WO2015197585A1 - Novel methylation catalysts - Google Patents

Novel methylation catalysts Download PDF

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Publication number
WO2015197585A1
WO2015197585A1 PCT/EP2015/064049 EP2015064049W WO2015197585A1 WO 2015197585 A1 WO2015197585 A1 WO 2015197585A1 EP 2015064049 W EP2015064049 W EP 2015064049W WO 2015197585 A1 WO2015197585 A1 WO 2015197585A1
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Prior art keywords
methylation
xylenol
cresol
oxide
catalyst
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French (fr)
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Werner Bonrath
Jan Schuetz
Fabrizio Cavani
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DSM IP Assets BV
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DSM IP Assets BV
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • 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 methylation catalysts comprising gallium oxide, which preferably further contain magnesium oxide.
  • the methylation 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 present invention is further directed to the use of such catalysts for the methylation of phenol and its methylated derivatives having one or two methyl groups such as o-cresol, m-cresol, p-cresol, 2,3- xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol and 3,5-xylenol.
  • the methylation catalyst comprises gallium oxide.
  • the methylation catalyst further comprises magnesium oxide.
  • the present invention is also directed to a methylation catalyst comprising gallium oxide and magnesium oxide.
  • gallium oxide and magnesium oxide also encompasses mixed oxides of gallium and magnesium, as well as any mixture of Ga 2 0 3 and MgO, and mixtures of any modifications thereof. These (mixed) oxides of gallium and magnesium do not have a spinel structure.
  • the methylation 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 methylation catalyst.
  • the methylation 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 methylation catalyst.
  • the weight-ratio of magnesium to gallium is 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 methylation 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.
  • the methylation 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.
  • 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
  • step d) filtering the solution obtained in step c) to obtain the solid methylation catalyst
  • step d) washing the solid methylation catalyst obtained in step d) with water;
  • step f) calcinating the dried solid methylation 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 HN0 3 .
  • Other acids may also be suitable, if other salts of Ga and Mg are used. Thus, it is e.g.
  • 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.
  • 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.
  • 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.
  • the calcination is carried out at 450 °C for 8 hours.
  • the present invention is also directed to the use of the methylation catalysts as described above for the methylation of a compound selected from the group consisting of phenol and its methylated derivatives having one or two methyl groups.
  • methylated phenol derivatives with one methyl group are ortho- cresol (o-cresol), meta-cresol (m-cresol) and para-cresol (p-cresol).
  • methylated phenol derivatives with two methyl groups are 2,3- xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol and 3,5-xylenol.
  • methylation reactions which may be catalyzed by the methylation catalysts according to the present invention as described above are: Methylation of phenol to o-cresol (see examples 1 -3),
  • preferred starting materials are phenol, o-cresol and 2,6-xylenol.
  • methylation reactions which may be catalyzed by the methylation catalysts according to the present invention as described above are: Methylation of m-cresol to 2,5-xylenol (the reaction conditions are similar to the methylation of o-cresol to 2,6-xylenol),
  • the reaction conditions are similar to the methylation of phenol to 2,6-xylenol.
  • the single methylation reactions are now described in more detail below.
  • 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 preferred methylation catalyst has a molar magnesium to gallium ratio in the range of from 0 : 1 to 10 : 1 , more preferably the molar magnesium to gallium ratio is 0 : 1.
  • the preferred temperature is in the range of from 350 to 450° C, preferably the temperature is around 400° C.
  • the pressure is in the range of from 1 to 10 bara (bar absolute), more preferably it is 1 bara.
  • the molar ratio of methanol to water to phenol is (2 to 5) : (0 to 5) : 1 , preferably the molar ratio is 10 : 0 : 1.
  • the preferred methylation catalyst has a molar magnesium to gallium ratio in the range of from 0 : 1 to 10 : 1 , more preferably the molar magnesium to gallium ratio is 0 : 1.
  • the preferred temperature is in the range of from 350 to 500° C, preferably the temperature is in the range of 400 to 450° C.
  • the pressure is in the range of from 1 to 10 bara (bar absolute), more preferably it is 1 bara.
  • the molar ratio of methanol to water to phenol is (3 to 15) : (0 to 5) : 1 , preferably the molar ratio is 10 : 0 : 1.
  • the preferred methylation catalyst has a molar magnesium to gallium ratio in the range of from 2 : 1 to 10 : 1 , more preferably the molar magnesium to gallium ratio is 10 : 1.
  • the preferred temperature is in the range of from 350 to 500° C, preferably the temperature is around 450° C.
  • the pressure is in the range of from 1 to 10 bara (bar absolute), more preferably it is 1 bara.
  • the molar ratio of methanol to water to phenol is (4 to 15) : (0 to 5) : 1 , preferably the molar ratio is 5 : 0 : 1.
  • the preferred methylation catalyst has a molar magnesium to gallium ratio in the range of from 0 : 1 to 10 : 1 , more preferably the molar magnesium to gallium ratio is 0 : 1.
  • the preferred temperature is in the range of from 300 to 450° C, preferably the temperature is in the range of from 350 to 400° C.
  • the pressure is in the range of from 1 to 10 bara (bar absolute), more preferably it is 1 bara.
  • the molar ratio of methanol to water to o-cresol is (2 to 15) : (0 to 7) : 1 , preferably the molar ratio is 5 : 0 : 1. Methylation of o-cresol to 2,4,6-trimethy pheno
  • the preferred methylation catalyst has a molar magnesium to gallium ratio in the range of from 2 : 1 to 6 : 1 , more preferably the molar magnesium to gallium ratio is 2 : 1.
  • the preferred temperature is in the range of from 300 to 400° C, preferably the temperature is around 350° C.
  • the pressure is in the range of from 1 to 10 bara (bar absolute), more preferably it is 1 bara.
  • the molar ratio of methanol to water to o-cresol is (3 to 15) : (0 to 5) : 1 , preferably the molar ratio is 5 : 5 : 1.
  • the preferred methylation catalyst has a molar magnesium to gallium ratio in the range of from 2 : 1 to 10 : 1 , more preferably the molar magnesium to gallium ratio is 10 : 1.
  • the preferred temperature is in the range of from 350 to 450° C, preferably the temperature is around 400 °C.
  • the pressure is in the range of from 1 to 10 bara (bar absolute), more preferably it is 1 bara.
  • the molar ratio of methanol to water to 2,6-xylenol is (2 to 15) : (0 to 5) : 1 , preferably the molar ratio is 5 : 5 : 1.
  • 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 3 Use of a Mg-Ga-oxide-catalyst with a weight ratio of M3 ⁇ 4 to Ga of 10 to 1
  • Example 4 Use of a Mg-Ga-oxide-catalyst with a weight ratio of M3 ⁇ 4 to Ga of 10 to 1
  • Example 7 Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 2 to 1
  • Example 8 Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 10 to 1
  • Example 9 Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 10 to 1
  • Example 10 Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 10 to 1
  • Example 11 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 2 to 1
  • Example 1 Use of Ga O j as catalyst
  • Example 15 Use of Ga?O j as catalyst
  • Example 16 Use of a Mg-Ga-oxide-catalvst with a weight ratio of Mg to Ga of 2 to 1
  • Example 17 Use of a Mg-Ga-oxide-catalvst with a weight ratio of Mg to Ga of 2 to 1
  • Example 18 Use of a Mg-Ga-oxide-catalvst with a weight ratio of Mg to Ga of 2 to 1
  • Example 19 Use of a Mg-Ga-oxide-catalvst with a weight ratio of Mg to Ga of 2 to 1
  • Example 20 Use of a Mg-Ga-oxide-catalvst with a weight ratio of Mg to Ga of 6 to 1
  • Example 21 Use of a Mg-Ga-oxide-catalvst with a weight ratio of Mg to Ga of 6 to 1
  • Example 22 Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 10 to 1
  • Example 23 Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 2 to 1
  • Example 24 Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 2 to 1
  • Example 25 Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 6 to 1
  • Example 27 Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 2 to 1
  • Example 28 Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 6 to 1
  • Example 29 Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 10 to 1
  • Example 30 Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 10 to 1
  • Example 31 Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 10 to 1
  • Example 32 Use of a Mg-Ga-oxide-cata yst with a weight ratio of Mg to Ga of 10 to 1
  • Mg(N0 3 ) 2 25.8 g of Mg(N0 3 ) 2 are dissolved in 1 10 mL of water, together with an amount of Ga in the form of Ga(N0 3 ) 3 necessary to obtain the desired Mg/Ga ratio.
  • the amount of Ga salt is 2.57 g.

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Abstract

The present invention is directed to methylation catalysts comprising gallium oxide, which preferably further contain magnesium oxide. In a preferred embodiment of the present invention, the methylation catalyst consists of gallium oxide and magnesium oxide. The present invention is further directed to the use of such catalysts for the methylation of phenol and its methylated derivatives having one or two methyl groups such as o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol and 3,5-xylenol.

Description

Novel methylation catalysts
The present invention is directed to methylation catalysts comprising gallium oxide, which preferably further contain magnesium oxide. In a preferred embodiment of the present invention, the methylation 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 present invention is further directed to the use of such catalysts for the methylation of phenol and its methylated derivatives having one or two methyl groups such as o-cresol, m-cresol, p-cresol, 2,3- xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol and 3,5-xylenol.
The invention is now described in more detail below. Methylation catalyst
In an embodiment of the present invention the methylation catalyst comprises gallium oxide.
In a preferred embodiment of this embodiment the methylation catalyst further comprises magnesium oxide. Thus, the present invention is also directed to a methylation catalyst comprising gallium oxide and magnesium oxide. The term "gallium oxide and magnesium oxide" also encompasses mixed oxides of gallium and magnesium, as well as any mixture of Ga203 and MgO, and mixtures of any modifications thereof. These (mixed) oxides of gallium and magnesium do not have a spinel structure. ln a further embodiment of the present invention the methylation 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 methylation catalyst. In another embodiment of the present invention the methylation 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 methylation catalyst.
In preferred embodiments of the methylation catalysts either comprising gallium oxide/s and magnesium oxide/s or consisting of gallium oxide/s and magnesium oxide/s the weight-ratio of magnesium to gallium is in the range of from 1 : 1 to 15:1. Especially preferred are those methylation catalysts where the weight- ratio of magnesium to gallium is either 2 : 1 or 6 : 1 or 10 : 1.
In a preferred embodiment of the present invention the methylation 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 methylation 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 methylation 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 methylation catalyst;
e) washing the solid methylation catalyst obtained in step d) with water;
f) drying the solid methylation catalyst obtained in step e);
g) calcinating the dried solid methylation 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 HN03. 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.
Use of the methylation catalysts
The present invention is also directed to the use of the methylation catalysts as described above for the methylation of a compound selected from the group consisting of phenol and its methylated derivatives having one or two methyl groups. Examples of methylated phenol derivatives with one methyl group are ortho- cresol (o-cresol), meta-cresol (m-cresol) and para-cresol (p-cresol).
Examples of methylated phenol derivatives with two methyl groups are 2,3- xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol and 3,5-xylenol.
Preferred examples of methylation reactions which may be catalyzed by the methylation catalysts according to the present invention as described above are: Methylation of phenol to o-cresol (see examples 1 -3),
methylation of phenol to 2,6-xylenol (see examples 4-8), methylation of phenol to 2,4,6-trimethylphenol (see examples 9-12),
methylation of o-cresol to 2,6-xylenol (see examples 13-22),
methylation of o-cresol to 2,4,6-trimethylphenol (see examples 23-25), and methylation of 2,6-xylenol to 2,4,6-trimethylphenol (see examples 26-32).
Thus, preferred starting materials are phenol, o-cresol and 2,6-xylenol.
Further examples of methylation reactions which may be catalyzed by the methylation catalysts according to the present invention as described above are: Methylation of m-cresol to 2,5-xylenol (the reaction conditions are similar to the methylation of o-cresol to 2,6-xylenol),
methylation of m-cresol to 2,3-xylenol (the reaction conditions are similar to the methylation of o-cresol to 2,6-xylenol),
methylation of m-cresol to 2,3,6-trimethylphenol (the reaction conditions are similar to the methylation of o-cresol to 2,4,6-trimethylphenol),
methylation of p-cresol to 2,4-xylenol (the reaction conditions are similar to the methylation of o-cresol to 2,6-xylenol),
methylation of p-cresol to 2,4,6-trimethylphenol (the reaction conditions are similar to the methylation of o-cresol to 2,4,6-trimethylphenol),
methylation of 2,3-xylenol to 2,3,6-trimethylphenol (the reaction conditions are similar to the methylation of o-cresol to 2,6-xylenol),
methylation of 2,4-xylenol to 2,4,6-trimethylphenol (the reaction conditions are similar to the methylation of o-cresol to 2,6-xylenol),
methylation of 2,5-xylenol to 2,3,6-trimethylphenol (the reaction conditions are similar to the methylation of m-cresol to 2,3-xylenol),
methylation of 3,5-xylenol to 2,3,5-trimethylphenol (the reaction conditions are similar to the methylation of m-cresol to 2,3-xylenol),
methylation of 3,5-xylenol to 2,3,5,6-tetramethylphenol (the reaction conditions are similar to the methylation of phenol to 2,6-xylenol). The single methylation reactions 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.
Methylation of phenol to o-cresol
The preferred methylation catalyst has a molar magnesium to gallium ratio in the range of from 0 : 1 to 10 : 1 , more preferably the molar magnesium to gallium ratio is 0 : 1.
The preferred temperature is in the range of from 350 to 450° C, preferably the temperature is around 400° C. Preferably the pressure is in the range of from 1 to 10 bara (bar absolute), more preferably it is 1 bara. The molar ratio of methanol to water to phenol is (2 to 5) : (0 to 5) : 1 , preferably the molar ratio is 10 : 0 : 1.
Methylation of phenol to 2,6-xylenol
The preferred methylation catalyst has a molar magnesium to gallium ratio in the range of from 0 : 1 to 10 : 1 , more preferably the molar magnesium to gallium ratio is 0 : 1.
The preferred temperature is in the range of from 350 to 500° C, preferably the temperature is in the range of 400 to 450° C. Preferably the pressure is in the range of from 1 to 10 bara (bar absolute), more preferably it is 1 bara.
The molar ratio of methanol to water to phenol is (3 to 15) : (0 to 5) : 1 , preferably the molar ratio is 10 : 0 : 1. Methylation of phenol to 2,4,6-trimethylphenol
The preferred methylation catalyst has a molar magnesium to gallium ratio in the range of from 2 : 1 to 10 : 1 , more preferably the molar magnesium to gallium ratio is 10 : 1.
The preferred temperature is in the range of from 350 to 500° C, preferably the temperature is around 450° C. Preferably the pressure is in the range of from 1 to 10 bara (bar absolute), more preferably it is 1 bara.
The molar ratio of methanol to water to phenol is (4 to 15) : (0 to 5) : 1 , preferably the molar ratio is 5 : 0 : 1.
Methylation of o-cresol to 2,6-xylenol
The preferred methylation catalyst has a molar magnesium to gallium ratio in the range of from 0 : 1 to 10 : 1 , more preferably the molar magnesium to gallium ratio is 0 : 1.
The preferred temperature is in the range of from 300 to 450° C, preferably the temperature is in the range of from 350 to 400° C. Preferably the pressure is in the range of from 1 to 10 bara (bar absolute), more preferably it is 1 bara. The molar ratio of methanol to water to o-cresol is (2 to 15) : (0 to 7) : 1 , preferably the molar ratio is 5 : 0 : 1. Methylation of o-cresol to 2,4,6-trimethy pheno
The preferred methylation catalyst has a molar magnesium to gallium ratio in the range of from 2 : 1 to 6 : 1 , more preferably the molar magnesium to gallium ratio is 2 : 1.
The preferred temperature is in the range of from 300 to 400° C, preferably the temperature is around 350° C. Preferably the pressure is in the range of from 1 to 10 bara (bar absolute), more preferably it is 1 bara. The molar ratio of methanol to water to o-cresol is (3 to 15) : (0 to 5) : 1 , preferably the molar ratio is 5 : 5 : 1.
Methylation of 2,6-xylenol to 2,4,6-trimethylphenol
The preferred methylation catalyst has a molar magnesium to gallium ratio in the range of from 2 : 1 to 10 : 1 , more preferably the molar magnesium to gallium ratio is 10 : 1.
The preferred temperature is in the range of from 350 to 450° C, preferably the temperature is around 400 °C. Preferably the pressure is in the range of from 1 to 10 bara (bar absolute), more preferably it is 1 bara.
The molar ratio of methanol to water to 2,6-xylenol is (2 to 15) : (0 to 5) : 1 , preferably the molar ratio is 5 : 5 : 1.
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 -3: Methylation of phenol to o-cresol
Example 1 : Use of Ga^Ch as catalyst
Selectivity = 86%
Conversion = 38%
Catalyst: Ga203 Feed: Phenol/Methanol (1:10) (molar ratio)
T = 400°C
Example 2: Use of Ga^Ch as catalyst
Selectivity: 66%
Conversion: 59%
Feed: MeOH/Phenol = 10: 1 (molar ratio)
Temperature: 400 °C Example 3: Use of a Mg-Ga-oxide-catalyst with a weight ratio of M¾ to Ga of 10 to 1
Selectivity: 54%
Conversion: 9%
Feed: MeOH /water/ Phenol = 10: 5 : 1 (molar ratio)
Temperature: 400° C
Examples 4-8: Methylation of phenol to 2,6-xylenol
Example 4: Use of a Mg-Ga-oxide-catalyst with a weight ratio of M¾ to Ga of 10 to 1
Selectivity: 89%
Conversion: 99%
Feed: MeOH/Phenol = 10: 1 (molar ratio)
Temperature: 500° C
Example 5: Use of Ga^Ch as catalyst
Selectivity: 64%
Conversion: 96%
Feed: MeOH/Phenol = 10: 1 (molar ratio) Temperature: 400 °C
Figure imgf000013_0001
Selectivity: 64%
Conversion: 90%
Feed: MeOH/Phenol = 10 : 1 (molar ratio)
Temperature: 450° C
Example 7: Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 2 to 1
Selectivity: 60%
Conversion: 91%
Feed: MeOH/Phenol = 10 : 1 (molar ratio)
Temperature: 400 °C
Example 8: Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 10 to 1
Selectivity: 59%
Conversion: 89%
Feed: MeOH/Phenol = 10 : 1 (molar ratio)
Temperature: 400 °C
Examples 9-12: Methylation of phenol to 2,4,6-trimethylphenol
Example 9: Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 10 to 1
Selectivity: 79%
Conversion: 100%
Feed: MeOH/Phenol = 5 : 1 (molar ratio) Temperature: 450° C
Example 10: Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 10 to 1
Selectivity: 62%
Conversion: 100%
Feed: MeOH /water/ Phenol = 10 : 5 : 1 (molar ratio)
Temperature: 410°C Example 11 : 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 12: 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 13-22: Methylation of o-creso to 2,6-xylenol
Example 13: Use of Ga^Ch as catalyst
Selectivity: 93%
Conversion: 18%
Feed: o-cresol/MeOH = 1 : 5 (molar ratio) Temperature: 350° C
Example 1 : Use of Ga Oj as catalyst
Selectivity: 91 %
Conversion: 37%
Feed: o-cresol/MeOH = 1 : 5 (molar ratio)
Temperature: 350° C
Example 15: Use of Ga?Oj as catalyst
Selectivity: 89%
Conversion: 25%
Feed: o-cresol/water/MeOH = 1 : 5 : 5 (molar ratio)
Temperature: 350° C
Example 16: Use of a Mg-Ga-oxide-catalvst with a weight ratio of Mg to Ga of 2 to 1
Selectivity: 92%
Conversion: 37%
Feed: o-cresol/MeOH = 1 : 5 (molar ratio)
Temperature: 350° C
Example 17: Use of a Mg-Ga-oxide-catalvst with a weight ratio of Mg to Ga of 2 to 1
Selectivity: 77%
Conversion: 67%
Feed: o-cresol/MeOH = 1 : 5 (molar ratio)
Temperature: 350° C Example 18: Use of a Mg-Ga-oxide-catalvst with a weight ratio of Mg to Ga of 2 to 1
Selectivity: 69%
Conversion: 60%
Feed: o-cresol/water/MeOH = 1 : 5 : 5 (molar ratio)
Temperature: 350° C
Example 19: Use of a Mg-Ga-oxide-catalvst with a weight ratio of Mg to Ga of 2 to 1
Selectivity: 67%
Conversion: 100%
Feed: o-cresol/water/MeOH = 1 : 5 : 5 (molar ratio)
Temperature: 400 °C Example 20: Use of a Mg-Ga-oxide-catalvst with a weight ratio of Mg to Ga of 6 to 1
Selectivity: 83%
Conversion: 45%
Feed: o-cresol/MeOH = 1 : 5 (molar ratio)
Temperature: 350T
Example 21 : Use of a Mg-Ga-oxide-catalvst with a weight ratio of Mg to Ga of 6 to 1
Selectivity: 63%
Conversion: 49%
Feed: o-cresol/water/MeOH = 1 : 5 : 5 (molar ratio)
Temperature: 350° C Example 22: Use of a Mg-Ga-oxide-catalyst with a weight ratio of Mg to Ga of 10 to 1
Selectivity: 86%
Conversion: 37%
Feed: o-cresol/MeOH = 1 : 5 (molar ratio)
Temperature: 350° C
Examples 23-25: Methylation of o-cresol to 2,4,6-trimethylphenol
Example 23: 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 24: 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 25: 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 = 1 : 5 : 5 (molar ratio)
Temperature: 350° C Examples 26-32: Methylation of 2,6-xylenol to 2.4,6-trimethylphenol
Example 26: Use of Ga2C>3 as catalyst
Selectivity: 66%
Conversion: 8%
Feed: 2,6-xylenol/water/MeOH = 1 : 5 : 5 (molar ratio)
Temperature: 400 °C
Example 27: 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 28: 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 29: 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 30: 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 31 : 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 32: Use of a Mg-Ga-oxide-cata yst 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
Example 33: Preparation of the catalysts
25.8 g of Mg(N03)2 are dissolved in 1 10 mL of water, together with an amount of Ga in the form of Ga(N03)3 necessary to obtain the desired Mg/Ga ratio. For example, for the catalyst with Mg/Ga 10/ 1 , the amount of Ga salt is 2.57 g.
Separately, 3.14 g of Na2C03 are dissolved in water, to prepare 20 ml of a second solution 1 M, and containing an overall amount of Na2C03 which corresponds to a number of moles 5 times the number of Ga+Mg moles. The pH of this latter solution is eventually adjusted to the value of 8.5 by means of concentrated HN03. Then the first solution is dropped into the second one, while keeping the pH at 8.5 and the temperature at 50-60° C; the pH is adjusted with concentrated NaOH. Then the solution is left under stirring for 30-45 min. The slurry is then filtered with a buchner, and the solid is then washed with abundant water until the elution water shows a pH about 7. The solid is then dried at 120° C for 4 h or at 1 10° C overnight. Then the dried solid is calcined in air for 8h at 450° C, in order to decompose the precursor and form the Mg/Ga mixed oxide.

Claims

Claims
1 . A methylation catalyst comprising gallium oxide.
2. The methylation catalyst according to claim 1 further comprising magnesium oxide.
3. The methylation catalyst according to claim 2 comprising mixed gallium and magnesium oxides.
4. The methylation catalyst according to claim 1 consisting of gallium oxide.
5. The methylation catalyst according to claim 4 neither containing titanium oxide nor indium oxide.
6. The methylation catalyst according to claim 2 or 3 consisting of gallium oxides and magnesium oxides.
7. The methylation catalyst according to claim 2, 3 or 6, whereby the weight- ratio of magnesium to gallium is in the range of from 1 : 1 to 15: 1 .
8. The methylation catalyst according to any one or more of the preceding claims, wherein the methylation catalyst does not contain iron oxide(s).
9. The methylation catalyst according to any one or more of the preceding claims, wherein the methylation catalyst is for the methylation of phenol and its methylated derivatives having one or two methyl groups, preferably wherein the methylation catalyst is for the methylation of phenol, o-cresol, m-cresol, p- cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol and 3,5-xylenol, more preferably wherein the methylation catalyst is for the methylation of phenol, o- cresol and 2,6-xylenol.
10. Use of the catalyst according to any one or more of the preceding claims for the methylation of a compound selected from the group consisting of phenol and its methylated derivatives having one or two methyl groups.
1 1 . The use according to claim 10, wherein the methylated derivative of phenol having one or two methyl groups is selected from the group consisting of o- cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol and 3,5-xylenol.
12. The use according to claim 10, wherein the compound is selected from the group consisting of phenol, o-cresol and 2,6-xylenol.
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