CN113583016A - Method for improving purity of crude pyromellitic dianhydride, device and application thereof - Google Patents
Method for improving purity of crude pyromellitic dianhydride, device and application thereof Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention relates to the field of chemical component purification, and particularly relates to a method for improving purity of crude pyromellitic dianhydride, and a device and application thereof. Experiments show that MTBE (methyl tertiary butyl ether) is used for washing one or more of pyromellitic acid, trimellitic acid and trimellitic anhydride in crude pyromellitic dianhydride, so that the product yield of high-purity pyromellitic dianhydride is improved, and the purity of purified pyromellitic dianhydride can reach more than 99.5%. In the whole process of preparing and purifying the pyromellitic dianhydride from the raw materials, the comprehensive yield of the pyromellitic dianhydride can be improved by over 7 percent.
Description
Technical Field
The invention relates to the field of chemical component purification, and particularly relates to a method for improving purity of crude pyromellitic dianhydride, and a device and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Polyimide is used as a special engineering material and has been widely applied to the fields of aviation, aerospace, microelectronics, nano-scale, liquid crystal, separation membranes, laser and the like. Because of its outstanding characteristics in performance and synthesis, it has been fully recognized as a structural material or a functional material, and its great application prospects have been fully realized.
As one of the raw materials of polyimide, the performance of pyromellitic dianhydride is directly related to the performance of polyimide products. The preparation of pyromellitic dianhydride is mainly divided into two methods: 1. durene is oxidized in gas phase. The method features simple process, no need of dewatering and anhydride-forming, no need of other oxidant (such as nitric acid, permanganic acid, chromic acid, etc.) except air, no need of catalyst separation procedure necessary for liquid phase, continuous production and easy realization of automatic operation. The raw material can also be 1,2, 4-trimethylbenzene, and the raw material is alkylated with propylene to generate 1,2, 4-trimethyl-5-propylbenzene in the presence of a catalyst, and then the 1,2, 4-trimethyl-5-propylbenzene is catalyzed and oxidized by gas phase air to obtain the pyromellitic dianhydride. 2. Is prepared from xylene (p-xylene or m-xylene) through chloromethylation, oxidizing and cyclizing.
The gas phase oxidation method is a method commonly used in China at present, and the pyromellitic dianhydride prepared by the method has a certain amount of mechanical impurities and the purity of 20-25 percent in the product is low.
The two methods for preparing the pyromellitic dianhydride have the problems of low purity of the pyromellitic dianhydride and purification. There are two industrial methods for purifying crude pyromellitic dianhydride, one is recrystallization after dissolution of acetone, and the other is sublimation.
However, the inventor researches and discovers that the recrystallization method has high requirement on the purity of the crude pyromellitic dianhydride, the purification is complex and tedious, and the crude pyromellitic dianhydride with the purity lower than 85 percent needs to be repeatedly purified for many times; the sublimation method has high production cost and complex process.
Disclosure of Invention
In order to solve the problems of high purity requirement, complex purification steps and limited purification effect of the crude pyromellitic dianhydride in the prior art, the invention provides a method for improving the purity of the crude pyromellitic dianhydride, a device and application thereof, and experiments show that MTBE (methyl tertiary butyl ether) is used as a separation solvent for the first time to improve the purity of low-purity pyromellitic dianhydride, improve the product yield of high-purity pyromellitic dianhydride, and ensure that the purity of purified pyromellitic dianhydride can reach more than 99.5 percent. In the whole process of preparing and purifying the pyromellitic dianhydride from the raw materials, the comprehensive yield of the pyromellitic dianhydride can be improved by over 7 percent.
Specifically, the invention is realized by the following technical scheme:
in a first aspect of the present invention, there is provided a method for improving purity of crude pyromellitic dianhydride, comprising: and washing one or more of pyromellitic acid, trimellitic acid and trimellitic anhydride in the crude pyromellitic dianhydride by using methyl tertiary butyl ether as a solvent.
In a second aspect of the present invention, there is provided an apparatus for increasing purity of crude pyromellitic dianhydride, comprising: the device comprises a washing kettle, a centrifugal machine, a condenser and drying equipment, wherein methyl tertiary butyl ether is filled in the washing kettle.
The third aspect of the invention provides an application of methyl tertiary butyl ether in the purification process of crude pyromellitic dianhydride.
The fourth aspect of the invention provides a method for improving the purity of crude pyromellitic dianhydride and/or an application of a device for realizing the method for improving the purity of the crude pyromellitic dianhydride in the purification of the crude pyromellitic dianhydride.
One or more technical schemes of the invention have the following beneficial effects:
1) experiments show that MTBE (methyl tertiary butyl ether) is used as a separation solvent to purify one or more of pyromellitic acid, trimellitic acid and trimellitic anhydride in crude pyromellitic dianhydride, so that the yield of high-purity pyromellitic dianhydride products is improved, and the purity of purified pyromellitic dianhydride can reach more than 99.5%.
2) In the whole process of preparing and purifying the pyromellitic dianhydride from the raw materials, the comprehensive yield of the pyromellitic dianhydride can be improved by over 7 percent.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 is a diagram showing an apparatus for carrying out a process for increasing the purity of crude pyromellitic dianhydride in example 2 of the present invention;
wherein: 1. a washing kettle, 2, a centrifuge, 3, a dryer, 4 and a condenser.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present disclosure. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
It is to be understood that the terms "top," "bottom," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the present invention and simplifying the description, and are not intended to indicate or imply that the referenced devices or elements must have the specified orientations, be constructed and operated in the specified orientations, and are not to be construed as limiting the present invention.
In order to solve the problems of high purity requirement, complex purification steps and limited purification effect of the crude pyromellitic dianhydride in the prior art, the invention provides a method for improving the purity of the crude pyromellitic dianhydride, a device and application thereof, and experiments show that MTBE (methyl tertiary butyl ether) is used as a separation solvent to improve the crude pyromellitic dianhydride for the first time, so that the product yield of the high-purity pyromellitic dianhydride is improved, and the purity of the purified pyromellitic dianhydride can reach more than 99.5%. In the whole process of preparing and purifying the pyromellitic dianhydride from the raw materials, the comprehensive yield of the pyromellitic dianhydride can be improved by over 7 percent.
Specifically, the invention is realized by the following technical scheme:
in a first aspect of the present invention, there is provided a method for improving purity of crude pyromellitic dianhydride, comprising: and washing one or more of pyromellitic acid, trimellitic acid and trimellitic anhydride in the crude pyromellitic dianhydride by using methyl tertiary butyl ether as a solvent.
Methyl tert-butyl ether (MTBE for short) is an organic compound with a structural formula of (CH)3)3COCH3. It is a colorless liquid. The ignition point is 460 ℃, and the explosion limit is 1.65-8.40%. Critical pressure of 3.43MPa, critical temperature of 223.95 ℃, viscosity (20 ℃) of 0.36 mPas. Slightly soluble in water, soluble in organic solvents, and capable of forming azeotropes with ethanol and the like. High octane number and low volatility. Stable in storage and not liable to generate peroxide. Motor octane number 101, research octane number 117. Obtained by catalytic etherification of methanol and isobutene-containing carbon four-fraction.
The impurities in the crude pyromellitic dianhydride prepared by the pyromellitic gas-phase oxidation method are mostly one or more of pyromellitic acid, trimellitic acid and trimellitic anhydride, and the research of the invention finds that compared with other washing reagents, the impurities in the crude pyromellitic dianhydride, such as one or more of pyromellitic acid, trimellitic acid and trimellitic anhydride, are separated because the solubility of the crude pyromellitic dianhydride in methyl tert-butyl ether is extremely low, and the solubility of the impurities in the methyl tert-butyl ether is higher.
In one or more embodiments of the present invention, the crude pyromellitic dianhydride is prepared by a pyromellitic gas phase oxidation process.
The method for preparing crude pyromellitic dianhydride by gas-phase oxidation of durene comprises the following steps: the gas phase durene and air are mixed and then enter a fixed bed reactor filled with catalyst to carry out oxidation reaction, and the reaction gas is condensed and crystallized in a trap after three-stage temperature reduction.
In one or more embodiments of the present invention, the purification method includes: mixing the crude pyromellitic dianhydride with methyl tertiary butyl ether, washing, centrifuging and drying.
The mixing aims to disperse the crude pyromellitic dianhydride in the methyl tertiary butyl ether, so as to avoid the agglomeration or precipitation of the crude pyromellitic dianhydride to influence the purification effect. The purpose of washing is to separate impurity components or impurity ions in the crude pyromellitic dianhydride from the crude pyromellitic dianhydride to improve the purity. The centrifugation is performed to separate pyromellitic dianhydride from the solvent and impurities dispersed in the solvent.
In one or more embodiments of the present invention, the weight ratio of the methyl tertiary-butyl ether to the crude pyromellitic dianhydride is 1-1.5:1, preferably 1:1, and the ratio can be adjusted according to the purity of the crude pyromellitic dianhydride product.
The purification effect of the crude pyromellitic dianhydride can be influenced by the variety and the using amount of the solvent, the extraction effect of the pyromellitic dianhydride is influenced by the excessive using amount of the methyl tertiary butyl ether, and the quality loss of the pyromellitic dianhydride is caused in the processes of multiple mixing, washing and centrifuging. If the dosage of the methyl tertiary butyl ether solvent is too small, pyromellitic dianhydride and impurities cannot be fully dispersed and separated, and the purity of the obtained pyromellitic dianhydride is still not high.
In one or more embodiments of the present invention, the crude pyromellitic dianhydride has a purity of not less than 40%. The solvent selected in some embodiments of the present invention is capable of washing out impurities from the crude pyromellitic dianhydride.
The recrystallization method has high requirement on the purity of the crude pyromellitic dianhydride, the purity of the crude pyromellitic dianhydride needs to be higher than 85 percent, and if the purity of the crude pyromellitic dianhydride is lower than 85 percent, repeated recrystallization is needed, the purification efficiency is low, and the loss is large.
The sublimation method can produce a large amount of wastewater, the reaction temperature is high, vacuum treatment is required, and the conditions are harsh.
In one or more embodiments of the invention, the washing conditions are: mixing at 20-25 deg.C for 60-90min under stirring at 30-40 r/min. The purpose of washing is to separate impurity components or impurity ions in the crude pyromellitic dianhydride from the crude pyromellitic dianhydride to improve the purity. The washing time is too short, so that impurities cannot be separated from the pyromellitic dianhydride, and the quality loss of the pyromellitic dianhydride is easily caused due to the too long washing time.
Through a large amount of experiments and data researches, the pyromellitic dianhydride is preferably mixed for 90min at 20 ℃ under the stirring of 40r/min, so that the washing efficiency of the pyromellitic dianhydride is higher.
The centrifugation is performed to separate pyromellitic dianhydride from the solvent and impurities dispersed in the solvent. In one or more embodiments of the invention, the centrifugation rate is 900-970r/min, preferably 950 r/min.
The experimental research shows that the centrifuged product contains a small amount of solvent, and the experimental research shows that when the solvent content of the centrifuged material is 5-15 wt%, the solvent containing impurities can be removed to a greater extent, and the excessive centrifugation can be avoided, so that the time and resources are wasted.
The centrifugation step can also be replaced by vacuum filtration under laboratory conditions.
The drying is performed to remove the residual solvent in the pyromellitic dianhydride, and in one or more embodiments of the present invention, the drying conditions are as follows: drying at 55-70 ℃ under the pressure of-0.02-0.04 MPa, preferably drying at 60 ℃ under the pressure of-0.02 MPa;
preferably, the mixing is carried out in an inert gas atmosphere, the inert gas is a protective gas, and the function is to replace air and prevent the air from forming explosive mixed gas with oxygen in the air; and secondly, the water in the air is prevented from hydrolyzing the pyromellitic dianhydride into acid to influence the yield.
In a second aspect of the present invention, there is provided an apparatus for implementing a method for increasing purity of crude pyromellitic dianhydride, comprising: the device comprises a washing kettle, a centrifugal machine, a condenser and drying equipment, wherein methyl tertiary butyl ether is filled in the washing kettle.
In one or more embodiments of the present invention, the washing kettle, the centrifuge, and the drying device are sequentially connected, and the condenser is located above the washing kettle, and is configured to collect gas in the washing kettle, so as to prevent solvent molecules from polluting the surrounding environment.
Preferably, the device also comprises a mother liquor solvent distillation recovery device which is connected with the condenser and used for recovering and reusing the solvent.
The condenser below sets up the condensing medium entry, and the top sets up the condensed liquid export, and the condensing medium gets into from the below, and the top flows for the solvent steam that the condensation scrubbing cauldron produced avoids the polluted environment, in order to improve the rate of utilization of solvent.
The third aspect of the invention provides an application of methyl tertiary butyl ether in the purification process of crude pyromellitic dianhydride.
The fourth aspect of the invention provides a method for improving the purity of crude pyromellitic dianhydride and/or an application of a device for realizing the method for improving the purity of the crude pyromellitic dianhydride in the purification of the crude pyromellitic dianhydride.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
Methyl tert-butyl ether and phenyl tert-butyl ether are analytically pure.
Example 1
As shown in figure 1, a crude pyromellitic dianhydride purification device, a washing kettle 1, a centrifuge 2 and a drying device 3 are connected in sequence, a condenser 4 is positioned above the washing kettle 1, and a mother liquor solvent distillation recovery device is connected with the condenser 4.
Be equipped with the stirring rake in the washing kettle 1, be used for the miscella and treat the purification sample, centrifuge 2 is used for separating liquid and solid, drying equipment 3 is used for the solid that dry centrifugation obtained, condenser 4 below sets up the condensing medium entry, the top sets up the condensed liquid export, the condensing medium gets into from the below, the top flows out, a solvent steam for condensation washing kettle 1 produces, avoid the polluted environment, in order to improve the rate of utilization of solvent, condenser 4 still is connected with mother liquor solvent distillation recovery unit.
Example 2
The preparation method of the crude pyromellitic dianhydride comprises the following steps: the gas phase durene and air are mixed and then enter a fixed bed reactor filled with catalyst to carry out oxidation reaction, and the reaction gas is condensed and crystallized in a trap after three-stage temperature reduction. The temperature of the primary catcher is 190 ℃, and the purity of the crude pyromellitic dianhydride can reach more than 98 percent; the temperature of the four-stage catcher is controlled to be 160 ℃, and the purity of the crude pyromellitic dianhydride is between 60 and 40 percent.
The method for purifying crude pyromellitic dianhydride by using the device described in embodiment 1 comprises the steps of weighing 10g of methyl tertiary butyl ether and 10g of crude pyromellitic dianhydride, mixing the crude pyromellitic dianhydride and the methyl tertiary butyl ether in a washing kettle 1, mixing and washing the mixture at 20 ℃ for 90min under the stirring of 40r/min, centrifuging the mixture in a centrifuge 2 at the centrifugal rate of 950r/min, and drying the centrifuged product in a drying device 3 at 60 ℃ under the pressure of-0.02 MPa.
Example 3
The difference from example 2 is that 15g of methyl-t-butyl ether and 10g of crude pyromellitic dianhydride were weighed.
Example 4
The difference from example 2 is that in the washing process, the mixture is washed for 60min at 25 ℃ under stirring at 30 r/min.
Example 5
The difference from example 2 is that the centrifugation rate during centrifugation was 970 r/min.
Comparative example 1
The difference from example 2 is that 20g of methyl-t-butyl ether and 10g of crude pyromellitic dianhydride were weighed.
Comparative example 2
The difference from example 2 is that 8g of methyl-t-butyl ether and 10g of crude pyromellitic dianhydride were weighed.
Comparative example 3
The difference from example 2 is that in the washing process, the mixture is washed for 90min at 20 ℃ under stirring at 50 r/min.
Comparative example 4
The difference from example 2 is that the centrifugation rate during centrifugation was 850 r/min.
Comparative example 5
The difference from example 2 is that 10g of 1, 4-dioxane was weighed, and the mixture was not separable and had no production value because of its high viscosity after mixing with crude pyromellitic dianhydride.
And (3) performance testing:
the method for testing the purity of pyromellitic dianhydride comprises the following steps: liquid chromatography conditions: c18 column, 250mm × 6mm, 5 μm stainless steel column;
and (3) eluting: volume ratio 0.01mol phosphoric acid aqueous solution: methanol: acetonitrile 80:5: 15;
flow rate: 0.8mL/min
TABLE 1 comparison of purity of pyromellitic dianhydride in examples 2 to 5 and comparative examples 1 to 5
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for improving purity of crude pyromellitic dianhydride is characterized by comprising the following steps: and washing one or more of pyromellitic acid, trimellitic acid and trimellitic anhydride in the crude pyromellitic dianhydride by using methyl tertiary butyl ether as a solvent.
2. The method for improving purity of crude pyromellitic dianhydride according to claim 1, wherein the crude pyromellitic dianhydride is prepared by a pyromellitic gas phase oxidation method.
3. The method for improving purity of crude pyromellitic dianhydride according to claim 1, comprising: mixing crude pyromellitic dianhydride with methyl tertiary butyl ether, washing, centrifuging and drying;
preferably, the weight ratio of the methyl tertiary butyl ether to the crude pyromellitic dianhydride is 1-1.5:1, preferably 1: 1;
preferably, the purity of the crude pyromellitic dianhydride is not less than 40%.
4. The method for improving purity of crude pyromellitic dianhydride according to claim 1, wherein the washing conditions are: mixing at 20-25 deg.C for 60-90min under stirring at 30-40r/min, preferably at 20 deg.C for 90min under stirring at 40 r/min.
5. The method for improving the purity of crude pyromellitic dianhydride according to claim 3, wherein the centrifugation rate is 900-970r/min, preferably 950 r/min;
preferably, the solvent content of the centrifuged material is 5 to 15 wt%.
6. The method for improving purity of crude pyromellitic dianhydride according to claim 3, wherein the drying conditions are: drying at 55-70 ℃ under the pressure of-0.02-0.04 MPa, preferably at 60 ℃ under the pressure of-0.02 MPa;
preferably, the mixing is performed in an inert gas atmosphere.
7. An apparatus for carrying out the method for improving the purity of crude pyromellitic dianhydride according to any one of claims 1 to 6, comprising: the device comprises a washing kettle, a centrifugal machine, a condenser and drying equipment, wherein methyl tertiary butyl ether is filled in the washing kettle.
8. The apparatus for realizing the method for improving the purity of the crude pyromellitic dianhydride according to claim 7, wherein the washing kettle, the centrifuge and the drying equipment are connected in sequence, and the condenser is positioned above the washing kettle;
preferably, the device also comprises a mother liquor solvent distillation recovery device which is connected with the condenser.
9. The application of methyl tertiary butyl ether in the purification process of crude pyromellitic dianhydride.
10. Use of the method for increasing the purity of crude pyromellitic dianhydride according to claim 1 and/or the apparatus for realizing the method for increasing the purity of crude pyromellitic dianhydride according to claim 7 or 8 for the purification of crude pyromellitic dianhydride.
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