CN115636735B - Process method for extracting and separating m-cresol and p-cresol mixture - Google Patents

Process method for extracting and separating m-cresol and p-cresol mixture Download PDF

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CN115636735B
CN115636735B CN202211326210.0A CN202211326210A CN115636735B CN 115636735 B CN115636735 B CN 115636735B CN 202211326210 A CN202211326210 A CN 202211326210A CN 115636735 B CN115636735 B CN 115636735B
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cresol
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CN115636735A (en
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任树行
吴卫泽
尹成磊
冯同旭
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Beijing University of Chemical Technology
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Abstract

The invention provides a process method for extracting and separating m-cresol and p-cresol mixtures, and relates to the field of separation of coal chemical fine chemicals. The method takes a m-cresol mixture as a raw material, dissolves the m-cresol mixture in normal hexane or toluene solvent, adopts 4-pyridine formamide, urea or oxalic acid as a solid extractant, separates one of the cresols through solid phase extraction, and then obtains single cresols with purity of more than 98% through back extraction. The method is simple and efficient in operation, the extractant can be recycled after back extraction, and the solvent and the back extractant can be recycled.

Description

Process method for extracting and separating m-cresol and p-cresol mixture
Technical Field
The invention relates to the field of separation of fine chemicals in coal chemical industry, in particular to a separation method of m-cresol and p-cresol mixtures.
Background
Coal tar is an important coal chemical product, and a series of crude phenol products can be obtained through reduced pressure rectification. Among them, m-cresol mixtures are one of the common crude phenol products. Because the difference of the boiling points of the m-cresol and the p-cresol is less than 1 ℃ and the m-cresol and the p-cresol cannot be separated in a conventional rectification mode, the method for separating the m-cresol and the p-cresol mixture is developed with high efficiency and low energy consumption, and has high application value.
There are several well-established processes in industry for the separation of mixtures of m-and p-cresol, mainly including complexation, alkylation, crystallization and adsorption.
The complex separation method is to add complexing agent into the mixture of m-cresol and p-cresol to make it produce complex reaction with selected single cresol to form a complex easy to separate, so as to obtain the separation method of single cresol. The method adopts oxalic acid, urea and the like as complexing agents, and generally adopts the processes of forming a complex by heating, separating the complex by cooling crystallization, decomplexing the complex and the like. The complex separation method has the advantages of low-cost and easily-obtained raw materials, recycling, higher reaction temperature, lower crystallization temperature, more complicated process, lower efficiency and high energy consumption.
The process flow of the alkylation separation method is as follows: under the condition of acid catalyst, m-cresol and isobutene are respectively reacted to obtain respective alkylated derivatives, the boiling points of the two products are greatly different, separation can be carried out through rectification, and then operations such as recrystallization, solvent extraction, hydrocarbon removal and the like are respectively carried out to obtain m-cresol and p-cresol products. The method has the advantages of simple process, capability of obtaining high-purity products, main stream separation process for industrial application, and still has the problems of lower recovery rate and recycling rate of the catalyst, high energy consumption, environmental pollution and the like.
The crystallization separation method is a method of performing crystallization separation by utilizing the difference in solubility of a cresol mixture in a solvent at different temperatures and the difference in melting point of the mixture. The method can obtain the cresol isomer monomer with high purity, but has limited production capacity, is not suitable for large-scale production, and has high energy consumption due to repeated temperature rise and reduction.
The adsorption separation method is to selectively adsorb one kind of cresol on the adsorbent by utilizing the different adsorption capacities of the adsorbent on the m-cresol and then desorb the cresol in a specific solvent, thereby separating the m-cresol and p-cresol mixture. As a novel separation method, the method has a good prospect, but the adsorption quantity is small, and the development of the adsorbent and the desorbent is still a trouble of puzzlement and development.
Based on the analysis, the complex separation process and high energy consumption are common problems of the existing method. Therefore, development of a novel m-cresol and p-cresol mixture separation method which is simple to operate, efficient, energy-saving and environment-friendly is needed.
Disclosure of Invention
The invention provides a method for efficiently separating a m-cresol mixture by solid phase extraction, aiming at the common problems in the traditional m-cresol mixture separation process. The method is based on a solid phase extraction technology, a m-cresol and p-cresol mixture is dissolved in a solvent to form a solution, then a solid extractant is added into the solution, single cresol in the solution is extracted and separated, and the high-efficiency separation of the m-cresol and p-cresol mixture is realized under a mild condition. The method takes the m-cresol and p-cresol mixture as raw materials, n-hexane or toluene as solvent, 4-pyridine formamide, urea or oxalic acid as extractant, and can separate single cresol with purity more than 98% from the m-cresol and p-cresol mixture. The method is simple and efficient in operation, the extractant, the solvent and the back extractant can be regenerated and recycled, and a new path is provided for separation of the m-cresol mixture.
The invention provides a process method for extracting and separating m-cresol and p-cresol mixture, which is characterized by comprising the following steps:
S1: dissolving m-cresol and p-cresol mixture in a solvent to prepare a solution, placing the solution in a separator, adding a solid extractant in proportion, controlling the temperature of the solution, stirring and extracting, and separating liquid and solid phases by a centrifugal or filtering mode after the extraction time is reached to obtain raffinate and extract solids;
S2: taking the extract solid in the step S1, adding a stripping agent, stirring at room temperature, carrying out stripping, and separating liquid-solid two phases by a centrifugal or filtering mode after the stripping time is reached: the solid phase after back extraction is a solid extractant and can be reused; the liquid phase after back extraction can obtain single cresol with purity more than 98% through normal pressure distillation, and the back extractant can be reused;
S3: and (3) taking raffinate in the step S1, and recovering the solvent and the residual m-cresol mixture by adopting atmospheric distillation.
The method according to claim 1, wherein the solvent in step S1 is selected from n-hexane and toluene.
The method according to claim 1, wherein the m-p-cresol mixture of step S1 is formulated at a solution concentration of 100g/L to 200g/L.
The method according to claim 1, wherein the solid extractant of step S1 is selected from the group consisting of 4-pyridinecarboxamide, urea, oxalic acid.
The method according to claim 1, wherein the molar ratio of the amount of the solid extractant added to the total phenol amount in step S1 is 0.3 to 0.9.
The process according to claim 1, wherein the extraction temperature in step S1 is 15 ℃ to 45 ℃.
The method according to claim 1, wherein the extraction time in step S1 is 10min to 60min.
The process according to claim 1, wherein the stripping agent of step S2 is selected from ethyl acetate, dichloromethane, diethyl ether.
The method according to claim 1, wherein the volume ratio of the stripping agent added to the solution in step S2 is 0.3-1.0.
The method according to claim 1, wherein the back extraction time in step S2 is 10min to 30min.
The extraction agent and m-cresol are separated through hydrogen bonding, and the screening of the extraction agent is based on the following principle: (1) The interaction energy between the extractant and the m-cresol is larger than the solvent free energy of the m-cresol in normal hexane or toluene solvent, so that the extractant can extract and separate the m-cresol from the solution; (2) The interaction energy of the extractant with m-cresol and p-cresol respectively is larger, so that the extractant has larger selectivity to the two cresols in the solution, and the cresols with larger interaction energy with the extractant in the solution are preferentially extracted. And combining molecular simulation calculation, and selecting 4-pyridine formamide, urea and oxalic acid as extracting agents.
Compared with the traditional separation method of the m-cresol and p-cresol mixture, the method for extracting and separating the m-cresol and p-cresol mixture has the following advantages: (1) The process flow is simple, the extractant and the solution are added and reacted at one time, and the operations of repeatedly dripping m-cresol mixture, solution and the like in the traditional process are avoided; (2) The separation condition is mild, the temperature of the separation process is between 15 ℃ and 45 ℃, the processes of high-temperature complexation or low-temperature crystallization and the like are not needed, and the energy consumption is low; (3) In the separation, organic solvent is adopted for back extraction, so that the separation is easy, the separation can be repeatedly used, and no phenol-containing wastewater is generated; and (4) continuous operation, and good product quality.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the following examples.
Example 1
Taking a mixture of m-cresol and p-cresol with the mass fraction of 70% as a raw material, and dissolving the mixture in n-hexane to prepare 200g/L solution. 1L of the solution is placed in a separator with a stirrer, 66.7g of urea (the molar ratio of the urea amount to the total phenol amount in the solution is 0.6) is added by taking urea as an extractant, and after stirring for 60min at 15 ℃, liquid-solid two phases are filtered and separated to obtain raffinate and extract solids.
After the extract solid was taken out, ethyl acetate was used as a stripping agent in an amount of 0.3L (volume ratio to the solution was 0.3), and after stirring at room temperature for 30 minutes, the liquid-solid two phases were separated by filtration. For the liquid phase solution after the back extraction, 97.4g of m-cresol was obtained by atmospheric distillation, the purity of m-cresol was 98.6%, and the yield was 68.6%. The solid phase after back extraction is urea and can be reused.
The raffinate was distilled at atmospheric pressure to recover n-hexane and to obtain 102.6g of a mixture of m-cresol and p-cresol, the mass fraction of which was 43%.
Example 2
Taking a mixture of m-cresol and p-cresol with the mass fraction of 70% as a raw material, and dissolving the mixture in n-hexane to prepare 200g/L solution. 1L of the solution is placed in a separator with a stirrer, 100.0g of urea (the molar ratio of the urea amount to the total phenol amount in the solution is 0.9) is added by taking urea as an extractant, and after stirring for 60min at 25 ℃, liquid-solid two phases are centrifugally separated to obtain raffinate and extract solids.
After the extract solid was taken out, ethyl acetate was used as a stripping agent in an amount of 1L (volume ratio to the solution: 1.0), and after stirring at room temperature for 10 minutes, the liquid-solid two phases were separated by centrifugation. For the liquid phase solution after the back extraction, 102.5g of m-cresol was obtained by atmospheric distillation, and the purity of m-cresol was 98.1% and the yield was 71.8%. The solid phase after back extraction is urea and can be reused.
The raffinate was distilled at atmospheric pressure to recover n-hexane and to obtain 97.5g of a mixture of m-cresol and p-cresol, the mass fraction of which was 40%.
Example 3
Taking a mixture of m-cresol and p-cresol with the mass fraction of 70% as a raw material, and dissolving the mixture in n-hexane to prepare 200g/L solution. 1L of the solution is placed in a separator with a stirrer, 66.7g of urea (the molar ratio of the urea amount to the total phenol amount in the solution is 0.6) is added by taking urea as an extractant, and after stirring for 60min at 20 ℃, liquid-solid two phases are filtered and separated to obtain raffinate and extract solids.
After the extract solid was taken out, ethyl acetate was used as a stripping agent in an amount of 0.5L (volume ratio to the solution was 0.5), and after stirring at room temperature for 20 minutes, the liquid-solid two phases were separated by filtration. For the liquid phase solution after the back extraction, 99.9g of m-cresol was obtained by atmospheric distillation, the purity of m-cresol was 98.5%, and the yield was 70.3%. The solid phase after back extraction is urea and can be reused.
The raffinate was distilled at atmospheric pressure to recover n-hexane and to obtain 100.1g of a mixture of m-cresol and p-cresol, the mass fraction of which was 42%.
Example 4
Taking a m-cresol mixture with the mass fraction of 60% of that of the p-cresol as a raw material, and dissolving the m-cresol mixture in toluene to prepare a solution with the mass fraction of 100 g/L. 1L of the solution is placed in a separator with a stirrer, 4-pyridine formamide is used as an extractant, 45.2g of 4-pyridine formamide (the molar ratio of the 4-pyridine formamide to the total phenol in the solution is 0.4) is added, and after stirring for 60min at 25 ℃, liquid-solid two phases are filtered and separated to obtain raffinate and extract solid.
Taking out the extract solid, taking diethyl ether as a stripping agent, adding the diethyl ether into the solution with the addition amount of 0.5L (the volume ratio of the diethyl ether to the solution is 0.5), stirring the solution for 30min at room temperature, and filtering to separate liquid phases and solid phases. For the liquid phase solution after the back extraction, 33.1g of p-cresol was obtained by atmospheric distillation, the purity of the p-cresol was 98.0%, and the yield was 54.0%. The solid phase after back extraction is 4-pyridine formamide, and can be reused.
Toluene was recovered from the raffinate by atmospheric distillation, and 66.9g of a mixture of m-cresol and p-cresol was obtained with a mass fraction of 41%.
Example 5
Taking a m-cresol mixture with the mass fraction of 60% of that of the p-cresol as a raw material, and dissolving the m-cresol mixture in normal hexane to prepare 200g/L solution. 1L of the solution is placed in a separator with a stirrer, oxalic acid is used as an extractant, 50.0g of oxalic acid (the molar ratio of the oxalic acid amount to the total phenol amount in the solution is 0.3) is added, and after stirring for 10min at 45 ℃, liquid-solid two phases are filtered and separated to obtain raffinate and extract solid.
After the extract solid was taken out, methylene chloride was used as a stripping agent in an amount of 0.5L (volume ratio to the solution was 0.5), and after stirring at room temperature for 30 minutes, the liquid-solid two phases were separated by filtration. For the liquid phase solution after the back extraction, 76.5g of p-cresol was obtained by atmospheric distillation, the purity of the p-cresol was 99.1%, and the yield was 63.2%. The solid phase after back extraction is oxalic acid, and can be reused.
The raffinate was distilled at atmospheric pressure to recover n-hexane and to obtain 123.5g of a mixture of m-cresol and p-cresol with a mass fraction of 36%.
Example 6
Taking a m-cresol mixture with the mass fraction of 60% of that of the p-cresol as a raw material, and dissolving the m-cresol mixture in normal hexane to prepare 200g/L solution. 1L of the solution is placed in a separator with a stirrer, 66.7g of oxalic acid (the molar ratio of the oxalic acid amount to the total phenol amount in the solution is 0.4) is added by taking oxalic acid as an extractant, and after stirring for 30min at 25 ℃, liquid-solid two phases are filtered and separated to obtain raffinate and extract solids.
After the extract solid was taken out, dichloromethane was used as a stripping agent in an amount of 1L (volume ratio to the solution: 1.0), and after stirring at room temperature for 10 minutes, the liquid-solid two phases were separated by filtration. For the liquid phase solution after the back extraction, 89.1g of p-cresol was obtained by atmospheric distillation, and the purity of p-cresol was 98.5%, and the yield was 73.1%. The solid phase after back extraction is oxalic acid, and can be reused.
The raffinate was distilled at atmospheric pressure to recover n-hexane and to obtain 110.9g of a mixture of m-cresol and p-cresol with a mass fraction of 29%.
Example 7
Taking a mixture of m-cresol and p-cresol with the mass fraction of 70% as a raw material, and dissolving the mixture in n-hexane to prepare 200g/L solution. 1L of the solution is placed in a separator with a stirrer, 66.7g of urea (the molar ratio of the urea amount to the total phenol amount in the solution is 0.6) is added by taking urea as an extractant, and after stirring for 40min at 25 ℃, liquid-solid two phases are filtered and separated to obtain raffinate A and extract solid B.
The extract solid B was taken out, and after stirring at room temperature for 30 minutes, the liquid-solid two phases were separated by filtration, with ethyl acetate as a stripping agent, in an amount of 0.5L (volume ratio to the solution: 0.5). For the liquid phase solution after the back extraction, 95.9g of m-cresol was obtained by atmospheric distillation, the purity of m-cresol was 98.5%, and the yield was 67.5%. The solid phase after back extraction is urea and can be reused.
The raffinate A is placed in a separator with a stirrer, oxalic acid is used as an extractant, 26.0g (the molar ratio of the oxalic acid amount to the total phenol amount in the solution is 0.3) of oxalic acid is added, and after stirring for 30min at 25 ℃, liquid-solid two phases are filtered and separated to obtain raffinate C and extract solid D.
After the extract solid D was taken out, methylene chloride was used as a stripping agent in an amount of 0.3L (volume ratio to the solution: 0.3), and after stirring at room temperature for 30 minutes, the liquid-solid two phases were separated by filtration. For the liquid phase solution after the back extraction, 39.8g of p-cresol was obtained by atmospheric distillation, the purity of the p-cresol was 98.1%, and the yield was 66.7%. The solid phase after back extraction is oxalic acid, and can be reused.
The raffinate C was distilled at atmospheric pressure to recover n-hexane and to obtain 64.2g of a mixture of m-cresol and p-cresol, the mass fraction of which was 70%.
Example 8
Taking a mixture of m-cresol and p-cresol with the mass fraction of 70% as a raw material, and dissolving the mixture in n-hexane to prepare 200g/L solution. 1L of the solution is placed in a separator with a stirrer, 66.7g of urea (the molar ratio of the urea amount to the total phenol amount in the solution is 0.6) is added by taking urea as an extractant, and after stirring for 60min at 25 ℃, liquid-solid two phases are filtered and separated to obtain raffinate and extract solids.
After the extract solid was taken out, ethyl acetate was used as a stripping agent in an amount of 0.5L (volume ratio to the solution was 0.5), and after stirring at room temperature for 10 minutes, the liquid-solid two phases were separated by filtration. For the liquid phase solution after the back extraction, 100.0g of m-cresol was obtained by atmospheric distillation, the purity of m-cresol was 98.6%, and the yield was 70.4%. The solid phase after back extraction is urea and can be reused.
The raffinate was distilled at atmospheric pressure to recover n-hexane and to obtain 100.0g of a mixture of m-cresol and p-cresol, the mass fraction of which was 41%.
The solid extractant after back extraction is used for the conditions again to obtain the m-cresol with the purity of 98.5 percent, the yield of the m-cresol is 70.1 percent, and the extraction separation performance is not changed.

Claims (7)

1. A process for the extractive separation of a mixture of m-and p-cresol, comprising the steps of:
S1: dissolving m-cresol and p-cresol mixture in a solvent to prepare a solution, placing the solution in a separator, adding a solid extractant in proportion, controlling the temperature of the solution, stirring and extracting, and separating liquid and solid phases by a centrifugal or filtering mode after the extraction time is reached to obtain raffinate and extract solids;
S2: taking the extract solid in the step S1, adding a stripping agent, stirring at room temperature, carrying out stripping, and separating liquid-solid two phases by a centrifugal or filtering mode after the stripping time is reached: the solid phase after back extraction is a solid extractant for re-extraction; the liquid phase after back extraction is distilled under normal pressure to obtain single cresol with purity more than 98 percent, and the back extractant is recycled;
s3: taking raffinate in the step S1, and recycling a solvent and the residual m-cresol mixture by adopting normal pressure distillation;
In the step S1, the solvent is selected from n-hexane and toluene; the solid extractant is selected from 4-pyridine formamide, urea and oxalic acid;
in step S2, the stripping agent is selected from ethyl acetate, dichloromethane, diethyl ether.
2. The method according to claim 1, wherein the m-p-cresol mixture of step S1 is formulated at a solution concentration of 100g/L to 200g/L.
3. The method according to claim 1, wherein the molar ratio of the amount of the solid extractant added to the total phenol amount in step S1 is 0.3 to 0.9.
4. The process according to claim 1, wherein the extraction temperature in step S1 is 15 ℃ to 45 ℃.
5. The method according to claim 1, wherein the extraction time in step S1 is 10min to 60min.
6. The method according to claim 1, wherein the volume ratio of the stripping agent added to the solution in step S2 is 0.3-1.0.
7. The method according to claim 1, wherein the back extraction time in step S2 is 10min to 30min.
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