JPWO2020183193A5

JPWO2020183193A5 -

Info

Publication number: JPWO2020183193A5
Application number: JP2021554664A
Authority: JP
Publication date: 2023-03-20

Claims

A method for producing a catalyst, comprising:
a) providing an uncalcined metal-modified porous silica support, wherein the modifier metal is selected from one or more of boron, magnesium, aluminum, zirconium, hafnium and titanium; the agent metal is present in a mononuclear or binuclear modifier metal moiety;
b) optionally removing solvent or liquid carrier from said modified silica support;
c) optionally drying the modified silica support;
d) treating the uncalcined metal-modified silica support with a catalytic metal, resulting in adsorption of the catalytic metal onto the metal-modified silica support;
e) calcining the impregnated silica support of step d).

An uncalcined catalytic intermediate comprising an uncalcined porous silica support modified with modifier metals, wherein said modifier metals are boron, magnesium, aluminum, zirconium, hafnium and titanium wherein said modifier metal is present in mononuclear or binuclear modifier metal moieties and catalyst metals adsorbed on said uncalcined modified silica support , the uncalcined catalytic intermediate.

A method of producing a catalyst, comprising:
a) providing a porous silica support having isolated silanol groups;
b) treating the porous silica support with a mononuclear or multinuclear modifier metal compound such that the modifier metal is adsorbed onto the surface of the silica support by reaction with the isolated silanol groups; wherein the adsorbed modifier metal atoms are sufficiently spaced from each other to substantially prevent their oligomerization with adjacent modifier metal atoms before, preferably after calcination, and Preferably, they are sufficiently spaced from each other to substantially prevent their dimerization or trimerization with their adjacent modifier metal atoms, wherein said modifier metals are boron, magnesium , aluminum, zirconium, hafnium and titanium;
c) optionally removing the solvent or liquid carrier from the modified silica support;
d) optionally drying the modified silica support;
e) treating an uncalcined modified silica support with a catalytic metal to result in adsorption of said catalytic metal onto said modified silica support;
f) calcining the impregnated silica support of step e).

The method of claim 1, wherein the modifier metal modified porous silica support is a modifier metal oxide-silica co-gel support.

3. The uncalcined catalytic intermediate of claim 2, comprising a porous modifier metal oxide-silica cogel support.

6. A catalyst comprising the intermediate of claim 2 or 5, wherein said uncalcined intermediate has been calcined.

Said calcination step is carried out at a temperature of at least 450°C, more preferably at least 475°C, most preferably at least 500°C, especially at least 600°C, more especially above 700°C and/or typically wherein the calcination temperature ranges from 400 to 1000°C, more typically from 500 to 900°C, most typically from 600 to 850°C. A method or catalyst according to any one of the preceding claims.

Process or catalyst or catalyst intermediate according to any one of the preceding claims, wherein said silica support is a hydrogel or xerogel , more preferably a xerogel.

the modifier metal is adsorbed onto the silica support surface, typically chemisorbed or physisorbed onto the silica support surface, more typically an adsorbate chemisorbed thereon; The process or catalyst or catalyst intermediate according to any one of claims 1-3 or 6-8 , wherein

Process or catalyst or catalyst intermediate according to any one of the preceding claims, wherein said modifier metal is selected from zirconium, hafnium or titanium , typically titanium.

Process or catalyst or catalyst according to any one of the preceding claims, wherein said catalytic metal is typically an alkali metal selected from cesium, potassium or rubidium , more typically cesium Intermediate.

12. The method or catalyst or catalyst intermediate of any one of claims 1 to 11 , wherein said silica support comprises said modifier metal at a level of <5 metal atoms per ^nm2 .

13. Any one of claims 1 to 12 , wherein at least 25% of the modifier metal on the support before or after catalytic metal calcination is present in the form of mononuclear or binuclear modifier metal moieties. process or catalyst or catalyst intermediate of

Adsorbed or co-gelled modifier metal cations are used in subsequent processing steps, such as impregnation of the catalyst metal and/or its oligomerization during calcination, more preferably with its adjacent modifier metal cations. 14. The process or catalyst or catalyst intermediate of any one of claims 1-13 , which are sufficiently separated from each other to substantially prevent dimerization, trimerization or oligomerization.

15. The process or catalyst or catalytic intermediate of any one of claims 1 to 14 , wherein said silica support comprises isolated silanol groups (-SiOH) at a level of <2.5 groups per ^nm2 . body.

said carriers at a level of >0.025 and <2.5 groups per ^nm2 , more preferably at a level of 0.05 to 1.5, most preferably 0.1 per ^nm2 ; 16. The method or catalyst or catalyst intermediate of any one of claims 1 to 15 , comprising said modifier metal moieties at a level of ∼1.0 moieties.

The silica component of the modified silica support is typically 80-99.9% by weight of the modified support, more typically 85-99.8% by weight, most typically Process or catalyst or catalyst intermediate according to any one of claims 1 to 16 , capable of forming 90-99.7% by weight.

Process or catalyst or catalyst intermediate according to any one of the preceding claims, wherein said silica support has an average pore size of 2-1000 nm, more preferably 3-500 nm, most preferably 5-250 nm. .

The catalytic metal is an adsorbate adsorbed onto the modified silica support surface of the catalyst, and typically the adsorbate is chemisorbed or physisorbed onto the modified silica support surface. The process or catalyst or catalyst intermediate according to any one of claims 1 to 18 , which may be, more typically chemisorbed thereon.

The catalyst metal, e.g. cesium, is at least 1 mol/100 (silicon + modifier metal) mol, more preferably at least 1.5 mol/100 (silicon + modifier metal) mol, most preferably at least can be present in the catalyst at a level of 2 mol/100 (silicon + modifier metal) mol and/or the level of catalytic metal is up to 10 mol/100 (silicon + modifier metal) mol, more preferably said catalyst 20. According to any one of claims 1 to 19 , up to 7.5 mol/100 (silicon + modifier metal) mol, most preferably up to 5 mol/100 (silicon + modifier metal) mol in Process or catalyst or catalyst intermediate.

The molar ratio of said catalyst metal:modifier metal in said catalyst is at least 1.4 or 1.5:1 and/or preferably between 1.4 and 5:1, such as between 1.5 and 4 :1, in particular in the range 1.5 to 3.6:1, typically for which said catalytic metal is cesium . Process or catalyst or catalyst intermediate.

said catalyst metal ranges from 0.5 to 7.0 mol/mol modifier metal, more preferably from 1.0 to 6.0 mol/mol, most preferably from 1.5 to 5.0 mol/mol modifier metal A process or catalyst or catalytic intermediate according to any one of claims 1 to 21 , which is present in

The level of catalytic metal in said catalyst is from 1 to 10 mol/100 (silicon + modifier metal) mol in said catalyst, more preferably from 2 to 8 mol/100 (silicon + modifier metal) mol, most preferably 23. The process or catalyst or catalyst intermediate of any one of claims 1 to 22 in the range of 2.5-6 mol/100 (silicon + modifier metal) mol.

Modifier metal levels between 0.067×10 ⁻² and 7.3×10 ⁻² mol/mol silica, more preferably between 0.13×10 ⁻² and 5.7×10 ⁻² mol/mol silica , most preferably 0.2×10 ⁻² to 3.5 ×10 ⁻² mol/mol silica.

Claim that the average pore volume of the catalyst particles can be less than 0.1 cm ³ /g, but is generally in the range of 0.1 to 5 cm ³ /g as measured by fluid, e.g. water, uptake. 25. Process or catalyst or catalyst intermediate according to any one of claims 1 to 24 .

A catalyst obtainable by the process according to any one of claims 1-25 .

A method of producing an ethylenically unsaturated carboxylic acid or ester, typically an α,β ethylenically unsaturated carboxylic acid or ester, comprising forming formaldehyde in the presence of a catalyst and optionally in the presence of an alcohol. or a suitable source thereof and a carboxylic acid or ester, wherein said catalyst is as claimed in any one of claims 6-26 .

A process for preparing an ethylenically unsaturated acid or ester, in the presence of a catalyst according to any one of claims 6 to 26 and optionally in the presence of an alkanol, of formula R ¹ - an alkanoic acid or ester of CH ₂ —COOR ³ and formaldehyde or a suitable source of formaldehyde of formula (I) as defined below

(wherein R5 is methyl and R6 is H;
X is O;
m is 1;
n is any value from 1 to 20), or any mixture thereof;
wherein R1 is hydrogen or an alkyl group having 1 to 12, more suitably 1 to 8, most suitably 1 to 4 carbon atoms, and R3 is also independently It can be hydrogen or an alkyl group having 1 to 12, more suitably 1 to 8 and most suitably 1 to 4 carbon atoms.

Said carboxylic acid or ester or respectively ester or acid of formula R ¹ -CH ₂ -COOR ³ is methyl propionate or propionic acid, typically the optional alkanol is methanol and ethylenically unsaturated 29. A method according to claim 27 or 28 , wherein the carboxylic acid or ester is methyl methacrylate or methacrylic acid.

30. The method or catalyst or catalyst intermediate of any one of claims 1 to 29 , wherein said moieties are uniformly distributed over the surface of said silica support.