WO2001051439A1 - Method for production of phenol and acetone by decomposition of cumene hydroperoxide - Google Patents

Method for production of phenol and acetone by decomposition of cumene hydroperoxide Download PDF

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Publication number
WO2001051439A1
WO2001051439A1 PCT/US2000/034442 US0034442W WO0151439A1 WO 2001051439 A1 WO2001051439 A1 WO 2001051439A1 US 0034442 W US0034442 W US 0034442W WO 0151439 A1 WO0151439 A1 WO 0151439A1
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neutralization
alkyl
crude product
temperature effects
substituted
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French (fr)
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Scott R. Keenan
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Sunoco Inc R&M
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Sunoco Inc R&M
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Priority to EP00986565A priority Critical patent/EP1248759B1/en
Priority to AU2001222783A priority patent/AU2001222783A1/en
Priority to JP2001551822A priority patent/JP3441723B2/en
Priority to DE60029008T priority patent/DE60029008T2/en
Publication of WO2001051439A1 publication Critical patent/WO2001051439A1/en
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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
    • C07C37/08—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by decomposition of hydroperoxides, e.g. cumene hydroperoxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/53—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of hydroperoxides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to an improved method for production of phenol and acetone by decomposition of cumene hydroperoxide to phenol, acetone, and - methylstyrene in the presence of an acidic catalyst.
  • the improvement comprises neutralization of the acidic catalyst after substantial completion of the decomposition by addition of a substituted amine.
  • phenol is oxidized in air to produce cumene hydroperoxide (CHP).
  • CHP cumene hydroperoxide
  • the CHP is then cleaved to phenol and acetone in the presence of an acidic catalyst.
  • This process also produces ⁇ -methylstyrene (AMS), along with other byproducts, including acetophenone, dimethylphenylcarbinol, and cumylphenols.
  • AMS ⁇ -methylstyrene
  • the acidic catalyst is a strong, and not heavily corrosive inorganic acid, such as sulfuric or phosphoric acid. The acidic catalyst must be removed or neutralized to prevent further, unwanted reactions in the downstream purification steps that produce the phenol and acetone products.
  • ion exchange resins are temperature sensitive, the crude product stream must be cooled substantially prior to contact with the resin. The need to cool the product stream increases energy costs significantly because the crude product stream must then be re-heated prior to downstream purification operations.
  • a further drawback of ion exchange resins is that they must be regenerated frequently, a labor-intensive and costly process which also results in formation of large amounts of aqueous waste.
  • ion exchange resins give a highly variable final pH in the crude product stream, adversely affecting final product yields, and can also release alkali salts which cause fouling of equipment.
  • a strong base such as sodium hydroxide or potassium hydroxide to neutralize the acidic catalyst is not desirable because it is difficult to achieve accurate pH control in a neutralization reaction between a strong acid and a strong base.
  • metal hydroxides generate salts that have a propensity to deposit on heat exchange surfaces, causing fouling and decreasing efficiency.
  • the present invention is directed to an improved method for production of phenol and acetone from cumene hydroperoxide by decomposition of cumene hydroperoxide in the presence of an acidic catalyst, wherein the improvement comprises neutralization of the acidic catalyst after substantial completion of the decomposition by addition of a substituted amine selected from the group consisting of: (i) a secondary or tertiary amine having from 4 to 21 carbon atoms and not having hydrolytically unstable substituents or acidic substituents; and (ii) a primary amine of formula
  • R 1 and R 2 are independently hydrogen or -C 12 alkyl
  • R 3 is hydrogen, Cr 2 alkyl or C ⁇ -C 12 alkyl substituted by hydroxyl, amino or dimethylamino, provided that at least two of R 1 , R 2 and R 3 are not hydrogen.
  • alkyl is used herein to refer to a saturated acyclic hydrocarbyl substituent group which may be linear or branched.
  • alkylene is used herein to refer to an acyclic hydrocarbyl substituent group having at least one carbon-carbon double bond, and which may be linear or branched.
  • secondary or tertiary amine is used herein to refer to an amine in which there is at least one nitrogen atom directly bonded to at least two carbon atoms.
  • acidic substituents is used herein to refer to substituents having a pKa value in aqueous media of less than about 5.
  • acidic substituents include the acid forms of carboxylates, nitrates, phosphates, phosphonates, sulfates and sulfonates.
  • hydrolytically unstable substituents is used herein to refer to those substituents that undergo substantial hydrolysis and/or condensation reactions at a pH in the range from about 3.5 to about 1.5 and a temperature in the range from about 30°C to about 180°C in a period of about two hours.
  • hydrolytically unstable groups are esters, anhydrides, amides, acid halides, amidines, aminals, enamines, aldehydes, ethers, acetals, hemi-acetals, ketals, hemi-ketals, epoxides and alkynes.
  • a substituted amine employed in the present invention contains no elements other than carbon, hydrogen, nitrogen and oxygen, and no functional groups containing nitrogen or oxygen other than amine and hydroxyl groups.
  • the substituted amine employed in the present invention allows neutralization of product streams from decomposition of cumene hydroperoxide at elevated temperatures with minimal formation of byproducts from reactions between the amine and organic constituents of the product stream, e.g., acetone.
  • Performing the neutralization at elevated temperatures i.e., temperatures near the normal process temperature for decomposition of the hydroperoxide, eliminates the need to cool the process stream prior to neutralization, and then reheat prior to performing purification operations.
  • the preferred temperature range for the neutralization process of this invention is from about 30°C to about 180°C, more preferably from about 60°C to about 160°C, and most preferably from about 120°C to about 160°C.
  • the amines employed in the present invention exhibit a final pH at a high temperature that is much closer to the final pH observed at low temperature.
  • These amines are more sterically hindered or are more highly substituted on the nitrogen. Without being bound to theory, it is believed that these amines do not undergo reactions with organic constituents of the product stream as readily due to the aforementioned characteristics, and are thus more efficient neutralizing agents, especially at high temperatures.
  • the method of the present invention allows better control of the post-neutralization pH of the product stream than conventional methods, especially when the neutralization is conducted at elevated temperatures.
  • the target final pH is in the range from about 2.0 to about 3.5, most preferably from about 2.2 to about 2.8.
  • the secondary or tertiary amine is selected from the group consisting of
  • R 4 and R 5 are independently hydrogen or methyl, and R , R 7 and R 8 are independently hydrogen or -C 4 alkyl;
  • R and R 10 are independently CrC 12 alkyl, C 2 -C 12 alkyl substituted by hydroxyl, arnino or dimethylamino, C -C 7 alkylene or R 9 and R 10 join with NR ⁇ to form a cyclic aliphatic amine having from 5 to 7 ring atoms, e.g., hexamethyleneimine, and R 11 is hydrogen, C 2 -C 12 alkyl, C 2 -C 12 alkyl substituted by hydroxyl, C 5 -C 6 cycloalkyl or C 3 -C 7 alkylene, provided that R 9 , R 10 and R 11 taken together contain at least six carbon atoms; and
  • R 12 , R 13 and R 14 are independently hydrogen or - alkyl.
  • the substituted amine is
  • R 9 and R 10 are independently C 2 -C 6 alkyl or C 2 -C 6 alkyl substituted by hydroxyl, or R 9 and R 10 join with NR 11 to form a cyclic aliphatic amine having from 6 to 7 ring atoms; and R 11 is hydrogen, C 2 -C 6 alkyl or C 2 -C 6 alkyl substituted by hydroxyl.
  • the substituted amine contains at least six carbon atoms.
  • Preferred amines in this embodiment of the invention are triethylamine, tri-n-propylamine, triisopropylamine, triisopropanolamine, di-n-propylamine, di-isopropylamine, di-n-butylamine, di-n- hexylamine and hexamethyleneimine. More preferably, R 9 , R 10 and R ⁇ are independently C 2 -C 6 alkyl or C 2 -C 6 alkyl substituted by hydroxyl. Particularly preferred amines in this embodiment of the invention are triethylamine, tri-n-propylamine, triisopropylamine and triisopropanolamine.
  • R 9 , R 10 and R n are independently C3-C6 alkyl or C -C 6 alkyl substituted by hydroxyl.
  • the most preferred amines in this embodiment are tri-n-propylamine, triisopropylamine and triisopropanolamine.
  • the substituted amine is
  • R 1 and R 2 are independently C1-C9 alkyl, and R 3 is C C 9 alkyl or -Cg alkyl
  • R and R are independently CpC alkyl, and R 3 is C 2 -C 9 alkyl.
  • Preferred amines include tert-amylamine (1,1- dimethylpropylamine) and tert-octylamine (1,1,3,3-tetramethylbutylamine). It is further preferred that R 1 and R 2 are methyl and R 3 is C 3 -C 9 alkyl. Most preferably, R 1 and R 2 are methyl and R 3 is C 5 -C alkyl. The most preferred amine in this embodiment of the invention is tert-octylamine.
  • the substituted amine is selected from the group consisting of a 2,6-dialkylaniline, N-methyl aniline and N,N-dimethylaniline.
  • Particularly preferred anilines of this type are 2,6-dimethylaniline, 2,6-diethylaniline and N-methylaniline.
  • tetraalkylammonium hydroxides where the alkyl groups independently contain from one to ten carbon atoms, are efficient neutralizing agents under the conditions described herein, as illustrated by Examples 29 and 30.
  • the following Examples are intended solely to illustrate certain preferred embodiments of the invention, and not to limit the invention.
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of hexamethylenediamine (HMD A). Results of pH measurement for each run are presented in the following table:
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of n-propylamine. Results of pH measurement for each run are presented in the following table:
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of iso-propylamine. Results of pH measurement for each run are presented in the following table:
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of tert-amylamine ("t- amylamine). Results of pH measurement for each run are presented in the following table:
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an a cumene solution of tert-octylamine ("t-octylamine"). Results of pH measurement for each run are presented in the following table:
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of BHMT. Results of pH measurement for each run are presented in the following table:
  • EXAMPLE 8 Temperature Effects on Neutralization of Crude Product with DYTEK®- EP.
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of 1,3- diaminopentane (available from Aldrich Chemical Co. under the name DYTEK®-EP). Results of pH measurement for each run are presented in the following table:
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of Di-n-propylamine ("Di-n-PrNH2"). Results of pH measurement for each run are presented in the following table:
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of Di-n-butylamine ("Di-n-BuNH2"). Results of pH measurement for each run are presented in the following table:
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of HMI. Results of pH measurement for each run are presented in the following table:
  • EXAMPLE 12 Temperature Effects on Neutralization of Crude Product with N- Methylaniline.
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of N-methylaniline ("N-MeAn"). Results of pH measurement for each run are presented in the following table:
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of aniline. Results of pH measurement for each run are presented in the following table:
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of 1,4-PDA. Results of pH measurement for each run are presented in the following table:
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of m-toluidine. Results of pH measurement for each run are presented in the following table:
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of o-toluidine. Results of pH measurement for each run are presented in the following table:
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of 2-ethylaniline ("2- EtAn"). Results of pH measurement for each run are presented in the following table:
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of 2-n-PrAn. Results of pH measurement for each run are presented in the following table:
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of 2-i-PrAn. Results of pH measurement for each run are presented in the following table:
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of pyridine. Results of pH measurement for each run are presented in the following table:
  • EXAMPLE 21 Temperature Effects on Neutralization of Crude Product with Tri-n- Propylamine.
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of tri-n-propylamine ("Tri-n-PrNH2"). Results of pH measurement for each run are presented in the following table:
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of tri-iso-propylamine ("Tri-i-PrNH2"). Results of pH measurement for each run are presented in the following table:
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of TIPA. Results of pH measurement for each run are presented in the following table:
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of 2,6-Di-MeAn. Results of pH measurement for each run are presented in the following table:
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of 2,6-Di-EtAn. Results of pH measurement for each run are presented in the following table:
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of 2,5-Di-tBuAn. Results of pH measurement for each run are presented in the following table:
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of 2,6-Di-iPrAn. Results of pH measurement for each run are presented in the following table:
  • EXAMPLE 28 Temperature Effects on Neutralization of Crude Product with Di-n- Hexylamine.
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of di-n-hexylamine ("Di-n-HexNH2"). Results of pH measurement for each run are presented in the following table:
  • EXAMPLE 29 Temperature Effects on Neutralization of Crude Product with Tetramethylammonium Hydroxide ("TMAH").
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of TMAH. Results of pH measurement for each run are presented in the following table:
  • EXAMPLE 30 Temperature Effects on Neutralization of Crude Product with Tetra-n- Butylammonium Hydroxide ("TBAH").
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of TBAH. Results of pH measurement for each run are presented in the following table:
  • EXAMPLE 31 Temperature Effects on Neutralization of Crude Product with Triethylamine ("TEA").
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of TEA. Results of pH measurement for each run are presented in the following table:
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of Di-i-PrNH2. Results of pH measurement for each run are presented in the following table:
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with ammonium hydroxide. Results of pH measurement for each run are presented in the following table:
  • Example 1 The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with aqueous solutions of sodium hydroxide. Results of pH measurement for each run are presented in the following tables:

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Abstract

An improved method for production of phenol and acetone by decomposition of cumene hydroperoxide in the presence of an acidic catalyst to phenol and acetone, wherein the improvement comprises neutralization of the acidic catalyst after substantial completion of the decomposition by addition of a substituted amine.

Description

METHOD FOR PRODUCTION OF PHENOL AND ACETONE BY DECOMPOSITION OF CUMENE
HYDROPEROXIDE
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to an improved method for production of phenol and acetone by decomposition of cumene hydroperoxide to phenol, acetone, and - methylstyrene in the presence of an acidic catalyst. The improvement comprises neutralization of the acidic catalyst after substantial completion of the decomposition by addition of a substituted amine.
Related Background Art
One of the predominant commercial processes for manufacture of phenol is the cumene oxidation process, in which cumene is oxidized in air to produce cumene hydroperoxide (CHP). The CHP is then cleaved to phenol and acetone in the presence of an acidic catalyst. This process also produces α-methylstyrene (AMS), along with other byproducts, including acetophenone, dimethylphenylcarbinol, and cumylphenols. Typically, the acidic catalyst is a strong, and not heavily corrosive inorganic acid, such as sulfuric or phosphoric acid. The acidic catalyst must be removed or neutralized to prevent further, unwanted reactions in the downstream purification steps that produce the phenol and acetone products. Typically, commercial processes for manufacture of phenol from CHP use inorganic bases, ion exchange resins, or a combination thereof to remove acidity from the crude product stream. Since ion exchange resins are temperature sensitive, the crude product stream must be cooled substantially prior to contact with the resin. The need to cool the product stream increases energy costs significantly because the crude product stream must then be re-heated prior to downstream purification operations. A further drawback of ion exchange resins is that they must be regenerated frequently, a labor-intensive and costly process which also results in formation of large amounts of aqueous waste. Moreover, ion exchange resins give a highly variable final pH in the crude product stream, adversely affecting final product yields, and can also release alkali salts which cause fouling of equipment.
The use of a strong base, such as sodium hydroxide or potassium hydroxide to neutralize the acidic catalyst is not desirable because it is difficult to achieve accurate pH control in a neutralization reaction between a strong acid and a strong base. Moreover, metal hydroxides generate salts that have a propensity to deposit on heat exchange surfaces, causing fouling and decreasing efficiency.
The use of ammonia to neutralize the acidic catalyst is disclosed in United States Patent No. 5,254,751 to Zakoshansky. In the process described in this reference, neutralization with ammonia is performed during the CHP decomposition, rather than after the decomposition. The disclosure states that the ammonium salts produced from addition of ammonia to the reaction mixture act as acidic catalysts for the remainder of the CHP decomposition reaction. This reference suggests that hydrazine and alkylamines having one to five carbon atoms are suitable for neutralization during CHP decomposition, but that ammonia is preferred, especially for neutralizing sulfuric acid. Zakoshansky also suggests a maximum operating temperature of 110°C SUMMARY OF THE INVENTION
The present invention is directed to an improved method for production of phenol and acetone from cumene hydroperoxide by decomposition of cumene hydroperoxide in the presence of an acidic catalyst, wherein the improvement comprises neutralization of the acidic catalyst after substantial completion of the decomposition by addition of a substituted amine selected from the group consisting of: (i) a secondary or tertiary amine having from 4 to 21 carbon atoms and not having hydrolytically unstable substituents or acidic substituents; and (ii) a primary amine of formula
Figure imgf000004_0001
wherein R1 and R2 are independently hydrogen or -C12 alkyl, and R3 is hydrogen, Cr 2 alkyl or CΪ-C12 alkyl substituted by hydroxyl, amino or dimethylamino, provided that at least two of R1, R2 and R3 are not hydrogen.
DETAILED DESCRIPTION OF THE INVENTION
The term "alkyl" is used herein to refer to a saturated acyclic hydrocarbyl substituent group which may be linear or branched. The term "alkylene" is used herein to refer to an acyclic hydrocarbyl substituent group having at least one carbon-carbon double bond, and which may be linear or branched. The term "secondary or tertiary amine" is used herein to refer to an amine in which there is at least one nitrogen atom directly bonded to at least two carbon atoms.
The term "acidic substituents" is used herein to refer to substituents having a pKa value in aqueous media of less than about 5. Examples of acidic substituents include the acid forms of carboxylates, nitrates, phosphates, phosphonates, sulfates and sulfonates. The term "hydrolytically unstable substituents" is used herein to refer to those substituents that undergo substantial hydrolysis and/or condensation reactions at a pH in the range from about 3.5 to about 1.5 and a temperature in the range from about 30°C to about 180°C in a period of about two hours. Examples of hydrolytically unstable groups are esters, anhydrides, amides, acid halides, amidines, aminals, enamines, aldehydes, ethers, acetals, hemi-acetals, ketals, hemi-ketals, epoxides and alkynes. Preferably, a substituted amine employed in the present invention contains no elements other than carbon, hydrogen, nitrogen and oxygen, and no functional groups containing nitrogen or oxygen other than amine and hydroxyl groups.
The substituted amine employed in the present invention allows neutralization of product streams from decomposition of cumene hydroperoxide at elevated temperatures with minimal formation of byproducts from reactions between the amine and organic constituents of the product stream, e.g., acetone. Performing the neutralization at elevated temperatures, i.e., temperatures near the normal process temperature for decomposition of the hydroperoxide, eliminates the need to cool the process stream prior to neutralization, and then reheat prior to performing purification operations. The preferred temperature range for the neutralization process of this invention is from about 30°C to about 180°C, more preferably from about 60°C to about 160°C, and most preferably from about 120°C to about 160°C.
Neutralization with relatively unsubstituted amines which are highly basic, relatively unsubstituted and sterically relatively unhindered, as suggested in the literature, e.g., ammonia, is not efficient, especially at elevated temperatures. This is believed to be due to consumption of the amine in reactions with acetone or other components of the process stream. As shown below in Example 33, addition of ammonium hydroxide to a typical product mixture at 140.3°C produces a much smaller change in pH than the same amount added at 22.5°C, indicating that a substantial amount of the ammonia is consumed in side reactions. Even at 100.2°C, the pH is significantly lower than that observed at 22.5°C. Addition of the relatively unsubstituted amines DYTEK®-A, hexamethylene diamine, or n-propylamine also produces a much smaller change in pH at high temperatures, as shown below in Examples 1-3.
In contrast, the amines employed in the present invention exhibit a final pH at a high temperature that is much closer to the final pH observed at low temperature. These amines are more sterically hindered or are more highly substituted on the nitrogen. Without being bound to theory, it is believed that these amines do not undergo reactions with organic constituents of the product stream as readily due to the aforementioned characteristics, and are thus more efficient neutralizing agents, especially at high temperatures.
The method of the present invention allows better control of the post-neutralization pH of the product stream than conventional methods, especially when the neutralization is conducted at elevated temperatures. Preferably, the target final pH is in the range from about 2.0 to about 3.5, most preferably from about 2.2 to about 2.8.
In a preferred embodiment of the invention, the secondary or tertiary amine is selected from the group consisting of
Figure imgf000006_0001
wherein R4and R5 are independently hydrogen or methyl, and R , R7 and R8 are independently hydrogen or -C4 alkyl;
Figure imgf000007_0001
wherein R and R10 are independently CrC12 alkyl, C2-C12 alkyl substituted by hydroxyl, arnino or dimethylamino, C -C7 alkylene or R9 and R10 join with NRπ to form a cyclic aliphatic amine having from 5 to 7 ring atoms, e.g., hexamethyleneimine, and R11 is hydrogen, C2-C12 alkyl, C2-C12 alkyl substituted by hydroxyl, C5-C6 cycloalkyl or C3-C7 alkylene, provided that R9, R10 and R11 taken together contain at least six carbon atoms; and
Figure imgf000007_0002
wherein R12, R13 and R14 are independently hydrogen or - alkyl.
In another preferred embodiment of the invention, the substituted amine is
Figure imgf000007_0003
wherein R9 and R10 are independently C2-C6 alkyl or C2-C6 alkyl substituted by hydroxyl, or R9 and R10 join with NR11 to form a cyclic aliphatic amine having from 6 to 7 ring atoms; and R11 is hydrogen, C2-C6 alkyl or C2-C6 alkyl substituted by hydroxyl. The substituted amine contains at least six carbon atoms. Preferred amines in this embodiment of the invention are triethylamine, tri-n-propylamine, triisopropylamine, triisopropanolamine, di-n-propylamine, di-isopropylamine, di-n-butylamine, di-n- hexylamine and hexamethyleneimine. More preferably, R9, R10 and Rπ are independently C2-C6 alkyl or C2-C6 alkyl substituted by hydroxyl. Particularly preferred amines in this embodiment of the invention are triethylamine, tri-n-propylamine, triisopropylamine and triisopropanolamine. Most preferably, R9, R10 and Rn are independently C3-C6 alkyl or C -C6 alkyl substituted by hydroxyl. The most preferred amines in this embodiment are tri-n-propylamine, triisopropylamine and triisopropanolamine.
In another preferred embodiment of the invention, the substituted amine is
Figure imgf000008_0001
wherein R1 and R2 are independently C1-C9 alkyl, and R3 is C C9 alkyl or -Cg alkyl
1 9 substituted by hydroxyl or amino. It is preferred that R and R are independently CpC alkyl, and R3 is C2-C9 alkyl. Preferred amines include tert-amylamine (1,1- dimethylpropylamine) and tert-octylamine (1,1,3,3-tetramethylbutylamine). It is further preferred that R1 and R2 are methyl and R3 is C3-C9 alkyl. Most preferably, R1 and R2 are methyl and R3 is C5-C alkyl. The most preferred amine in this embodiment of the invention is tert-octylamine.
In another preferred embodiment of the invention, the substituted amine is selected from the group consisting of a 2,6-dialkylaniline, N-methyl aniline and N,N-dimethylaniline. Particularly preferred anilines of this type are 2,6-dimethylaniline, 2,6-diethylaniline and N-methylaniline.
Other organic bases are suitable for use in the method of the present invention, although not preferred. For example, tetraalkylammonium hydroxides, where the alkyl groups independently contain from one to ten carbon atoms, are efficient neutralizing agents under the conditions described herein, as illustrated by Examples 29 and 30. The following Examples are intended solely to illustrate certain preferred embodiments of the invention, and not to limit the invention.
EXAMPLES
EXAMPLE 1: Temperature Effects on Neutralization of Crude Product with "DYTEK® A" Amine.
A Vi" stainless steel tube capped at one end, with a %" stainless steel ball valve at the other end, was used as a static reactor for the elevated-temperature runs. At temperatures above about 80°C, the exit of the valve was sealed with a septum cap which was secured with wire. The tube was sufficiently long so that a 10 mL charge of crude product at room temperature left about 1 cm of void space in the tube itself. The crude product had an acid content of 34-38 ppm as sulfuric acid. A solution of 1% 2-methyl-l,5- pentanediamine (available from Aldrich Chemical Co. under the name "DYTEK® A") in water was added via a gas-tight syringe with a needle sufficiently long to reach the center of the void space, with vigorous shaking and mixing for 30 seconds after addition. For the low-temperature (22.5°C) runs, the solutions were mixed in a glass beaker for pH measurement. The results of the pH measurement for each run are summarized in the following table, along with the amount of amine added in that run, and the temperature of the run in °C (T). The change in pH with temperature is reported as "% off target", which is the pH of the low-temperature run minus the pH of the higher-temperature run divided by the pH of the low-temperature run, expressed as a percentage.
Figure imgf000011_0001
EXAMPLE 2: Temperature Effects on Neutralization of Crude Product with Hexamethylenediamine.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of hexamethylenediamine (HMD A). Results of pH measurement for each run are presented in the following table:
Figure imgf000011_0002
EXAMPLE 3: Temperature Effects on Neutralization of Crude Product with n- Propylamine.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of n-propylamine. Results of pH measurement for each run are presented in the following table:
Figure imgf000012_0001
EXAMPLE 4: Temperature Effects on Neutralization of Crude Product with iso- Propylamine.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of iso-propylamine. Results of pH measurement for each run are presented in the following table:
Figure imgf000012_0002
EXAMPLE 5: Temperature Effects on Neutralization of Crude Product with tert- Amylamine.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of tert-amylamine ("t- amylamine). Results of pH measurement for each run are presented in the following table:
Figure imgf000013_0001
EXAMPLE 6: Temperature Effects on Neutralization of Crude Product with tert- octylamine.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an a cumene solution of tert-octylamine ("t-octylamine"). Results of pH measurement for each run are presented in the following table:
Figure imgf000013_0002
EXAMPLE 7: Temperature Effects on Neutralization of Crude Product with Bis(hexamethylene)triamine ("BHMT").
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of BHMT. Results of pH measurement for each run are presented in the following table:
Figure imgf000014_0001
EXAMPLE 8: Temperature Effects on Neutralization of Crude Product with DYTEK®- EP.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of 1,3- diaminopentane (available from Aldrich Chemical Co. under the name DYTEK®-EP). Results of pH measurement for each run are presented in the following table:
Figure imgf000014_0002
EXAMPLE 9: Temperature Effects on Neutralization of Crude Product with Di-n- Propylamine.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of Di-n-propylamine ("Di-n-PrNH2"). Results of pH measurement for each run are presented in the following table:
Figure imgf000015_0001
EXAMPLE 10: Temperature Effects on Neutralization of Crude Product with Di-n- Butylamine.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of Di-n-butylamine ("Di-n-BuNH2"). Results of pH measurement for each run are presented in the following table:
Figure imgf000015_0002
EXAMPLE 11: Temperature Effects on Neutralization of Crude Product with Hexamethyleneimine ("HMF).
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of HMI. Results of pH measurement for each run are presented in the following table:
Figure imgf000016_0001
EXAMPLE 12: Temperature Effects on Neutralization of Crude Product with N- Methylaniline.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of N-methylaniline ("N-MeAn"). Results of pH measurement for each run are presented in the following table:
Figure imgf000016_0002
EXAMPLE 13: Temperature Effects on Neutralization of Crude Product with Aniline.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of aniline. Results of pH measurement for each run are presented in the following table:
Figure imgf000017_0001
EXAMPLE 14: Temperature Effects on Neutralization of Crude Product with 1,4- Phenylenediamine ("1,4-PDA").
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of 1,4-PDA. Results of pH measurement for each run are presented in the following table:
Figure imgf000017_0002
EXAMPLE 15: Temperature Effects on Neutralization of Crude Product with m- Toluidine.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of m-toluidine. Results of pH measurement for each run are presented in the following table:
Figure imgf000018_0001
EXAMPLE 16: Temperature Effects on Neutralization of Crude Product with o- Toluidine.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of o-toluidine. Results of pH measurement for each run are presented in the following table:
Figure imgf000018_0002
EXAMPLE 17: Temperature Effects on Neutralization of Crude Product with 2- Ethylaniline.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of 2-ethylaniline ("2- EtAn"). Results of pH measurement for each run are presented in the following table:
Figure imgf000019_0001
EXAMPLE 18: Temperature Effects on Neutralization of Crude Product with 2-n- Propylaniline ("2-n-PrAn").
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of 2-n-PrAn. Results of pH measurement for each run are presented in the following table:
Figure imgf000019_0002
EXAMPLE 19: Temperature Effects on Neutralization of Crude Product with 2-iso- Propylaniline ("2-i-PrAn").
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of 2-i-PrAn. Results of pH measurement for each run are presented in the following table:
Figure imgf000020_0001
EXAMPLE 20: Temperature Effects on Neutralization of Crude Product with Pyridine.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of pyridine. Results of pH measurement for each run are presented in the following table:
Figure imgf000020_0002
EXAMPLE 21: Temperature Effects on Neutralization of Crude Product with Tri-n- Propylamine.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of tri-n-propylamine ("Tri-n-PrNH2"). Results of pH measurement for each run are presented in the following table:
Figure imgf000021_0001
EXAMPLE 22: Temperature Effects on Neutralization of Crude Product with Tri-iso- Propylamine.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of tri-iso-propylamine ("Tri-i-PrNH2"). Results of pH measurement for each run are presented in the following table:
Figure imgf000021_0002
EXAMPLE 23: Temperature Effects on Neutralization of Crude Product with Triisopropanolamine ("TIPA").
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of TIPA. Results of pH measurement for each run are presented in the following table:
Figure imgf000022_0001
EXAMPLE 24: Temperature Effects on Neutralization of Crude Product with 2,6- Dimethylaniline ("2,6-Di-MeAn").
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of 2,6-Di-MeAn. Results of pH measurement for each run are presented in the following table:
Figure imgf000022_0002
EXAMPLE 25: Temperature Effects on Neutralization of Crude Product with 2,6- Diethylaniline ("2,6-Di-EtAn").
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of 2,6-Di-EtAn. Results of pH measurement for each run are presented in the following table:
Figure imgf000023_0001
EXAMPLE 26: Temperature Effects on Neutralization of Crude Product with 2,5-Di-tert- butylaniline ("2,5-Di-tBuAn").
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of 2,5-Di-tBuAn. Results of pH measurement for each run are presented in the following table:
Figure imgf000023_0002
EXAMPLE 27: Temperature Effects on Neutralization of Crude Product with 2,6- Diisoproρylaniline ("2,6-Di-iPrAn").
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of 2,6-Di-iPrAn. Results of pH measurement for each run are presented in the following table:
Figure imgf000024_0001
EXAMPLE 28: Temperature Effects on Neutralization of Crude Product with Di-n- Hexylamine.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of di-n-hexylamine ("Di-n-HexNH2"). Results of pH measurement for each run are presented in the following table:
Figure imgf000024_0002
EXAMPLE 29: Temperature Effects on Neutralization of Crude Product with Tetramethylammonium Hydroxide ("TMAH").
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of TMAH. Results of pH measurement for each run are presented in the following table:
Figure imgf000025_0001
EXAMPLE 30: Temperature Effects on Neutralization of Crude Product with Tetra-n- Butylammonium Hydroxide ("TBAH").
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of TBAH. Results of pH measurement for each run are presented in the following table:
Figure imgf000025_0002
EXAMPLE 31: Temperature Effects on Neutralization of Crude Product with Triethylamine ("TEA").
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with an aqueous solution of TEA. Results of pH measurement for each run are presented in the following table:
Figure imgf000026_0001
EXAMPLE 32: Temperature Effects on Neutralization of Crude Product with Diisopropylamine ("Di-i-PrNH2").
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with a cumene solution of Di-i-PrNH2. Results of pH measurement for each run are presented in the following table:
Figure imgf000026_0002
EXAMPLE 33: Temperature Effects on Neutralization of Crude Product with Ammonium Hydroxide.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with ammonium hydroxide. Results of pH measurement for each run are presented in the following table:
Figure imgf000027_0001
EXAMPLE 34: Temperature Effects on Neutralization of Crude Product with Sodium Hydroxide.
The method and apparatus described in Example 1 were used to determine temperature effects on neutralization of crude product with aqueous solutions of sodium hydroxide. Results of pH measurement for each run are presented in the following tables:
Figure imgf000027_0002
The preceding Examples are intended to describe certain preferred embodiments of the present invention. It should be appreciated, however, that obvious additions and modifications of the invention will be apparent to one skilled in the art. The invention is not limited except as set forth in the claims.

Claims

WHAT IS CLAIMED IS:
1. An improved method for production of phenol and acetone from cumene hydroperoxide by decomposition of cumene hydroperoxide in the presence of an acidic catalyst, wherein the improvement comprises neutralization of said acidic catalyst after substantial completion of said decomposition by addition of a substituted amine selected from the group consisting of:
(i) a secondary or tertiary amine having from 4 to 21 carbon atoms and not having hydrolytically unstable substituents or acidic substituents; and (ii) a primary amine of formula
Figure imgf000029_0001
wherein R1 and R2 are independently hydrogen or Cj-C12 alkyl, and R3 is hydrogen, Q- C12 alkyl or Cι-C1 alkyl substituted by hydroxyl, amino or dimethylamino, provided that at least two of R1, R2 and R3 are not hydrogen.
2. The method of claim 1 in which said neutralization is performed at a temperature in the range from about 120°C to about 160°C.
3. The method of claim 1 in which said secondary or tertiary amine is selected from the group consisting of
Figure imgf000029_0002
wherein R4and R5 are independently hydrogen or methyl, and R6, R7 and R8 are independently hydrogen or -C4 alkyl;
Figure imgf000030_0001
wherein R and R are independently CrC12 alkyl, C2-C12 alkyl substituted by hydroxyl, amino or dimethylamino, C3-C alkylene or R9 and R10 join with NR11 to form a cyclic aliphatic amine having from 5 to 7 ring atoms, and R11 is hydrogen, C2-C12 alkyl, C2-C12 alkyl substituted by hydroxyl, C5-C6 cycloalkyl or C3-C7 alkylene, provided that R9, R10 and R11 taken together contain at least six carbon atoms; and
Figure imgf000030_0002
wherein R12, R13 and R14 are independently hydrogen or CrC4 alkyl.
4. The method of claim 3 in which said neutralization is performed to a final pH in the range from about 2.0 to about 3.5.
5. The method of claim 4 in which said substituted amine is
Figure imgf000030_0003
wherein R9 and R10 are independently C2-C6 alkyl or C -C6 alkyl substituted by hydroxyl, or R9 and R10 join with NR11 to form a cyclic aliphatic amine having from 6 to 7 ring atoms; and R11 is hydrogen, C2-C6 alkyl or C2-C6 alkyl substituted by hydroxyl.
6. The method of claim 5 in which R9, R10 and R11 are independently C2-C6 alkyl or C2-C6 alkyl substituted by hydroxyl.
7. The method of claim 6 in which said neutralization is performed at a temperature in the range from about 60°C to about 160°C.
8. The method of claim 7 in which said neutralization is performed to a final pH in the range from about 2.2 to about 2.8.
9. The method of claim 8 in which said neutralization is performed at a temperature in the range from about 120°C to about 160°C.
10. The method of claim 4 in which said substituted amine is
Figure imgf000031_0001
wherein R1 and R2 are independently -C9 alkyl, and R3 is -C9 alkyl or -C9 alkyl substituted by hydroxyl or amino.
11. The method of claim 10 in which R!and R2 are independently C1-C9 alkyl, and R3 is C2-C9 alkyl.
12. The method of claim 11 in which R and R are methyl and R is C3-C9 alkyl.
13. The method of claim 12 in which R1 and R2 are methyl and R3 is C5-C9 alkyl.
14. The method of claim 13 in which said neutralization is performed at a temperature in the range from about 60°C to about 160°C.
15. The method of claim 14 in which said neutralization is performed to a final pH in the range from about 2.2 to about 2.8.
16. The method of claim 15 in which said neutralization is performed at a temperature in the range from about 120°C to about 160°C.
PCT/US2000/034442 2000-01-10 2000-12-19 Method for production of phenol and acetone by decomposition of cumene hydroperoxide Ceased WO2001051439A1 (en)

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JP2001551822A JP3441723B2 (en) 2000-01-10 2000-12-19 Production method of phenol and acetone by decomposition of cumene hydroperoxide
DE60029008T DE60029008T2 (en) 2000-01-10 2000-12-19 PROCESS FOR THE PREPARATION OF PHENOL AND ACETONE BY DECOMPOSITION OF CUMOLHYDROPEROXYD

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015161466A1 (en) * 2014-04-23 2015-10-29 Dow Global Technologies Llc Neutralization of acidic catalysts in production of phenol

Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2003222202A1 (en) * 2002-02-08 2003-09-02 General Electric Company Process and catalyst for purifying phenol
RU2217409C2 (en) 2002-02-08 2003-11-27 Общество с ограниченной ответственностью "Петрофенол" Method and catalyst for production of paracumylphenol
RU2217408C2 (en) * 2002-02-08 2003-11-27 Общество с ограниченной ответственностью "Петрофенол" Method and catalyst for cumene treatment of phenol
KR20070002039A (en) * 2004-03-31 2007-01-04 제너럴 일렉트릭 캄파니 How to prepare phenol
US7141700B1 (en) 2005-08-19 2006-11-28 Uop Llc Decomposition of cumene hydroperoxide
US7141701B1 (en) 2005-08-19 2006-11-28 Uop Llc Decomposition of cumene hydroperoxide
US7888537B2 (en) * 2006-12-29 2011-02-15 Uop Llc Solid acid catalyst and process for decomposition of cumene hydroperoxide
WO2012134549A1 (en) 2011-03-28 2012-10-04 Exxonmobil Chemical Patents Inc. Production of cyclohexylbenzene hydroperoxide
US9029611B2 (en) 2010-02-05 2015-05-12 Exxonmobil Chemical Patents Inc. Dehydrogenation of cyclohexanone to produce phenol
WO2011096989A1 (en) 2010-02-05 2011-08-11 Exxonmobil Chemical Patents Inc. Dehydrogenation of cyclohexanone to produce phenol
US20110306800A1 (en) 2010-06-09 2011-12-15 Scott Roy Keenan Method for the decomposition of cumene hydroperoxide
CN103097351B (en) 2010-09-14 2016-03-09 埃克森美孚化学专利公司 The method for oxidation of phenylcyclohexane
CN103052618B (en) 2010-09-14 2015-08-05 埃克森美孚化学专利公司 Produce the method for phenol
US8921610B2 (en) 2010-09-14 2014-12-30 Exxonmobil Chemical Patents Inc. Oxidation of alkylbenzenes
CN105646156B (en) 2010-09-14 2018-07-13 埃克森美孚化学专利公司 The method for being used to prepare phenol
US9242918B2 (en) 2010-09-14 2016-01-26 Exxonmobil Chemical Patents Inc. Dehydrogenation processes and phenol compositions
WO2012036826A2 (en) 2010-09-14 2012-03-22 Exxonmobil Chemical Patents Inc. Processes for producing phenol
WO2012067711A1 (en) 2010-11-16 2012-05-24 Exxonmobil Chemical Patents Inc. Process for producing phenol
KR101538084B1 (en) 2010-12-17 2015-07-21 엑손모빌 케미칼 패턴츠 인코포레이티드 Dehydrogenation catalyst and process
SG192612A1 (en) 2011-02-18 2013-09-30 Exxonmobil Chem Patents Inc Process for producing cyclohexylbenzene
US9017641B2 (en) 2011-02-21 2015-04-28 Exxonmobil Chemical Patents Inc. Hydrogen purification process
WO2012118542A1 (en) 2011-02-28 2012-09-07 Exxonmobil Chemical Patents Inc. Process for producing phenol
SG193427A1 (en) 2011-03-28 2013-10-30 Exxonmobil Chem Patents Inc Dehydrogenation process
WO2013052216A1 (en) 2011-10-07 2013-04-11 Exxonmobil Chemical Patents Inc. Process for producing phenol from cyclohexylbenzene hydroperoxide
US8981158B2 (en) 2011-12-19 2015-03-17 Exxonmobil Chemical Patents Inc. Oxidation of cyclohexylbenzene
WO2013109348A1 (en) 2012-01-18 2013-07-25 Exxonmobil Chemical Patents Inc. Process for producing phenol
US8865957B2 (en) * 2012-03-09 2014-10-21 Honeywell Intenational Inc. Method for producing alpha-methyl styrene from cumene
FR3012138B1 (en) 2013-10-22 2015-10-30 Arkema France USE OF ALKANE-SULFONIC ACID FOR THE PREPARATION OF PHENOLIC ALCOHOL
CN113135819B (en) * 2021-04-29 2022-07-15 北京工业大学 A kind of method that improves the yield of m-dicumene oxidation to prepare resorcinol

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0085289A1 (en) * 1981-12-24 1983-08-10 Monsanto Company Process for direct neutralization of product mixture resulting from acid catalyzed cleavage of alkyl aromatic hydroperoxides
US5254751A (en) * 1992-09-14 1993-10-19 General Electric Company Method for the decomposition of cumene hydroperoxide by acidic catalyst to phenol and acetone

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4267379A (en) * 1978-12-04 1981-05-12 Gulf Research & Development Company Decomposition of cumene hydroperoxide and recovery of boron trifluoride catalyst
US5491268A (en) 1994-09-23 1996-02-13 General Electric Company Process for removal of acidic compounds from phenol process streams

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0085289A1 (en) * 1981-12-24 1983-08-10 Monsanto Company Process for direct neutralization of product mixture resulting from acid catalyzed cleavage of alkyl aromatic hydroperoxides
US5254751A (en) * 1992-09-14 1993-10-19 General Electric Company Method for the decomposition of cumene hydroperoxide by acidic catalyst to phenol and acetone

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015161466A1 (en) * 2014-04-23 2015-10-29 Dow Global Technologies Llc Neutralization of acidic catalysts in production of phenol
US9890099B2 (en) 2014-04-23 2018-02-13 Dow Global Technologies Llc Neutralization of acidic catalysts in the production of phenol
EP3134378A4 (en) * 2014-04-23 2018-02-14 Dow Global Technologies LLC Neutralization of acidic catalysts in production of phenol

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