Mesoporous mixed oxide catalyst comprising silicon

Patent metadata

Field	Value
Publication number	US-11213802-B2
Application number	US-201615744106-A
Country	US
Kind code	B2
Filing date	Jul 5, 2016
Priority date	Jul 13, 2015
Publication date	Jan 4, 2022
Grant date	Jan 4, 2022

Abstract

A mesoporous mixed oxide catalyst that comprises silicon and at least one metal M that is selected from the group that consists of the elements of groups 4 and 5 of the periodic table and mixtures thereof, with the mass of metal M being between 0.1 and 20% of the mixed oxide mass.

First claim

The invention claimed is:

1. A catalyst comprising a mesoporous mixed oxide that comprises silicon and at least one metal M that is selected from the group consisting of tantalum, niobium, zirconium, and mixtures thereof, with the mass of metal M being between 0.1 and 20% of the mixed oxide mass, with said mixed oxide being a solid mixed oxide of both silicon and metal M, having M-O—Si bonds, said mixed oxide having a specific surface area of at least 600 m 2 /g, a pore volume of at least 1 ml/g and a mean diameter of the pores of between 4.5 and 17 nm, the specific surface area being a B.E.T. specific surface area that is determined by nitrogen adsorption in accordance with the ASTM D 3663-78 standard established from the BRUNAUER-EMMETT-TELLER method, the pore volume V corresponding to the volume that is observed for the partial pressure P/P 0 max of the nitrogen adsorption-desorption isotherm determined by the Barrett-Joyner-Halenda model, the diameter of the mesopores ϕ being determined by the formula 4000.V/S BET .

2. The catalyst according to claim 1 , further comprising a metal M′, with said metal M′ being a metal that is selected from the group consisting of the elements of groups 11 and 12 of the periodic table and mixtures thereof, with the mass of metal M′ being between 0.1 and 20% of the mixed oxide mass.

3. The catalyst according to claim 2 , in which said metal M′ is selected from the group consisting of silver, copper, zinc and mixtures thereof.

4. The catalyst according to claim 1 , in which said mixed oxide is mesostructured.

5. The catalyst according to claim 1 that is shaped in the form of balls, pellets, granules, or extrudates, or rings.

6. The catalyst according to claim 5 , further comprising at least one porous oxide material that has the role of a binder, with said porous oxide material being silica, magnesia, clays, titanium oxide, lanthanum oxide, cerium oxide, boron phosphates, or mixtures of at least two of the oxides.

7. A method for preparation of the catalyst according to claim 1 via metallo-organic modern sol-gel by precipitation/gelling that comprises at least the following:
(a) dissolution of at least one alkoxide precursor of formula Si(OR) 4-a R′ a , where R═H, methyl, ethyl and R′ is an alkyl chain or a functionalized alkyl chain of the element Si in aqueous, organic or aquo-organic medium, optionally in the presence of an acid or a base, so as to form an optionally colloidal solution,
(b) addition to the solution that is obtained during (a) of at least one precursor of the metal M, in the pure state or dissolved in a suitable medium with said solution that is obtained from the operation (a), such that said medium does not demix or precipitate when it is brought into contact with the solution obtained from (a) under the conditions of (b),
(c) precipitation of the Si-based mixed oxide, at least the metal M by the addition of an acid, a base, or by application of a specific reaction temperature,
(d) filtration followed by optional washing cycles or evaporation of the suspension that is obtained during (c),
(e) at least one heat treatment of mixed oxide that is obtained in (d) so as to obtain said catalyst.

8. The method for preparation of the catalyst according to claim 7 , in which said heat treatment (e) is drying followed by calcination, with said drying being carried out in an oven in a temperature range of 20 to 200° C. during a period of less than 72 hours, with said calcination being carried out in air in an oven in a temperature range of 300 to 800° C. during a period of less than 24 hours.

9. A process for the production of 1,3-butadiene from a feedstock that comprises at least ethanol, comprising contacting said feedstock with a catalyst according to claim 1 , at a temperature of between 300 and 400° C., a pressure of between 0.15 and 0.5 MPa, and a volumetric flow rate of between 0.5 and 5 h −1 .

10. The process according to claim 9 , in which the temperature is between 320° C. and 380° C.

11. The process according to claim 9 , in which the pressure is between 0.15 and 0.3 MPa.

12. The process according to claim 9 , in which the volumetric flow rate is between 1 and 4 h −1 .

Assignees

• Ifp Energies Now
• Michelin & Cie

Inventors

• Cadran Nicolas
• Chaumonnot Alexandra
• Lambert Arnold

Classifications

• C07C2521/08

  Silica · CPC title

• B01J23/20

  Vanadium, niobium or tantalum · CPC title

• C07C1/20

  starting from organic compounds containing only oxygen atoms as heteroatoms · CPC title

• C07C2523/06

  of zinc, cadmium or mercury · CPC title

• C07C2523/20

  Vanadium, niobium or tantalum · CPC title