Process for regenerating a catalyst for the hydroformylation of olefins in the gas phase
The present invention relates to a simple process for regenerating a hydroformylation catalyst consisting of a heterogenized catalyst system on a support consisting of a porous ceramic material. The invention also relates to a process for the start-up of the hydroformylation reaction after regeneration according to the invention.
1. A process for regenerating a hydroformylation catalyst consisting of a heterogenized catalyst system, in a vessel,
wherein the catalyst system comprises a metal of Group 8 or 9 of the Periodic Table of the Elements and at least one organic phosphorus-containing ligand and is present heterogenized on a support, wherein the support consists of a porous ceramic material and is in the form of granules or in the form of a monolith,
wherein the process comprises at least the following steps:
a) filling the vessel with a solution consisting of the phosphorus-containing ligand and a solvent, and allowing it to stand for at least one hour, and
b) discharging the solution from the vessel.
2. The process according to claim 1 , wherein the solution in the reactor in step a) is kept for at least 12 hours.
3. The process according to claim 1 ,
wherein the process is carried out in situ in the reactor in which the hydroformylation catalyst is present.
4. The process according to claim 1 , wherein the solvent of the solution is dichloromethane, THF, pentanol, propanal, propanol or pentanal.
5. The process according to claim 1 , wherein the solution in step b) is discharged hydrostatically.
6. The process according to claim 1 , wherein step a) is carried out at ambient temperature.
7. The process according to claim 1 , further comprising:
raising the temperature in step b) and flushing the reactor with an inert gas when raising the temperature in step b).
8. The process according to claim 7 , wherein the inert gas is nitrogen, helium, neon, CO 2 or argon.
9. The process according to claim 1 , wherein the support consists of a porous ceramic material which is selected from the group consisting of a silicate ceramic, an oxidic ceramic, a nitridic ceramic, a carbidic ceramic, a silicidic ceramic and mixtures thereof.
10. The process according to claim 1 , wherein a washcoat is applied to the support which is composed of the same or another ceramic material.
11. The process according to claim 10 , wherein the amount of washcoat on the support is ≤20% by weight, based on the total amount of the support.
12. The process according to claim 1 , wherein the organic phosphorus-containing ligand of the catalyst system has the general formula (I)
R′-A-R″-A-R′″ (I)
where R′, R″ and R′″ are each organic radicals, with the proviso that R′ and R′″ are non-identical, and both A are each a bridging —O—P(—O) 2 group, wherein two of the three oxygen atoms —O— are each attached to the radical R′ and to the radical R′″.
13. The process according to claim 1 , wherein the catalyst system additionally comprises a stabilizer.
14. The process according to claim 1 , wherein the reactor is started up after regeneration of the hydroformylation catalyst, wherein the process is characterized in that
a gaseous feedstock mixture comprising C2- to C8-olefins to be hydroformylated together with a synthesis gas mixture is introduced into the reactor, and
the composition of the feedstock mixture and/or the composition of the synthesis gas mixture is varied in two or more steps at a constant volume flow rate in that the proportion of C2- to C8-olefins to be hydroformylated in the feedstock mixture and/or the proportion of synthesis gas in the synthesis gas mixture is increased in a stepwise manner,
wherein a maximum conversion of the C2- to C8-olefins used of 40 to 90% during the entire start-up is not exceeded.
15. The process according to claim 14 , wherein an inert gas is added to the feedstock mixture and/or to the synthesis gas mixture to reduce the proportion of C2- to C8-olefins and/or to reduce the proportion of synthesis gas and the addition of the inert gas is reduced in a stepwise manner corresponding to the stepwise increase of the proportion of C2- to C8-olefins and/or of the proportion of synthesis gas.
16. The process according to claim 1 , wherein the solution in the reactor in step a) is kept for at least 24 hours.
17. The process according to claim 2 , wherein the process is carried out in situ in the reactor in which the hydroformylation catalyst is present.
18. The process according to claim 2 , wherein the solvent of the solution is dichloromethane, THF, pentanol, propanal, propanol or pentanal.
19. The process according to claim 2 , wherein the solution in step b) is discharged hydrostatically.
20. The process according to claim 2 , wherein step a) is carried out at ambient temperature.