Production of n-pentanal from low-butene feedstock mixtures

Patent metadata

Field	Value
Publication number	US-9845276-B2
Application number	US-201715491173-A
Country	US
Kind code	B2
Filing date	Apr 19, 2017
Priority date	May 19, 2016
Publication date	Dec 19, 2017
Grant date	Dec 19, 2017

Abstract

The invention is concerned with the issue of how to produce n-pentanal by hydroformylation from feedstock mixtures comprising a small proportion of n-butene and a large proportion of n-butane. Specifically, solutions for further optimizing established processes for hydroformylation of such low-butene mixtures in terms of material utilization are sought. The present invention has for its object to enhance the material utilization of the feedstock mixture in the production of n-pentanal from feedstock mixtures having a small proportion of n-butene and a large proportion of n-butane. The process shall be capable of economic operation on an industrial scale. In particular an existing oxo plant shall be honed to achieve better raw material utilization. This object is achieved by a combination of a hydroformylation and a dehydrogenation, wherein said combination has the special feature that the dehydrogenation is arranged after the hydroformylation in the downstream direction and is thus markedly smaller than conventional dehydrogenations provided upstream. A skillful product removal effectively removes contaminants formed in the process.

First claim

The invention claimed is:

1. A process for producing n-pentanal comprising the steps of:
a) providing a feedstock mixture having the following composition which sums to 100 wt %:
n-butane: 70 wt % to 90 wt %;
n-butene: 10 wt % to 30 wt %;
1-butene: 0 wt % to 3 wt %;
isobutene: 0 wt % to 3 wt %;
isobutane: 0 wt % to 3 wt %;
1,3-butadiene: 0 wt % to 1 wt %;
other substances: 0 wt % to 1 wt %;

b) mixing the feedstock mixture with a recyclate to obtain a feed;
c) treating the feed with carbon monoxide and hydrogen in the presence of a first catalyst system to convert at least a portion of the n-butene present in the feed into aldehydes by hydroformylation to obtain a hydroformylation mixture;
d) recovering a primary product fraction from the hydroformylation mixture, wherein the primary product fraction has the following composition which sums to 100 wt %:
n-pentanal: 90 wt % to 98.5 wt %;
2-methylbutanal: 0 wt % to 5 wt %;
3-methylbutanal: 0 wt % to 3 wt %;
other substances: 0 wt % to 2 wt %;

e) recovering a subsidiary fraction from the hydroformylation mixture, wherein the subsidiary fraction has the following composition which sums to 100 wt %:
n-butane: 80 wt % to 92 wt %;
n-butene: 8 wt % to 20 wt %;
other substances: 0 wt % to 1 wt %;

f) subjecting the subsidiary fraction to a dehydrogenation in the presence of a second catalyst system to obtain a dehydrogenation mixture having the following composition which sums to 100 wt %:
n-butene: 50 wt % to 60 wt %;
n-butane: 40 wt % to 50 wt %;
methane: 0 wt % to 4 wt %;
ethene: 0 wt % to 3 wt %;
propene: 0 wt % to 2 wt %;
1,3-butadiene: 0 wt % to 3 wt %;
other substances: 0 wt % to 1 wt %;

g) subjecting the dehydrogenation mixture to a selective hydrogenation in the presence of a third catalyst system to obtain a hydrogenation mixture having the following composition which sums to 100 wt %:
n-butene: 50 wt % to 60 wt %;
n-butane: 40 wt % to 50 wt %;
1,3-butadiene: 0 ppm by weight to 500 ppm by weight;
other substances: 0 wt % to 5 wt %;

h) direct use of the hydrogenation mixture as recyclate
or
purification of the hydrogenation mixture to obtain the recyclate.

2. The process according to claim 1 , wherein the second catalyst system is a solid comprising at least platinum, tin and aluminum oxide and that the dehydrogenation is effected in the gas phase at a pressure of 0.8*10 5 Pa to 1.2*10 5 Pa and a temperature of 450° C. to 700° C.

3. The process according to claim 1 , wherein at least two reactors, each heated and each filled with the second catalyst system, are provided for the dehydrogenation and the reactors are chargeable with subsidiary fraction individually or simultaneously in parallel and/or serially as desired.

4. The process according to claim 3 , wherein the reactors are electrically heated.

5. The process according to claim 1 , wherein the dehydrogenation mixture is liquefied by compression and cooling and the selective hydrogenation is effected in the liquid phase at a pressure of 18*10 5 Pa to 22*10 5 Pa and a temperature of 40° C. to 80° C.

6. The process according to claim 5 , wherein the heat recovered during cooling is used for preheating the subsidiary fraction.

7. The process according to claim 5 , wherein the compression is effected in two successive compression stages and that the cooling provided is an intercooling arranged between the compression stages.

8. The process according to claim 1 , wherein the second catalyst system is a solid comprising aluminum oxide and chromium oxide and that the dehydrogenation is effected in the gas phase at a pressure of 0.8*10 5 Pa to 1.2*10 5 Pa and a temperature of 600° C. to 700° C.

9. The process according to claim 1 , wherein the second catalyst system is a solid comprising aluminum oxide and magnesiochromite and that the dehydrogenation is effected in the gas phase at a pressure of 0.8*10 5 Pa to 1.2*10 5 Pa and a temperature of 600° C. to 700° C.

10. The process according to claim 1 , wherein the dehydrogenation is effected without addition of an oxidant.

11. The process according to claim 1 , wherein the dehydrogenation is effected with addition of oxygen, wherein the added amount of oxygen based on the mass of the n-butane present in the subsidiary fraction is
1.4 wt % to 14 wt %.

12. The process according to claim 1 , wherein the hydrogenation mixture is mixed with the feedstock mixture as a recyclate without purification.

13. The process according to claim 1 , wherein the hydroformylation mixture is exclusively separated into the primary product fraction and the subsidiary fraction.

14. The process according to claim 1 , wherein the hydroformylation mixture is separated into a low boiler fraction, the subsidiary fraction and the primary product fraction.

15. The process according to claim 14 , wherein the hydroformylation mixture is separated into the low boiler fraction, the subsidiary fraction, the primary product fraction and into a secondary product fraction, wherein the secondary product fraction has the following composition which sums to 100 wt %:
propanal: 50 wt % to 70 wt %;
n-butanal: 30 wt % to 50 wt %;
other substances: 0 wt % to 10 wt %.

16. The process according to claim 1 , wherein the mass flow of the subsidiary fraction is less than 4 kg/s and the apparatus of the dehydrogenation is of a size configured for continuous processing of this mass flow.

17. The process according to claim 1 , wherein the subsidiary fraction is recovered by distillation with subsequent hydrogenation.

18. A method of a plant for dehydrogenation of alkanes comprising at least a heated reactor filled with a second catalyst system for retrofitting an existing plant for producing n-pentanal from feedstock mixtures comprising the step of hydroformylating of n-butene and n-butane where the plant for dehydrogenation is arranged downstream of the plant for hydroformylation, and feeding said plant for dehydrogenation with a subsidiary fraction from the hydroformylation and the effluent from the dehydrogenation is recycled into the hydroformylation with or without purification.

19. The process according to claim 2 , wherein at least two reactors, each heated and each filled with the second catalyst system, are provided for the dehydrogenation and the reactors are chargeable with subsidiary fraction individually or simultaneously in parallel and/or serially as desired.

20. The process according to claim 2 , wherein the dehydrogenation mixture is liquefied by compression and cooling and the selective hydrogenation is effected in the liquid phase at a pressure of 18*10 5 Pa to 22*10 5 Pa and a temperature of 40° C. to 80° C.

Assignees

• Evonik Degussa Gmbh

Inventors

• Franke Robert
• Altmann Lena
• Hecht Corinna
• Dercks Benedikt
• Spohr Hanna
• Zanthoff Horst-Werner

Classifications

• C07C5/03

  of non-aromatic carbon-to-carbon double bonds · CPC title

• C07C45/505 Primary

  Asymmetric hydroformylation · CPC title

• C07C5/3337

  of the platinum group · CPC title

• C07C2523/54

  combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 · CPC title

• B01J8/0496

  Heating or cooling the reactor · CPC title