CN115814452A - Methyl methacrylate separation and purification method and device - Google Patents
Methyl methacrylate separation and purification method and device Download PDFInfo
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- CN115814452A CN115814452A CN202211316173.5A CN202211316173A CN115814452A CN 115814452 A CN115814452 A CN 115814452A CN 202211316173 A CN202211316173 A CN 202211316173A CN 115814452 A CN115814452 A CN 115814452A
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Abstract
The invention discloses a method and a device for separating and purifying methyl methacrylate, belonging to the field of chemical industry. The device includes formaldehyde knockout tower and MMA refining tower, the top output of formaldehyde knockout tower link to each other with product centrifugal extractor, an output of product centrifugal extractor pass through methanol aqueous solution storage tank and retrieve the tower with the methyl alcohol and link to each other, another output links to each other with MMA refining tower through mixing the ester storage tank, the output and the extractant recovery tower at MMA refining tower top link to each other. The method has simple and efficient process flow, and has less equipment of a rectifying tower system and good separation effect compared with a azeotropic rectifying route.
Description
Technical Field
The invention belongs to the technical field of chemical product separation, and relates to a method and a device for separating and purifying methyl methacrylate.
Background
Methyl Methacrylate (MMA) is an important organic chemical raw material and polymer monomer, is mainly used for producing organic glass (PMMA), molding compounds, acrylic fibers, coatings, medical functional polymer materials and the like, and is a high-end material in the fields of aerospace, electronic information, optical fibers, robots and the like.
The predominant process routes for producing MMA include Acetone Cyanohydrin (ACH) process, tert-butanol/isobutylene oxidation process, ethylene carbonylation process. At present, the domestic MMA production mainly adopts an ACH method, but the method has the defects of high investment cost, long process flow, serious equipment corrosion and the like; the ethylene carbonylation method has the advantages of mild reaction conditions, advanced technology, no generation of virulent intermediate products, good operation of the put-into-production device and the like, and gradually becomes a research hotspot in recent years.
Patent CN103833551A introduces a purification and separation method for producing methyl methacrylate by oxidation of tert-butyl alcohol/isobutylene, in the patent, MMA is purified by extraction of normal hexane and water, and after recovery of normal hexane, impurity ester is removed from an extract phase, and a product MMA is obtained by separation. However, the feed liquor composition and reaction path of the process are very different compared to the ethylene carbonylation process, and the patent is silent as to whether the extraction process is suitable for the latter separation process.
Patent CN103524345A discloses a product separation process for preparing methyl acrylate from methyl acetate, which is characterized in that a device system consisting of a formaldehyde separation tower, an extraction tower, a methyl acrylate refining tower and a methanol recovery tower is adopted for separation, so that the high-efficiency separation and recovery of methyl acetate, methyl acrylate and formaldehyde are realized. Compared with the ethylene carbonylation method, the main difference is the difference of the reaction product and the extracting agent of the process.
Patent CN106699560A introduces a separation device and a separation method for methyl methacrylate-containing material flow, and an extraction agent is used for breaking a material azeotropic system, so that the separation difficulty is reduced. Wherein, the recovery rates of the Methyl Propionate (MP) and the MMA are both more than 99.9 percent, the purity of the MMA is more than 99.8 percent, but the separation process is suitable for raw material reaction liquid with low methanol content and no formaldehyde component.
Patent CN112374989B provides a separation method of a mixture containing formaldehyde and methanol, especially for a mixture of methyl methacrylate containing a large amount of methanol and formaldehyde, the removal rate of formaldehyde and methanol is high, but the separation process is suitable for a system in which the proportion of methyl propionate in a raw material liquid is greater than that of methanol.
Most of the prior publications relate to a product separation method for preparing MMA by an isobutene method, and the obtained crude product system is simpler and has smaller separation difficulty; the components of a crude product system obtained by preparing MMA through an ethylene carbonylation method are complex, reaction liquids can form a plurality of binary or ternary azeotropic systems mutually, and cannot be separated through ordinary rectification.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method and a device for separating and purifying Methyl Methacrylate (MMA), wherein a crude product system containing the MMA is separated by adopting double extraction and rectification processes, so that a qualified MMA product is obtained.
The technical scheme adopted by the invention is as follows:
the utility model provides a methyl methacrylate separation and purification device, the device includes formaldehyde knockout tower and MMA refining tower, the top output of formaldehyde knockout tower link to each other with product centrifugal extraction machine, an output of product centrifugal extraction machine pass through methanol aqueous solution storage tank and link to each other with methyl alcohol recovery tower, another output links to each other with MMA refining tower through mixing the ester storage tank, the output and the extractant recovery tower at MMA refining tower top link to each other.
A method for separating and purifying methyl methacrylate by using the device comprises the following steps:
cooling a methyl methacrylate-containing crude product material flow from an aldol condensation reaction system, feeding the cooled methyl methacrylate-containing crude product material flow into a formaldehyde separation tower, separating a wastewater solution containing a formaldehyde component from the bottom of the tower, and further sending the solution to an outside sewage treatment plant for further treatment; meanwhile, the extractant and the top component of the formaldehyde separation tower are sent to a centrifugal extractor for separation;
conveying the water phase of the centrifugal extractor to a methanol water solution storage tank, and then conveying the water phase to a methanol recovery tower for further recovering methanol; and (3) conveying the oil phase of the centrifugal extractor to a mixed ester storage tank, conveying the oil phase to an MMA refining tower, obtaining a high-purity MMA product at the bottom of the tower, conveying the components at the top of the tower to an extractant recovery tower for separation, returning the components at the top of the extractant recovery tower to the centrifugal extractor for recycling, and returning the tower bottom liquid to an aldol condensation reaction system.
In some specific embodiments: cooling a crude product stream containing Methyl Methacrylate (MMA) from an aldol condensation reaction system, feeding the cooled crude product stream into a formaldehyde separation tower, separating a wastewater solution containing a formaldehyde component at the bottom of the tower, and further sending the solution to an outside sewage treatment plant for further treatment, wherein the main components of materials at the top of the tower are methyl methacrylate, methyl propionate, methanol and water; meanwhile, an extracting agent and a tower top component of the formaldehyde separation tower are sent to a centrifugal extractor;
under the action of centrifugal extraction, dividing a crude product material flow containing MMA into a water phase and an oil phase, conveying the water phase to a methanol water solution storage tank by using a centrifugal pump, and conveying the oil phase to a mixed ester storage tank by using a centrifugal pump; conveying the oil phase material flow obtained by extraction to an MMA refining tower, obtaining a high-purity MMA product at the bottom of the tower, mainly containing methyl propionate and n-hexane components at the top of the tower, conveying the methyl propionate and n-hexane components to an extractant recovery tower for separation, returning the material flow containing n-hexane at the top of the extractant recovery tower 3 to a centrifugal extractor for recycling, and returning the tower bottom liquid containing methyl propionate to an aldol condensation reaction system; and conveying the water phase material flow obtained by centrifugal extraction to a methanol recovery tower for further recovering methanol, and further conveying the methanol-containing wastewater solution in the tower bottom of the methanol recovery tower to the outside.
The crude product containing Methyl Methacrylate (MMA) comprises methyl methacrylate, methanol, methyl propionate, water, formaldehyde and the like.
The content of methanol in the crude product containing Methyl Methacrylate (MMA) is 15-50%.
The extracting agent is water and normal hexane or water, different adding modes are adopted in the centrifugal extraction process, water can be selected as single-component extraction, and a double-component extraction mode of mixing water and normal hexane can also be selected.
The mass ratio of water in the extracting agent to the materials at the top of the formaldehyde separating tower is 0.5-1.0.
The mass ratio of the normal hexane in the extracting agent to the material at the top of the formaldehyde separation tower is 0.4-0.8.
The operating pressure of the formaldehyde separation tower is 0.01-0.1 MPa, and the operating temperature is 35-60 ℃.
The operating pressure of the MMA refining tower is 0.03-0.5 MPa, and the operating temperature is 60-120 ℃.
The operating pressure of the extractant recovery tower is 0.03-0.5 MPa, and the operating temperature is 70-90 ℃.
The operating pressure of the methanol recovery tower is 0.03-0.5 MPa, and the operating temperature is 70-110 ℃.
The technical scheme of the invention is as follows: the pressure is absolute pressure.
The invention has the beneficial effects that:
1. aiming at the MMA-containing crude product stream, the method disclosed by the invention adopts double extraction to break an azeotropic system, so that the product separation difficulty is greatly reduced.
2. The method has simple and efficient process flow, and has less equipment of a rectifying tower system and good separation effect compared with a azeotropic rectifying route.
Drawings
FIG. 1 is a process flow diagram of a method and an apparatus for separating and purifying methyl methacrylate according to an embodiment of the present invention. In the figure, a 1-formaldehyde separation tower; 2-MMA refining column; 3-an extractant recovery column; 4-methanol recovery column; 5-centrifugal extractor of the product; 6-mixed ester storage tank; 7-methanol aqueous solution storage tank.
Detailed Description
In order to better illustrate the present invention, the following examples of the present invention are described in detail, which are carried out on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of the present invention is not limited to the following examples.
As shown in figure 1, the device for separating and purifying methyl methacrylate comprises a formaldehyde separation tower 1 and an MMA refining tower 2, wherein the output end of the top of the formaldehyde separation tower 1 is connected with a product centrifugal extractor 5, one output end of the product centrifugal extractor 5 is connected with a methanol recovery tower 4 through a methanol aqueous solution storage tank 7, the other output end of the product centrifugal extractor is connected with the MMA refining tower 2 through a mixed ester storage tank 6, and the output end of the top of the MMA refining tower 2 is connected with an extractant recovery tower 3.
Example 1:
as shown in fig. 1: a separation and purification device for methyl methacrylate comprises a formaldehyde separation tower 1, a product centrifugal extractor 5, a mixed ester storage tank 6, a methanol water solution storage tank 7, an MMA refining tower 2, an extractant recovery tower 3 and a methanol recovery tower 4;
the MMA-containing crude product material flow from the aldol condensation reaction system consists of methanol, methyl propionate, methyl methacrylate, formaldehyde, water, methyl methylpropionate and heavy components, the material flow enters a formaldehyde separation tower 1 after being cooled, a wastewater solution containing the formaldehyde component is separated from the bottom of the tower, and the solution is further treated outside the world; the main components of the top liquid of the formaldehyde separation tower 1 are methyl methacrylate, methyl propionate, methanol and water, and meanwhile, the extracting agent and the top components of the formaldehyde separation tower are added into a mixer together and are fully mixed and conveyed to a centrifugal extractor 5; under the action of centrifugal extraction, crude product material flow containing MMA is subjected to layering and is divided into a water phase and an oil phase, and the water phase and the oil phase are respectively conveyed to a methanol water solution storage tank 7 and a mixed ester storage tank 6 by adopting centrifugal pumps; conveying the oil phase material flow obtained by extraction to an MMA refining tower 2, obtaining a high-purity MMA product at the bottom of the tower, wherein the tower top liquid mainly comprises methyl propionate and n-hexane components; then conveying the tower top liquid of the MMA refining tower to an extractant recovery tower 3, wherein the main purpose is to separate two components of methyl propionate and n-hexane, simultaneously circulating the extractant obtained at the tower top to a centrifugal extractor 5 for recycling, and returning the tower bottom liquid to an aldol condensation reaction system; and conveying the water phase material flow obtained by centrifugal extraction to a methanol recovery tower 4 for further recovering methanol, wherein the tower kettle is mainly a wastewater solution containing methanol and is conveyed to the outside for treatment.
The method for separating the material containing the methyl methacrylate by adopting the flow comprises the following steps:
according to the scheme shown in FIG. 1, the composition of the MMA-containing crude product stream from the aldol condensation reaction system is determined by using two extractants (water + n-hexane): 15% of methanol, 60% of methyl propionate, 15% of methyl methacrylate, 5% of formaldehyde, 4% of water, 0.9% of methyl methacrylate and 0.1% of heavy components. Wherein,
the mass ratio of water in the extracting agent to the materials at the top of the formaldehyde separating tower is 0.5, and the mass ratio of normal hexane in the extracting agent to the materials at the top of the formaldehyde separating tower is 0.4. The operating pressure of the formaldehyde separation tower is 0.01MPa, and the operating temperature is 35-60 ℃; the operating pressure of the MMA refining tower is 0.03MPa, and the operating temperature is 60-120 ℃; the operating pressure of the extractant recovery tower is 0.03MPa, and the operating temperature is 70-90 ℃; the operating pressure of the methanol recovery tower is 0.03MPa, and the operating temperature is 70-110 DEG C
The device performance index is as follows:
1. the purity of the methyl methacrylate product liquid is 99.9 percent;
2. the recovery rate of methanol was 84.7%;
3. the recovery rate of the methyl propionate is 69.3 percent;
TABLE 1 composition of the two-phase stream obtained by extraction
Example 2:
according to the scheme shown in FIG. 1, the composition of the MMA-containing crude product stream from the aldol condensation reaction system is determined by using two extractants (water + n-hexane): 30% of methanol, 45% of methyl propionate, 12% of methyl methacrylate, 4% of formaldehyde, 8% of water, 0.2% of methyl methacrylate and 0.8% of heavy components. Wherein,
the mass ratio of water in the extracting agent to the material at the top of the formaldehyde separating tower is 0.8, the mass ratio of normal hexane in the extracting agent to the material at the top of the formaldehyde separating tower is 0.6, the operating pressure of the formaldehyde separating tower is 0.05MPa, and the operating temperature is 35-60 ℃; the operating pressure of the MMA refining tower is 0.2MPa, and the operating temperature is 60-120 ℃; the operating pressure of the extractant recovery tower is 0.3MPa, and the operating temperature is 70-90 ℃; the operating pressure of the methanol recovery tower is 0.3MPa, and the operating temperature is 70-110 ℃;
the device performance index is as follows: :
1. the purity of the methyl methacrylate product liquid is 98.9 percent;
2. the recovery rate of methanol was 84.1%;
3. the recovery rate of the methyl propionate is 87.6 percent;
TABLE 2 composition of the two-phase stream obtained by extraction
Example 3:
according to the scheme shown in FIG. 1, the composition of the MMA-containing crude product stream from the aldol condensation reaction system is determined by using two extractants (water + n-hexane): 50% of methanol, 30% of methyl propionate, 12% of methyl methacrylate, 3% of formaldehyde, 4% of water, 0.3% of methyl methacrylate and 0.7% of heavy components. Wherein,
the mass ratio of water in the extracting agent to the material at the top of the formaldehyde separating tower is 1.0, the mass ratio of normal hexane in the extracting agent to the material at the top of the formaldehyde separating tower is 0.8, the operating pressure of the formaldehyde separating tower is 0.1MPa, and the operating temperature is 35-60 ℃; the operating pressure of the MMA refining tower is 0.5MPa, and the operating temperature is 60-120 ℃; the operating pressure of the extractant recovery tower is 0.5MPa, and the operating temperature is 70-90 ℃; the operating pressure of the methanol recovery tower is 0.5MPa, and the operating temperature is 70-110 ℃;
the device performance index is as follows:
1. the purity of the methyl methacrylate product liquid is 95.7 percent;
2. the recovery rate of methanol is 84.6%;
3. the recovery rate of the methyl propionate is 92.3 percent;
TABLE 3 composition of the two-phase stream obtained by extraction
Example 4:
according to the scheme shown in FIG. 1, the composition of the MMA-containing crude product stream from the aldol condensation reaction system is determined by using an extractant (water): 50% of methanol, 30% of methyl propionate, 12% of methyl methacrylate, 3% of formaldehyde, 4% of water, 0.3% of methyl methacrylate and 0.7% of heavy component. Wherein
The mass ratio of water in the extracting agent to the materials at the top of the formaldehyde separating tower is 0.7, the operating pressure of the formaldehyde separating tower is 0.08MPa, and the operating temperature is 35-60 ℃; the operating pressure of the MMA refining tower is 0.1MPa, and the operating temperature is 60-120 ℃; the operating pressure of the extractant recovery tower is 0.3MPa, and the operating temperature is 70-90 ℃; the operating pressure of the methanol recovery tower is 0.3MPa, and the operating temperature is 70-110 ℃;
the device performance index is as follows:
1. the purity of the methyl methacrylate product liquid is 99.9 percent;
2. the recovery rate of methanol is 37.3;
3. the recovery rate of the methyl propionate is 78.7 percent;
TABLE 4 composition of the two-phase stream obtained by extraction
Claims (9)
1. A methyl methacrylate separation and purification device is characterized in that: the device includes formaldehyde knockout tower (1) and MMA refining tower (2), the top output of formaldehyde knockout tower (1) link to each other with product centrifugal extraction machine (5), an output of product centrifugal extraction machine (5) link to each other with methyl alcohol recovery tower (4) through methyl alcohol aqueous solution storage tank (7), another output links to each other with MMA refining tower (2) through mixing ester storage tank (6), the output and the extractant recovery tower (3) at MMA refining tower (2) top link to each other.
2. A method for separating and purifying methyl methacrylate by using the device of claim 1, which is characterized in that: the method comprises the following steps:
(1) Cooling a crude product stream containing Methyl Methacrylate (MMA) from an aldol condensation reaction system, feeding the cooled crude product stream into a formaldehyde separation tower (1), separating a wastewater solution containing a formaldehyde component at the bottom of the tower, and further sending the solution to an outside sewage treatment field for treatment; meanwhile, the extractant and the components at the top of the formaldehyde separation tower (1) are sent to a centrifugal extractor (5) for separation;
(2) Conveying the water phase of the centrifugal extractor (5) to a methanol water solution storage tank (7), and then conveying the water phase to a methanol recovery tower (4) for further recovering methanol; the oil phase of the centrifugal extractor (5) is firstly conveyed to a mixed ester storage tank (6), then is conveyed to an MMA refining tower (2), a high-purity MMA product is obtained at the bottom of the tower, the components at the top of the tower are conveyed to an extractant recovery tower (3) for separation, the components at the top of the extractant recovery tower (3) are returned to the centrifugal extractor for recycling, and the tower bottom liquid is returned to an aldol condensation reaction system.
3. The method of claim 2, wherein: the content of methanol in a crude product containing Methyl Methacrylate (MMA) is 15 to 50 percent.
4. The method of claim 2, wherein: in the step (1), the extracting agent is water and n-hexane or the extracting agent is water.
5. The method of claim 4, wherein: the mass ratio of water in the extracting agent to the material at the top of the formaldehyde separation tower is 0.5 to 1.0, and the mass ratio of n-hexane in the extracting agent to the material at the top of the formaldehyde separation tower is 0.4 to 0.8.
6. The method of claim 2, wherein: the operating pressure of the formaldehyde separation tower is 0.01 to 0.1MPa, and the operating temperature is 35 to 60 ℃.
7. The method of claim 2, wherein: the operating pressure of the MMA refining tower is 0.03 to 0.5MPa, and the operating temperature is 60 to 120 ℃.
8. The method of claim 2, wherein: the operation pressure of the extractant recovery tower is 0.03 to 0.5MPa, and the operation temperature is 70 to 90 ℃.
9. The method of claim 2, wherein: the operating pressure of the methanol recovery tower is 0.03 to 0.5MPa, and the operating temperature is 70 to 110 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115850073A (en) * | 2022-11-28 | 2023-03-28 | 中国海洋石油集团有限公司 | Method and device for preparing methyl methacrylate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115850073A (en) * | 2022-11-28 | 2023-03-28 | 中国海洋石油集团有限公司 | Method and device for preparing methyl methacrylate |
| CN115850073B (en) * | 2022-11-28 | 2024-07-09 | 中国海洋石油集团有限公司 | Method and device for preparing methyl methacrylate |
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