CN112225650A - Refining method for obtaining high-purity methylal by purifying industrial-grade methylal - Google Patents
Refining method for obtaining high-purity methylal by purifying industrial-grade methylal Download PDFInfo
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Abstract
The invention relates to a refining method for obtaining high-purity methylal by purifying industrial-grade methylal, which mainly solves the technical problem that the high-purity methylal is difficult to obtain by a methylal-methanol azeotropic system in the industrial-grade methylal, and comprises the following steps: a) feeding the industrial-grade methylal (1) and the extractant (2) into an extraction and rectification tower (3), separating a first fraction (4) at the top of the tower, and obtaining a first tower bottom liquid (5) at the bottom of the tower; b) the first fraction (4) enters a product tower (6), light components separated from the tower top are returned to the extraction and rectification tower, and a high-purity methylal product is obtained at the tower bottom; and optional step c), the first tower bottom liquid enters a methanol tower, and after a methanol component is removed from the tower top, the methanol tower bottom liquid can be recycled or subjected to post-treatment.
Description
Technical Field
The invention relates to a refining method of high-purity methylal, in particular to a refining method of methylal with the content higher than 99 percent, which is prepared by separating methanol from industrial-grade methylal.
Background
Methylal is also called Dimethoxymethane (DMM), is colorless, transparent and volatile combustible liquid, has excellent physical and chemical properties and is widely concerned. The methylal has good solubility and water solubility and strong degreasing capability; the low boiling point and strong volatility make it have environmental protection advantage in the aspect of replacing freon and chlorine-containing solvent, therefore, it is widely used in products such as cosmetics, medicines, household products, industrial automobile products, pesticides, leather glazing agent, cleaning agent, rubber industry, paint, printing ink and the like.
The methylal has various catalytic synthesis production processes, and the traditional methylal production method mainly comprises a methylene dichloride method, a dimethyl sulfoxide method, a calcium chloride method and an acid catalytic batch method. At present, methanol and formaldehyde or paraformaldehyde are mainly prepared by catalysis, the methanol and the formaldehyde react in a synthesis tower under the catalysis of concentrated sulfuric acid, the generated methylal is distilled off from the top of the tower, the temperature of the top of the tower is controlled to be 41.5-42 ℃, and unreacted methanol is separated from a product for recycling. But the purity of the industrial-grade methylal is not high because the formaldehyde and the methanol have azeotropy under normal pressure; when the methylal is concentrated by adopting a general rectification method, a methylal-methanol azeotropic system is formed at the top of the tower, the purity of the product is more than 89-92 percent, and the high-purity product is not easy to obtain.
The low concentration of methylal can only be used for solvent addition or fuel additives, and the purity of methylal at present greatly limits downstream application of methylal. The development and application space of methylal and downstream products thereof is huge, and high-purity methylal is required in many application occasions. Especially, when methylal is used as a raw material to synthesize polyoxymethylene dimethyl ethers, methylal with higher purity is often needed as a raw material, so that the influence of methanol and water on the performance of the catalyst is avoided. Therefore, the purification of technical grade products to obtain high purity methylal has very important significance and market demand.
After azeotropic distillation, drying and precise distillation, the content of methylal can reach about 99 percent. The disadvantages of these methods are low purity of reaction products, complicated purification process, high utilization cost of the dried by-products, and difficulty in obtaining high purity, especially electronic grade methylal products with purity of over 99.70%.
At present, the preparation of high-purity methylal is also receiving wide attention, and methods for purifying methylal are researched by a pressure swing distillation method, an extractive distillation method and the like. CN104761430A introduces a process for separating methylal and methanol by pressure swing thermal coupling rectification, wherein a mixed solution of methanol and methylal is continuously circulated between a high-pressure tower and a low-pressure tower, and the methylal with high purity can be prepared by utilizing the change of the azeotropic composition of the methylal-methanol under different pressures, the purity of the refined methylal reaches 99.9 percent, and the recovery rate of each component is close to 100 percent. However, this method requires repeated distillation of a large amount of material in high-pressure and atmospheric distillation columns, and the energy consumption is high in actual operation.
CN104961631A describes a purification method of methylal, which comprises the following steps of extracting methylal with water: adding a certain amount of water into methylal with the mass concentration of less than 95 wt%, fully stirring uniformly, standing for layering, taking the supernatant, adding a drying agent into the supernatant, and drying to obtain methylal with the mass concentration of more than 99.5%. The method has the advantages of low cost, simple purification process, mild conditions and large purification amount, is beneficial to industrial continuous production, but generates a large amount of waste water, and the regeneration of the drying agent also faces a great problem.
The extractive distillation is a common preparation method of a high-purity solvent, and in the extractive distillation of high-purity methylal, organic solvents such as polyhydric alcohol or derivatives thereof are mostly used as an extractant. The method comprises the following steps of (1) mixing a polyethylene glycol dimethyl ether solvent and industrial-grade methylal in Chinese patent 200710022224.2, adding the mixture into a distillation tower for normal-pressure rectification, and collecting methylal fraction at the tower top temperature of 42-42.5 ℃; and repeatedly carrying out extraction rectification on the purified methylal fraction to obtain high-purity methylal. CN101092337 and CN201834867U describe extraction and refining methods using ethylene glycol and glycerol as extracting agents, respectively; chinese patent CN1160392 describes a method for extractive distillation of an extractant for polyalkylene glycols or their derivatives, in which water and methanol are removed by countercurrent gas-liquid contact of the methylal to be separated with polyalkylene glycols or their derivatives having a high boiling point and not forming an azeotropic mixture with the methylal, and the methylal is purified to 99.5%. The disadvantages are that the requirement on the initial concentration of the raw material is high, and 98.3 percent of methylal is required to be used as the raw material. Research on N, N-Dimethylformamide (DMF) as an extracting agent also shows that the DMF as the extracting agent can be used for obtaining a product with the purity of 99.9 percent. CN109651080A adopts ethylene glycol and ionic liquid as extraction agents, which can improve the relative volatility between methylal and methanol, improve the separation efficiency and obtain methylal and methanol with higher purity. These extractants are costly and highly polluting and are not suitable for long-term use in large quantities.
In recent years, the preparation of polyoxymethylene dimethyl ether (PODEN) is receiving wide attention, PODE 3-5 is an ideal component of a diesel fuel additive with a great application prospect, and PODE is reported to be produced in a large scale.
Disclosure of Invention
The invention aims to solve the technical problem that a methylal-methanol azeotropic system in industrial-grade methylal is difficult to obtain high-purity methylal, and provides a refining method for refining and purifying industrial-grade methylal serving as a raw material to obtain high-purity methylal.
In order to solve the technical problems, the invention adopts the technical scheme that: a refining method of high-purity methylal comprises the following steps:
(a) feeding the industrial-grade methylal 1 and the extractant 2 into an extraction rectifying tower 3, separating a first fraction 4 from the tower top, and obtaining a first tower bottom liquid 5 from the tower bottom;
(b) the first fraction 4 enters a product tower 6, light components 7 of the product tower are separated from the tower top, and a high-purity methylal product 8 is obtained from the tower bottom;
and optionally step (c): the first tower bottom liquid 5 passes through a methanol tower 9, and after a methanol component 10 is removed from the tower top, the methanol tower bottom liquid 11 can be recycled or post-treated.
In the technical scheme, the purity of the industrial-grade methylal in the step (a) is preferably not more than 93%, and more preferably 85-92%; wherein the content of methanol is preferably 6-15%, and the content of water is preferably 0.1-2%.
In the above technical solution, the extractant in step (a) is preferablyPolyoxymethylene dimethyl ether (PODEN) polymer, more preferably PODE2、PODE3、PODE4、PODE5At least one of; most preferably PODE2And contain PODE2A mixture of (a).
In the above technical solution, the extractant in step (a) may contain water, wherein the water content is preferably 0 to 5%, and more preferably 0.5 to 3%.
In the above technical solution, the amount of the extractant used in the step (a) is preferably 0.1 to 2 times of the mass of the raw material (i.e., the industrial grade methylal), and more preferably 0.5 to 1.5 times of the mass of the raw material. .
In the above technical scheme, the number of theoretical plates of the extractive distillation column in the step (a) is preferably 10 to 30 theoretical plates, and more preferably 15 to 25 theoretical plates; the operating pressure of the extractive distillation tower is preferably normal pressure; the reflux ratio of the extraction and rectification tower is preferably 1-10, and more preferably 2-6.
In the above technical solution, the extractive distillation column in step (a) preferably has two feed inlets, wherein the extractant preferably enters the column from the upper feed inlet; the industrial methylal preferably enters the tower from a lower feed inlet; the two feed inlets are preferably 3-30 theoretical plates apart, and more preferably 4-6 theoretical plates apart.
In the above technical scheme, the operating pressure of the product tower in the step (b) is preferably 0.1-0.8 MPa, and the reflux ratio is preferably 0.1-5.
In the above technical solution, the mass percentage of the methylal (DMM) in the high purity methylal product fraction 8 obtained in the step (b) is preferably 99 to 99.9%.
In the above technical solution, the methanol tower in the step (c) is an atmospheric distillation tower, and the overhead fraction is a methanol component, wherein the purity of methanol is preferably not less than 97%.
In the above technical solution, the methanol tower in step (c) may preferably further comprise a vaporization permeable membrane dehydration system and a corresponding vacuum system and cooling system.
In the above technical solution, the vapor permeable membrane in step (c) is preferably a NaA molecular sieve membrane.
In the above technical solution, the light component 7 of the product tower and the methanol tower bottoms 11 are preferably recycled.
Among the above-described embodiments, the most preferable embodiment is PODE2-5Is used as an extracting agent.
Unless otherwise specified,% referred to in the present invention means weight percent or weight percent content.
We surprisingly found that the process is mainly based on rectification, after PODE materials are added as an extracting agent, the material balance of a methylal-methanol-water system is broken, the high-purity preparation of methylal can be realized through conventional rectification, the operation is simple, the efficiency is high, the influence of an azeotropic system in the methylal materials is greatly reduced, the rectification efficiency is improved, the energy consumption is low, and the continuous operation can be realized. The purity of methylal in the product fraction obtained by the process reaches over 99 percent, and the methanol with the purity of over 99 percent is obtained at the same time, so that the smooth operation of continuous rectification can be ensured.
By adopting the technical scheme of the invention, the purity of methylal in the obtained product fraction reaches more than 99%, and the methanol with the purity of more than 99% is obtained, so that the smooth operation of continuous rectification can be ensured, and a better technical effect is obtained.
Drawings
FIG. 1 is a process flow diagram of an embodiment of the present invention.
Feeding the industrial-grade methylal 1 and the extracting agent 2 into an extraction rectifying tower 3, and separating a first fraction 4 from the tower top to obtain a first tower bottom liquid 5; the first fraction 4 enters a product tower 6, light components 7 of the product tower are separated from the tower top and return to an extraction and rectification tower, and a high-purity methylal product 8 is obtained at the tower bottom; the first tower bottom liquid 5 passes through a methanol tower 9, after a methanol component 10 is removed from the tower top, the methanol tower bottom liquid 11 can be recycled or post-treated. The methanol tower bottoms 11 can be recycled as an extractant.
Detailed Description
[ example 1 ]
The raw material is industrial-grade methylal, and the extracting agent is PODE2. Raw material enters the extractive distillation containing 10 theoretical plates from a lower feed inletThe extracting agent enters the extraction rectifying tower from the upper feeding port, and the dosage of the extracting agent is 0.5 time of that of the raw materials; performing extractive distillation under the conditions that the temperature of the top of the tower is 42 ℃, the temperature of the bottom of the tower is 92 ℃ and the reflux ratio is 10, separating a first fraction from the top of the tower, and obtaining a first bottom liquid from the bottom of the tower; the first fraction enters a product tower, the operating pressure of the product tower is normal pressure, and the temperature of a tower kettle is 42 ℃; rectifying under the condition that the reflux ratio is 1, separating out light components of a product tower from the tower top, returning the light components to a lower feed inlet of the extraction and rectification tower, and obtaining a methylal product at the tower kettle; and (3) feeding the first tower bottom liquid into a methanol tower, rectifying under the normal pressure condition, and after removing light components under the condition that the tower top reflux ratio is 3, recycling or post-treating the methanol tower bottom liquid. The methanol tower bottom liquid is used as an extracting agent for recycling. The composition of the materials is shown in Table 1.
TABLE 1
[ COMPARATIVE EXAMPLE 1 ]
The raw material is industrial-grade methylal, no extractant is added, and the raw material is directly rectified, and other conditions are the same as those in example 1.
[ example 2 ]
The raw material is industrial-grade methylal, and the extracting agent is PODE3-5. The raw material enters an extraction and rectification tower containing 15 theoretical plates from a lower feed inlet, and an extractant enters the extraction and rectification tower from an upper feed inlet, wherein the dosage of the extractant is 0.25 time of that of the raw material; performing extractive distillation at the conditions of the tower top temperature of 41.5 ℃, the tower bottom temperature of 120 ℃ and the reflux ratio of 8, and separating a first fraction from the tower top to obtain a first tower bottom liquid; the first fraction enters a product tower, the operating pressure of the product tower is 0.3MPa, and the temperature of a tower kettle is 76.7 ℃; rectifying under the condition that the reflux ratio is 4, separating out light components of a product tower from the tower top, returning the light components to a lower feed inlet of the extraction and rectification tower, and obtaining a methylal product at the tower kettle; and (3) feeding the first tower bottom liquid into a methanol tower, rectifying under the normal pressure condition, and after removing light components under the condition that the tower top reflux ratio is 2, recycling or post-treating the methanol tower bottom liquid. First of allThe alcohol tower bottom liquid is used as an extracting agent for recycling. The composition of the materials is shown in Table 2.
TABLE 2
[ example 3 ]
The raw material is industrial-grade methylal, and the extracting agent is PODE2Wherein the water content is 5%. Raw materials enter an extraction and rectification tower containing 20 theoretical plates from a lower feed inlet, and an extracting agent enters the extraction and rectification tower from an upper feed inlet, wherein the dosage of the extracting agent is equal to that of the raw materials; performing extractive distillation under the conditions that the temperature of the top of the tower is 41.5 ℃, the temperature of the bottom of the tower is 85 ℃ and the reflux ratio is 6, and separating a first fraction from the top of the tower to obtain a first bottom liquid; the first fraction enters a product tower, the operating pressure of the product tower is 0.4MPa, and the temperature of a tower kettle is 87.4 ℃; rectifying under the condition that the reflux ratio is 3, separating out light components of a product tower from the tower top, returning the light components to a lower feed inlet of the extraction and rectification tower, and obtaining a methylal product at the tower kettle; and (3) feeding the first tower bottom liquid into a methanol tower, rectifying under the normal pressure condition, removing light components under the condition that the tower top reflux ratio is 4, feeding the methanol tower bottom liquid into a pervaporation membrane system containing a NaA molecular sieve membrane tube for dehydration, and recycling dehydrated materials or carrying out aftertreatment. The methanol tower bottom liquid is used as an extracting agent for recycling. The composition of the materials is shown in Table 3.
TABLE 3
[ example 4 ]
The raw material is industrial-grade methylal, and the extracting agent is PODE3. The raw material enters an extraction and rectification tower containing 25 theoretical plates from a lower feed inlet, and an extractant enters the extraction and rectification tower from an upper feed inlet, wherein the dosage of the extractant is 1.5 times of that of the raw material; performing extractive distillation at the conditions of tower top temperature of 41.5 ℃, tower bottom temperature of 120 ℃ and reflux ratio of 4, and separating out a first fraction from the tower top to obtain a first tower bottom liquid; the first fraction is fed to a product column, the operating pressure of which0.5MPa, and the temperature of a tower kettle is 96.28 ℃; rectifying under the condition that the reflux ratio is 2, separating out light components of a product tower from the tower top, returning the light components to a lower feed inlet of the extraction and rectification tower, and obtaining a methylal product at the tower kettle; and (3) feeding the first tower bottom liquid into a methanol tower, rectifying under the normal pressure condition, and after removing light components under the condition that the tower top reflux ratio is 3, recycling or post-treating the methanol tower bottom liquid. The methanol tower bottom liquid is used as an extracting agent for recycling. The composition of the materials is shown in Table 4.
TABLE 4
[ example 5 ]
The raw material is industrial-grade methylal, and the extracting agent is PODE2-3Wherein the water content is 2%. The raw material enters an extraction and rectification tower containing 30 theoretical plates from a lower feed inlet, and an extractant enters the extraction and rectification tower from an upper feed inlet, wherein the dosage of the extractant is 0.3 time of that of the raw material; performing extractive distillation under the conditions that the temperature of the top of the tower is 41.5 ℃, the temperature of the bottom of the tower is 106 ℃ and the reflux ratio is 2, and separating a first fraction from the top of the tower to obtain a first bottom liquid; the first fraction enters a product tower, the operating pressure of the product tower is 0.7MPa, and the temperature of a tower kettle is 110.65 ℃; rectifying under the condition that the reflux ratio is 5, separating out light components of a product tower from the tower top, returning the light components to a lower feed inlet of the extraction and rectification tower, and obtaining a methylal product at the tower kettle; and (3) feeding the first tower bottom liquid into a methanol tower, rectifying under the normal pressure condition, and after removing light components under the condition that the tower top reflux ratio is 1, recycling or post-treating the methanol tower bottom liquid. The methanol tower bottoms can be used as an extracting agent for recycling or can be sent to a PODE separation unit. The composition of the materials is shown in Table 5.
TABLE 5
[ example 6 ]
The raw material is industrial-grade methylal, and the extracting agent is PODE2-5Wherein the water content is 2.8%. Raw material enters from a lower feed inletThe extraction and rectification tower comprises 20 theoretical plates, an extractant enters the extraction and rectification tower from an upper feed inlet, and the dosage of the extractant is equal to that of the raw material; performing extractive distillation at the conditions of tower top temperature of 41.5 ℃, tower bottom temperature of 85 ℃ and reflux ratio of 5, and separating out a first fraction from the tower top to obtain a first tower bottom liquid; the first fraction enters a product tower, the operating pressure of the product tower is 0.4MPa, and the temperature of a tower kettle is 87.4 ℃; rectifying under the condition that the reflux ratio is 3, separating out light components of a product tower from the tower top, returning the light components to a lower feed inlet of the extraction and rectification tower, and obtaining a methylal product at the tower kettle; and (3) feeding the first tower bottom liquid into a methanol tower, rectifying under the normal pressure condition, removing light components under the condition that the tower top reflux ratio is 4, feeding the methanol tower bottom liquid into a pervaporation membrane system containing a NaA molecular sieve membrane tube for dehydration, and recycling dehydrated materials or carrying out aftertreatment. The methanol tower bottom liquid is used as an extracting agent for recycling. The composition of the materials is shown in Table 6.
TABLE 6
Claims (10)
1. A refining method of high-purity methylal comprises the following steps:
(a) the industrial-grade methylal (1) and the extractant (2) enter an extraction rectifying tower (3), a first fraction (4) is separated from the top of the tower, and a first tower bottom liquid (5) is obtained from the bottom of the tower;
(b) the first fraction (4) enters a product tower (6), light components (7) separated from the tower top of the product tower return to the extraction and rectification tower, and a high-purity methylal product (8) is obtained at the tower bottom;
and optional step (c), the first tower bottom liquid (5) enters a methanol tower (9), and after the methanol component (10) is removed from the tower top, the methanol tower bottom liquid (11) can be recycled or subjected to post-treatment.
2. The process according to claim 1, wherein the purity of the industrial-grade methylal in the step (a) is not more than 93%.
3. The process according to claim 1, wherein the extractant used in the step (a) is a polymethoxydimethyl ether polymer, preferably comprising PODE2、PODE3、PODE4、PODE5At least one of (1).
4. The method according to claim 1 or 3, wherein the extractant used in the step (a) optionally contains water, and the water content is 0 to 5%.
5. The method according to claim 1, wherein the number of theoretical plates of the extractive distillation column in the step (a) is 10 to 30 theoretical plates, the operation pressure is normal pressure, and the reflux ratio is 1 to 10.
6. The method according to claim 1, wherein the operation pressure of the product column in the step (b) is 0.1 to 0.8MPa, and the reflux ratio is 0.1 to 5.
7. The method according to claim 1, wherein the high purity methylal product obtained in the step (b) contains 99 to 99.9% by weight of methylal.
8. The method according to claim 1, wherein the methanol column in the step (c) is an atmospheric distillation column, and the purity of methanol in the methanol component at the top of the column is not less than 97%.
9. The method according to claim 1 or 8, wherein said methanol column in the step (c) further comprises a vapor permeation membrane dehydration system and a vacuum system and a cooling system.
10. The method according to claim 1, wherein the amount of the extractant used in the step (a) is 0.1 to 2 times the mass of the starting material.
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| CN113511965B (en) * | 2021-04-29 | 2023-04-25 | 潍坊惠丰化工有限公司 | Process method for concentrating dilute formaldehyde aqueous solution by composite solvent extraction |
| CN113429269A (en) * | 2021-07-29 | 2021-09-24 | 南通江山农药化工股份有限公司 | Pressurized rectification purification process equipment for methylal |
| CN114591155A (en) * | 2022-02-17 | 2022-06-07 | 安徽东至广信农化有限公司 | Methylal rectification process |
| CN115745756A (en) * | 2022-11-17 | 2023-03-07 | 凯瑞环保科技股份有限公司 | Methylal purification method |
| CN115745756B (en) * | 2022-11-17 | 2024-04-16 | 凯瑞环保科技股份有限公司 | Methylal purification method |
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