Synthesis of a MoVNbTe shell catalyst for oxidative dehydrogenation of ethane to ethylene
A novel coated catalyst having an outer shell which is composed of a catalyst material having high surface area and contains molybdenum, vanadium, tellurium and niobium, and the use of this catalyst for the oxidative dehydrogenation of ethane to ethene or the oxidation of propane to acrylic acid and also a process for producing the catalyst is disclosed.
1. A coated catalyst comprising an inert support and a catalytically active outer shell which comprises
a mixed oxide material of the formula
Mo i V a Nb b Te c O x
present in an M1 phase, where a is 0.2-0.3, b is 0.05-0.2, c is 0.05-0.25, and x is
selected such that the overall charge of the empirical formula is zero; wherein the coated catalyst has a BET surface area of more than 30 m 2 /g.
2. The coated catalyst as claimed in claim 1 , wherein the coated catalyst has a mercury pore volume of greater than 0.1 cm 3 /g.
3. The coated catalyst as claimed in claim 1 , wherein the coated catalyst has a mercury pore volume in the shell of greater than 0.2 cm 3 /g, based on the mass of the shell.
4. The coated catalyst as claimed in claim 1 , wherein the inert support is selected from the group consisting of silicon oxide, aluminum oxide, steatite, mullite and cordierite.
5. The coated catalyst as claimed in claim 1 , wherein the coated catalyst has a catalytically active outer shell having a layer thickness in the range from 200 to 400 μm.
6. A process for producing a coated catalyst as claimed in claim 1 , comprising the steps:
a) production of a mixture of starting compounds, which contains molybdenum, vanadium, niobium and a tellurium-containing starting compound in which tellurium is present in the oxidation state+4 and also oxalic acid and at least one further oxo ligand,
b) hydrothermal treatment of the mixture of starting compounds at a temperature of from 100 to 300° C., to give a product suspension,
c) isolation and drying of the mixed oxide material present in the product suspension resulting from step b),
d) optionally calcination of the mixed oxide material obtained in step c) under inert gas at from 300 to 450° C.,
e) production of a coating suspension containing the mixed oxide material from step d) with addition of organic and/or inorganic binders,
f) coating of an inert catalyst support with the coating suspension from step e) by spraying the coating suspension into an agitated bed of the inert catalyst supports and optionally
g) calcination of the catalyst particles from step f) at a temperature of from 80 to 400° C.
7. The process as claimed in claim 6 , wherein the tellurium-containing starting compound is tellurium dioxide or a compound of the formula M x n+ TeO 3 (where n=1 or 2 and x=2/n) where M is an alkali metal or an alkaline earth metal.
8. The process as claimed in claim 6 , wherein the mixture of starting compounds is present as an aqueous suspension.
9. The process as claimed in claim 6 , wherein the mixture of starting compounds contains a dicarboxylic acid, a diol or another compound having two hydroxy groups in adjacent positions as further oxo ligand.
10. The process as claimed in claim 6 , wherein the mixture of starting compounds contains molybdenum trioxide.
11. The process as claimed in claim 6 , wherein the mixture of starting compounds contains vanadium pentoxide.
12. The process as claimed in claim 6 , wherein the mixture of starting compounds contains citric acid as further oxo ligand.
13. The process as claimed in claim 6 , wherein the mixture of starting compounds contains citric acid and glycol as further oxo ligands.
14. A catalyst powder comprising
a mixed oxide material of the formula
Mo i V a Nb b Te c O x
present in an M1 phase, where a is 0.2-0.3, b is 0.05-0.2, c is 0.05-0.25, and x is
selected such that the overall charge of the empirical formula is zero; wherein the catalyst powder has a BET surface area of more than 30 m 2 /g.