US 11,655,158 B2
Isomorphous substitution of metals during the synthesis of a zeolite framework
Svetlana Mintova, Basly (FR); Jean-Pierre Gilson, Fouesnant (FR); Nikolai Nesterenko, Nivelles (BE); Delphine Minoux, Nivelles (BE); Cindy Aquino, Watermael-Boitsfort (BE); Julien Grand, Viroflay (FR); and Florent Dubray, Caen (FR)
Assigned to TOTALENERGIES ONETECH, Courbevoie (FR); and CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE (CNRS), Paris (FR)
Appl. No. 17/768,391
Filed by TotalEnergies OneTech, Courbevoie (FR); and CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE (CNRS), Paris (FR)
PCT Filed Oct. 13, 2020, PCT No. PCT/EP2020/078770
§ 371(c)(1), (2) Date Apr. 12, 2022,
PCT Pub. No. WO2021/074144, PCT Pub. Date Apr. 22, 2021.
Claims priority of application No. 19315122 (EP), filed on Oct. 14, 2019.
Prior Publication US 2022/0363556 A1, Nov. 17, 2022
Int. Cl. C01B 39/48 (2006.01)
CPC C01B 39/48 (2013.01) [C01P 2002/72 (2013.01); C01P 2002/82 (2013.01); C01P 2002/85 (2013.01); C01P 2002/86 (2013.01); C01P 2004/03 (2013.01); C01P 2004/04 (2013.01); C01P 2006/12 (2013.01); C01P 2006/14 (2013.01)] 20 Claims
OG exemplary drawing
 
1. A method for the preparation of a synthetic zeolite material, containing at least one metal M selected from W, V, Mo, Nb, Sn, Zr, Ag, Co, Ni, Cu, Ti, In and Zn or any mixture thereof, wherein the silicon to metal M molar ration Si/M ranging from 117 to 65440 as determined by inductively coupled plasma optical emission spectrometry, wherein said method comprises the following steps:
a) contacting at least one source of silicon, at least one tetraalkylammonium hydroxide structure-directing agent, and water, so as to obtain an aqueous suspension having the following molar composition (I):
1SiO2:y TAA2O: z H2O
in which: 0.04<y<0.40, 8<z<120.
b) ageing between 1 h and 100 h the aqueous suspension from step a) at a temperature ranging from 10° C. to 50° C., so as to obtain a clear suspension;
c) heating for at least 30 min the clear suspension of step b) at a temperature ranging from 40° C. to 180° C.;
d) cooling the solution obtained at step c) to 20° C. and adding at least one source of alkali metal M′ selected from a lithium, sodium, potassium, or caesium salt of a metal M, to obtain a gel having the molar composition (II):
xMnOm: 1SiO2:y TAA2O:w M′2O:z H2O
In which: the M′/M ratio varies from 0.1 to 4
0.04<y<0.40,
8<z<120,
0.0004<x<0.15,
0.0004<w<0.30,
n is an integer equal to 1 or 2, and
m is an integer and 1<m<6;
e) ageing said gel obtained at step d) at a temperature ranging from 10° C. to 35° C. for at least 30 min
f) heating the solution obtained at step e) at a temperature ranging from 40° C. to 180° C., for at least 30 min
g) separating the solid from said liquid obtained at step f)
h) calcining said solid obtained at step g) in a sealed bottle with a relative humidity of 50 to 80% to obtain said synthetic zeolite material.