CN106966850B - Preparation method of high-purity 1-methylnaphthalene - Google Patents
Preparation method of high-purity 1-methylnaphthalene Download PDFInfo
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- CN106966850B CN106966850B CN201710259373.4A CN201710259373A CN106966850B CN 106966850 B CN106966850 B CN 106966850B CN 201710259373 A CN201710259373 A CN 201710259373A CN 106966850 B CN106966850 B CN 106966850B
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- methylnaphthalene
- organic layer
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- metal halide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
Abstract
The invention relates to a preparation method of high-purity 1-methylnaphthalene, which comprises the following steps: (a) adding industrial methylnaphthalene fraction into an acid solution for acid washing, standing and layering to obtain a first organic layer; (b) adding the first organic layer into an alkaline solution for alkaline washing, and standing for layering to obtain a second organic layer; (c) adding ethanethiol, metal halide and a catalyst into the second organic layer to perform a reflux reaction; the mass ratio of the second organic layer to the ethanethiol to the metal halide to the catalyst is 100: 80-150: 1-5: 0.5 to 2; the catalyst is a mixture of copper oxide and aluminum trioxide, and the mass ratio of the copper oxide to the aluminum trioxide is 1: 1-3; (d) and (c) filtering and rectifying the product obtained in the step (c). Thus, the selective removal of 2-methylnaphthalene can be realized, and the purity of 1-methylnaphthalene is greatly improved.
Description
Technical Field
The invention relates to a preparation method of oil agent methylnaphthalene, in particular to a preparation method of high-purity 1-methylnaphthalene.
Background
The 1-methylnaphthalene (α -methylnaphthalene) is a colorless oily liquid, has naphthalene-like smell, can volatilize with vapor, is inflammable, insoluble in water, and easily soluble in ether and ethanol, has a relative density (20 ℃) of 1.025, a boiling point of 245 ℃ and a flash point of 82.2 ℃, is a main raw material for producing a disperse dye auxiliary agent (dispersant), can also be used as a heat carrier and a solvent, a surfactant, a sulfur extractant, a plasticizer and a fiber dyeing auxiliary agent, and can also be used for producing a standard fuel for measuring the cetane number and the cetane number.
At present, α -methylnaphthalene and β -methylnaphthalene are extracted from industrial methylnaphthalene fraction mainly by adopting distillation, crystallization and suction filtration methods, namely the industrial methylnaphthalene fraction is directly immersed into a rectifying tower for rectification, and in order to improve the product purity, purification is carried out in a crystallizer according to different crystallization points of α -methylnaphthalene and β -methylnaphthalene, so that the process has the defects of raw material waste and low extraction rate.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of high-purity 1-methylnaphthalene.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of high-purity 1-methylnaphthalene comprises the following steps:
(a) adding industrial methylnaphthalene fraction into an acid solution for acid washing, standing and layering to obtain a first organic layer;
(b) adding the first organic layer into an alkaline solution for alkaline washing, and standing for layering to obtain a second organic layer;
(c) adding ethanethiol, metal halide and a catalyst into the second organic layer to perform a reflux reaction; the mass ratio of the second organic layer to the ethanethiol to the metal halide to the catalyst is 100: 80-150: 1-5: 0.5 to 2;
(d) and (c) filtering and rectifying the product obtained in the step (c).
Optimally, the catalyst is a mixture of copper oxide and aluminum trioxide, and the mass ratio of the copper oxide to the aluminum trioxide is 1: 1 to 3.
Optimally, in the step (a), the acidic solution is a sulfuric acid solution with the mass concentration of 10-30%.
Further, in the step (a), the pickling temperature is 40-60 ℃.
Preferably, in the step (b), the alkaline solution is a sodium bicarbonate solution with a mass concentration of 5-10%.
Further, in the step (b), the alkali washing temperature is 70-90 ℃.
Preferably, in step (c), the metal halide is aluminum chloride or zinc chloride.
Optimally, in the step (d), the rectification conditions include tower top temperature of 175-190 ℃, tower top absolute pressure of 50-100 kPa and reflux ratio of 8-12.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: the preparation method of the high-purity 1-methylnaphthalene of the invention carries out acid washing and alkali washing on industrial methylnaphthalene distillate in sequence, and carries out reflux reaction on ethanethiol, metal halide and catalyst, thus realizing the selective removal of 2-methylnaphthalene, greatly improving the purity of the 1-methylnaphthalene to 99.9 percent at most.
Detailed Description
The preparation method of the high-purity 1-methylnaphthalene comprises the following steps: (a) adding industrial methylnaphthalene fraction into an acid solution for acid washing, standing and layering to obtain a first organic layer; (b) adding the first organic layer into an alkaline solution for alkaline washing, and standing for layering to obtain a second organic layer; (c) adding ethanethiol, metal halide and a catalyst into the second organic layer to perform a reflux reaction; the mass ratio of the second organic layer to the ethanethiol to the metal halide to the catalyst is 100: 80-150: 1-5: 0.5 to 2; the catalyst is a mixture of copper oxide and aluminum trioxide, and the mass ratio of the copper oxide to the aluminum trioxide is 1: 1-3; (d) and (c) filtering and rectifying the product obtained in the step (c). The industrial methylnaphthalene distillate is sequentially subjected to acid washing and alkali washing, and reflux reaction is carried out on ethanethiol, metal halide and a catalyst, so that the 2-methylnaphthalene can be selectively removed, and the purity of the 1-methylnaphthalene is greatly improved.
In the step (a), the acidic solution is preferably a sulfuric acid solution with the mass concentration of 10-30%; the pickling temperature is 40-60 ℃. In the step (b), the alkaline solution is preferably a sodium bicarbonate solution with the mass concentration of 5-10%; the alkali washing temperature is 70-90 ℃. In step (c), the metal halide is preferably aluminum chloride or zinc chloride. In the step (d), the rectification conditions are preferably that the tower top temperature is 175-190 ℃, the tower top absolute pressure is 50-100 kPa, and the reflux ratio is 8-12.
The following detailed description of preferred embodiments of the invention is provided:
example 1
This example provides a method for preparing high purity 1-methylnaphthalene, which comprises the following steps:
(a) adding industrial methylnaphthalene fraction (mainly containing 1-methylnaphthalene, 2-methylnaphthalene, quinoline and indole) into an excessive sulfuric acid solution (usually the volume ratio of the industrial methylnaphthalene to the industrial methylnaphthalene is 1: 5-10) with the mass concentration of 10%, carrying out acid washing at 40 ℃, standing for layering, and removing a water layer to obtain a first organic layer;
(b) adding the organic layer into a sodium bicarbonate solution with the mass concentration of 5%, performing alkali washing at 70 ℃ to enable the organic layer to be close to neutral (the test paper does not change color), standing for layering, and removing a water layer to obtain a second organic layer;
(c) adding ethanethiol, metal halide and a catalyst into the second organic layer to carry out reflux reaction (the reflux temperature is about 40 ℃); the mass ratio of the second organic layer to the ethanethiol to the aluminum chloride to the catalyst is 100: 80: 1: 0.5, the catalyst is copper oxide and aluminum trioxide according to the mass ratio of 1: 1;
(d) filtering the product of the step (c) by a conventional filter with an activated carbon fiber filling layer, and then introducing the product into a rectifying tower for rectification: the temperature at the top of the tower is 175 ℃, the absolute pressure at the top of the tower is 50kPa, the reflux ratio is 8, and the distillate at the top of the tower is collected and cooled to obtain the 1-methylnaphthalene with the purity of 99.5 percent.
Example 2
This example provides a method for preparing high purity 1-methylnaphthalene, which comprises the following steps:
(a) adding industrial methylnaphthalene fraction (mainly containing 1-methylnaphthalene, 2-methylnaphthalene, quinoline and indole) into an excessive sulfuric acid solution (usually the volume ratio of the industrial methylnaphthalene to the industrial methylnaphthalene is 1: 1-3) with the mass concentration of 30% to carry out acid washing at the temperature of 60 ℃, standing for layering, and removing a water layer to obtain a first organic layer;
(b) adding the organic layer into a sodium bicarbonate solution with the mass concentration of 10%, performing alkali washing at the temperature of 90 ℃ to enable the organic layer to be close to neutrality (the test paper does not change color), standing for layering, and removing a water layer to obtain a second organic layer;
(c) adding ethanethiol, metal halide and a catalyst into the second organic layer to carry out reflux reaction (the reflux temperature is about 40 ℃); the mass ratio of the second organic layer to the ethanethiol to the aluminum chloride to the catalyst is 100: 150: 5: 2, the catalyst is copper oxide and aluminum trioxide according to the mass ratio of 1: 3;
(d) filtering the product of the step (c) by a conventional filter with an activated carbon fiber filling layer, and then introducing the product into a rectifying tower for rectification: the temperature at the top of the tower is 190 ℃, the absolute pressure at the top of the tower is 100kPa, the reflux ratio is 12, and the distillate at the top of the tower is collected and cooled to obtain the 1-methylnaphthalene with the purity of 99.6 percent.
Example 3
This example provides a method for preparing high purity 1-methylnaphthalene, which comprises the following steps:
(a) adding industrial methylnaphthalene fraction (mainly containing 1-methylnaphthalene, 2-methylnaphthalene, quinoline and indole) into an excessive sulfuric acid solution (usually the volume ratio of industrial methylnaphthalene to the industrial methylnaphthalene is 1: 5) with the mass concentration of 20% to carry out acid washing at the temperature of 50 ℃, standing for layering, and removing a water layer to obtain a first organic layer;
(b) adding the organic layer into 8% sodium bicarbonate solution, performing alkali washing at 80 deg.C to make it nearly neutral (the test paper does not change color), standing for layering, and discarding the water layer to obtain a second organic layer;
(c) adding ethanethiol, metal halide and a catalyst into the second organic layer to carry out reflux reaction (the reflux temperature is about 40 ℃); the mass ratio of the second organic layer to the ethanethiol to the aluminum chloride to the catalyst is 100: 100: 2: 1, the catalyst is copper oxide and aluminum trioxide according to the mass ratio of 1: 2;
(d) filtering the product of the step (c) by a conventional filter with an activated carbon fiber filling layer, and then introducing the product into a rectifying tower for rectification: the temperature at the top of the tower is 180 ℃, the absolute pressure at the top of the tower is 80kPa, the reflux ratio is 10, and the distillate at the top of the tower is collected and cooled to obtain the 1-methylnaphthalene with the purity of 99.9 percent.
Comparative example 1
This example provides a process for the preparation of high purity 1-methylnaphthalene essentially identical to that of example 3, except that: in the step (c), no catalyst is added, and finally, the 1-methylnaphthalene with the purity of 75 percent is obtained after the distillate at the top of the tower is cooled.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (7)
1. A preparation method of high-purity 1-methylnaphthalene is characterized by comprising the following steps:
(a) adding industrial methylnaphthalene fraction into an acid solution for acid washing, standing and layering to obtain a first organic layer;
(b) adding the first organic layer into an alkaline solution for alkaline washing, and standing for layering to obtain a second organic layer;
(c) adding ethanethiol, metal halide and a catalyst into the second organic layer to perform a reflux reaction; the mass ratio of the second organic layer to the ethanethiol to the metal halide to the catalyst is 100: 80-150: 1-5: 0.5 to 2;
(d) filtering and rectifying the product obtained in the step (c); in the step (c), the catalyst is a mixture of copper oxide and aluminum trioxide, and the mass ratio of the copper oxide to the aluminum trioxide is 1: 1 to 3.
2. The method for producing high-purity 1-methylnaphthalene according to claim 1, wherein: in the step (a), the acidic solution is a sulfuric acid solution with a mass concentration of 10-30%.
3. The method for producing high-purity 1-methylnaphthalene according to claim 1, wherein: in the step (a), the pickling temperature is 40-60 ℃.
4. The method for producing high-purity 1-methylnaphthalene according to claim 1, wherein: in the step (b), the alkaline solution is a sodium bicarbonate solution with the mass concentration of 5-10%.
5. The method for producing high-purity 1-methylnaphthalene according to claim 1 or 4, characterized in that: in the step (b), the alkali washing temperature is 70-90 ℃.
6. The method for producing high-purity 1-methylnaphthalene according to claim 1, wherein: in step (c), the metal halide is aluminum chloride or zinc chloride.
7. The method for producing high-purity 1-methylnaphthalene according to claim 1, wherein: in the step (d), the rectification conditions include tower top temperature of 175-190 ℃, tower top absolute pressure of 50-100 kPa and reflux ratio of 8-12.
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| CN109289930B (en) * | 2018-11-19 | 2021-08-24 | 鹏辰新材料科技股份有限公司 | Method for efficiently separating and purifying 1-methylnaphthalene |
| CN115073257B (en) * | 2022-08-03 | 2023-10-27 | 连云港鹏辰特种新材料有限公司 | Method for separating and purifying 1-methylnaphthalene from methylnaphthalene enrichment mother liquor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6130536A (en) * | 1984-07-23 | 1986-02-12 | Nippon Steel Chem Co Ltd | Purification of methylnaphthalene |
| CN1122320A (en) * | 1994-11-02 | 1996-05-15 | 武汉钢铁(集团)公司 | Method and apparatus for extracting alpha-methyl naphthalene and beta-methylnaphthalene |
| CN101270028A (en) * | 2007-03-23 | 2008-09-24 | 宝山钢铁股份有限公司 | Purification process of alpha-methylnaphthalene |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6130536A (en) * | 1984-07-23 | 1986-02-12 | Nippon Steel Chem Co Ltd | Purification of methylnaphthalene |
| CN1122320A (en) * | 1994-11-02 | 1996-05-15 | 武汉钢铁(集团)公司 | Method and apparatus for extracting alpha-methyl naphthalene and beta-methylnaphthalene |
| CN101270028A (en) * | 2007-03-23 | 2008-09-24 | 宝山钢铁股份有限公司 | Purification process of alpha-methylnaphthalene |
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