devices can be adopted;
preferably, the diameter of the rotor of the super-gravity rectifying machine is 650-1100 mm, and the height of the inner cavity of the rectifying machine is 900-1600 mm;
preferably, the packing adopted by the rotor in the hypergravity rectifying machine is integral structured packing, and the integral structured packing is selected from any one or a combination of at least two of foam silicon carbide ripple structured packing, foam nickel structured packing, titanium alloy structured packing, fin guide plate structured packing and modified plastic structured packing, and more preferably foam silicon carbide ripple structured packing.
Preferably, the integral structured packing has an inner diameter of 10-300 mm, an outer diameter of 50-1000 mm and a height of 20-500 mm.
In the method, after the decompression hypergravity rectification is finished, high-purity acetic acid is extracted from light components, and a mixture containing acetic acid and unsaturated olefin is extracted from heavy components;
the high-purity acetic acid has the purity of more than 99.5 percent and the recovery rate of the acetic acid of more than 60 percent;
the mixture containing acetic acid and unsaturated olefin, wherein the content of acetic acid is 50-95 wt%, the content of unsaturated olefin is 3-30 wt%, and the mixture contains organic nitrogen-containing substances and trace alkane.
The concentration of unsaturated olefin in the mixture containing acetic acid and unsaturated olefin is increased, the acetic acid and the unsaturated olefin can be further separated by adopting water washing, pressure swing rectification and other modes, and the separated unsaturated olefin can be used for producing spice products such as menthol, nerol, ambroxol and the like, or the acetic acid can be recovered by adopting multiple times of gravity rectification and the like.
The organic nitrogen-containing substance contained in the mixture containing acetic acid and unsaturated olefin can also be recovered and used by distillation and concentration.
The byproduct acetic acid in the linalyl acetate production process contains unsaturated alkene myrcene, alpha-terpinene, limonene and the like, and the azeotropic phenomenon of the byproduct acetic acid and the acetic acid exists in the rectification process, so that the high-purity acetic acid is difficult to obtain. The invention adopts the hypergravity rectification technology to purify the byproduct acetic acid, strengthens interphase mass transfer by utilizing centrifugal force, can increase the content of light components in gas phase products, and achieves more excellent separation effect. Meanwhile, the relative volatility of the unsaturated olefins can be changed by adding organic nitrogen-containing substances, so that the separation effect on an azeotropic system is remarkably improved.
The invention changes the relative volatility of unsaturated olefin in the azeotropic system by adding organic nitrogen-containing substances, improves the stability of the unsaturated olefin, and realizes the separation of the unsaturated olefin and acetic acid by mass transfer strengthening effect of the hypergravity rectification to obtain high-purity acetic acid byproducts.
Detailed Description
The following examples will further illustrate the process provided by the present invention, but the invention is not limited to the examples listed and should include any other known modifications within the scope of the claimed invention.
Example main raw material source information:
n, N-di-tert-butyl alcohol amine: 99wt%, of the carbofuran technologies limited;
caprolactam-tetrabutylammonium fluoride: 99wt%, of the carbofuran technologies limited;
mono (2-hydroxyethyl) ammonium formate: 99wt%, of the carbofuran technologies limited;
bis (2-hydroxyethyl) ammonium acetate: 99wt%, of the carbofuran technologies limited;
trioctylamine: 99wt%, ala Ding Keji Co., ltd;
aniline: 99wt%, ala Ding Keji Co., ltd;
4-dimethylaminopyridine: 99wt%, of the carbofuran technologies limited;
acetic acid as a byproduct to be purified: the linalool and acetic anhydride esterification process is used for preparing linalyl acetate and is recovered, and the linalool and the acetic anhydride are subjected to esterification reaction under the catalysis of 4-dimethylaminopyridine, the top light component of the tower after linalyl acetate is separated by rectification, and the top light component of the tower is obtained after the acetic anhydride is recovered by further rectification;
unless otherwise specified, the other materials are all common materials purchased in the market.
Hypergravity rectifier: the number of stages is 3, the diameter of the rotor is 650mm, the height of the inner cavity of the rectifying machine is 900mm, and BZ650-3P of Hangzhou Keli chemical equipment is available;
foam silicon carbide corrugated structured packing: inner diameter 150mm, outer diameter 650mm, height 200mm, hangzhou Keli chemical equipment limited SUS316L;
fin baffle structured packing: inner diameter 150mm, outer diameter 650mm, height 200mm, hangzhou Keli chemical equipment limited SUS316L;
foam nickel structured packing: inner diameter 150mm, outer diameter 650mm, height 200mm, hangzhou Keli chemical equipments limited SUS316L.
The product composition analysis method comprises the following steps: gas chromatograph: agilent7820A, column HP-5 (30 m×320 μm×0.25 μm), sample inlet temperature: 150 ℃; the split ratio is 50:1; carrier gas flow rate: 25ml/min; heating program: maintaining at 50deg.C for 1min, heating to 90deg.C at 10deg.C/min, maintaining at 180deg.C at 5deg.C/min, maintaining for 0min, and maintaining at 30deg.C/min to 280 deg.C for 6min. Detector temperature: 280 ℃.
Example 1
The supergravity rectifying machine uses structured packing as foam silicon carbide corrugated structured packing;
the mass percentage of the acetic acid which is a byproduct to be purified is 95.73 percent of acetic acid, 2.15 percent of myrcene, 0.36 percent of alpha-terpinene, 0.97 percent of limonene and 0.79 percent of other unsaturated olefins (terpinene, ocimene and the like).
N, N-di-tert-butyl alcohol amine is added into acetic acid which is a byproduct to be purified according to the proportion of 0.5wt%, then the acetic acid enters a hypergravity rectifying machine at the flow rate of 150Kg/h to carry out continuous decompression hypergravity rectifying operation, the vacuum degree (absolute pressure) in the rectifying process is 1KPa, the rotating speed is 500rpm, the temperature is 50 ℃, and the reflux ratio is 2:1. The light component extracted in the rectification process is high-purity acetic acid, and the extraction flow is 110Kg/h; the residual heavy component is a mixture containing acetic acid and unsaturated olefin, and the extraction flow rate is 40Kg/h;
the high-purity acetic acid purified in this example had an acetic acid purity of 99.56wt% and, in addition, had an unsaturated olefin impurity content of 0.32wt% myrcene and 0.12wt% limonene; the recovery of acetic acid was 76.26%.
The rest comprises a mixture of acetic acid and unsaturated olefin, wherein the mass percentage of the acetic acid is 83.40 percent, and the rest comprises myrcene, alpha-terpinene, limonene, N-di-tert-butyl alcohol amine and other unsaturated olefins.
Example 2
The hypergravity rectifying machine uses structured packing as fin guide plate structured packing;
the mass percentage of the acetic acid which is a byproduct to be purified is 95.73 percent of acetic acid, 2.15 percent of myrcene, 0.36 percent of alpha-terpinene, 0.97 percent of limonene and 0.79 percent of other unsaturated olefins (terpinene, ocimene and the like).
N, N-di-tert-butyl alcohol amine is added into acetic acid which is a byproduct to be purified according to the proportion of 1.0wt%, then the acetic acid enters a hypergravity rectifying machine at the flow rate of 150Kg/h to carry out continuous decompression hypergravity rectifying operation, the vacuum degree (absolute pressure) in the rectifying process is 0.5KPa, the rotating speed is 1500rpm, the temperature is 45 ℃, and the reflux ratio is 2:1. The light component extracted in the rectification process is high-purity acetic acid, and the extraction flow is 116Kg/h; the residual heavy component is a mixture containing acetic acid and unsaturated olefin, and the extraction flow rate is 34Kg/h;
the high-purity acetic acid purified in this example had an acetic acid purity of 99.67wt% and, in addition, had an unsaturated olefin impurity content of 0.24wt% myrcene and 0.09wt% limonene; the recovery rate of acetic acid was 80.52%.
The rest comprises a mixture of acetic acid and unsaturated olefin, wherein the mass percentage of the acetic acid is 78.07 percent, and the rest comprises myrcene, alpha-terpinene, limonene, N-di-tert-butyl alcohol amine and other unsaturated olefins.
Example 3
The supergravity rectifying machine uses structured packing as foam silicon carbide corrugated structured packing;
the mass percentage of the acetic acid which is a byproduct to be purified consists of 97.23 percent of acetic acid, 1.72 percent of myrcene, 0.11 percent of alpha-terpinene, 0.37 percent of limonene and 0.57 percent of other unsaturated olefins (terpinene, ocimene and the like).
Caprolactam-tetrabutylammonium fluoride is added into acetic acid which is a byproduct to be purified according to the proportion of 2.0 weight percent, then the mixture enters a hypergravity rectifying machine at the flow rate of 150Kg/h to carry out continuous decompression hypergravity rectifying operation, the vacuum degree (absolute pressure) in the rectifying process is 3KPa, the rotating speed is 3000rpm, the temperature is 60 ℃, and the reflux ratio is 1:1. The light component extracted in the rectification process is high-purity acetic acid, and the extraction flow is 132Kg/h; the residual heavy component is a mixture containing acetic acid and unsaturated olefin, and the extraction flow rate is 18Kg/h;
the high-purity acetic acid purified in this example had an acetic acid purity of 99.93wt% and, in addition, had an unsaturated olefin impurity content of 0.05wt% myrcene and 0.02wt% limonene; the recovery rate of acetic acid was 90.44%.
The rest comprises a mixture of acetic acid and unsaturated olefin, wherein the mass percentage of the acetic acid is 61.22%, and the rest comprises myrcene, alpha-terpinene, limonene, caprolactam-tetrabutylammonium fluoride and other unsaturated olefins.
Example 4
The hypergravity rectifying machine uses structured packing as fin guide plate structured packing;
the mass percentage of the acetic acid which is a byproduct to be purified consists of 97.23 percent of acetic acid, 1.72 percent of myrcene, 0.11 percent of alpha-terpinene, 0.37 percent of limonene and 0.57 percent of other unsaturated olefins (terpinene, ocimene and the like).
Adding mono (2-hydroxyethyl) ammonium formate into acetic acid which is a byproduct to be purified according to the proportion of 5.0wt%, and then feeding the acetic acid into a hypergravity rectifying machine at the flow rate of 150Kg/h for continuous decompression hypergravity rectifying operation, wherein the vacuum degree (absolute pressure) in the rectifying process is 10KPa, the rotating speed is 2000rpm, the temperature is 80 ℃, and the reflux ratio is 2:1. The light component extracted in the rectification process is high-purity acetic acid, and the extraction flow is 103Kg/h; the residual heavy component is a mixture containing acetic acid and unsaturated olefin, and the extraction flow rate is 47Kg/h;
the high-purity acetic acid purified in this example had an acetic acid purity of 99.51wt% and, in addition, had an unsaturated olefin impurity content of 0.42wt% myrcene and 0.07wt% limonene; the recovery rate of acetic acid was 70.28%.
The rest comprises a mixture of acetic acid and unsaturated olefin, wherein the mass percentage of the acetic acid is 76.72 percent, and the rest comprises myrcene, alpha-terpinene, limonene, mono (2-hydroxyethyl) ammonium formate and other unsaturated olefins.
Example 5
The supergravity rectifying machine uses structured packing as foam silicon carbide corrugated structured packing;
the mass percentage of the acetic acid which is a byproduct to be purified is 98.34 percent of acetic acid, 1.17 percent of myrcene, 0.06 percent of alpha-terpinene, 0.32 percent of limonene and 0.11 percent of other unsaturated olefins (terpinene, ocimene and the like).
And adding di (2-hydroxyethyl) ammonium acetate into acetic acid which is a byproduct to be purified according to the proportion of 1.0wt%, and then feeding the acetic acid into a hypergravity rectifying machine at the flow rate of 150Kg/h for continuous decompression hypergravity rectifying operation, wherein the vacuum degree (absolute pressure) in the rectifying process is 20KPa, the rotating speed is 2500rpm, the temperature is 90 ℃, and the reflux ratio is 2:1. The light component extracted in the rectification process is high-purity acetic acid, and the extraction flow is 109Kg/h; the residual heavy component is a mixture containing acetic acid and unsaturated olefin, and the extraction flow rate is 41Kg/h;
the high-purity acetic acid purified in this example had an acetic acid purity of 99.65wt% and, in addition, had an unsaturated olefin impurity content of 0.31wt% myrcene and 0.04wt% limonene; the recovery rate of acetic acid was 73.63%.
The rest comprises a mixture of acetic acid and unsaturated olefin, wherein the mass percentage of the acetic acid is 91.26 percent, and the rest comprises myrcene, alpha-terpinene, limonene, di (2-hydroxyethyl) ammonium acetate and other unsaturated olefins.
Example 6
The supergravity rectifying machine uses structured packing as foam silicon carbide corrugated structured packing;
the mass percentage of the acetic acid which is a byproduct to be purified is 98.34 percent of acetic acid, 1.17 percent of myrcene, 0.06 percent of alpha-terpinene, 0.32 percent of limonene and 0.11 percent of other unsaturated olefins (terpinene, ocimene and the like).
Caprolactam-tetrabutylammonium fluoride is added into acetic acid which is a byproduct to be purified according to the proportion of 1.0 weight percent, then the mixture enters a hypergravity rectifying machine at the flow rate of 150Kg/h to carry out continuous decompression hypergravity rectifying operation, the vacuum degree (absolute pressure) in the rectifying process is 1KPa, the rotating speed is 2000rpm, the temperature is 60 ℃, and the reflux ratio is 1:2. The light component extracted in the rectification process is high-purity acetic acid, and the extraction flow is 142Kg/h; the residual heavy component is a mixture containing acetic acid and unsaturated olefin, and the extraction flow rate is 8Kg/h;
the high-purity acetic acid purified in this example had an acetic acid purity of 99.92wt% and, in addition, had an unsaturated olefin impurity content of 0.07wt% myrcene and 0.01wt% limonene; the acetic acid recovery was 96.19%.
The rest comprises a mixture of acetic acid and unsaturated olefin, wherein the mass percentage of the acetic acid is 51.86 percent, and the rest comprises myrcene, alpha-terpinene, limonene, caprolactam-tetrabutylammonium fluoride and other unsaturated olefins.
Example 7
The purification procedure of example 1 was followed except that N, N-di-tert-butylethanolamine was replaced with trioctylamine, and the other procedures and parameters were the same as in example 1.
The light component extracted in the rectification process is high-purity acetic acid, and the extraction flow is 100Kg/h; the residual heavy component is a mixture containing acetic acid and unsaturated olefin, and the extraction flow rate is 50Kg/h;
the high-purity acetic acid purified in this example had an acetic acid purity of 98.91wt% and, in addition, had an unsaturated olefin impurity content of 0.85wt% of myrcene and 0.24wt% of α -terpinene; the recovery rate of acetic acid was 68.88%.
The rest comprises a mixture of acetic acid and unsaturated olefin, wherein the mass percentage of the acetic acid is 87.93 percent, and the rest comprises myrcene, alpha-terpinene, limonene, trioctylamine and other unsaturated olefins.
Example 8
The purification procedure of example 1 was followed except that N, N-di-tert-butylalcohol amine was replaced with aniline, and the other procedures and parameters were the same as in example 1.
The light component extracted in the rectification process is high-purity acetic acid, and the extraction flow is 88Kg/h; the residual heavy component is a mixture containing acetic acid and unsaturated olefin, and the extraction flow rate is 62Kg/h;
the high-purity acetic acid purified in this example had an acetic acid purity of 99.12wt%, and further had an unsaturated olefin impurity content of 0.65wt% of myrcene and 0.23wt% of α -terpinene; the recovery of acetic acid was 60.74%.
The rest comprises a mixture of acetic acid and unsaturated olefin, wherein the mass percentage of the acetic acid is 89.76 percent, and the rest comprises myrcene, alpha-terpinene, limonene, aniline and other unsaturated olefins.
Comparative example 1
The purification process of example 1 was followed except that no N, N-di-t-butylalcohol amine was added in a proportion of 0.5%, and acetic acid as a by-product to be purified was directly fed into a hypergravity rectifier for rectification, and other operations and parameters were the same as in example 1.
The light component extracted in the rectification process of the comparative example is purified acetic acid, the extraction flow is 50Kg/h, the purity of the acetic acid is 97.74wt%, and in addition, the impurity content of unsaturated olefin is 1.49wt% of myrcene, 0.09wt% of alpha-terpinene, 0.56% of limonene and 0.12% of other components; the recovery rate of acetic acid was 34.03%.
The residual weight component is a mixture containing acetic acid and unsaturated olefin, the extraction flow rate is 100Kg/h, wherein the mass percent of the acetic acid is 94.73%, and the residual components are myrcene, alpha-terpinene, limonene and other unsaturated olefins.
Comparative example 2
The purification method of example 1 was followed except that the hypergravity rectifying machine was replaced with a rectifying column having a theoretical plate number of 25, and other operations and parameters were the same as in example 1.
The light component extracted in the rectification process of the comparative example is purified acetic acid, the extraction flow is 50Kg/h, the purity of the acetic acid is 99.53wt%, and in addition, the impurity content of unsaturated olefin is 0.32wt% of myrcene and 0.15% of limonene; the acetic acid recovery was 34.17%.
The residual weight component is a mixture containing acetic acid and unsaturated olefin, the extraction flow is 100Kg/h, wherein the mass percent of the acetic acid is 93.11 percent, and the residual components are myrcene, alpha-terpinene, limonene, N-di-tert-butyl alcohol amine and other unsaturated olefins.
Comparative example 3
The mass percentage of the acetic acid mixed solution which is a by-product to be purified is 95.73 percent of acetic acid, 2.15 percent of myrcene, 0.36 percent of alpha-terpinene, 0.97 percent of limonene and 0.79 percent of other (terpinene, ocimene and the like). The acetic acid as a by-product to be purified enters a rectifying tower with the theoretical plate number of 25 at the flow rate of 150Kg/h for continuous rectification operation, the vacuum degree (absolute pressure) in the rectification process is 1KPa, the rotating speed is 500rpm, the temperature is 50 ℃, and the reflux ratio is 3:1.
The light component extracted in the rectification process of the comparative example is purified acetic acid, the extraction flow is 50Kg/h, the purity of the acetic acid is 96.92wt%, and in addition, the impurity content of unsaturated olefin is 1.61wt% of myrcene, 0.25wt% of alpha-terpinene, 0.83% of limonene and 0.39% of other components; the acetic acid recovery was 33.75%.
The residual weight component is a mixture containing acetic acid and unsaturated olefin, the extraction flow is 100Kg/h, wherein the mass percent of the acetic acid is 94.42 percent, and the residual components are myrcene, alpha-terpinene, limonene and other unsaturated olefins.
Claims (15)
1. The method is characterized in that organic nitrogen-containing substances are added into acetic acid which is a byproduct to be purified and is obtained in the production of linalyl acetate, and then acetic acid is obtained through decompression hypergravity rectification, so that separation and purification are completed;
the by-product acetic acid to be purified comprises the following components in percentage by mass: 95-99 wt% of acetic acid and 1-5 wt% of unsaturated alkene; wherein the unsaturated alkene comprises myrcene 0.5-4wt%, alpha-terpinene 0.1-3wt%, limonene 0.1-3wt% and trace other unsaturated alkene;
the organic nitrogen-containing substance is selected from any one or a combination of at least two of mono (2-hydroxyethyl) ammonium formate, di (2-hydroxyethyl) ammonium acetate, caprolactam-tetrabutylammonium chloride, caprolactam-tetrabutylammonium fluoride and N, N-di-tert-butyl alcohol amine.
2. The purification method according to claim 1, wherein linalyl acetate is prepared by an esterification process of linalool with acetic anhydride and linalool with ketene.
3. The purification method according to claim 2, wherein linalyl acetate is prepared by reacting linalool with acetic anhydride under the catalytic action of trioctyl ammonia and/or 4-dimethylaminopyridine catalyst.
4. The purification method according to claim 1, wherein the by-product acetic acid to be purified comprises the following components in percentage by mass: 97 to 99 weight percent of acetic acid and 1 to 3 weight percent of unsaturated alkene; wherein the unsaturated alkene comprises myrcene 0.5-2wt%, alpha-terpinene 0.1-1wt% and limonene 0.1-1wt%.
5. The purification method according to claim 1, wherein the organic nitrogen-containing substance is added in an amount of 0.1 to 5% by mass of acetic acid as a by-product to be purified.
6. The method according to claim 5, wherein the organic nitrogen-containing substance is added in an amount of 0.5 to 2% by mass of acetic acid as a by-product to be purified.
7. The method according to claim 1, wherein the vacuum degree is 0.1 to 100KPa, the rotation speed is 200 to 3000rpm, and the temperature is 40 to 110 ℃.
8. The method according to claim 7, wherein the vacuum degree is 0.5 to 20KPa, the rotation speed is 500 to 2500rpm, and the temperature is 45 to 90 ℃.
9. The purification method according to claim 1, wherein the reduced pressure hypergravity distillation is performed by a hypergravity distillation machine which is a multistage hypergravity distillation machine with a number of stages of 1 to 3.
10. The purification method according to claim 9, wherein the rotor diameter of the super gravity rectifying machine is 650-1100 mm, and the height of the inner cavity of the rectifying machine is 900-1600 mm.
11. The purification method according to claim 1, wherein the reflux ratio of the rectification process is 1:5 to 10:1.
12. The purification method of claim 11, wherein the reflux ratio of the rectification process is 1:2 to 2:1.
13. The purification method according to claim 9, wherein the packing adopted by the rotor in the hypergravity rectifying machine is integral structured packing, and the integral structured packing is selected from any one or a combination of at least two of foam silicon carbide corrugated structured packing, foam nickel structured packing, titanium alloy structured packing, fin guide plate structured packing and modified plastic structured packing.
14. The purification process according to claim 13, wherein the monolithic structured packing has an inner diameter of 10 to 300mm, an outer diameter of 50 to 1000mm and a height of 20 to 500mm.
15. The method according to claim 1, wherein the purity of the acetic acid after purification is 99.5% or more and the recovery rate of acetic acid is 60% or more.
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