Process for regenerating a catalyst for the hydroformylation of olefins in the gas phase

Patent metadata

Field	Value
Publication number	US-11951466-B2
Application number	US-202217716170-A
Country	US
Kind code	B2
Filing date	Apr 8, 2022
Priority date	May 18, 2021
Publication date	Apr 9, 2024
Grant date	Apr 9, 2024

Abstract

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.

First claim

The invention claimed is:

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.

Assignees

• Evonik Oxeno Gmbh & Co Kg

Inventors

• Franke Robert
• Arsenjuk Linda
• Schüller Jessika
• Stenger Frank
• Fleischer Vinzenz
• Kristen Marc Oliver

Classifications

• B01J38/50 Primary

  using organic liquids · CPC title

• B01J31/185 Primary

  Phosphites ((RO)3P) , their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof · CPC title

• B01J31/4046 Primary

  containing rhodium · CPC title

• B01J31/4053

  with recovery of phosphorous catalyst system constituents · CPC title

• B01J38/68

  including substantial dissolution or chemical precipitation of a catalyst component in the ultimate reconstitution of the catalyst · CPC title