Process for hydroformylating short-chain olefins in the gas phase

Patent metadata

Field	Value
Publication number	US-10654784-B2
Application number	US-201916574217-A
Country	US
Kind code	B2
Filing date	Sep 18, 2019
Priority date	Oct 5, 2018
Publication date	May 19, 2020
Grant date	May 19, 2020

Abstract

The invention relates to a process for hydroformylating short-chain olefins, especially C2 to C5 olefins, in which the catalyst system is in heterogenized form on a support of a porous ceramic material, and to plants for performing this process.

First claim

The invention claimed is:

1. A process for hydroformylating C2 to C8 olefins in a reaction zone using a heterogenized catalyst system, wherein the process is
a gaseous feed mixture containing the C2 to C8 olefins is passed together with synthesis gas over a support composed of a porous ceramic material on which the catalyst system comprising a metal from group 8 or 9 of the Periodic Table of the Elements, at least one organic phosphorus-containing ligand, a stabilizer and optionally an ionic liquid is in heterogenized form; and
the support is a block of a ceramic material, to which a washcoat composed of the same or a different ceramic material with respect to the ceramic material of the support is applied.

2. The process according to claim 1 , wherein the organic phosphorus-containing ligand in the hydroformylation catalyst system preferably has the general formula (VI)
R′-A-R″-A-R′″  (VI)

where R′, R″ and R′″ are each organic radicals, with the proviso that R′ and R′″ are not identical, and each A is a bridging —O—P(—O) 2 — group, where two of the three oxygen atoms —O— are respectively bonded to the R′ radical and the R′″ radical.

3. The process according to claim 1 , wherein the stabilizer is an organic amine compound containing at least one 2,2,6,6-tetramethylpiperidine unit of formula (I):

4. The process according to claim 1 , wherein the porous ceramic material of which the support consists 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.

5. The process according to claim 4 , wherein the silicate ceramic is selected from aluminosilicate, magnesium silicate, and mixtures thereof; the oxidic ceramic is selected from γ-alumina, α-alumina, titanium dioxide, beryllium oxide, zirconium oxide, aluminium titanate, barium titanate, zinc oxide, iron oxides (ferrites) and mixtures thereof; the nitridic ceramic is selected from silicon nitride, boron nitride, aluminium nitride and mixtures thereof; the carbidic ceramic is selected from silicon carbide, boron carbide, tungsten carbide or mixtures thereof; and the silicidic ceramic is molybdenum silicide.

6. The process according to claim 4 , wherein the porous ceramic material of which the support consists is a carbidic ceramic.

7. The process according to claim 6 , wherein the carbidic ceramic is selected from silicon carbide, boron carbide, tungsten carbide or mixtures thereof.

8. The process according to claim 1 , wherein the amount of washcoat present on the support is ≤20% by weight, based on the total amount of the support.

9. The process according to claim 1 , wherein the support composed of the ceramic material has one or more channels in main through-flow direction.

10. The process according to claim 1 , wherein the hydroformylation is conducted at a temperature in the range from 65 to 200° C.

11. The process according to claim 1 , wherein the pressure in the hydroformylation is not greater than 35 bar.

12. The process according to claim 1 , wherein the support composed of the ceramic material has one or more continuous channels in main through-flow direction.

13. The process according to claim 1 , wherein the hydroformylation is conducted at a temperature in the range from 75 to 175° C.

14. The process according to claim 1 , wherein the hydroformylation is conducted at a temperature in the range from 85 to 150° C.

15. The process according to claim 1 , wherein the pressure in the hydroformylation is not greater than 30 bar.

16. The process according to claim 1 , wherein the pressure in the hydroformylation is not greater than 25 bar.

17. The process according to claim 2 , wherein the stabilizer is an organic amine compound containing at least one 2,2,6,6-tetramethylpiperidine unit of formula (I):

18. The process according to claim 2 , wherein the porous ceramic material of which the support consists 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.

19. The process according to claim 18 , wherein the silicate ceramic is selected from aluminosilicate, magnesium silicate, and mixtures thereof; the oxidic ceramic is selected from γ-alumina, α-alumina, titanium dioxide, beryllium oxide, zirconium oxide, aluminium titanate, barium titanate, zinc oxide, iron oxides (ferrites) and mixtures thereof; the nitridic ceramic is selected from silicon nitride, boron nitride, aluminium nitride and mixtures thereof; the carbidic ceramic is selected from silicon carbide, boron carbide, tungsten carbide or mixtures thereof; and the silicidic ceramic is molybdenum silicide.

20. The process according to claim 18 , wherein the porous ceramic material of which the support consists is a carbidic ceramic.

Assignees

• Evonik Operations Gmbh

Inventors

• Hasselberg Jennifer
• Franke Robert
• Stenger Frank
• Kreis Peter
• Hecht Corinna
• Kristen Marc Oliver

Classifications

• C07C47/02

  Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen · CPC title

• B01J27/22

  Carbides · CPC title

• C07C45/50 Primary

  by oxo-reactions · CPC title

• B01J2231/321

  Hydroformylation, metalformylation, carbonylation or hydroaminomethylation · CPC title

• B01J31/0237

  Amines · CPC title