[go: up one dir, main page]

WO2015197586A1 - Manufacture of 2,4,6-trimethylphenol - Google Patents

Manufacture of 2,4,6-trimethylphenol Download PDF

Info

Publication number
WO2015197586A1
WO2015197586A1 PCT/EP2015/064050 EP2015064050W WO2015197586A1 WO 2015197586 A1 WO2015197586 A1 WO 2015197586A1 EP 2015064050 W EP2015064050 W EP 2015064050W WO 2015197586 A1 WO2015197586 A1 WO 2015197586A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
range
oxide
process according
temperature
Prior art date
Application number
PCT/EP2015/064050
Other languages
French (fr)
Inventor
Werner Bonrath
Jan Schuetz
Fabrizio Cavani
Original Assignee
Dsm Ip Assets B.V.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dsm Ip Assets B.V. filed Critical Dsm Ip Assets B.V.
Publication of WO2015197586A1 publication Critical patent/WO2015197586A1/en

Links

Classifications

    • 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
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom

Definitions

  • the present invention is directed to a process for the manufacture of 2,4,6- trimethylphenol by reacting phenol or ortho-cresol (o-cresol) or 2,6-xylenol with methanol in the gas phase and in the presence of a catalyst, whereby the catalyst comprises gallium oxide, which preferably further contains magnesium oxide.
  • the catalyst consists of gallium oxide and magnesium oxide.
  • the term "consisting of" in the context of the present invention means that the total amount of gallium oxide and magnesium oxide ideally sums up to 100 weight-%. It is, however, not excluded that small amounts of impurities (such as e.g.
  • any other metal or non-reactive additives may be present in amounts of less than 5 weight-%, preferably less than 1 weight-%, more preferably less than 0.5 weight-%, based on the total weight of the methylation catalyst.
  • the term "gallium oxide and magnesium oxide” also encompasses mixed oxides of gallium and magnesium, as well as any mixture of Ga 2 C>3 and MgO, and mixtures of any modifications thereof.
  • the catalyst comprising Ga 2 0 3 and MgO has a weight ratio of Mg to Ga from 1 :1 to 15:1.
  • 2,4,6-Trimethylphenol is an important intermediate for TMHQ (2,3,5- trimethylhydrochinone) being itself one of the building blocks of Vitamin E.
  • the reaction sequence starting with 2,4,6-trimethylphenol and leading to TMHQ is e.g. described in US 4,612,401 (Rhone Poulenc), DE 2 314 600 (Teijin) and EP-A 084 158 (Mitsubishi) and shown in the following scheme 1.
  • the catalyst comprises gallium oxide.
  • the catalyst further comprises magnesium oxide.
  • a catalyst comprising gallium oxide and magnesium oxide may also be used.
  • gallium oxide and magnesium oxide also be used.
  • the catalyst consists of gallium oxide.
  • the term "consisting of" in the context of the present invention means that the total amount of gallium oxide ideally is 100 weight-%. It is, however, not excluded that small amounts of impurities (such as e.g. any other metal) or non- reactive additives may be present in amounts of less than 5 weight-%, preferably less than 1 weight-%, more preferably less than 0.5 weight-%, based on the total weight of the catalyst.
  • the catalyst consists of gallium oxide and magnesium oxide.
  • mixed oxides of gallium and magnesium are encompassed, as well as any mixture of Ga 2 0 3 and MgO, and mixtures of any modifications thereof.
  • the term "consisting of" in the context of the present invention means that the total amount of gallium oxide and magnesium oxide ideally sums up to 100 weight-%. It is, however, not excluded that small amounts of impurities (such as e.g. any other metal) or non-reactive additives may be present in amounts of less than 5 weight-%, preferably less than 1 weight-%, more preferably less than 0.5 weight-%, based on the total weight of the catalyst.
  • the catalysts either comprising gallium oxide/s and magnesium oxide/s or consisting of gallium oxide/s and magnesium oxide/s have a weight-ratio of magnesium to gallium in the range of from 1 :1 to 15:1.
  • the weight-ratio of magnesium to gallium is either 2 : 1 or 6 : 1 or 10 : 1.
  • the best results obtained with phenol are catalysts with a weight ratio of Mg to Ga of 10:1.
  • the best results obtained with o-cresol are catalysts with a weight ratio of Mg to Ga of 2:1.
  • the best results obtained with 2,6-xylenol are catalysts with a weight ratio of Mg to Ga of 10:1.
  • the catalyst consisting of gallium oxide with all preferences and limitations as given above does neither contain titanium oxide nor indium oxide in contrast to US 5,245,089 and US
  • a sodium carbonate solution with a concentration in the range of 0.3 to 2 M (preferably with a concentration in the range of 0.8 to 1.5 M) and a pH value in the range of 7.5 to 10 (preferably a pH value in the range of 8 to 9), whereby the molar ratio of sodium carbonate to the sum of gallium nitrate and optionally magnesium nitrate is 5 : 1 ;
  • step c) dropping the solution obtained in step a) into the solution obtained in step b) under stirring, while adjusting the pH to a value in the range of 6 to 8 (preferably to a value in the range of 6.5 to 7.5) and keeping the temperature in the range of 50 to 60°C;
  • step d) filtering the solution obtained in step c) to obtain the solid catalyst
  • step d) washing the solid catalyst obtained in step d) with water;
  • step f) calcinating the dried solid catalyst obtained in step f) in air.
  • This step is usually performed at room temperature, but may be also performed at temperatures above room temperature. It is only important that the salts, i.e. gallium nitrate and optionally magnesium nitrate, become dissolved.
  • the pressure at which this step is performed is not critical. It is also possible to use other magnesium or gallium salts such as magnesium halogenides or gallium halogenides as long as the salts are removed by the calcination step g).
  • the pH value is adjusted by means of concentrated HNO3.
  • Other acids may also be suitable, if other salts of Ga and Mg are used.
  • concentrated hydrogen chloride it is e.g. possible to use concentrated hydrogen chloride if Ga chloride and Mg chloride are used.
  • the pH is preferably adjusted with concentrated sodium hydroxide.
  • Other bases such as other alkaline bases and earth alkaline bases may also be suitable as long as the formed salts are better soluble than MgO and Ga 2 0 3 . Stirring is continued for about 30 to 45 minutes. Step d)
  • the washing with water is preferably continued until the elution water shows a pH value of 7.
  • the drying may be carried out at a temperature in the range of from 100 to 150°C for 4 to 48 hours. In one embodiment of the process of the present invention the drying is carried out at 120°C for 4 hours, in another embodiment of the process of the present invention the drying is carried out at 110°C for 12 hours. Step g)
  • the calcination is preferably carried out at a temperature in the range of from 400 to 600° C, for a time in the range of 4 to 15 hours. More preferably the calcination is carried out at 450 °C for 8 hours.
  • the GHSV gas hourly space velocity
  • the GHSV is thereby in the range of from 3200 h “1 to 4000 h "1 , more preferably the GHSV is around 3600 h "1 .
  • the reaction i.e. the methylation of phenol to 2,4,6-trimethylphenol
  • the reaction is carried out at a temperature in the range of from 250 to 600° C, preferably at a temperature in the range of from 400 to 500° C.
  • the molar ratio of phenol to methanol is in the range of from 1 :3 to 1 :30, more preferably it is in the range of from 1 :3 to 1 : 15, most preferably it is in the range of from 1 :3 to 1 :8.
  • the pressure is in the range of from 1 to 10 bara (bar absolute), more preferably it is 1 bara.
  • the reaction water may also be present.
  • the molar amount of water is at most 20 times the molar amount of phenol.
  • the reaction i.e. the methylation of o-cresol to 2,4,6-trimethylphenol
  • the reaction is carried out at a temperature in the range of from 250 to 600° C, preferably at a temperature in the range of from 400 to 500° C.
  • the molar ratio of o-cresol to methanol is in the range of from 1 :2 to 1 :30, more preferably it is in the range of from 1 :2 to 1 : 15, most preferably it is in the range of from 1 :3 to 1 :8.
  • the pressure is in the range of from 1 to 10 bara (bar absolute), more preferably it is 1 bara.
  • the reaction i.e. the methylation of 2,6-xylenol to 2,4,6- trimethylphenol, is carried out at a temperature in the range of from 250 to 600° C, preferably at a temperature in the range of from 400 to 500° C.
  • the molar ratio of 2,6-xylenol to methanol is in the range of from 1 : 1 to 1 :20, more preferably it is in the range of from 1 :2 to 1 : 15, most preferably it is in the range of from 1 :2 to 1 :6.
  • the pressure is in the range of from 1 to 10 bara (bar absolute), more preferably it is 1 bara.
  • reaction water may also be present which is very advantageous in this reaction because it strongly limits the deactivation of the catalyst.
  • the molar amount of water is at most 20 times the molar amount of 2,6-xylenol.
  • 1 cm 3 of catalyst is loaded in the reactor, with particles having a size in the range of from 30 to 60 mesh, prepared by compressing the powder into particles, then crushed and sieved.
  • the liquid mixture is then prepared, with the desired methanol/ phenolic compound molar ratio, loaded in the syringe and installed on the pump.
  • the gas flow rate is then set up and regulated (typically N 2 ), with a flow rate that is typically equal to 20 mL/min (when the reaction temperature is 400°C).
  • the temperature of the reactor is then raised, and when the needed temperature is reached, the reaction time is started.
  • Typical conditions are: 1 second of contact time (GHSV 3600 h "1 ), calculated on the basis of the overall gas/vapour flow.
  • the overall content of organics in the inlet flow (phenol + methanol) is between 15 and 18 volume%; it may change within this interval because the N 2 flow is changed in function of the reaction temperature used. Moreover, if also water is fed, by means of a second syringe and pump, the N 2 flow is decreased proportionally, so to keep the overall flow of inert (after vaporisation of water) constant.
  • the amount of organic fed (and vaporised) is typically 0.46 mL/h.
  • the outlet flow is made bubbling in a isopropanol solution, and the compounds which cannot be condensed are then sent to the vent.
  • the syringe is stopped, and the N 2 is let flow for some minutes more.
  • the isopropanol solution is transferred in a vessel, brought to 25 ml_ volume with isopropanol, then 20 microL of standard are added (n-decane), and then the mixture is analysed by GC (Thermo Instrumento, capillary column HP5, FID detector).
  • Example 1 Use of a Mg-Ga-oxide-cata yst with a weight ratio of M3 ⁇ 4 to Ga of 10 to 1 Selectivity: 79%
  • Example 2 Use of a Mg-Ga-oxide-catalyst with a weight ratio of M3 ⁇ 4 to Ga of 10 to 1 Selectivity: 62%
  • Example 3 Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 10 to 1 Selectivity: 66%
  • Example 4 Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 2 to 1 Selectivity: 45%
  • Example 5 Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 2 to 1 Selectivity: 58%
  • Example 6 Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 2 to 1 Selectivity: 54%
  • Example 7 Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 6 to 1
  • Example 8 Use of Ga 2 03 as catalyst
  • Example 9 Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 2 to 1 Selectivity: 78%
  • Example 10 Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 6 to 1 Selectivity: 69%
  • Example 1 1 Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 10 to 1
  • Example 12 Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 10 to 1
  • Example 13 Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 10 to 1
  • Example 14 Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 10 to 1

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The present invention is directed to a process for the manufacture of 2,4,6-trimethylphenol by reacting phenol or ortho-cresol or 2,6-xylenol with methanol in the gas phase and in the presence of a catalyst, whereby the catalyst comprises Ga2O3 or additionally MgO. Catalysts consisting of Ga2O3 or catalysts consisting of Ga2O3 and MgO may also be used successfully.

Description

Manufacture of 2,4,6-trimethylphenol
The present invention is directed to a process for the manufacture of 2,4,6- trimethylphenol by reacting phenol or ortho-cresol (o-cresol) or 2,6-xylenol with methanol in the gas phase and in the presence of a catalyst, whereby the catalyst comprises gallium oxide, which preferably further contains magnesium oxide. In a preferred embodiment of the present invention, the catalyst consists of gallium oxide and magnesium oxide. The term "consisting of" in the context of the present invention means that the total amount of gallium oxide and magnesium oxide ideally sums up to 100 weight-%. It is, however, not excluded that small amounts of impurities (such as e.g. any other metal) or non-reactive additives may be present in amounts of less than 5 weight-%, preferably less than 1 weight-%, more preferably less than 0.5 weight-%, based on the total weight of the methylation catalyst. The term "gallium oxide and magnesium oxide" also encompasses mixed oxides of gallium and magnesium, as well as any mixture of Ga2C>3 and MgO, and mixtures of any modifications thereof. Preferably the catalyst comprising Ga203 and MgO has a weight ratio of Mg to Ga from 1 :1 to 15:1.
2,4,6-Trimethylphenol is an important intermediate for TMHQ (2,3,5- trimethylhydrochinone) being itself one of the building blocks of Vitamin E. The reaction sequence starting with 2,4,6-trimethylphenol and leading to TMHQ is e.g. described in US 4,612,401 (Rhone Poulenc), DE 2 314 600 (Teijin) and EP-A 084 158 (Mitsubishi) and shown in the following scheme 1.
Figure imgf000002_0001
Scheme 1
The process of the present invention is now further described in more detail below. Catalyst
In an embodiment of the present invention the catalyst comprises gallium oxide.
In a preferred embodiment of this embodiment the catalyst further comprises magnesium oxide. Thus, a catalyst comprising gallium oxide and magnesium oxide may also be used. The term "gallium oxide and magnesium oxide" also
encompasses mixed oxides of gallium and magnesium, as well as any mixture of Ga2C>3 and MgO, and mixtures of any modifications thereof. These (mixed) oxides of gallium and magnesium do not have a spinel structure.
In a further embodiment of the present invention the catalyst consists of gallium oxide. The term "consisting of" in the context of the present invention means that the total amount of gallium oxide ideally is 100 weight-%. It is, however, not excluded that small amounts of impurities (such as e.g. any other metal) or non- reactive additives may be present in amounts of less than 5 weight-%, preferably less than 1 weight-%, more preferably less than 0.5 weight-%, based on the total weight of the catalyst.
In another embodiment of the present invention the catalyst consists of gallium oxide and magnesium oxide. Hereby also mixed oxides of gallium and magnesium are encompassed, as well as any mixture of Ga203 and MgO, and mixtures of any modifications thereof. The term "consisting of" in the context of the present invention means that the total amount of gallium oxide and magnesium oxide ideally sums up to 100 weight-%. It is, however, not excluded that small amounts of impurities (such as e.g. any other metal) or non-reactive additives may be present in amounts of less than 5 weight-%, preferably less than 1 weight-%, more preferably less than 0.5 weight-%, based on the total weight of the catalyst.
In preferred embodiments of the present invention the catalysts either comprising gallium oxide/s and magnesium oxide/s or consisting of gallium oxide/s and magnesium oxide/s have a weight-ratio of magnesium to gallium in the range of from 1 :1 to 15:1. Especially preferred are those catalysts where the weight-ratio of magnesium to gallium is either 2 : 1 or 6 : 1 or 10 : 1. The best results obtained with phenol are catalysts with a weight ratio of Mg to Ga of 10:1. The best results obtained with o-cresol are catalysts with a weight ratio of Mg to Ga of 2:1. The best results obtained with 2,6-xylenol are catalysts with a weight ratio of Mg to Ga of 10:1. In a preferred embodiment of the present invention the catalyst with all
preferences and limitations as given above does not contain iron oxide in contrast to the catalysts disclosed in EP-A 019 476.
In a further preferred embodiment of the present invention the catalyst consisting of gallium oxide with all preferences and limitations as given above does neither contain titanium oxide nor indium oxide in contrast to US 5,245,089 and US
3,418,379, respectively.
Process for the manufacture of the catalysts
Usually the catalysts are prepared as follows:
a) dissolving gallium nitrate and optionally magnesium nitrate in the desired ratio in water;
b) providing a sodium carbonate solution with a concentration in the range of 0.3 to 2 M (preferably with a concentration in the range of 0.8 to 1.5 M) and a pH value in the range of 7.5 to 10 (preferably a pH value in the range of 8 to 9), whereby the molar ratio of sodium carbonate to the sum of gallium nitrate and optionally magnesium nitrate is 5 : 1 ;
c) dropping the solution obtained in step a) into the solution obtained in step b) under stirring, while adjusting the pH to a value in the range of 6 to 8 (preferably to a value in the range of 6.5 to 7.5) and keeping the temperature in the range of 50 to 60°C;
d) filtering the solution obtained in step c) to obtain the solid catalyst;
e) washing the solid catalyst obtained in step d) with water;
f) drying the solid catalyst obtained in step e);
g) calcinating the dried solid catalyst obtained in step f) in air.
The steps are now described in more detail below. Step a)
This step is usually performed at room temperature, but may be also performed at temperatures above room temperature. It is only important that the salts, i.e. gallium nitrate and optionally magnesium nitrate, become dissolved. The pressure at which this step is performed is not critical. It is also possible to use other magnesium or gallium salts such as magnesium halogenides or gallium halogenides as long as the salts are removed by the calcination step g).
Step b)
If needed the pH value is adjusted by means of concentrated HNO3. Other acids may also be suitable, if other salts of Ga and Mg are used. Thus, it is e.g. possible to use concentrated hydrogen chloride if Ga chloride and Mg chloride are used.
Step c)
The pH is preferably adjusted with concentrated sodium hydroxide. Other bases such as other alkaline bases and earth alkaline bases may also be suitable as long as the formed salts are better soluble than MgO and Ga203. Stirring is continued for about 30 to 45 minutes. Step d)
For filtering any suitable filter such as a Biichner filter may be used. Step e)
The washing with water is preferably continued until the elution water shows a pH value of 7.
Step f )
The drying may be carried out at a temperature in the range of from 100 to 150°C for 4 to 48 hours. In one embodiment of the process of the present invention the drying is carried out at 120°C for 4 hours, in another embodiment of the process of the present invention the drying is carried out at 110°C for 12 hours. Step g)
The calcination is preferably carried out at a temperature in the range of from 400 to 600° C, for a time in the range of 4 to 15 hours. More preferably the calcination is carried out at 450 °C for 8 hours.
The methylation reactions according to the present invention are now described in more detail below. The GHSV (gas hourly space velocity) is thereby in the range of from 3200 h"1 to 4000 h"1, more preferably the GHSV is around 3600 h"1.
Processes of the present invention
a) Methylation of phenol to 2,4,6-trimethylphenol (see also examples 1 -3)
Preferably the reaction, i.e. the methylation of phenol to 2,4,6-trimethylphenol, is carried out at a temperature in the range of from 250 to 600° C, preferably at a temperature in the range of from 400 to 500° C.
Preferably the molar ratio of phenol to methanol is in the range of from 1 :3 to 1 :30, more preferably it is in the range of from 1 :3 to 1 : 15, most preferably it is in the range of from 1 :3 to 1 :8.
Preferably the pressure is in the range of from 1 to 10 bara (bar absolute), more preferably it is 1 bara. During the reaction water may also be present. Hereby the molar amount of water is at most 20 times the molar amount of phenol. b) Methylation of o-creso to 2,4,6-trimethylphenol (see also examples 5-7)
Preferably the reaction, i.e. the methylation of o-cresol to 2,4,6-trimethylphenol, is carried out at a temperature in the range of from 250 to 600° C, preferably at a temperature in the range of from 400 to 500° C. Preferably the molar ratio of o-cresol to methanol is in the range of from 1 :2 to 1 :30, more preferably it is in the range of from 1 :2 to 1 : 15, most preferably it is in the range of from 1 :3 to 1 :8.
Preferably the pressure is in the range of from 1 to 10 bara (bar absolute), more preferably it is 1 bara.
During the reaction water may also be present. Hereby the molar amount of water is at most 20 times the molar amount of o-cresol. c) Methylation of 2,6-xylenol to 2,4,6-trimethy pheno (see also examples 8-14)
Preferably the reaction, i.e. the methylation of 2,6-xylenol to 2,4,6- trimethylphenol, is carried out at a temperature in the range of from 250 to 600° C, preferably at a temperature in the range of from 400 to 500° C.
Preferably the molar ratio of 2,6-xylenol to methanol is in the range of from 1 : 1 to 1 :20, more preferably it is in the range of from 1 :2 to 1 : 15, most preferably it is in the range of from 1 :2 to 1 :6.
Preferably the pressure is in the range of from 1 to 10 bara (bar absolute), more preferably it is 1 bara.
During the reaction water may also be present which is very advantageous in this reaction because it strongly limits the deactivation of the catalyst. Hereby the molar amount of water is at most 20 times the molar amount of 2,6-xylenol.
The invention is now further illustrated in the following non-limiting examples.
Examples
All examples have been carried out according to the general procedure. General procedure
In a typical experiment, 1 cm3 of catalyst is loaded in the reactor, with particles having a size in the range of from 30 to 60 mesh, prepared by compressing the powder into particles, then crushed and sieved. The liquid mixture is then prepared, with the desired methanol/ phenolic compound molar ratio, loaded in the syringe and installed on the pump. The gas flow rate is then set up and regulated (typically N2), with a flow rate that is typically equal to 20 mL/min (when the reaction temperature is 400°C). The temperature of the reactor is then raised, and when the needed temperature is reached, the reaction time is started. Typical conditions are: 1 second of contact time (GHSV 3600 h"1 ), calculated on the basis of the overall gas/vapour flow. The overall content of organics in the inlet flow (phenol + methanol) is between 15 and 18 volume%; it may change within this interval because the N2 flow is changed in function of the reaction temperature used. Moreover, if also water is fed, by means of a second syringe and pump, the N2 flow is decreased proportionally, so to keep the overall flow of inert (after vaporisation of water) constant. The amount of organic fed (and vaporised) is typically 0.46 mL/h.
During the experiment, the outlet flow is made bubbling in a isopropanol solution, and the compounds which cannot be condensed are then sent to the vent. After 50 minutes of reaction time, the syringe is stopped, and the N2 is let flow for some minutes more. The isopropanol solution is transferred in a vessel, brought to 25 ml_ volume with isopropanol, then 20 microL of standard are added (n-decane), and then the mixture is analysed by GC (Thermo Instrumento, capillary column HP5, FID detector).
Examples 1 -4: Methylation of phenol to 2,4,6-trimethylphenol
Example 1 : Use of a Mg-Ga-oxide-cata yst with a weight ratio of M¾ to Ga of 10 to 1 Selectivity: 79%
Conversion: 100%
Feed: MeOH/ Phenol = 5 : 1 (molar ratio)
Temperature: 450° C
Example 2: Use of a Mg-Ga-oxide-catalyst with a weight ratio of M¾ to Ga of 10 to 1 Selectivity: 62%
Conversion: 100%
Feed: MeOH /water/ Phenol = 10 : 5 : 1 (molar ratio)
Temperature: 410°C
Example 3: Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 10 to 1 Selectivity: 66%
Conversion: 100%
Feed: MeOH/Phenol = 10 : 1 (molar ratio)
Temperature: 450° C
Example 4: Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 2 to 1 Selectivity: 45%
Conversion: 100%
Feed: MeOH /water/ Phenol = 10 : 5 : 1 (molar ratio)
Temperature: 400° C
Examples 5-7: Methylation of o-cresol to 2,4,6-trimethylphenol
Example 5: Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 2 to 1 Selectivity: 58%
Conversion: 76%
Feed: o-cresol/water/MeOH = 1 : 5 : 5 (molar ratio)
Temperature: 350° C
Example 6: Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 2 to 1 Selectivity: 54%
Conversion: 76%
Feed: o-cresol/MeOH = 1 : 5 (molar ratio)
Temperature: 350° C
Example 7: Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 6 to 1
Selectivity: 46%
Conversion: 53% Feed: o-cresol/water/MeOH
Temperature: 350° C
Examples 8-14: Methylation of 2,6-xylenol to 2,4,6-trimethylphenol
Example 8: Use of Ga203 as catalyst
Selectivity: 66%
Conversion: 8%
Feed: 2,6-xylenol/water/MeOH = 1 : 5 : 5 (molar ratio)
Temperature: 400° C
Example 9: Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 2 to 1 Selectivity: 78%
Conversion: 51 %
Feed: 2,6-xylenol/water/MeOH = 1 : 5 : 5 (molar ratio)
Temperature: 400° C
Example 10: Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 6 to 1 Selectivity: 69%
Conversion: 42%
Feed: 2,6-xylenol/water/MeOH = 1 : 5 : 5 (molar ratio)
Temperature: 400° C
Example 1 1 : Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 10 to 1
Selectivity: 96%
Conversion: 74%
Feed: 2,6-xylenol/water/MeOH = 1 : 5 : 5 (molar ratio)
Temperature: 400° C
Example 12: Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 10 to 1
Selectivity: 84%
Conversion: 38% Feed: 2,6-xylenol/MeOH = 1 : 5 (molar ratio)
Temperature: 400° C
Example 13: Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 10 to 1
Selectivity: 93%
Conversion: 28%
Feed: 2,6-xylenol/MeOH = 1 : 2.5 (molar ratio)
Temperature: 400° C
Example 14: Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 10 to 1
Selectivity: 94%
Conversion: 52%
Feed: 2,6-xylenol/water/MeOH = 1 : 2.5 : 2.5 (molar ratio)
Temperature: 400° C

Claims

Claims
1 . Process for the manufacture of 2,4,6-trimethylphenol by reacting phenol or o- cresol or 2,6-xylenol with methanol in the gas phase and in the presence of a catalyst, whereby the catalyst comprises Ga2C>3.
2. The process according to claim 1 , whereby the catalyst further comprises MgO.
3. The catalyst according to claim 2, whereby the catalyst has a Mg/Ga ratio from 1 : 1 to 15: 1 .
4. The process according to claim 1 , whereby the catalyst consists of Ga203 and does preferably neither contain titanium oxide nor indium oxide.
5. The process according to claim 1 or 2, whereby the catalyst consists of Ga203 and MgO, preferably with a Mg/Ga ratio from 1 : 1 to 15: 1 .
6. The process according to any one or more of the preceding claims, whereby the catalyst does not contain iron oxide(s).
7. The process according to any one or more of the preceding claims, whereby the reaction is carried out at a temperature in the range of from 250 to 600° C, preferably at a temperature in the range of from 400 to 500° C.
8. The process according to any one or more of the preceding claims, whereby in case phenol is reacted with methanol, the molar ratio of phenol to methanol is in the range of from 1 :3 to 1 :30.
9. The process according to any one or more of the preceding claims, whereby in case o-cresol is reacted with methanol, the molar ratio of o-cresol to methanol is in the range of from 1 :2 to 1 :30.
10. The process according to any of the preceding claims, whereby in case 2,6- xylenol is reacted with methanol, the molar ratio of 2,6-xylenol to methanol is in the range of from 1 : 1 to 1 :20.
1 1 . The process according to any of the preceding claims, whereby water is present during the reaction.
12. The process according to claim 1 1 , whereby the molar amount of water is at most 20 times the molar amount of phenol, o-cresol and 2,6-xylenol, respectively.
PCT/EP2015/064050 2014-06-24 2015-06-23 Manufacture of 2,4,6-trimethylphenol WO2015197586A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP14173672.8 2014-06-24
EP14173672 2014-06-24

Publications (1)

Publication Number Publication Date
WO2015197586A1 true WO2015197586A1 (en) 2015-12-30

Family

ID=50980962

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2015/064050 WO2015197586A1 (en) 2014-06-24 2015-06-23 Manufacture of 2,4,6-trimethylphenol

Country Status (1)

Country Link
WO (1) WO2015197586A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3418379A (en) * 1965-02-12 1968-12-24 Dow Chemical Co Alkylation process
GB1451091A (en) * 1973-10-04 1976-09-29 Teijin Ltd Preparation of 2,4,6-trimethylphenol
EP0019476A2 (en) * 1979-05-16 1980-11-26 Mitsui Petrochemical Industries, Ltd. Catalyst and process for producing ortho-methyl substituted phenols using it
US5245089A (en) * 1992-10-23 1993-09-14 Eastman Kodak Company Alkylation reactions catalyzed by gallium-modified titanium dioxide
US5371306A (en) * 1992-12-31 1994-12-06 Korea Advanced Institute Of Science And Technology Modified magnesium oxide catalyst

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3418379A (en) * 1965-02-12 1968-12-24 Dow Chemical Co Alkylation process
GB1451091A (en) * 1973-10-04 1976-09-29 Teijin Ltd Preparation of 2,4,6-trimethylphenol
EP0019476A2 (en) * 1979-05-16 1980-11-26 Mitsui Petrochemical Industries, Ltd. Catalyst and process for producing ortho-methyl substituted phenols using it
US5245089A (en) * 1992-10-23 1993-09-14 Eastman Kodak Company Alkylation reactions catalyzed by gallium-modified titanium dioxide
US5371306A (en) * 1992-12-31 1994-12-06 Korea Advanced Institute Of Science And Technology Modified magnesium oxide catalyst

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JYH-HARNG KE ET AL: "Ortho-Alkylation of Phenol with Methanol Using Pb-Cr Promoted Magnesium Oxide Catalysts", JOURNAL OF THE CHINESE CHEMICAL SOCIETY, vol. 51, no. 6, 1 December 2004 (2004-12-01), pages 1407 - 1410, XP055209472, ISSN: 0009-4536, DOI: 10.1002/jccs.200400206 *
WON CHOON CHOI ET AL: "Balancing acidity and basicity for highly selective and stable modified MgO catalysts in the alkylation of phenol with methanol", CATALYSIS TODAY, vol. 63, no. 2-4, 1 December 2000 (2000-12-01), pages 229 - 236, XP055209419, ISSN: 0920-5861, DOI: 10.1016/S0920-5861(00)00464-8 *

Similar Documents

Publication Publication Date Title
US8907136B2 (en) Catalysts and methods for alcohol dehydration
CN111659377A (en) Carbonylation catalyst for high-selectivity synthesis of dimethyl carbonate, preparation and application thereof
WO2013181237A1 (en) Catalytic dehydration of aryl alcohols to diaryl ethers
WO2015197586A1 (en) Manufacture of 2,4,6-trimethylphenol
WO2013181238A1 (en) Catalytic dehydration of aryl alcohols to diaryl ethers
WO2015197587A1 (en) Manufacture of o-cresol
JP3225564B2 (en) Manufacturing method of aluminum alkoxide
CN109092295B (en) Isopropyl benzene catalyst and preparation method thereof
CN105008051A (en) Catalysts and methods for alcohol dehydration
CN106102904A (en) The method for preparation with the catalyst of the intensity of rising and the volume contraction of reduction
EP3549907A1 (en) Method of producing chlorine via hydrogen chloride oxidation
CN104582837A (en) Catalysts and methods for alcohol dehydration
WO2015197585A1 (en) Novel methylation catalysts
JPS58166936A (en) Catalyst for producing carboxylic ester and use thereof
CN109092300B (en) Catalyst for preparing isopropyl benzene by hydrogenation
CN109096029B (en) Preparation method of isopropyl benzene
CN109092301B (en) Catalyst for preparing isopropyl benzene and preparation method thereof
EP0126552A2 (en) Process for producing carbonyl compounds
EP2644586B1 (en) Process for preparing adamantane polyol
CN104602807B (en) Catalyst And Method for dehydration of alcohols
US6392066B1 (en) Epoxidation of olefins using lanthanide-promoted silver catalysts
JP4753175B2 (en) Carbon-carbon coupling method using high temperature and high pressure water
CN113527048A (en) Process for isomerizing transHFO-1234 ze and catalyst support therefor
CN111072745A (en) Preparation method of 6-methylene-7-ketocholic acid
US20160096792A1 (en) Catalysts and methods for alcohol dehydration

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15732211

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15732211

Country of ref document: EP

Kind code of ref document: A1