CN114213217A - Production method and application of p-phenylphenol - Google Patents
Production method and application of p-phenylphenol Download PDFInfo
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- CN114213217A CN114213217A CN202111442839.7A CN202111442839A CN114213217A CN 114213217 A CN114213217 A CN 114213217A CN 202111442839 A CN202111442839 A CN 202111442839A CN 114213217 A CN114213217 A CN 114213217A
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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
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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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
- C07C37/64—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring
Abstract
The invention discloses a production method and application of p-phenylphenol, which comprises the following steps: heating biphenyl and sulfuric acid for sulfonation reaction, neutralizing 4-phenyl benzenesulfonic acid in a sulfonation reaction product by using sodium sulfite to generate 4-phenyl sodium sulfonate and sulfur dioxide, collecting sulfur dioxide gas, cooling after neutralization, and filtering to obtain 4-phenyl sodium sulfonate solid; carrying out alkali fusion reaction on the 4-sodium phenyl benzenesulfonate solid and molten solid sodium hydroxide to generate sodium p-phenylphenol and sodium sulfite; diluting the alkali fusion material with water, introducing collected sulfur dioxide for acidification reaction to generate p-phenylphenol and sodium sulfite, standing and separating to obtain crude p-phenylphenol and mother liquor, and finally rectifying to obtain p-phenylphenol. The method provided by the invention has the advantages of simple and easily-obtained raw materials, good economical efficiency of reaction atoms, high yield, high product quality and low industrialization cost, and is a feasible industrialized production method for p-phenylphenol.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a production method and application of p-phenylphenol.
Background
P-phenylphenol, english name: 4-Biphenylol, CAS number: 92-69-3, is an important intermediate of the bactericide, namely the bitertanol, can be used for preparing oil-soluble resin and an emulsifier, and can be used as a component of corrosion-resistant paint, a printing and dyeing carrier and the like; the red light sensitizing dye and the green light sensitizing dye synthesized by the method are one of the main raw materials of color films, and can also be used as analytical reagents. The preparation methods of p-phenylphenol reported in the current literature mainly comprise the following steps:
recovery method from distillation residue of phenol production by p-phenylphenol sulfonation, diphenyl sulfone alkali fusion method, biphenyl sulfonation method, cyclohexanone and phenol synthesis method, etc. The method is concretely as follows:
1. recovery method in production of phenol by sulfonation method
In the production of phenol by the alkali fusion process of benzene sulfonation, a mixture of phenylphenol (a mixture of ortho-and para-phenylphenol) as a by-product may be produced due to the reaction between sodium phenolate molecules. The recovery process of the phenylphenol generally comprises the steps of distilling distillation residues in vacuum, separating out mixed phenylphenol distillation sections, carrying out interception until the vacuum degree is 53.2-66.5 Kpa and the temperature is 65-75 ℃, obtaining phenol water with the phenol content of not more than 10%, and carrying out secondary distillation, wherein the temperature is higher than 100 ℃ but not higher than 135 ℃; and then, by utilizing the difference of the solubility of the ortho-position phenyl phenol and the para-position phenyl phenol in trichloroethylene, cooling, crystallizing and separating the para-position phenyl phenol from the solution, filtering and separating to obtain a filter cake which is qualified para-position phenyl phenol, and keeping the ortho-position phenyl phenol in the mother liquor, thus separating the ortho-position phenyl phenol from the para-position phenyl phenol. The method can effectively increase the benefit of a device for producing phenol by benzene sulfonation through an alkali fusion method on one hand, and can reduce the pollution of the device to the environment on the other hand. However, with the rapid development of petrochemical industry in China, the existing device for producing phenol by benzene sulfonation, which accounts for 15% of the total production capacity, through an alkali fusion method is gradually replaced by an isopropyl benzene method.
2. Alkali fusion process for diphenyl sulfone
The Nippon Mingyu company applies for the patent of alkali fusion of diphenyl sulfone to prepare ortho-phenylphenol and para-phenylphenol, and the technological process comprises the following steps: adding potassium hydroxide heated to 340 ℃ into a reactor, adding viscous diphenyl sulfone, stirring the reaction mixture at 340-370 ℃ for 1h, dissolving the cooled melt in water, acidifying with hydrochloric acid to pH 5, and extracting and distilling with diethyl ether to obtain a mixture of phenol, ortho-phenylphenol and para-phenylphenol. The overall yield of reaction product was 91.2%. The diphenyl sulfone used as the raw material in the method is expensive, has a plurality of byproducts, high reaction temperature, large equipment investment and low industrialization value.
3. Biphenyl sulfonation process
The production of p-phenylphenol by biphenyl sulfonation alkali fusion has been industrialized for many years abroad, for example, Bayer company in Germany, Sansho chemical company in Japan, etc. adopt the method for production, the technology is relatively mature, but the production method has the defects of overlong route, harsh alkali fusion reaction conditions, more three wastes, low yield, etc., and needs to be further improved and perfected in production and practice. The method takes biphenyl as a raw material, produces biphenyl-4-sulfonic acid through sulfonation, generates crude p-phenylphenol through alkali fusion and neutralization, and obtains the product through sublimation. At present, researchers have selected concentrated sulfuric acid as sulfonating agent to replace chlorosulfonic acid (ClSO) in the prior art3H) The generation of hydrochloric acid gas can be avoided, and a hydrochloric acid absorption and treatment device is omitted; chlorosulfonic acid which has strong corrosivity, severe smoke generation and extreme environmental pollution is avoided; volatile toxic solvents of o-nitroethylbenzene and carbon tetrachloride are not used, so that the operating environment is improved, and the cost is reduced; the biphenyl-4-sulfonic acid sodium salt can be sent to the alkali fusion reaction only by filtering, and does not need drying, thereby simplifying the operation and reducing the energy consumption. And obtaining a qualified product after alkali fusion, dilution, neutralization and drying. However, neutralization with hydrochloric acid or sulfuric acid generally produces a large amount of inorganic salts.
4. Synthesis of cyclohexanone phenol
The reactants cyclohexanone and phenol are condensed in concentrated hydrochloric acid, and then are dehydrogenated under the catalysis of 5 percent Pd/C/MgO of a catalyst to obtain p-phenylphenol and phenol. The product yield of the synthesis method can reach more than 90 percent based on cyclohexanone, and phenol can be recycled. The method is simple and has good economic effect, and the defects are that the Pd/C catalytic activity has great influence on the reaction and the reaction time is long. The chemical reaction formula is as follows:
disclosure of Invention
In view of the disadvantages of the prior art, the present invention aims to provide a method for producing p-phenylphenol and applications thereof, which are used for solving the problems of expensive raw materials or unstable sources, high catalyst requirements, large equipment investment, etc. in the prior art.
In order to achieve the above and other related objects, the present invention provides in a first aspect a process for producing p-phenylphenol and use thereof, comprising the steps of:
(1) sulfonation: mixing biphenyl and sulfuric acid, heating, performing sulfonation reaction, and evaporating water generated by the reaction and unreacted biphenyl under reduced pressure after the reaction is finished;
(2) neutralizing: adding the sulfonation reaction product obtained in the step (1) into a sodium sulfite aqueous solution while the sulfonation reaction product is hot, neutralizing 4-phenyl benzenesulfonic acid to generate 4-sodium phenyl sulfonate and sulfur dioxide, collecting generated sulfur dioxide gas and using the sulfur dioxide gas for subsequent acidification of sodium phenyl phenolate, cooling after neutralization, and filtering to obtain 4-sodium phenyl benzenesulfonate solid;
(3) alkali fusion: adding solid sodium hydroxide into an alkali fusion kettle, heating to melt, adding the 4-phenyl sodium benzenesulfonate solid obtained in the step (2) to perform alkali fusion reaction, and generating sodium p-phenylphenol and sodium sulfite;
(4) acidifying: adding the alkali fusion material obtained in the step (3) into water for dilution, introducing the sulfur dioxide collected in the step (2) for acidification reaction to generate p-phenylphenol and sodium sulfite, standing for layering, and separating to obtain crude p-phenylphenol and mother liquor;
(5) and (3) rectification: and rectifying the crude p-phenylphenol to obtain the p-phenylphenol.
Further, the production method also comprises the step (6) of recovering sodium sulfite: and (4) carrying out evaporative concentration, crystallization, centrifugal separation and drying on the mother liquor discharged in the neutralization step (2) and the acidification step (4) to obtain a sodium sulfite byproduct, wherein evaporative condensate in the evaporative concentration process is recycled.
Further, in the step (1), the sulfuric acid is concentrated sulfuric acid or fuming sulfuric acid with the content of 98%.
Further, the sulfonation reaction of the step (1) is as follows: dropwise adding concentrated sulfuric acid into the molten biphenyl at the temperature of 100-150 ℃, and keeping the reaction for 1-3 hours at the temperature of 90-160 ℃ after the dropwise adding is finished.
Furthermore, in the step (1), the feeding molar ratio of the biphenyl to the sulfuric acid is (1.0-2.0) to 1.0, and preferably (1.0-1.2) to 1.0.
Further, in the step (1), water generated by the reaction and unreacted biphenyl are evaporated out under reduced pressure at the temperature of 60-150 ℃ and the pressure of 0.0001-0.01 MPa.
Further, in the step (2), the manner of neutralizing the 4-phenylbenzenesulfonic acid in the sulfonation reaction product obtained in the step (1) with sodium sulfite is as follows:
adding the sulfonation reaction product obtained in the step (1) into a sodium sulfite aqueous solution while the sulfonation reaction product is hot, and neutralizing 4-phenylbenzenesulfonic acid;
or, diluting the sulfonation reaction product obtained in the step (1) with water, and then adding sodium sulfite solid to neutralize 4-phenyl benzenesulfonic acid.
Further, in the step (2), the concentration of the sodium sulfite aqueous solution is 10-25%.
Furthermore, in the step (2), the molar use ratio of the sulfonation reaction product to sodium sulfite is 1.0 (1.0-1.2), and preferably 1.0 (1.02-1.10).
Further, in the step (2), when the pH value of the solution is 5.0-6.0, the neutralization is finished.
In the step (3), the molar ratio of the solid sodium hydroxide to the solid sodium 4-phenylbenzenesulfonate is (1.5-5.0): 1.0, preferably (1.5-3.0): 1.
Further, in the step (3), the temperature is raised to 250-400 ℃ to melt the solid sodium hydroxide.
Further, in the step (3), the temperature of the alkali fusion reaction is 280-320 ℃, and the reaction is stopped when the content of the 4-phenylsulfonic acid sodium salt is less than 1.0% by HPLC analysis.
Further, in the step (4), the alkali fusion material is added into water with the mass 2-4 times that of the 4-sodium phenylsulfonate for dilution.
Further, in the step (4), the acidification reaction temperature is less than 50 ℃ until the pH of the reaction solution is 5.0-6.0.
Further, in the step (5), the rectification temperature is 140-150 ℃ and the pressure is 1000-1500 Pa.
The process for synthesizing p-phenylphenol has the following reaction chemical formula:
in a second aspect the present invention provides the use of a process according to the first aspect for the production of p-phenylphenol.
As described above, the production method of p-phenylphenol and the application thereof of the present invention have the following beneficial effects: the method for producing the p-phenylphenol provided by the invention has the advantages of simple and easily obtained raw materials, good reaction atom economy, high yield, high product quality and low industrial cost, and is a feasible industrial production method.
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 production method of p-phenylphenol, which comprises the following steps:
(1) sulfonation: mixing biphenyl and sulfuric acid, heating, performing sulfonation reaction, and evaporating water generated by the reaction and unreacted biphenyl under reduced pressure at 60-150 ℃ and 0.0001-0.01 MPa after the reaction is finished;
(2) neutralizing: adding the sulfonation reaction product obtained in the step (1) into a sodium sulfite aqueous solution while the sulfonation reaction product is hot, neutralizing 4-phenyl benzenesulfonic acid to generate 4-sodium phenyl sulfonate and sulfur dioxide, collecting generated sulfur dioxide gas and using the sulfur dioxide gas for subsequent acidification of sodium phenyl phenolate, cooling after the neutralization is finished (the pH value is 5.0-6.0), and filtering to obtain 4-sodium phenyl benzenesulfonate solid;
(3) alkali fusion: adding solid sodium hydroxide into an alkali fusion kettle, heating to 250-400 ℃ to melt the solid sodium hydroxide, adding the 4-phenyl sodium benzenesulfonate solid obtained in the step (2) to perform alkali fusion reaction to generate sodium p-phenylphenol and sodium sulfite, and stopping the reaction when the content of the 4-phenyl sodium benzenesulfonate is less than 1.0% by HPLC analysis;
(4) acidifying: adding the alkali fusion material obtained in the step (3) into water for dilution, introducing the sulfur dioxide collected in the step (2) for acidification reaction to generate p-phenylphenol and sodium sulfite, standing for layering, and separating to obtain crude p-phenylphenol and mother liquor;
(5) and (3) rectification: rectifying the crude p-phenylphenol to obtain p-phenylphenol;
in another embodiment of the present invention, the process for producing p-phenylphenol further comprises (6) sodium sulfite recovery: and (4) carrying out evaporative concentration, crystallization, centrifugal separation and drying on the mother liquor discharged in the neutralization step (2) and the acidification step (4) to obtain a sodium sulfite byproduct, wherein evaporative condensate in the evaporative concentration process is recycled.
Specifically, in the step (1), the sulfuric acid is concentrated sulfuric acid or fuming sulfuric acid with the content of 98%.
Specifically, the sulfonation reaction in step (1) is: dropwise adding concentrated sulfuric acid into the molten biphenyl at the temperature of 100-150 ℃, and keeping the reaction for 1-3 hours at the temperature of 90-160 ℃ after the dropwise adding is finished.
Specifically, in the step (1), the feeding molar ratio of the biphenyl to the sulfuric acid is (1.0-2.0) to 1.0, and preferably (1.0-1.2) to 1.0.
Specifically, in the step (2), the 4-phenylbenzenesulfonic acid in the sulfonation reaction product obtained in the step (1) is neutralized by sodium sulfite in a manner selected from one of the following two manners:
adding the sulfonation reaction product obtained in the step (1) into a sodium sulfite aqueous solution while the product is hot, and neutralizing 4-phenylbenzenesulfonic acid; wherein the concentration of the adopted sodium sulfite aqueous solution is 10-25%.
② diluting the sulfonation reaction product obtained in the step (1) with water, and then adding sodium sulfite solid to neutralize 4-phenyl benzenesulfonic acid.
Specifically, in the step (2), the molar use ratio of the sulfonation reaction product to sodium sulfite is 1.0 (1.0-1.2), and preferably 1.0 (1.02-1.10).
Specifically, in the step (3), the molar ratio of the solid sodium hydroxide to the solid sodium 4-phenylbenzenesulfonate is (1.5-5.0): 1.0, preferably (1.5-3.0): 1.
Specifically, in the step (3), the temperature of the alkali fusion reaction is 280-320 ℃.
Specifically, in the step (4), the alkali fusion material is added into water with the mass 2-4 times that of the 4-sodium phenylsulfonate for dilution.
Specifically, in the step (4), the acidification reaction temperature is less than 50 ℃ until the pH of the reaction liquid is 5.0-6.0.
Specifically, in the step (5), the rectification temperature is 140-150 ℃ and the pressure is 1000-1500 Pa.
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 only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
The production method of p-phenylphenol in this example was as follows:
1. sulfonation: adding 171.1kg of biphenyl (99 percent and 1.1kmol) into a 1000L enamel reaction kettle, heating to 100 ℃, slowly dripping 100kg (1.0kmol) of concentrated sulfuric acid with the content of 98 percent into the reaction kettle for 60 minutes, wherein the temperature of reaction materials rises in the dripping process, controlling the reaction temperature to be 110-120 ℃, heating to 130 ℃ after finishing dripping, and preserving heat for 2 hours to generate 4-phenylbenzenesulfonic acid; then, at the temperature of 60-70 ℃ and under the pressure of 0.001MPa, water generated by the reaction and unreacted biphenyl are evaporated out under reduced pressure.
2. Neutralizing: and (2) slowly adding the reaction liquid obtained in the step (1) into 529.2kg (1.05 kmol) of sodium sulfite aqueous solution with the mass fraction of 25%, neutralizing 4-phenyl benzenesulfonic acid to generate 4-sodium phenyl sulfonate and sulfur dioxide, collecting generated sulfur dioxide gas and using the gas for subsequent acidification of sodium phenyl phenolate, cooling after neutralization, and filtering to obtain the sodium 4-phenyl benzenesulfonate.
3. Alkali fusion: adding 104kg of solid NaOH (with the content of 96 percent and 2.5kmol) into an alkali fusion kettle, heating to 280 ℃ for fusion, slowly adding 4-phenyl sodium benzenesulfonate for alkali fusion reaction to generate sodium p-phenylphenol and sodium sulfite, and stopping the reaction when the content of the 4-phenyl sodium benzenesulfonate is less than 1.0 percent by HPLC analysis.
4. Acidifying: and (3) adding the alkali fusion material into 520kg of water for dilution, introducing the sulfur dioxide collected in the step (2), carrying out an acidification reaction at the temperature of less than 50 ℃, reacting until the pH value of a reaction solution is 5.0 to generate p-phenylphenol and sodium sulfite, standing for layering, and separating crude p-phenylphenol and a mother solution.
5. And (3) rectification: rectifying the crude p-phenylphenol at 140-142 ℃ and 1300Pa to obtain 161.6kg of p-phenylphenol with the content of 99.6 percent and the yield of 94.7 percent.
6. Sodium sulfite recovery: adding active carbon into the mother liquor discharged from the acidification procedure for decolorization, performing triple effect evaporation and concentration to obtain a sodium sulfite byproduct, and sampling and analyzing to obtain the sodium sulfite product with the sodium sulfite content of 97.5%.
Example 2
The production method of p-phenylphenol in this example was as follows:
1. sulfonation: adding 186.7kg of biphenyl (99 percent and 1.2kmol) into a 1000L enamel reaction kettle, heating to 150 ℃, slowly dripping 100kg (1.0kmol) of concentrated sulfuric acid with the content of 98 percent into the reaction kettle for 60 minutes, controlling the reaction temperature to be 135-150 ℃, and preserving the temperature at 150 ℃ for 1 hour after dripping to generate 4-phenylbenzenesulfonic acid; and then, evaporating water generated by the reaction and unreacted biphenyl under reduced pressure at 90-100 ℃ and 0.005 MPa.
2. Neutralizing: slowly adding the reaction solution in the step (1) into 756kg (1.2 kmol) of sodium sulfite aqueous solution with the mass fraction of 20%, neutralizing 4-phenyl benzenesulfonic acid to generate 4-sodium phenyl sulfonate and sulfur dioxide, collecting generated sulfur dioxide gas and using the gas for subsequent acidification of sodium phenyl phenolate, cooling after neutralization, and filtering to obtain the 4-sodium phenyl benzenesulfonate.
3. Alkali fusion: 125kg of solid NaOH (content: 96%, 3.0kmol) is added into an alkali fusion kettle, the solid NaOH is heated to 320 ℃ for fusion, 4-phenyl sodium benzenesulfonate is slowly added for alkali fusion reaction to generate sodium p-phenylphenol and sodium sulfite, and the reaction is stopped when the content of the 4-phenyl sodium benzenesulfonate is less than 1.0% by HPLC analysis.
4. Acidifying: and (3) adding the alkali fusion material into 650kg of water for dilution, introducing the sulfur dioxide collected in the step (2), carrying out an acidification reaction at the temperature of less than 50 ℃, reacting until the pH value of a reaction solution is 5.0 to generate p-phenylphenol and sodium sulfite, standing for layering, and separating crude p-phenylphenol and a mother solution.
5. And (3) rectification: the crude p-phenylphenol is rectified at 145-148 ℃ and 1500Pa to obtain 158kg of p-phenylphenol, the content is 99.0%, and the yield is 92.0%.
6. Sodium sulfite recovery: adding active carbon into the mother liquor discharged from the acidification procedure for decolorization, performing triple effect evaporation and concentration to obtain a sodium sulfite byproduct, and sampling and analyzing to obtain a sodium sulfite product with the sodium sulfite content of 98.5%.
Example 3
The production method of p-phenylphenol in this example was as follows:
1. sulfonation: adding 155.6kg of biphenyl (99 percent and 1.0kmol) into a 1000L enamel reaction kettle, heating to 120 ℃, slowly dripping 100kg (1.0kmol) of concentrated sulfuric acid with the content of 98 percent into the reaction kettle for 60 minutes, controlling the reaction temperature to be 100-120 ℃, and preserving the temperature at 90 ℃ for 3 hours after dripping to generate 4-phenylbenzenesulfonic acid; then, at the temperature of 60-70 ℃ and under the pressure of 0.01MPa, water generated by the reaction and unreacted biphenyl are evaporated out under reduced pressure.
2. Neutralizing: slowly adding the reaction solution in the step (1) into 924kg (1.10 kmol) of sodium sulfite aqueous solution with the mass fraction of 15%, neutralizing 4-phenyl benzenesulfonic acid to generate 4-sodium phenyl sulfonate and sulfur dioxide, collecting generated sulfur dioxide gas and using the gas for subsequent acidification of sodium phenyl phenolate, cooling after neutralization, and filtering to obtain the 4-sodium phenyl benzenesulfonate.
3. Alkali fusion: adding 62.5kg of solid NaOH (with the content of 96 percent and the content of 1.5kmol) into an alkali fusion kettle, heating to 300 ℃ for fusion, slowly adding 4-phenyl sodium benzenesulfonate for alkali fusion reaction to generate sodium p-phenylphenol and sodium sulfite, and stopping the reaction when the content of the 4-phenyl sodium benzenesulfonate is less than 1.0 percent through HPLC analysis.
4. Acidifying: and (3) adding the alkali fusion material into 520kg of water for dilution, introducing the sulfur dioxide collected in the step (2), carrying out an acidification reaction at the temperature of less than 50 ℃, reacting until the pH value of a reaction solution is 6.0 to generate p-phenylphenol and sodium sulfite, standing for layering, and separating crude p-phenylphenol and a mother solution.
5. And (3) rectification: the crude p-phenylphenol is rectified at the temperature of 148-150 ℃ and the pressure of 1000Pa to obtain 150.5kg of p-phenylphenol, the content is 98.7 percent, and the yield is 86.4 percent.
6. Sodium sulfite recovery: and (3) adding activated carbon into the mother liquor discharged from the acidification procedure for decolorization, performing triple-effect evaporation and concentration to obtain a sodium sulfite byproduct, and sampling and analyzing to obtain a sodium sulfite product with the sodium sulfite content of 96.3%.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned 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 production method of p-phenylphenol is characterized by comprising the following steps:
(1) sulfonation: mixing biphenyl and sulfuric acid, heating, performing sulfonation reaction, and evaporating water generated by the reaction and unreacted biphenyl under reduced pressure after the reaction is finished;
(2) neutralizing: neutralizing 4-phenyl benzenesulfonic acid in the sulfonation reaction product obtained in the step (1) by using sodium sulfite to generate 4-phenyl sodium sulfonate and sulfur dioxide, collecting generated sulfur dioxide gas and using the sulfur dioxide gas for subsequent acidification of sodium phenyl phenolate, cooling after neutralization, and filtering to obtain 4-phenyl sodium sulfonate solid;
(3) alkali fusion: adding solid sodium hydroxide into an alkali fusion kettle, heating to melt, adding the 4-phenyl sodium benzenesulfonate solid obtained in the step (2) to perform alkali fusion reaction, and generating sodium p-phenylphenol and sodium sulfite;
(4) acidifying: adding the alkali fusion material obtained in the step (3) into water for dilution, introducing the sulfur dioxide collected in the step (2) for acidification reaction to generate p-phenylphenol and sodium sulfite, standing for layering, and separating to obtain crude p-phenylphenol and mother liquor;
(5) and (3) rectification: and rectifying the crude p-phenylphenol to obtain the p-phenylphenol.
2. The process for producing a p-phenylphenol according to claim 1, characterized in that: also comprises the step (6) of recovering sodium sulfite: and (4) carrying out evaporative concentration, crystallization, centrifugal separation and drying on the mother liquor discharged in the neutralization step (2) and the acidification step (4) to obtain a sodium sulfite byproduct, wherein evaporative condensate in the evaporative concentration process is recycled.
3. The process for producing a p-phenylphenol according to claim 1, characterized in that: the sulfonation reaction in the step (1) is as follows: dropwise adding concentrated sulfuric acid into the molten biphenyl at the temperature of 100-150 ℃, and keeping the reaction for 1-3 hours at the temperature of 90-160 ℃ after the dropwise adding is finished.
4. The process for producing a p-phenylphenol according to claim 1, characterized in that: in the step (1), the feeding molar ratio of the biphenyl to the sulfuric acid is (1.0-2.0) to 1.0.
5. The process for producing a p-phenylphenol according to claim 1, characterized in that: in the step (1), water generated by the reaction and unreacted biphenyl are evaporated out under reduced pressure at the temperature of 60-150 ℃ and the pressure of 0.0001-0.01 MPa.
6. The process for producing a p-phenylphenol according to claim 1, characterized in that: in the step (2), the sodium sulfite is used for neutralizing the 4-phenylbenzenesulfonic acid in the sulfonation reaction product obtained in the step (1) in the following way:
adding the sulfonation reaction product obtained in the step (1) into a sodium sulfite aqueous solution while the sulfonation reaction product is hot, and neutralizing 4-phenylbenzenesulfonic acid; or, diluting the sulfonation reaction product obtained in the step (1) with water, and then adding sodium sulfite solid to neutralize 4-phenyl benzenesulfonic acid.
7. The process for producing a p-phenylphenol according to claim 1, characterized in that: in the step (2), the molar use ratio of the sulfonation reaction product to sodium sulfite is 1.0 (1.0-1.2).
8. The process for producing a p-phenylphenol as claimed in claim 1, characterized in that: in the step (3), the molar use ratio of the solid sodium hydroxide to the solid sodium 4-phenylbenzenesulfonate is (1.5-5.0): 1.0;
and/or in the step (3), heating to 250-400 ℃ to melt the solid sodium hydroxide;
and/or in the step (3), the alkali fusion reaction temperature is 280-320 ℃, and the reaction is stopped when the content of the 4-sodium phenylsulfonate is less than 1.0% by HPLC analysis.
9. The process for producing a p-phenylphenol according to claim 1, characterized in that: in the step (4), the acidification reaction temperature is less than 50 ℃ until the pH of the reaction liquid is 5.0-6.0.
10. Use of a process according to any one of claims 1 to 9 in the production of p-phenylphenol.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114835560A (en) * | 2022-06-13 | 2022-08-02 | 连云港市三联化工有限公司 | Preparation method of 4-hydroxybiphenyl |
| CN114853575A (en) * | 2022-06-13 | 2022-08-05 | 连云港市三联化工有限公司 | Production process of p-phenylphenol for mother liquor recycling |
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| CN1566053A (en) * | 2003-07-04 | 2005-01-19 | 江西麒麟化工有限公司 | Process for producing para phenyl phenol |
| CN111362780A (en) * | 2020-04-21 | 2020-07-03 | 哈密盛典科技有限公司 | Method for producing resorcinol by using sulfur trioxide |
| CN212595652U (en) * | 2020-06-12 | 2021-02-26 | 哈密盛典科技有限公司 | Resorcinol alkali fusion tubular reactor and resorcinol production system |
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| CN1566053A (en) * | 2003-07-04 | 2005-01-19 | 江西麒麟化工有限公司 | Process for producing para phenyl phenol |
| CN111362780A (en) * | 2020-04-21 | 2020-07-03 | 哈密盛典科技有限公司 | Method for producing resorcinol by using sulfur trioxide |
| CN212595652U (en) * | 2020-06-12 | 2021-02-26 | 哈密盛典科技有限公司 | Resorcinol alkali fusion tubular reactor and resorcinol production system |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114835560A (en) * | 2022-06-13 | 2022-08-02 | 连云港市三联化工有限公司 | Preparation method of 4-hydroxybiphenyl |
| CN114853575A (en) * | 2022-06-13 | 2022-08-05 | 连云港市三联化工有限公司 | Production process of p-phenylphenol for mother liquor recycling |
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