Two-stage hydroformylation process with circulating gas and silp technology

Patent metadata

Field	Value
Publication number	US-2016304426-A1
Application number	US-201415103842-A
Country	US
Kind code	A1
Filing date	Dec 10, 2014
Priority date	Dec 13, 2013
Publication date	Oct 20, 2016
Grant date	—

Abstract

The invention relates to processes for preparing aldehydes by hydroformylation of alkenes, in which an alkene-containing feed mixture is subjected to a primary hydroformylation with synthesis gas in the presence of a homogeneous catalyst system, the primary hydroformylation being effected in a primary reaction zone from which a cycle gas containing at least some of the products and unconverted reactants of the primary hydroformylation are drawn off continuously and partly condensed, with recycling of uncondensed components of the cycle gas into the primary reaction zone, and with distillative separation of condensed components of the cycle gas in an aldehyde removal stage to give an aldehyde-rich mixture and a low-aldehyde mixture. The problem that it addresses is that of developing the process such that it achieves high conversions and affords aldehyde in good product quality even in the case of a deteriorating raw material position. More particularly, a solution is to be found for making legacy oxo process plants capable of utilizing lower-value raw material sources. This problem is solved by separating the low-aldehyde mixture into a retentate and a permeate by means of a membrane separation unit in such a way that alkenes present in the low-aldehyde mixture become enriched in the permeate, while alkanes present in the low-aldehyde mixture become enriched in the retentate. The alkene-rich permeate is then transferred into a secondary reaction zone and subjected to a secondary hydroformylation therein with synthesis gas in the presence of an SILP catalyst system. The reaction product obtained from the secondary hydroformylation is recycled into the aldehyde removal stage.

First claim

What is claimed is:

1 . Process for preparing aldehydes by hydroformylation of alkenes, in which an alkene-containing feed mixture is subjected to a primary hydroformylation with synthesis gas in the presence of a homogeneous catalyst system, the primary hydroformylation being effected in a primary reaction zone from which a cycle gas containing at least some of the products and unconverted reactants of the primary hydroformylation are drawn off continuously and partly condensed, with recycling of uncondensed components of the cycle gas into the primary reaction zone, and with distillative separation of condensed components of the cycle gas in an aldehyde removal stage to give an aldehyde-rich mixture and a low-aldehyde mixture, wherein the low-aldehyde mixture is separated into a retentate and a permeate by means of a membrane separation unit in such a way that alkenes present in the low-aldehyde mixture become enriched in the permeate, while alkanes present in the low-aldehyde mixture become enriched in the retentate, and in that the permeate is transferred into a secondary reaction zone and subjected to a secondary hydroformylation therein with synthesis gas in the presence of an SILP catalyst system, with supply of the reaction product obtained from the secondary hydroformylation to the aldehyde removal stage.

2 . Process according to claim 1 , wherein the feed mixture used is a C 3 mixture containing between 10% and 90% by weight of alkenes having three carbon atoms, based on the total weight of the feed mixture.

3 . Process according to claim 1 , wherein the feed mixture used is a C 4 mixture containing between 10% and 90% by weight of alkenes having four carbon atoms, based on the total weight of the feed mixture.

4 . Process according to claim 1 , wherein a first feed mixture and a second feed mixture are used, whereby the first feed mixture used is a C 3 mixture containing between 10% and 90% by weight of alkenes having three carbon atoms, based on the total weight of the first feed mixture, whereby the second feed mixture used is a C 4 mixture containing between 10% and 90% by weight of alkenes having four carbon atoms, based on the total weight of the second feed mixture, whereby there is parallel preparation of C 4 aldehydes from the C 3 mixture and C 5 aldehydes from the C 4 mixture, with the proviso that the C 3 mixture is subjected to a primary C 3 hydroformylation with synthesis gas in the presence of a homogeneous catalyst system, the primary C 3 hydroformylation being effected in a primary C 3 reaction zone from which a C 3 cycle gas containing at least some of the products and unconverted reactants of the primary C 3 hydroformylation are drawn off continuously and partly condensed, and uncondensed components of the C 3 cycle gas being recycled into the primary C 3 reaction zone, and the condensed components of the C 3 cycle gas being separated by distillation in a C 4 aldehyde removal stage to give a C 4 aldehyde-rich mixture and a low-C 4 aldehyde mixture, and in that the C 4 mixture is subjected to a primary C 4 hydroformylation with synthesis gas in the presence of a homogeneous catalyst system, the primary C 4 hydroformylation being effected in a primary C 4 reaction zone from which a C 4 cycle gas containing at least some of the products and unconverted reactants of the primary C 4 hydroformylation are drawn off continuously and partly condensed, and uncondensed components of the C 4 cycle gas being recycled into the primary C 4 reaction zone, and the condensed components of the C 4 cycle gas being separated by distillation in a C 5 aldehyde removal stage to give a C 5 aldehyde-rich mixture and a low-C 5 aldehyde mixture, wherein, optionally, the low-C 4 aldehyde mixture or the low-C 5 aldehyde mixture is fed to the membrane separation unit and the resultant permeate is subjected to the secondary hydroformylation in the presence of the SILP catalyst system, and wherein the reaction product obtained from the secondary hydroformylation is fed to the corresponding C 4 or C 5 aldehyde removal stage.

5 . Process according to claim 1 , wherein the membrane separation unit comprises at least one membrane having a separation-active membrane material, whereby the membrane separation unit has been provided with a carrier medium capable of entering into compounds with alkenes for which the membrane material has a higher permeability than for the corresponding non-compounded alkenes.

6 . Process according to claim 1 , wherein the SILP catalyst system of the secondary hydroformylation comprises the following components:
a) a solid porous carrier material; b) an ionic liquid; c) a metal selected from group 9 of the Periodic Table of the Elements; d) a phosphorus-containing organic ligand; e) optionally an organic amine.

7 . Process according to any of claim 1 , wherein the permeate enters the secondary reaction zone in gaseous form.

8 . Process according to claim 7 , wherein the permeate is obtained at least partly in liquid form in the membrane separation unit and, prior to entry into the secondary reaction stage, is evaporated by the action of heat by means of an evaporator.

9 . Process according to claim 7 , wherein the permeate is obtained in gaseous form in the membrane separation unit.

10 . Process according to claim 1 , wherein the homogeneous catalyst system of the primary hydroformylation comprises rhodium and at least one phosphine or phosphite or phosphoramidite ligand, the homogeneous catalyst system being fully dissolved in a liquid phase of the reaction mixture of the primary reaction zone.

11 - 16 . (canceled)

17 . Process for preparing aldehydes by hydroformylation of alkenes, in which an alkene-containing feed mixture is subjected to a primary hydroformylation with synthesis gas in the presence of a homogeneous catalyst system, the primary hydroformylation being effected in a primary reaction zone from which a cycle gas containing at least some of the products and unconverted reactants of the primary hydroformylation are drawn off continuously and partly condensed, with recycling of uncondensed components of the cycle gas into the primary reaction zone, and with distillative separation of condensed components of the cycle gas in an aldehyde removal stage to give an aldehyde-rich mixture and a low-aldehyde mixture, wherein the cycle gas, prior to the partial condensation thereof, is separated into a retentate and a permeate by means of a membrane separation unit in such a way that alkenes present in the cycle gas become enriched in the permeate, while alkanes present in the cycle gas become enriched in the retentate, and in that the permeate is transferred into a secondary reaction zone and subjected to a secondary hydroformylation therein with synthesis gas in the presence of an SILP catalyst system, with supply of the reaction product obtained from the secondary hydroformylation to the partial condensation stage.

18 . Process according to claim 17 , wherein the membrane separation unit comprises at least one membrane having a separation-active membrane material, wherein the membrane separation unit has been provided with a carrier medium capable of entering into compounds with alkenes for which the membrane material has a higher permeability than for the corresponding non-compounded alkenes.

19 . Process according to claim 17 , wherein the SILP catalyst system of the secondary hydroformylation comprises the following components:
a) a solid porous carrier material; b) an ionic liquid; c) a metal selected from group 9 of the Periodic Table of the Elements; d) a p

Assignees

• Becker Marc
• Dyballa Katrin Marie
• Franke Robert
• Fridag Dirk
• Hahn Hanna
• Lazar Marina
• Priske Markus
• Stochniol Guido

Inventors

• Becker Marc
• Dyballa Katrin Marie
• Franke Robert
• Fridag Dirk
• Hahn Hanna
• Lazar Marina
• Priske Markus
• Stochniol Guido

Classifications

• B01D2311/02

  Specific process operations before starting the membrane separation process · CPC title

• B01J31/1845

  the ligands containing phosphorus (phosphines B01J31/24) · CPC title

• C07C45/79

  by solid-liquid treatment; by chemisorption · CPC title

• B01J31/0292

  immobilised on a substrate · CPC title

• B01D2311/06

  Specific process operations in the permeate stream · CPC title