CN113880696A - Separation and purification method of m-cresol and p-cresol - Google Patents
Separation and purification method of m-cresol and p-cresol Download PDFInfo
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- CN113880696A CN113880696A CN202111175795.6A CN202111175795A CN113880696A CN 113880696 A CN113880696 A CN 113880696A CN 202111175795 A CN202111175795 A CN 202111175795A CN 113880696 A CN113880696 A CN 113880696A
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- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 title claims abstract description 95
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000000746 purification Methods 0.000 title claims abstract description 16
- 238000000926 separation method Methods 0.000 title abstract description 11
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000007788 liquid Substances 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 239000003377 acid catalyst Substances 0.000 claims abstract description 21
- 238000001179 sorption measurement Methods 0.000 claims abstract description 21
- 239000000047 product Substances 0.000 claims abstract description 20
- 230000029936 alkylation Effects 0.000 claims abstract description 19
- 238000006900 dealkylation reaction Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 230000020335 dealkylation Effects 0.000 claims abstract description 9
- 239000012467 final product Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 20
- WYSSJDOPILWQDC-UHFFFAOYSA-N 2,4-ditert-butyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1C(C)(C)C WYSSJDOPILWQDC-UHFFFAOYSA-N 0.000 claims description 10
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 10
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 7
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical group OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 5
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 5
- 230000002401 inhibitory effect Effects 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical group CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- 238000003795 desorption Methods 0.000 claims 1
- 229940100198 alkylating agent Drugs 0.000 abstract description 7
- 239000002168 alkylating agent Substances 0.000 abstract description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000007547 defect Effects 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 239000004826 Synthetic adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- -1 step 2) Chemical compound 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/685—Processes comprising at least two steps in series
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/74—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/82—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/86—Purification; separation; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention belongs to the technical field of separation and purification of chemical products, and particularly relates to a separation and purification method of m-cresol and p-cresol, which comprises the following steps: 1) adding meta-para-mixed phenol and a liquid acid catalyst into an alkylation reaction container at one time, introducing the meta-para-mixed phenol and the liquid acid catalyst into a gas-liquid reaction tower from a liquid inlet pipe when the temperature rises to 60 ℃, simultaneously introducing isobutene gas into the gas-liquid reaction tower from a gas inlet pipe, and contacting the meta-para-mixed phenol and the liquid acid catalyst to perform alkylation reaction; 2) introducing the obtained alkylation product into a catalyst adsorption tower, a light component removal tower and a rectifying tower in sequence, and rectifying and collecting fractions with different temperatures; 3) and respectively placing the target fractions into a dealkylation reaction vessel, and adding a dealkylation catalyst for reaction to obtain a final product. The method utilizes the gas-liquid reaction tower to realize the alkylation reaction of the alkylating agent and the mixed m-cresol and p-cresol, so that the isobutene can be fully contacted with the atomized raw material, the conversion rate of the mixed phenol and the utilization rate of the isobutene are improved, and the problems of high energy consumption and potential safety hazard caused by liquefying the alkylating agent are effectively avoided.
Description
Technical Field
The invention belongs to the technical field of separation and purification of chemical products, and particularly relates to a separation and purification method of m-cresol and p-cresol.
Background
Cresol is an organic chemical intermediate with a wide range of uses. Wherein, the paracresol can be used in the industrial departments of pesticide, dye, plastic, medicine, and the like. M-cresol is an important raw material for synthesizing organic intermediates, and has important application in color film developers, synthetic resins, adhesives and the like. Therefore, the high-purity m-cresol and p-cresol have good market prospect and great development potential, and have extremely important influence on the development of economy and chemical industry in China. However, although the separation of m-cresol and p-cresol by alkylation process has been done in China, the method still has many defects, and industrial production cannot be realized. Therefore, the realization of the industrialization of m-cresol and p-cresol is very important at present. At present, the domestic technology for separating m-cresol and p-cresol mostly adopts an intermittent reaction kettle, and high-purity isobutene and mixed m-cresol and p-cresol are subjected to gas-phase alkylation reaction to obtain an alkylation product, and then the high-purity m-cresol and p-cresol are obtained through separation.
Patent specification CN106810422A discloses a method for separating m-cresol and p-cresol by liquid phase alkylation. The method utilizes a new process that the isobutene mixed gas and the m-cresol and p-cresol mixture are subjected to alkylation reaction and separation in a fixed bed reactor under the liquid phase state at the same time to obtain the m-cresol and the p-cresol, and the pure m-cresol and p-cresol are obtained by taking the isobutene mixed gas as an alkylating agent and the m-cresol and p-cresol mixture as raw materials through liquid phase alkylation reaction and separation. The method overcomes the defects of low utilization rate of an alkylating agent and serious environmental pollution in the gas-phase alkylation reaction in the prior art, and simultaneously overcomes the defect of high production cost caused by using high-purity isobutene as the alkylating agent in the gas-phase alkylation reaction.
However, the method for separating m-cresol and p-cresol by alkylation still has the defects that the method consumes more energy for liquefying isobutene, so that the integral separation and purification cost is higher, and the potential safety hazard is increased due to high pressure.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a method for separating and purifying m-cresol and p-cresol.
In order to achieve the technical purpose and achieve the technical effect, the invention is realized by the following technical scheme:
a method for separating and purifying m-cresol and p-cresol comprises the following steps:
1) adding the m-p-cresol and the liquid acid catalyst into an alkylation reaction container at one time, starting stirring and heating, introducing the mixture into a gas-liquid reaction tower from a liquid inlet pipe when the temperature rises to 60 ℃, simultaneously introducing isobutene gas into the gas-liquid reaction tower from a gas inlet pipe, contacting the isobutene gas with the atomized m-p-cresol and the liquid acid catalyst for alkylation reaction, and circularly and continuously introducing the isobutene gas for reaction until all m-p-cresol in the raw materials is converted into an alkylation product;
2) introducing the obtained alkylation product into a catalyst adsorption tower, adsorbing and removing the catalyst by the catalyst adsorption tower, feeding the feed liquid passing through the catalyst adsorption tower into a light component removal tower, and removing dissolved isobutene by the light component removal tower; transferring the bottom material of the light component removal tower to a rectifying tower, heating and rectifying the rectifying tower under the pressure condition of 5-15kPa, collecting fractions with different temperatures, wherein the working temperature of the rectifying tower is 150-;
3) and respectively placing the target fraction into a dealkylation reaction vessel, adding a dealkylation catalyst, heating and stirring, heating to 120-150 ℃, maintaining for 5-7 hours, and then finishing the reaction to obtain the final product, namely the p-cresol or the m-cresol.
Further, in the method for separating and purifying m-cresol and p-cresol as described above, in step 1), the liquid acid catalyst is benzenesulfonic acid or a benzenesulfonic acid homologue.
Further, in the method for separating and purifying m-cresol and p-cresol as described above, in the step 1), the internal environment of the gas-liquid reaction tower is preheated to 60 ℃ before the raw material is introduced into the gas-liquid reaction tower.
Further, in the method for separating and purifying m-cresol and p-cresol as described above, in the step 1), the temperature of the reaction system of the gas-liquid reaction tower is kept below 90 ℃ during the alkylation reaction.
Further, in the method for separating and purifying m-cresol and p-cresol as described above, in the step 1), the gas inlet pipe of the gas-liquid reaction tower maintains a slight negative pressure capable of inhibiting the formation of oligomers due to the self-polymerization of isobutylene gas during the alkylation reaction.
Further, in the method for separating and purifying m-cresol and p-cresol as described above, in step 1), the alkylation product is a substituted derivative: 2, 6-di-tert-butyl-p-cresol and 4, 6-di-tert-butyl-m-cresol.
Further, in the method for separating and purifying m-cresol and p-cresol as described above, in the step 2), the adsorption tower is periodically desorbed by water, and then the liquid acid catalyst is recovered by concentration.
Further, in the method for separating and purifying m-cresol and p-cresol, in the step 2), the working pressure of the lightness-removing tower is 5-15kPa, and the working temperature is less than or equal to 150 ℃.
Further, in the method for separating and purifying m-cresol and p-cresol, step 2), 2, 6-di-tert-butyl-p-cresol and 4, 6-di-tert-butyl-m-cresol with high purity can be obtained at the top of the rectifying tower.
Further, in the method for separating and purifying m-cresol and p-cresol as described above, in step 3), the dealkylation catalyst is methyl benzenesulfonic acid or a mesoporous molecular sieve catalyst.
The invention has the beneficial effects that:
the invention utilizes the gas-liquid reaction tower to realize the alkylation reaction of the alkylating agent and the mixed m-cresol and p-cresol, so that the isobutene can be fully contacted with the atomized raw material, the contact area of the isobutene and the atomized raw material is increased, the conversion rate of the mixed phenol and the utilization rate of the isobutene are improved, and the problems of high energy consumption and potential safety hazard caused by liquefying the alkylating agent are effectively avoided.
Of course, it is not necessary for any one product that embodies the invention to achieve all of the above advantages simultaneously.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The liquid acid catalyst is benzenesulfonic acid or its homologue.
The dealkylation catalyst is methyl benzene sulfonic acid or mesoporous molecular sieve catalyst.
The following embodiments are relevant to the present invention:
example 1
A method for separating and purifying m-cresol and p-cresol is characterized by comprising the following steps:
1) adding meta-para-phenol and a liquid acid catalyst into an alkylation reaction container at one time, starting stirring and heating, introducing the mixture into a gas-liquid reaction tower from a liquid inlet pipe when the temperature rises to 60 ℃, simultaneously introducing isobutene gas into the gas-liquid reaction tower from a gas inlet pipe, and preheating the internal environment of the gas-liquid reaction tower to 60 ℃ before introducing raw materials. In the alkylation reaction process, the temperature of the reaction system of the gas-liquid reaction tower is kept below 90 ℃, and the gas inlet pipe of the gas-liquid reaction tower maintains a slight negative pressure capable of inhibiting the isobutene gas from self-polymerizing to form oligomers. The isobutene gas contacts the atomized meta-para-phenol and the liquid acid catalyst to carry out alkylation reaction, and the isobutene gas is circularly and continuously introduced for reaction until all the meta-para-cresol in the raw material is converted into an alkylation product; the alkylation product is a substituted derivative: 2, 6-di-tert-butyl-p-cresol and 4, 6-di-tert-butyl-m-cresol;
2) introducing the obtained alkylation product into a catalyst adsorption tower, adsorbing and removing the catalyst by the catalyst adsorption tower, desorbing by using water periodically by the adsorption tower, and concentrating and recovering the liquid acid catalyst.
The feed liquid passing through the catalyst adsorption tower enters a light component removal tower, and dissolved isobutene is removed by the light component removal tower; the working pressure of the lightness-removing tower is 10kPa, and the working temperature is less than or equal to 150 ℃.
Transferring the bottom material of the light component removal tower to a rectifying tower, heating and rectifying the rectifying tower under the pressure condition of 10kPa, collecting fractions with different temperatures, wherein the working temperature of the rectifying tower is 150-; 2, 6-di-tert-butyl-p-cresol and 4, 6-di-tert-butyl-m-cresol with high purity can be obtained at the top of the rectifying tower;
3) and respectively placing the target fractions into a dealkylation reaction vessel, adding a dealkylation catalyst, heating and stirring, heating to 130 ℃, maintaining for 6 hours, and finishing the reaction to obtain the final product, namely the p-cresol or the m-cresol.
Example 2
A method for separating and purifying m-cresol and p-cresol is characterized by comprising the following steps:
1) adding meta-para-phenol and a liquid acid catalyst into an alkylation reaction container at one time, starting stirring and heating, introducing the mixture into a gas-liquid reaction tower from a liquid inlet pipe when the temperature rises to 60 ℃, simultaneously introducing isobutene gas into the gas-liquid reaction tower from a gas inlet pipe, and preheating the internal environment of the gas-liquid reaction tower to 60 ℃ before introducing raw materials. In the alkylation reaction process, the temperature of the reaction system of the gas-liquid reaction tower is kept below 90 ℃, and the gas inlet pipe of the gas-liquid reaction tower maintains a slight negative pressure capable of inhibiting the isobutene gas from self-polymerizing to form oligomers. The isobutene gas contacts the atomized meta-para-phenol and the liquid acid catalyst to carry out alkylation reaction, and the isobutene gas is circularly and continuously introduced for reaction until all the meta-para-cresol in the raw material is converted into an alkylation product; the alkylation product is a substituted derivative: 2, 6-di-tert-butyl-p-cresol and 4, 6-di-tert-butyl-m-cresol;
2) introducing the obtained alkylation product into a catalyst adsorption tower, adsorbing and removing the catalyst by the catalyst adsorption tower, desorbing by using water periodically by the adsorption tower, and concentrating and recovering the liquid acid catalyst.
The feed liquid passing through the catalyst adsorption tower enters a light component removal tower, and dissolved isobutene is removed by the light component removal tower; the working pressure of the lightness-removing tower is 5kPa, and the working temperature is less than or equal to 150 ℃.
Transferring the bottom material of the light component removal tower to a rectifying tower, heating and rectifying the rectifying tower under the pressure condition of 5kPa, collecting fractions with different temperatures, wherein the working temperature of the rectifying tower is 150-; 2, 6-di-tert-butyl-p-cresol and 4, 6-di-tert-butyl-m-cresol with high purity can be obtained at the top of the rectifying tower;
3) and respectively placing the target fractions into a dealkylation reaction vessel, adding a dealkylation catalyst, heating and stirring, heating to 120 ℃, maintaining for 5-7 hours, and finishing the reaction to obtain the final product, namely the p-cresol or the m-cresol.
Example 2
A method for separating and purifying m-cresol and p-cresol is characterized by comprising the following steps:
1) adding meta-para-phenol and a liquid acid catalyst into an alkylation reaction container at one time, starting stirring and heating, introducing the mixture into a gas-liquid reaction tower from a liquid inlet pipe when the temperature rises to 60 ℃, simultaneously introducing isobutene gas into the gas-liquid reaction tower from a gas inlet pipe, and preheating the internal environment of the gas-liquid reaction tower to 60 ℃ before introducing raw materials. In the alkylation reaction process, the temperature of the reaction system of the gas-liquid reaction tower is kept below 90 ℃, and the gas inlet pipe of the gas-liquid reaction tower maintains a slight negative pressure capable of inhibiting the isobutene gas from self-polymerizing to form oligomers. The isobutene gas contacts the atomized meta-para-phenol and the liquid acid catalyst to carry out alkylation reaction, and the isobutene gas is circularly and continuously introduced for reaction until all the meta-para-cresol in the raw material is converted into an alkylation product; the alkylation product is a substituted derivative: 2, 6-di-tert-butyl-p-cresol and 4, 6-di-tert-butyl-m-cresol;
2) introducing the obtained alkylation product into a catalyst adsorption tower, adsorbing and removing the catalyst by the catalyst adsorption tower, desorbing by using water periodically by the adsorption tower, and concentrating and recovering the liquid acid catalyst.
The feed liquid passing through the catalyst adsorption tower enters a light component removal tower, and dissolved isobutene is removed by the light component removal tower; the working pressure of the lightness-removing tower is 15kPa, and the working temperature is less than or equal to 150 ℃.
Transferring the bottom material of the light component removal tower to a rectifying tower, heating and rectifying the rectifying tower under the pressure condition of 15kPa, collecting fractions with different temperatures, wherein the working temperature of the rectifying tower is 150-; 2, 6-di-tert-butyl-p-cresol and 4, 6-di-tert-butyl-m-cresol with high purity can be obtained at the top of the rectifying tower;
3) and respectively placing the target fractions into a dealkylation reaction vessel, adding a dealkylation catalyst, heating and stirring, heating to 150 ℃, maintaining for 7 hours, and finishing the reaction to obtain the final product, namely the p-cresol or the m-cresol.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (10)
1. A method for separating and purifying m-cresol and p-cresol is characterized by comprising the following steps:
1) adding the m-p-cresol and the liquid acid catalyst into an alkylation reaction container at one time, starting stirring and heating, introducing the mixture into a gas-liquid reaction tower from a liquid inlet pipe when the temperature rises to 60 ℃, simultaneously introducing isobutene gas into the gas-liquid reaction tower from a gas inlet pipe, contacting the isobutene gas with the atomized m-p-cresol and the liquid acid catalyst for alkylation reaction, and circularly and continuously introducing the isobutene gas for reaction until all m-p-cresol in the raw materials is converted into an alkylation product;
2) introducing the obtained alkylation product into a catalyst adsorption tower, adsorbing and removing the catalyst by the catalyst adsorption tower, feeding the feed liquid passing through the catalyst adsorption tower into a light component removal tower, and removing dissolved isobutene by the light component removal tower; transferring the bottom material of the light component removal tower to a rectifying tower, heating and rectifying the rectifying tower under the pressure condition of 5-15kPa, collecting fractions with different temperatures, wherein the working temperature of the rectifying tower is 150-;
3) and respectively placing the target fraction into a dealkylation reaction vessel, adding a dealkylation catalyst, heating and stirring, heating to 120-150 ℃, maintaining for 5-7 hours, and then finishing the reaction to obtain the final product, namely the p-cresol or the m-cresol.
2. The method for separating and purifying m-cresol and p-cresol as claimed in claim 1, wherein the purification step comprises the following steps: in the step 1), the liquid acid catalyst is benzene sulfonic acid or benzene sulfonic acid homologues.
3. The method for separating and purifying m-cresol and p-cresol as claimed in claim 1, wherein the purification step comprises the following steps: in the step 1), the internal environment of the gas-liquid reaction tower is preheated to 60 ℃ before the raw materials are introduced.
4. The method for separating and purifying m-cresol and p-cresol as claimed in claim 1, wherein the purification step comprises the following steps: in the step 1), in the alkylation reaction process, the temperature of a reaction system of the gas-liquid reaction tower is kept below 90 ℃.
5. The method for separating and purifying m-cresol and p-cresol as claimed in claim 1, wherein the purification step comprises the following steps: in the step 1), in the alkylation reaction process, the gas inlet pipe of the gas-liquid reaction tower maintains a slight negative pressure capable of inhibiting the isobutene gas from self-polymerizing to form oligomers.
6. The method for separating and purifying m-cresol and p-cresol as claimed in claim 1, wherein the purification step comprises the following steps: in step 1), the alkylation product is a substituted derivative: 2, 6-di-tert-butyl-p-cresol and 4, 6-di-tert-butyl-m-cresol.
7. The method for separating and purifying m-cresol and p-cresol as claimed in claim 1, wherein the purification step comprises the following steps: in the step 2), the adsorption tower is used for desorption by water periodically, and then the liquid acid catalyst is recovered by concentration.
8. The method for separating and purifying m-cresol and p-cresol as claimed in claim 1, wherein the purification step comprises the following steps: in the step 2), the working pressure of the lightness-removing tower is 5-15kPa, and the working temperature is less than or equal to 150 ℃.
9. The method for separating and purifying m-cresol and p-cresol as claimed in claim 1, wherein the purification step comprises the following steps: in the step 2), high-purity 2, 6-di-tert-butyl-p-cresol and 4, 6-di-tert-butyl-m-cresol can be obtained at the top of the rectifying tower.
10. The method for separating and purifying m-cresol and p-cresol as claimed in claim 1, wherein the purification step comprises the following steps: in the step 3), the dealkylation catalyst is methyl benzenesulfonic acid or a mesoporous molecular sieve catalyst.
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WO2024108895A1 (en) * | 2022-11-23 | 2024-05-30 | 江苏迈达新材料股份有限公司 | Recycling and reusing method for heavy alkylphenol |
Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1313270A (en) * | 2000-03-13 | 2001-09-19 | 锦州石化天元集团公司 | Process for preparing 2,6-di-tear-butyl p-cresol |
CN101353293A (en) * | 2008-07-16 | 2009-01-28 | 天津天大天海化工新技术有限公司 | Method for producing 2-tertiary butyl-p-cresol and 6-tertiary butyl-m-cresol |
CN101857529A (en) * | 2010-06-07 | 2010-10-13 | 吴鸿宾 | Method for preparing chemical intermediates by using mixed o/m/p-cresol |
CN101863742A (en) * | 2010-06-07 | 2010-10-20 | 吴鸿宾 | Separation method of m-cresol and p-cresol mixture |
CN102311318A (en) * | 2010-06-29 | 2012-01-11 | 如皋市金陵化工有限公司 | Processing technique of 2,6-ditbutyl-4-methylphenol |
CN102898281A (en) * | 2012-11-06 | 2013-01-30 | 孙浩翔 | Method for co-producing 2, 6-butylated hydroxytoluene and m-cresol as well 6-tertiry butyl m-cresol by utilizing cresol mixture |
CN103212438A (en) * | 2013-05-02 | 2013-07-24 | 天津北洋国精科技股份有限公司 | Catalyst for alkylation separation of m-cresol and p-cresol and separation method |
CN104474731A (en) * | 2014-11-27 | 2015-04-01 | 天津天大天海化工新技术有限公司 | Reactive distillation column and method for reactive distillation and pyrolysis of alkylphenol |
CN104496758A (en) * | 2014-12-02 | 2015-04-08 | 安徽海华科技股份有限公司 | M-cresol and p-cresol alkylated continuous reaction method |
CN106810422A (en) * | 2017-01-16 | 2017-06-09 | 河北工业大学 | A kind of method that liquid-phase alkylation method separates M-and P-cresols |
CN108250048A (en) * | 2016-12-29 | 2018-07-06 | 湖南长岭石化科技开发有限公司 | A kind of method for detaching metacresol and paracresol and a kind of hydrocarbylation process and a kind of cleavage method |
CN111393266A (en) * | 2020-02-21 | 2020-07-10 | 江苏迈达新材料股份有限公司 | BHT alkylation tail gas isobutene recovery process |
CN111960925A (en) * | 2020-07-23 | 2020-11-20 | 安徽海华科技有限公司 | Preparation method of 2, 6-di-tert-butyl-p-cresol |
-
2021
- 2021-10-09 CN CN202111175795.6A patent/CN113880696A/en active Pending
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1313270A (en) * | 2000-03-13 | 2001-09-19 | 锦州石化天元集团公司 | Process for preparing 2,6-di-tear-butyl p-cresol |
CN101353293A (en) * | 2008-07-16 | 2009-01-28 | 天津天大天海化工新技术有限公司 | Method for producing 2-tertiary butyl-p-cresol and 6-tertiary butyl-m-cresol |
CN101857529A (en) * | 2010-06-07 | 2010-10-13 | 吴鸿宾 | Method for preparing chemical intermediates by using mixed o/m/p-cresol |
CN101863742A (en) * | 2010-06-07 | 2010-10-20 | 吴鸿宾 | Separation method of m-cresol and p-cresol mixture |
CN102311318A (en) * | 2010-06-29 | 2012-01-11 | 如皋市金陵化工有限公司 | Processing technique of 2,6-ditbutyl-4-methylphenol |
CN102898281A (en) * | 2012-11-06 | 2013-01-30 | 孙浩翔 | Method for co-producing 2, 6-butylated hydroxytoluene and m-cresol as well 6-tertiry butyl m-cresol by utilizing cresol mixture |
CN103212438A (en) * | 2013-05-02 | 2013-07-24 | 天津北洋国精科技股份有限公司 | Catalyst for alkylation separation of m-cresol and p-cresol and separation method |
CN104474731A (en) * | 2014-11-27 | 2015-04-01 | 天津天大天海化工新技术有限公司 | Reactive distillation column and method for reactive distillation and pyrolysis of alkylphenol |
CN104496758A (en) * | 2014-12-02 | 2015-04-08 | 安徽海华科技股份有限公司 | M-cresol and p-cresol alkylated continuous reaction method |
CN108250048A (en) * | 2016-12-29 | 2018-07-06 | 湖南长岭石化科技开发有限公司 | A kind of method for detaching metacresol and paracresol and a kind of hydrocarbylation process and a kind of cleavage method |
CN106810422A (en) * | 2017-01-16 | 2017-06-09 | 河北工业大学 | A kind of method that liquid-phase alkylation method separates M-and P-cresols |
CN111393266A (en) * | 2020-02-21 | 2020-07-10 | 江苏迈达新材料股份有限公司 | BHT alkylation tail gas isobutene recovery process |
CN111960925A (en) * | 2020-07-23 | 2020-11-20 | 安徽海华科技有限公司 | Preparation method of 2, 6-di-tert-butyl-p-cresol |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2024108895A1 (en) * | 2022-11-23 | 2024-05-30 | 江苏迈达新材料股份有限公司 | Recycling and reusing method for heavy alkylphenol |
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