CN115745749A - Method for recycling heavy alkylphenol - Google Patents
Method for recycling heavy alkylphenol Download PDFInfo
- Publication number
- CN115745749A CN115745749A CN202211471773.9A CN202211471773A CN115745749A CN 115745749 A CN115745749 A CN 115745749A CN 202211471773 A CN202211471773 A CN 202211471773A CN 115745749 A CN115745749 A CN 115745749A
- Authority
- CN
- China
- Prior art keywords
- heavy
- alkylphenol
- alkylphenols
- reaction
- recycling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention discloses a method for recycling heavy alkylphenol, belonging to the technical field of organic synthesis processes, and specifically comprising the following steps: 1) Adding the heavy alkylphenol and the catalyst into a three-mouth bottle according to a certain proportion, and uniformly stirring; 2) Heating to a certain temperature to carry out dealkylation reaction; 3) Discharging isobutene generated by the reaction from the top of the condensing tube, and introducing the isobutene into an absorption bottle; 4) After dealkylation is finished, the main products are mixed cresol and mono-tert-butyl cresol, and light components are removed by normal pressure distillation at a certain temperature; 5) Distilling at a certain temperature under negative pressure to remove the phenol mixture; 6) Finally, a small amount of residue is discharged for solid waste treatment. The method for recycling the heavy alkylphenol not only greatly improves the utilization value of the heavy alkylphenol, but also reduces the generation of a large amount of hazardous wastes.
Description
Technical Field
The invention belongs to the technical field of organic synthesis processes, and particularly relates to a method for recycling heavy alkylphenol.
Background
The chemical name of antioxidant BHT is 2,6-di-tert-butyl-4-methylphenol, which is one of important phenolic antioxidants and is also a high-efficiency alkylphenol antioxidant recognized in the world. The antioxidant has the advantages of good oil solubility, high antioxidant efficiency, strong adaptability, no pollution and the like, is one of the first choice antioxidant varieties of various industries and products, is widely applied to different industries such as gasoline, lubricating oil, aviation kerosene, plastics, rubber products, cosmetics, medicines and the like, and can also be used for food antioxidation, especially for antioxidation of oil and fat foods.
At present, a solvent crystallization method is generally adopted in the purification process of antioxidant BHT, alcohol is recovered from crystallization mother liquor by atmospheric distillation, then front fraction, back fraction and crude BHT are separated by vacuum rectification, rectification residual liquor is called heavy alkylphenol, the main component is a mixture of BHT and other high-boiling point alkylphenols, and the total content of the alkylphenols is more than 90%. At present, heavy alkylphenol is generally treated as waste liquid, the treatment cost is high, the environmental protection is not realized, and in order to change the current situation, a recycling method of the heavy alkylphenol is urgently needed to be explored.
Disclosure of Invention
The present invention aims to provide a method for recycling heavy alkylphenols, which solves the problems of the prior art.
In order to achieve the purpose, the invention provides the following technical scheme: a heavy alkyl phenol recovery and reuse method, said method adopts heavy alkyl phenol (antioxidant BHT rectification raffinate) under the influence of catalyst, take place dealkylation, isobutene produced is introduced into absorption bottle, carry on the alkylation; after dealkylation is finished, mixed liquid (main products are mixed cresol and mono-tertiary butyl cresol) is obtained, light components (isobutene dimer and trimer) are distilled under normal pressure, and the light components are recovered to be used as a solvent; distilling the phenol mixture under negative pressure, recycling the phenol mixture for alkylation reaction, or directly selling the phenol mixture; finally, a small amount of residue is discharged for solid waste treatment.
Further, the heavy alkylphenol and the catalyst are added into a three-neck flask according to a certain proportion, the catalyst is preferably concentrated sulfuric acid or sulfonic acid, and the mass ratio of the heavy alkylphenol to the catalyst is preferably 100:0.3 to 2.
Further, the dealkylation reaction is preferably carried out at a temperature of 150-180 ℃.
Further, isobutene generated by the reaction is discharged from the top of a condensation pipe and is introduced into an absorption bottle prepared with p-cresol and a catalyst, and the mass ratio of p-cresol to catalyst is preferably 100:1 to 4, preferably the alkylation reaction temperature is 60 to 70 ℃.
Further, the light components are distilled out at normal pressure, and the distillation temperature is preferably 100-130 ℃.
Further, the negative pressure distillation is preferably carried out at a pressure of-0.06 to-0.10 MPa and a distillation temperature of 160-190 ℃.
Compared with the prior art, the invention has the beneficial effects that:
according to the method for recycling the heavy alkylphenol, each ton of the heavy alkylphenol is subjected to dealkylation reaction under the action of the acid catalyst, about 350kg of isobutylene, 500kg of mixed phenol, 105kg of solvent and about 45kg of residue are recycled, the economic benefit generated by each ton of the heavy alkylphenol is greater than 1 ten thousand RMB, the hazardous waste is reduced by about 95%, the profit space of the antioxidant BHT is greatly increased, the economic benefit is considerable, the recycling equipment is simple, the economic benefit generated by recycling the heavy alkylphenol is good, the utilization value of the heavy alkylphenol is greatly increased, and meanwhile, the generation of a large amount of hazardous waste is reduced.
Drawings
FIG. 1 is a flow chart of a method for recycling heavy alkylphenols according to the present invention.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. 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.
Referring to fig. 1, an embodiment of the present invention provides a method for recycling heavy alkylphenol, including the following steps:
1) Adding the heavy alkylphenol and the catalyst into a three-mouth bottle according to a certain proportion, and uniformly stirring;
2) Heating to a certain temperature to carry out dealkylation reaction;
3) Discharging isobutene generated by the reaction from the top of the condensing tube, and introducing the isobutene into an absorption bottle;
4) After dealkylation is finished, the main products are mixed cresol and mono-tert-butyl cresol, and light components are removed by normal pressure distillation at a certain temperature;
5) Distilling at a certain temperature under negative pressure to remove the phenol mixture;
6) Finally, a small amount of residue is discharged for solid waste treatment.
In this embodiment, the heavy alkylphenol obtained in step 1) and the catalyst are added into a three-necked flask according to a certain ratio, wherein the catalyst is preferably concentrated sulfuric acid or sulfonic acid, and the mass ratio of the heavy alkylphenol to the catalyst is preferably 100:0.3 to 2.
In this embodiment, the dealkylation reaction in step 2) is preferably controlled at a temperature of 150 to 180 ℃.
In this embodiment, the isobutylene generated by the reaction in step 3) is discharged from the top of the condensation tube, and is introduced into an absorption bottle prepared with p-cresol and catalyst, preferably, the mass ratio of p-cresol to catalyst is 100:1 to 4, preferably the alkylation reaction temperature is 60 to 70 ℃.
In this example, the light components are distilled off at atmospheric pressure in step 4), preferably at a distillation temperature of from 100 to 130 ℃.
In the embodiment, the negative pressure distillation in the step 5) is preferably carried out at a pressure of-0.06 to-0.10 MPa, and the distillation temperature is preferably 160-190 ℃.
The invention is further described below with reference to the following examples:
example 1
215.1g of heavy alkylphenol and 4.0g of concentrated sulfuric acid are added into a three-neck flask, the mixture is uniformly stirred, and is heated by an electric heating jacket, the dealkylation temperature is 130-160 ℃, and the reaction lasts about 2 hours. Distilling at 100-130 deg.C under normal pressure to remove light components; and distilling under negative pressure at the temperature of 160-190 ℃ and the pressure of-0.09 MPa to remove the phenolic mixture, wherein the weight of each substance is as follows: 72.4g of isobutylene, 91.8g of phenol, 19.5g of a solvent and 35.4g of a residue.
Example 2
215.3g of heavy alkylphenol and 3.0g of concentrated sulfuric acid are added into a three-neck flask, the mixture is uniformly stirred, an electric heating jacket is used for heating, the dealkylation temperature is 150-175 ℃, and the reaction lasts for about 2 hours. Distilling at 100-130 deg.C under normal pressure to remove light components; and distilling under negative pressure at the temperature of 160-190 ℃ and the pressure of-0.09 MPa to remove the phenolic mixture, wherein the weight of each substance is as follows: 75.8g of isobutylene, 107.6g of phenol, 23.7g of a solvent and 11.2g of a residue.
Example 3
215.0g of heavy alkylphenol and 2.0g of concentrated sulfuric acid are added into a three-neck flask, the mixture is uniformly stirred, an electric heating jacket is used for heating, the dealkylation temperature is 150-185 ℃, and the reaction lasts about 2 hours. Distilling at 100-130 deg.C under normal pressure to remove light components; and distilling under negative pressure at the temperature of 160-190 ℃ and the pressure of-0.09 MPa to remove the phenolic mixture, wherein the weight of each substance is as follows: 76.1g of isobutylene, 108.4g of phenol, 23.2g of solvent and 9.7g of residue.
In summary, from the implementation results of the above examples 1-3, it can be seen that when the raw materials are added in the same proportion, by using the method for recycling heavy alkylphenols of the present invention, each ton (1000 kg) of heavy alkylphenols undergoes dealkylation reaction under the action of the acidic catalyst, about 350kg of isobutylene, 500kg of mixed phenols, 105kg of solvent and about 45kg of residue are recycled, each ton of heavy alkylphenols generates economic benefit greater than 1 ten thousand yuan, and the hazardous waste is reduced by about 95%, the profit margin of the antioxidant BHT is greatly increased, the economic benefit is very considerable, the equipment used for recycling is simple, the economic benefit generated by recycling heavy alkylphenols is good, the utilization value of heavy alkylphenols is greatly increased, and the generation of a large amount of hazardous waste is reduced.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (9)
1. A method for recycling heavy alkylphenol is characterized by comprising the following steps:
1) Adding the heavy alkylphenol and the catalyst into a three-mouth bottle according to a certain proportion, and uniformly stirring;
2) Heating to a certain temperature to carry out dealkylation reaction;
3) Discharging isobutene generated by the reaction from the top of the condensing tube, and introducing the isobutene into an absorption bottle;
4) After dealkylation is finished, the main products are mixed cresol and mono-tert-butyl cresol, and light components are removed by normal pressure distillation at a certain temperature;
5) Distilling at a certain temperature under negative pressure to remove the phenol mixture;
6) Finally, a small amount of residue is discharged for solid waste treatment.
2. The method for recycling heavy alkylphenols as claimed in claim 1, wherein: the mass ratio of the heavy alkylphenol to the catalyst in the step 1) is 100:0.3-4.
3. The method for recycling heavy alkylphenols as claimed in claim 1, wherein: and (3) controlling the temperature to be 120-190 ℃ in the step 2) and carrying out dealkylation reaction.
4. The method for recycling heavy alkylphenols as claimed in claim 1, wherein: discharging the isobutene generated in the reaction in the step 3) from the top of a condensation pipe, introducing the isobutene into an absorption bottle prepared with p-cresol and a catalyst, and carrying out alkylation reaction at the reaction temperature of 60-80 ℃.
5. The method for recycling heavy alkylphenols as claimed in claim 1, wherein: and (3) when the BHT content is less than 1% by sampling from the three-mouth bottle in the step 4), ending the dealkylation reaction.
6. The method for recycling heavy alkylphenols as claimed in claim 5, wherein: at 90-140 deg.C, the light components, mainly including dimerization and trimerization of isobutene, are removed by atmospheric distillation, and recovered as solvent.
7. The method for recycling heavy alkylphenols as claimed in claim 1, wherein: and (5) distilling to remove the phenolic mixture at the temperature of 150-190 ℃ under negative pressure.
8. The method for recycling heavy alkylphenols as claimed in claim 7, wherein: the phenol mixture is mainly m/p-cresol and mono-tert-butyl cresol, the content is more than 95 percent, and the phenol mixture is recycled and reused for alkylation reaction or directly sold.
9. The method for recycling heavy alkylphenols as claimed in claim 1, wherein: a small amount of residue discharged in the step 6) is organic residue.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211471773.9A CN115745749A (en) | 2022-11-23 | 2022-11-23 | Method for recycling heavy alkylphenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211471773.9A CN115745749A (en) | 2022-11-23 | 2022-11-23 | Method for recycling heavy alkylphenol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115745749A true CN115745749A (en) | 2023-03-07 |
Family
ID=85335637
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211471773.9A Pending CN115745749A (en) | 2022-11-23 | 2022-11-23 | Method for recycling heavy alkylphenol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115745749A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB591796A (en) * | 1944-06-13 | 1947-08-28 | Gulf Research Development Co | Improvement in catalytic dealkylation of alkyl aromatic compounds |
| GB940378A (en) * | 1959-03-24 | 1963-10-30 | Consolidation Coal Co | Dealkylation of branched-chain ªÐ-alkylated phenols |
| US4150243A (en) * | 1975-12-05 | 1979-04-17 | Bayer Aktiengesellschaft | Process for the dealkylation of tert.-alkyl substituted phenols |
| CN101863742A (en) * | 2010-06-07 | 2010-10-20 | 吴鸿宾 | Separation method of m-cresol and p-cresol mixture |
| CN111072437A (en) * | 2019-11-11 | 2020-04-28 | 山东京博木基材料有限公司 | Method for preparing isobutene by catalytic cracking of tert-butyl methyl phenol |
| US20210139399A1 (en) * | 2019-02-04 | 2021-05-13 | China Petroleum & Chemical Corporatoin | Dealklylation and transalkylation of mixed phenols to make cresols |
| CN114213218A (en) * | 2021-11-12 | 2022-03-22 | 南京晶典抗氧化技术研究院有限公司 | Production method of antioxidant BHT |
-
2022
- 2022-11-23 CN CN202211471773.9A patent/CN115745749A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB591796A (en) * | 1944-06-13 | 1947-08-28 | Gulf Research Development Co | Improvement in catalytic dealkylation of alkyl aromatic compounds |
| GB940378A (en) * | 1959-03-24 | 1963-10-30 | Consolidation Coal Co | Dealkylation of branched-chain ªÐ-alkylated phenols |
| US4150243A (en) * | 1975-12-05 | 1979-04-17 | Bayer Aktiengesellschaft | Process for the dealkylation of tert.-alkyl substituted phenols |
| CN101863742A (en) * | 2010-06-07 | 2010-10-20 | 吴鸿宾 | Separation method of m-cresol and p-cresol mixture |
| US20210139399A1 (en) * | 2019-02-04 | 2021-05-13 | China Petroleum & Chemical Corporatoin | Dealklylation and transalkylation of mixed phenols to make cresols |
| CN111072437A (en) * | 2019-11-11 | 2020-04-28 | 山东京博木基材料有限公司 | Method for preparing isobutene by catalytic cracking of tert-butyl methyl phenol |
| CN114213218A (en) * | 2021-11-12 | 2022-03-22 | 南京晶典抗氧化技术研究院有限公司 | Production method of antioxidant BHT |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102010285B (en) | Method for extracting methyl cyclopentadiene from ethylene cracked C9 heavy fractions | |
| CN101054340A (en) | Method of separating and purifying o/p-dihydroxy benzene prepared by phenol hydroxylation | |
| CN110372512B (en) | Separation and purification process of dimethyl carbonate | |
| JPH08310978A (en) | Joint thermal decomposition of tar from bisphenol a production process and tar from phenol production process | |
| CN113105316B (en) | Method for extracting acetophenone and styrene from phenol tar waste liquid | |
| CN105085191A (en) | Resorcinol separating device and process | |
| CN111138347B (en) | Industrial method and device for water diversion of vinyl pyridine compounds | |
| CN1290682A (en) | Method for preparing phenol, methyl-ethyl ketones and acetone | |
| CN112574783B (en) | Method for comprehensively utilizing styrene tar | |
| CN115745749A (en) | Method for recycling heavy alkylphenol | |
| EP2234955B1 (en) | Process for recovering sulfonic acid catalyst and noble products from acrylate heavy ends | |
| US3407237A (en) | Preparation of hydroxylated aromatic compounds | |
| CN109704937A (en) | Furfural and the method for secondary low-boiling-point substance continuous rectification purification | |
| CN1868992A (en) | Alkylphenol coproduction technology | |
| CN113698279B (en) | Method for separating and extracting 3, 5-xylenol from industrial xylenol | |
| US2917487A (en) | Method of separating 2,4-xylenol and 2,5-xylenol by selective resinification | |
| US2931787A (en) | Method for recovering purified phenolic isomers from low boiling cresylic acids | |
| CN114751812A (en) | Method for producing diethoxymethane from paraformaldehyde | |
| CN111378467A (en) | Method for treating cyclohexane oxidation by-products | |
| CN110563069B (en) | Comprehensive utilization method of nitrobenzene tar and aniline wastewater | |
| KR20210032163A (en) | Method for decomposing phenol-based by-product | |
| US3509028A (en) | Drying p-cresol by distillation with toluene | |
| CN111848359B (en) | Method for separating phenolic substances in medium and low temperature coal tar | |
| EP2814793B1 (en) | Method for isolation of cymene | |
| CN115286488B (en) | Method for extracting m-p-ethyl phenol and industrial xylenol from mixed xylenol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |