CN115160128A - Preparation method of ice crystal acrylic acid - Google Patents
Preparation method of ice crystal acrylic acid Download PDFInfo
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- CN115160128A CN115160128A CN202210764289.9A CN202210764289A CN115160128A CN 115160128 A CN115160128 A CN 115160128A CN 202210764289 A CN202210764289 A CN 202210764289A CN 115160128 A CN115160128 A CN 115160128A
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- 229940090181 propyl acetate Drugs 0.000 claims description 5
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- PMKQSEYPLQIEAY-UHFFFAOYSA-N trans-caffeoyl-L-malic acid Natural products OC(=O)CC(C(O)=O)OC(=O)C=CC1=CC=C(O)C(O)=C1 PMKQSEYPLQIEAY-UHFFFAOYSA-N 0.000 description 2
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
Abstract
The invention belongs to the technical field of chemical separation, and particularly discloses a preparation method of ice crystal acrylic acid, which comprises the following steps of (1) taking a crude acrylic acid aqueous solution as a raw material, adding an extracting agent, extracting, separating a water phase from an organic phase, leaving water-soluble impurities in the water phase, and enriching acrylic acid and other oil-soluble impurities in the organic phase; adding a polymerization inhibitor into the organic phase, and distilling under reduced pressure to separate an extracting agent and an acrylic acid solution; and carrying out melt crystallization treatment on the obtained acrylic acid solution to obtain high-purity ice crystal acrylic acid. The method has the advantages of high purity of the obtained product, stable product index, convenience for continuous production, low operation energy consumption and the like, simultaneously, no impurities such as succinic anhydride and the like are separated out to influence the crystallization process and the purity of the acrylic acid in the crystallization process, and the method is particularly suitable for purifying the crude acrylic acid aqueous solution produced by taking a bio-based material as a raw material.
Description
Technical Field
The invention relates to the technical field of chemical separation, in particular to a preparation method of ice crystal acrylic acid.
Background
Acrylic acid is an unsaturated organic acid, and contains carbon-carbon double bonds and carboxyl structures in molecules, so that a series of compounds can be derived to form a large class of acrylic acid products. At present, the acrylic acid industry with unique characteristics is formed in the field of modern chemical industry, and the acrylic acid industry becomes an important derivative of propylene like polypropylene, acrylonitrile and propylene oxide. The excellent polymerization and esterification capability of the acrylic acid provides an extremely important intermediate for the synthesis and preparation of various fine chemicals. The hydrogen at the alpha and beta positions of acrylic acid is easily substituted, and the carboxyl can generate ester, amide, acyl chloride, acid anhydride and the like; the double bonds of the copolymer have the universality of double bonds, are chemically active, can be homopolymerized and copolymerized, have wide application range and are important chemical raw materials; acrylic acid and esters thereof can be used as high molecular monomers; in addition, it can be used as a raw material for adhesives, paints, resins, etc.; the resin synthesized by the product can be respectively used in the industries of pharmacy, leather, textile, paper making, chemical fiber, rubber, building material, plastic, packaging material, water treatment, oil exploitation and the like. In recent years, the demand for superabsorbent resins has been increasing, and the purity of acrylic acid as a raw material has been also increasing, and thus, new demands for purification of acrylic acid have been made. However, since acrylic acid contains carbon-carbon double bonds, it is easily polymerized in a high temperature environment, which affects product quality and yield. Therefore, it is very important to develop a purification technique applied to the production of high-purity acrylic acid.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention aims to provide a process for producing ice crystal acrylic acid, which uses an acrylic acid solution as a raw material and obtains ice crystal acrylic acid of high purity through extraction, evaporation and crystallization operations.
In order to achieve the above objects and other related objects, the present invention provides a method for preparing ice crystal acrylic acid, comprising the steps of:
(1) Taking a crude acrylic acid aqueous solution as a raw material, adding an extracting agent, extracting, separating a water phase (raffinate phase) from an organic phase (extract phase), and allowing water-soluble impurities to remain in the water phase and acrylic acid and other oil-soluble impurities to be enriched in the organic phase;
(2) Adding a polymerization inhibitor into the organic phase, and distilling under reduced pressure to separate an extracting agent and an acrylic acid solution;
(3) And carrying out melt crystallization treatment on the obtained acrylic acid solution to obtain a high-purity ice crystal acrylic acid product.
Further, in the step (1), the crude acrylic acid aqueous solution is an acrylic acid aqueous solution prepared by a bio-based method.
Further, the crude acrylic acid aqueous solution comprises the following components in percentage by weight: 25-45% of water and 50-70% of acrylic acid.
Further, in the step (1), the extractant is selected from at least one of ethyl acetate, propyl acetate and triethyl citrate.
Further, in the step (1), the amount of the extractant added is 0.5 to 1.0 time, preferably 0.6 to 0.8 time, the mass of the crude acrylic acid aqueous solution.
Further, in the step (2), the polymerization inhibitor is at least one selected from hydroquinone, hydroquinone monomethyl ether and phenothiazine compounds.
Further, in the step (2), the reduced pressure distillation process comprises: under the distillation pressure of 8-12 kPa, the extractant is distilled out, then the pressure is reduced to 2-5 kPa, and the acrylic acid solution is distilled out.
Further, in the step (2), when the extracting agent is distilled out, the distillation temperature is 80-320 ℃, and preferably 100-320 ℃; more preferably, when the extractant is selected from ethyl acetate and/or propyl acetate, the distillation temperature is 100-150 ℃, and when the extractant is selected from triethyl citrate, the distillation temperature is 294-320 ℃.
Further, in the step (2), when the acrylic acid solution is distilled off, the distillation temperature is 30 to 100 ℃.
Further, in the step (2), the acrylic acid solution obtained by distillation has an acrylic acid mass percentage of 96% or more, preferably 97 to 99%.
Further, in the step (3), the melt crystallization mode is: slowly cooling the acrylic acid solution under the stirring state to separate out acrylic acid crystals, and filtering under the constant temperature state when the crystal content (namely solid content) reaches 25-50% to obtain crystals and mother liquor; separating the crystal from the mother liquor, continuously repeating the crystallization operation on the crystal to obtain high-purity ice crystal acrylic acid crystal, repeating the crystallization after the mother liquor is recovered, and finally recovering the obtained residual liquor into the crude acrylic acid aqueous solution in the step (1) to perform extraction, reduced pressure distillation and melt crystallization together.
Optionally, the temperature is reduced to-20 to 13 ℃ to precipitate acrylic acid crystals, preferably-10 to 10 ℃, and more preferably 3 to 5 ℃.
Optionally, the filtration means is spin centrifugation.
Optionally, the constant temperature during filtration is-20 to 10 ℃, preferably-10 to 10 ℃, and more preferably 3 to 5 ℃.
Further, in the step (3), the purity of the obtained ice crystal acrylic acid crystal is more than or equal to 99.7 percent, and preferably more than or equal to 99.8 percent.
As described above, the method for producing ice crystal acrylic acid of the present invention has the following advantageous effects:
the invention takes acrylic acid solution as raw material, and obtains high-purity ice crystal acrylic acid product through extraction, distillation and crystallization purification operations. The method has the advantages of high purity of the obtained product, stable product index, convenience for continuous production, low operation energy consumption and the like, and simultaneously, in the crystallization process, impurities such as succinic anhydride and the like are not separated out to influence the crystallization process and the purity of the acrylic acid. The method is suitable for purifying the acrylic acid aqueous solution, and is particularly suitable for producing crude acrylic acid aqueous solution by taking a bio-based material as a raw material.
Drawings
FIG. 1 is a schematic view showing a process flow of a process for producing ice crystal acrylic acid according to the present invention.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The invention provides a preparation method of ice crystal acrylic acid, which is combined with the figure 1, crude acrylic acid aqueous solution is taken as a raw material, and is extracted to separate a water phase from an organic phase, so that water-soluble impurities are left in the water phase, and acrylic acid and other oil-soluble impurities are enriched in the organic phase; after extraction and liquid separation are finished, adding a polymerization inhibitor into the extraction phase, uniformly mixing, and then carrying out reduced pressure distillation on the extraction phase to separate an extracting agent and acrylic acid; and then carrying out melt crystallization on the obtained acrylic acid, wherein the melt crystallization is to gradually cool the acrylic acid melt liquid under the stirring condition, separate out the acrylic acid crystal part, control the temperature of the crystallization liquid when the solid content reaches about 25-50%, enter the slurry into a temperature-controlled filtering device under the constant temperature state, separate the mother liquid from the crystal, recover and repeatedly crystallize the mother liquid, further recover and purify the acrylic acid in the mother liquid, melt and crystallize the filter cake (namely the crystal) obtained by centrifugation, and carry out the next-stage purification treatment according to the purity requirement of the acrylic acid until the high-purity ice crystal acrylic acid product is obtained.
Specifically, the crude acrylic acid aqueous solution is an acrylic acid aqueous solution prepared by a bio-based method.
Specifically, the crude acrylic acid aqueous solution comprises the following components in percentage by weight: 25-45% of water and 50-70% of acrylic acid.
Specifically, the extractant is at least one of ethyl acetate, propyl acetate and triethyl citrate, and the addition amount of the extractant is 0.5 to 1.0 time of the mass of the crude acrylic acid aqueous solution; the polymerization inhibitor is at least one of hydroquinone, hydroquinone monomethyl ether and phenothiazine compounds.
Specifically, the reduced pressure distillation process comprises the following steps: under the distillation pressure of 8-12 kPa, the extractant is distilled out, then the pressure is reduced to 2-5 kPa, and the acrylic acid solution is distilled out. Wherein, when the extractant is distilled, the distillation temperature is 80-320 ℃, and preferably 100-320 ℃; more preferably, when the extractant is selected from ethyl acetate and/or propyl acetate, the distillation temperature is 100-150 ℃, and when the extractant is selected from triethyl citrate, the distillation temperature is 294-320 ℃. When the acrylic acid solution is distilled, the distillation temperature is 30-120 ℃.
Specifically, the acrylic acid solution obtained by distillation has an acrylic acid mass percentage of 96% or more, preferably 97 to 99%.
Specifically, the melt crystallization mode is as follows: slowly cooling the acrylic acid solution to-20-13 ℃ under the stirring state, separating out acrylic acid crystals, and filtering under the constant temperature state (-20-10 ℃) when the crystal content (namely solid content) reaches 25-50% to obtain crystals and mother liquor; separating the crystal from the mother liquid, continuously repeating the crystallization operation on the crystal to obtain the high-purity ice crystal acrylic acid crystal, recycling the mother liquid, then repeating the crystallization, finally recycling the obtained residual liquid into the crude acrylic acid aqueous solution, and carrying out extraction, reduced pressure distillation and melt crystallization together.
The present invention will be described in detail with reference to the following specific examples. It should also be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention, and that numerous insubstantial modifications and adaptations of the invention described above will occur to those skilled in the art. The specific process parameters and the like of the following examples are also merely examples of suitable ranges, i.e., those skilled in the art can select from suitable ranges through the description herein and are not limited to the specific values of the following examples.
Example 1
Unless otherwise specified below, the percentage contents are all percentages by weight.
The raw material of the acrylic acid aqueous solution prepared by bio-based method is 45.2% of water, 50.9% of acrylic acid, 1.8% of hydroxy propionic acid, 0.8% of glycerol and 1.3% of others.
Firstly, adding ethyl acetate with the mass of 0.7 time of that of crude acrylic acid aqueous solution, fully mixing the two, standing and separating, wherein the lower layer is a water phase, the upper layer is an oil phase, removing the lower water phase through liquid separation, adding hydroquinone monomethyl ether as a polymerization inhibitor into the upper oil phase, and fully mixing. Putting the oil phase (extraction phase) into a rotary evaporator for reduced pressure distillation, wherein the early stage of the distillation pressure is 10kPa, the distillation temperature is 120 ℃, and ethyl acetate is distilled out; the pressure was further reduced to 3kPa at a distillation temperature of 142 ℃ to distill off the acrylic acid solution. By extraction and distillation, a 98.6% acrylic acid solution was obtained. Slowly cooling the acrylic acid solution to 5 ℃ in a temperature control device with stirring, slowly separating out crystals, controlling the content of the crystals to be 35.0%, then filtering in a filtering device (adopting a rotary scraper type centrifuge) with preset temperature (5 ℃) to obtain crystals and mother liquor, and continuously repeating the crystallization operation of the crystals to obtain ice crystal acrylic acid crystals with the purity of 99.9%; and repeatedly crystallizing the mother liquor according to the method after recovering, and finally recovering the residual liquid into the crude acrylic acid aqueous solution.
The change of the contents of the respective components of the crude acrylic acid aqueous solution in the purification process and the single-pass yield and the total yield of acrylic acid in this example are shown in Table 1 below.
TABLE 1
Example 2
Unless otherwise specified below, the percentage contents are all percentages by weight.
The raw material of the aqueous solution of crude acrylic acid prepared by bio-based method is 25.1% of the aqueous solution of crude acrylic acid, the acrylic acid content is 70.4%, the maleic anhydride content is 2.1%, the dimer content is 0.7%, the acrolein content is 1.1%, and the other content is 0.6%.
Firstly, adding ethyl acetate with the mass of 0.8 time of that of crude acrylic acid aqueous solution, fully mixing the two, standing and separating, wherein the lower layer is a water phase, the upper layer is an oil phase, removing the lower water phase through liquid separation, adding hydroquinone monomethyl ether as a polymerization inhibitor into the upper oil phase, and fully mixing. Putting the oil phase (extraction phase) into a rotary evaporator for reduced pressure distillation, wherein the early stage of the distillation pressure is 10kPa, the distillation temperature is 100 ℃, and ethyl acetate is distilled out; the pressure was further reduced to 3kPa at a distillation temperature of 72 ℃ to distill off the acrylic acid solution. By extraction and distillation, a 97.3% acrylic acid solution was obtained. Slowly cooling the acrylic acid solution to 3 ℃ in a temperature control device with stirring, slowly separating out crystals, controlling the content of the crystals to be 25.0%, then filtering in a filtering device (adopting a rotary scraper type centrifuge) with the preset temperature of 3 ℃ to obtain the crystals and mother liquor, and continuously repeating the crystallization operation to obtain the ice crystal acrylic acid crystals with the purity of 99.8%; and after mother liquor is recovered, the mother liquor is repeatedly crystallized according to the method, and finally the obtained residual liquid is recovered into a crude acrylic acid aqueous solution.
The change of the contents of the respective components of the crude acrylic acid aqueous solution in the purification process and the single-pass yield and the total yield of acrylic acid in this example are shown in Table 2 below.
TABLE 2
Example 3
Unless otherwise specified below, the percentage contents are all percentages by weight.
The raw material of the aqueous solution of crude acrylic acid prepared by bio-based method is 30.2% of the aqueous solution of crude acrylic acid, 65.3% of acrylic acid content, 1.9% of maleic anhydride, 0.9% of dimer, 1.1% of acrolein and 0.6% of the rest.
Firstly, adding 0.6 mass time of triethyl citrate into a crude acrylic acid aqueous solution, fully mixing the two, standing and separating the two, wherein the lower layer is a water phase, the upper layer is an oil phase, removing the lower water phase through liquid separation, adding hydroquinone monomethyl ether as a polymerization inhibitor into the upper oil phase, and fully mixing. Putting the oil phase (extraction phase) into a rotary evaporator for reduced pressure distillation, wherein the distillation pressure is 12kPa at the early stage, the distillation temperature is 295 ℃, and triethyl citrate is distilled out; the pressure was further reduced to 5kPa at a distillation temperature of 79 ℃ to distill off the acrylic acid solution. By extraction and distillation, a 97.3% acrylic acid solution was obtained. Slowly cooling the acrylic acid solution to 3 ℃ in a temperature control device with stirring, slowly separating out crystals, controlling the content of the crystals to be 50.0%, then filtering in a filtering device (adopting a rotary scraper type centrifuge) with preset temperature (3 ℃) to obtain crystals and mother liquor, and continuously repeating the crystallization operation of the crystals to obtain ice crystal acrylic acid crystals with the purity of 99.9%; and repeatedly crystallizing the mother liquor according to the method after recovering, and finally recovering the residual liquid into the crude acrylic acid aqueous solution.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Those skilled in the art can modify or change the above-described embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A preparation method of ice crystal acrylic acid is characterized by comprising the following steps:
(1) Taking a crude acrylic acid aqueous solution as a raw material, adding an extracting agent, extracting, separating a water phase from an organic phase, leaving water-soluble impurities in the water phase, and enriching acrylic acid and other oil-soluble impurities in the organic phase;
(2) Adding a polymerization inhibitor into the organic phase, and distilling under reduced pressure to separate an extracting agent and an acrylic acid solution;
(3) And carrying out melt crystallization treatment on the obtained acrylic acid solution to obtain a high-purity ice crystal acrylic acid product.
2. The process for producing ice crystal acrylic acid according to claim 1, characterized in that: in the step (1), the crude acrylic acid aqueous solution is an acrylic acid aqueous solution prepared by a bio-based method.
3. The process for producing ice crystal acrylic acid according to claim 1 or 2, characterized in that: the acrylic acid aqueous solution comprises the following components in percentage by weight: 25-45% of water and 50-70% of acrylic acid.
4. The process for producing ice crystal acrylic acid according to claim 1, characterized in that: in the step (1), the extracting agent is selected from at least one of ethyl acetate, propyl acetate and triethyl citrate;
and/or in the step (1), the addition amount of the extracting agent is 0.5 to 1.0 time of the mass of the crude acrylic acid aqueous solution.
5. The process for producing ice crystal acrylic acid according to claim 1, characterized in that: in the step (2), the polymerization inhibitor is at least one selected from hydroquinone, hydroquinone monomethyl ether and phenothiazine compounds.
6. The process for producing ice crystal acrylic acid according to claim 1, characterized in that: in the step (2), the reduced pressure distillation process comprises the following steps: under the distillation pressure of 8-12 kPa, ethyl acetate is distilled out, then the pressure is reduced to 2-5 kPa, and acrylic acid solution is distilled out.
7. The process for producing ice crystal acrylic acid according to claim 1, characterized in that: in the step (2), the mass percent of acrylic acid in the distilled acrylic acid solution is more than 96%.
8. The process for producing ice crystal acrylic acid according to claim 1, characterized in that: in the step (2), the distillation temperature is 80-320 ℃.
9. The process for producing ice crystal acrylic acid according to claim 1, characterized in that: the melt crystallization mode is as follows: slowly cooling the acrylic acid solution under the stirring state to separate out acrylic acid crystals, and filtering under the constant temperature state when the crystal content reaches 25-50% to obtain crystals and mother liquor; separating the crystal from the mother liquor, continuously repeating the crystallization operation on the crystal to obtain high-purity ice crystal acrylic acid crystal, recycling the mother liquor, then repeating the crystallization, finally recycling the obtained residual liquor into the crude acrylic acid aqueous solution in the step (1), and performing extraction, reduced pressure distillation and melt crystallization together.
10. The process for producing ice crystal acrylic acid according to claim 1, characterized in that: in the step (3), the purity of the obtained ice crystal acrylic acid crystals is more than or equal to 99.7%.
Applications Claiming Priority (2)
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