Method and device for the hydroformylation of isobutene and for the separation of the product mixture

Patent metadata

Field	Value
Publication number	US-9353040-B2
Application number	US-201314380647-A
Country	US
Kind code	B2
Filing date	Feb 11, 2013
Priority date	Feb 23, 2012
Publication date	May 31, 2016
Grant date	May 31, 2016

Abstract

The invention relates to a method for producing a product mixture ( 2 ) by means of the technical hydroformylation of a hydrocarbon stream ( 1 ) that contains isobutene, and for separating the product mixture ( 2 ) that is obtained, as well as to a device for the claimed method and to the use of a claimed device. The problem addressed thereby is that of providing a method and an associated device that allow the amount of high-boiling substances in the product mixture ( 2 ) to be kept as low as possible and thus the yield of the reaction to be increased. The problem is solved by the use of a nano-filtration device (M) for separating the catalyst from the product mixture ( 2 ), said device having especially high permeability to 3-methylbutanoic acid.

First claim

The invention claimed is:

1. A method for preparing a product mixture from an isobutene-containing hydrocarbon stream and for separating the resulting product mixture, said method comprising:
a) hydroformylating an isobutene-containing hydrocarbon stream in a hydroformylation reactor in the presence of a transition metal complex catalyst, thereby obtaining a product mixture comprising 3-methylbutanal, conversion products in the form of high boilers, 3-methylbutanoic acid, the transition metal complex catalyst, and the free ligands thereof,
b) separating the product mixture with a nanofiltration device comprising one or more membrane separation stages, such that the transition metal complex catalyst and the free ligands thereof are enriched in the resulting retentate of the nanofiltration device with respect to 3-methylbutanal and 3-methylbutanoic acid, and such that 3-methylbutanal and 3-methylbutanoic acid are each enriched in the resulting permeate of the nanofiltration device with respect to the transition metal complex catalyst, the concentration of the 3-methylbutanoic acid being lower in the resulting retentate than in the permeate,
c) separating the resulting permeate of the nanofiltration device with a thermal separating device comprising one or more separation stages into at least one first fraction and a second fraction, wherein the first fraction has a higher concentration of 3-methylbutanal than the second fraction and a lower concentration of conversion products in the form of high boilers and 3-methylbutanoic acid than the second fraction, and
d) recycling at least a substream of the resulting retentate of the nanofiltration device into the hydroformylation reactor,
wherein:
one or more nanofiltration membranes are used in the nanofiltration device; and
the one or more membranes has a retention for 3-methylbutanoic acid of −1 or less.

2. The method according to claim 1 , wherein:
one or more process parameters in a) are set such that the total concentration of conversion products in the form of high boilers and 3-methylbutanoic acid, based on the weight of the overall product mixture, is 30% by weight or less; and
the parameter(s) to be set are selected from the group consisting of pressure, temperature, mean residence time, composition of the synthesis gas, concentration of the transition metal and transition metal-ligand ratio of the transition metal complex catalyst.

3. The method according to claim 1 , wherein a) is performed with at least one of
a pressure in the range from 0.2 to 8 MPa,
a temperature in the range from 70 to 130° C.,
a mean residence time in the range from 1 to 4 h,
a synthesis gas composition CO:H 2 of 1:3 to 3:1, and/or
a transition metal concentration in the range from 10 to 100 ppm, and
a transition metal/ligand ratio in the range from 1:4 to 1:50.

4. The method according to claim 1 , wherein at least one of the following conditions is satisfied
the transition metal of the transition metal complex catalyst is rhodium, and
the ligand(s) of the transition metal complex catalyst is/are selected from the group
consisting of organophosphorus ligands.

5. The method according to claim 1 , wherein the transition metal of the transition metal complex catalyst is rhodium or cobalt.

6. The method according to claim 1 , wherein the one or more membranes has a retention for 3-methylbutanoic acid of −5 or less.

7. The method according to claim 1 , wherein:
the one or more nanofiltration membranes comprise one or more polymers which comprise imide groups; and
said polymers are selected such that the retention of the nanofiltration membrane for 3-methylbutanoic acid is −1 or less.

8. The method according to claim 1 , wherein the one or more nanofiltration membranes have a separation limit of from 150 to 2000 g/mol.

9. The method according to claim 1 , wherein:
one or more nanofiltration membranes in the nanofiltration device comprise one or more polymers which comprise imide groups; and
said polymers being selected such that the separation limit of the nanofiltration membrane is from 150 to 2000 g/mol.

10. The method according to claim 1 , wherein b) is performed
at a temperature in the range from 10 to 150° C.,
and/or
at a transmembrane pressure in the range from 0.5 to 6 MPa,
and/or
at a Reynolds number between 55 and 13 500,

and/or
in the presence of carbon monoxide and/or hydrogen in the feed, in the retentate and in the permeate of each membrane separation stage.

11. The method according to claim 1 , wherein the thermal separation comprises a distillation in which the first fraction is obtained as the top product and the second fraction as the bottom product.

12. The method according to claim 1 , comprising:
hydroformylating an isobutenic hydrocarbon stream in the presence of a rhodium complex catalyst having one or more organophosphorus ligands at a pressure in the range from 0.2 to 8 MPa and a temperature in the range from 70 to 130° C. with a mean residence time in the range from 1 to 4 h, a synthesis gas composition CO:H 2 of 1:3 to 3:1, a rhodium concentration in the reactor in the range from 10 to 100 ppm and a rhodium/ligand ratio in the range from 1:4 to 1:50,
separating the product mixture of the hydroformylation with a nanofiltration device at a temperature in the range from 10 to 150° C., a transmembrane pressure in the range from 0.5 to 6 MPa, at a Reynolds number between 170 and 900, and a partial carbon monoxide pressure of greater than 0.2 MPa into feed, retentate and permeate of each membrane separation stage,
thermally separating the resulting permeate of the nanofiltration device by distillation into a first fraction and a second fraction, wherein the first fraction comprises a higher concentration of 3-methylbutanal than the second fraction and a lower concentration of high boilers than the second fraction, and
recycling at least a substream of the resulting retentate of the nanofiltration device into the hydroformylation reactor.

13. The method according to claim 1 , further comprising monitoring the concentration of 3-methylbutanoic acid in the resulting retentate of the nanofiltration device, and optionally in the product mixture and/or in the resulting permeate of the nanofiltration device.

14. The method according to claim 13 , wherein, on exceedance of a fixed maximum concentration of the 3-methylbutanoic acid in the resulting retentate of the nanofiltration device, the recycling of the resulting retentate into the hydroformylation reactor is stopped.

15. The method according to claim 13 , wherein, on exceedance of a fixed maximum concentration of 3-methylbutanoic acid in the feed of the nanofiltration device, one or more process parameters in a) are modified such that the concentration of 3-methylbutanoic acid in the feed of the nanofiltration device is lowered below the fixed maximum.

16. An apparatus for performance of the process according to claim 1 , comprising
a hydroformylation reactor for hydroformylation of an isobutenic hydrocarbon stream in the presence of a transition metal complex catalyst,
a nanofiltration device comprising one or more membrane separation stages for separation of the product mixture formed in the hydroformylation reactor, such that the transition metal complex catalyst and the free ligands thereof are enriched in the resulting retentate of the nanofiltration device with respect to 3-methylbutanal and 3-methylbutanoic acid, and 3-methylbutanal and 3-methylbutanoic acid are enriched in the resulting permeate of the nanofiltration device with respect to the tr

Assignees

• Baumgarten Goetz
• GRAβ MICHAEL
• Kaizik Alfred
• Winterberg Markus
• Lueken Hans-Gerd
• Hamers Bart
• Priske Markus
• Fridag Dirk
• Franke Robert
• Hess Dieter
• Evonik Degussa Gmbh

Inventors

• Baumgarten Goetz
• GRAβ MICHAEL
• Kaizik Alfred
• Winterberg Markus
• Lueken Hans-Gerd
• Hamers Bart
• Priske Markus
• Fridag Dirk
• Franke Robert
• Hess Dieter

Classifications

• B01D61/027

  Nanofiltration · CPC title

• C07C45/82

  by distillation · CPC title

• C07C51/235

  of —CHO groups or primary alcohol groups · CPC title

• C07C51/43 Primary

  by change of the physical state, e.g. crystallisation · CPC title

• C07C45/50 Primary

  by oxo-reactions · CPC title