Process for preparing cyclohexane with starting materials originating from a steamcracking process

Patent metadata

Field	Value
Publication number	US-10081580-B2
Application number	US-201314053634-A
Country	US
Kind code	B2
Filing date	Oct 15, 2013
Priority date	Oct 18, 2012
Publication date	Sep 25, 2018
Grant date	Sep 25, 2018

Abstract

The present invention relates to a process for preparing cyclohexane by isomerizing a hydrocarbon mixture (HM 1 ) comprising methylcyclopentane (MCP) in the presence of a catalyst. The catalyst is preferably an acidic ionic liquid. The starting material used is a stream (S 1 ) which originates from a steamcracking process. The hydrocarbon mixture (HM 1 ) obtained from this stream (S 1 ) in an apparatus for aromatics removal has a reduced aromatics content compared to stream (S 1 ), and (HM 1 ) may optionally also be (virtually) free of aromatics. Depending on the type and amount of the aromatics remaining in the hydrocarbon mixture (HM 1 ), especially in the case that benzene is present, the isomerization may additionally be preceded by performance of a hydrogenation of (HM 1 ). In addition, depending on the presence of other components of (HM 1 ), further purification steps may optionally be performed prior to or after the isomerization or hydrogenation. High-purity (on-spec) cyclohexane is preferably isolated from the hydrocarbon mixture (HM 2 ) obtained in the isomerization, the specifications being, for example, those applicable to the use of the cyclohexane for the preparation, known to those skilled in the art, of caprolactam.

First claim

The invention claimed is:

1. A process for preparing cyclohexane, comprising the following steps:
a) isomerizing a hydrocarbon mixture (HM 1 ) comprising methylcyclopentane (MCP) in the presence of an isomerization catalyst to obtain a hydrocarbon mixture (HM 2 ) comprising cyclohexane, wherein the catalyst is an acidic ionic liquid,
(HM 1 ) being obtained from an apparatus for aromatics removal connected downstream of a steamcracking process, wherein a feed containing an aromatic entering the apparatus for aromatics removal comprises a stream (S 1 ) originating from the steamcracking process, and

b) isolating cyclohexane from the hydrocarbon mixture (HM 2 ); wherein the process comprises step a-1), which is performed prior to step a), comprising
a-1) hydrogenating the hydrocarbon mixture (HM 1 ) comprising methylcyclopentane (MCP) and at least one aromatic to obtain a hydrocarbon mixture (HM 1 a ) having methylcyclopentane (MCP) and a reduced amount of the at least one aromatic compared to (HM 1 ), with use of (HM 1 a ) rather than (HM 1 ) in the subsequent steps a) and b).

2. The process according to claim 1 , wherein the apparatus for aromatics removal is an extractive aromatics distillation, or the hydrocarbon mixture (HM 1 ) has a lower concentration of aromatics than the feed stream (S 1 ) to the apparatus for aromatics removal.

3. The process according to claim 1 , wherein the aromatic present in the hydrocarbon mixture (HM 1 ) is benzene or the hydrocarbon mixture (HM 1 a ) comprises an increased amount of cyclohexane compared to (HM 1 ).

4. The process according to claim 1 , wherein the hydrogenation of the hydrocarbon mixture (HM 1 ) is performed in the presence of a hydrogenation catalyst comprising, as an active metal, at least one element of groups 8 to 10 of the Periodic Table of the Elements.

5. The process according to claim 4 , wherein the hydrogenation catalyst comprises nickel or ruthenium.

6. The process according to claim 1 , wherein the hydrocarbon mixture (HM 1 ) comprises benzene, methylcyclopentane (MCP) and at least one further compound selected from cyclohexane, cyclopentane, olefins and acyclic C5-C8-alkanes.

7. The process according to claim 1 , wherein step a) is preceded by distillative separation of at least one compound selected from linear or branched C5-alkanes, cyclopentane and linear or branched C6-alkanes from the hydrocarbon mixture (HM 1 ).

8. The process according to claim 1 , additionally comprising step a-2), which is performed prior to step a) comprising
a-2) feeding the hydrocarbon mixture (HM 1 ) into a distillation apparatus (D 1 ), (HM 1 ) comprising methylcyclopentane (MCP), at least one alkane having 7 or more carbon atoms and optionally an aromatic, the at least one alkane having 7 or more carbon atoms being removed in (D 1 ) from (HM 1 ) to obtain a hydrocarbon mixture (HM 1 b )
comprising methylcyclopentane (MCP) and a reduced amount of at the least one alkane having 7 or more carbon atoms compared to (HM 1 ), and (HM 1 b ) being used rather than (HM 1 ) in the subsequent steps a) and b).

9. The process according to claim 8 , wherein the step a-2) has the following component steps:
d1) feeding the hydrocarbon mixture (HM 1 ) comprising
i) benzene,
ii) MCP,
iii) dimethylpentanes (DMP),
iv) cyclohexane and
v) optionally at least one further compound selected from olefins and C 5 -C 8 -alkanes into the distillation apparatus (D 1 ),

d2) removing a stream (S 3 ) comprising DMP from an outlet of the distillation apparatus (D 1 ), the outlet being at the bottom of (D 1 ),
d3) removing the hydrocarbon mixture (HM 1 b ) comprising benzene or MCP from an outlet of the distillation apparatus (D 1 ), the outlet being at the top of (D 1 ).

10. The process according to claim 9 , wherein the hydrocarbon mixture (HM 1 b ) comprises at least 95% of the portion consisting of benzene and MCP present in the hydrocarbon mixture (HM 1 ), or the hydrocarbon mixture (HM 1 b ) comprises at most 0.1% by weight (based on the total amount of benzene and MCP in (HM 1 b )), of DMP.

11. The process according to claim 10 , wherein the hydrocarbon mixture (HM 1 b ) comprises at most 0.015% by weight (based on the total amount of benzene and MCP in (HM 1 b )) of 2,4-DMP.

12. The process according to claim 9 , wherein the stream (S 3 ) is introduced into a distillation apparatus (D 2 ), cyclohexane being separated from DMP in (D 2 ), and (D 2 ) comprising an extractive distillation column or the cyclohexane-enriched stream drawn off from (D 2 ) comprising at most 0.1% by weight of 2,4-DMP.

13. The process according to claim 12 , wherein the cyclohexane/DMP separation comprises the following steps i) to iii) and optionally step iv), the distillation apparatus (D 2 ) being formed by the three components (D 2 - 1 ) to (D 2 - 3 ):
i) a rectifying column (D 2 - 1 ) in which the majority of the high boilers having a standard boiling point >84° C. (based on the amount in the feed to (D 2 - 1 )) is removed via the bottom and the majority of the cyclohexane and other compounds having a standard boiling point of 79 to 84° C. (based on the amount in the feed to D 2 - 1 ) is removed via the top,
ii) an extractive distillation column (D 2 - 2 ) in which the top product from (D 2 - 1 ) is combined with an extraction aid and distilled in such a way that the majority of the extraction aid and of the cyclohexane is drawn off via the bottom and the majority of the other compounds having a standard boiling point of 79 to 84° C. present in the top product from (D 2 - 1 ) is drawn off from (D 2 - 2 ) via the top,
iii) a regeneration column (D 2 - 3 ) in which the majority of the cyclohexane present in the bottom stream from (D 2 - 2 ) is drawn off via the top and the majority of the extraction aid present in the bottom stream from (D 2 - 2 ) is drawn off via the bottom, and
iv) optionally a hydrogenation apparatus into which either stream (S 3 ) or the top product from (D 2 - 3 ) is conducted.

14. The process according to claim 13 , wherein cyclohexane which originates from the distillation apparatus (D 2 ) is combined with the cyclohexane which has been prepared in the isomerization in step a).

15. The process according to claim 1 , wherein, in step b), cyclohexane is isolated in a purity of at least 98% by weight.

16. The process according to claim 15 , wherein the purity is least 99.9% by weight.

17. The process according to claim 1 , wherein the hydrocarbon mixture (HM 2 ) comprising cyclohexane, MCP, possibly acyclic C5-C6-alkanes and possibly higher-boiling components than cyclohexane is fed into a distillation column (D 4 ), and the majority of the MCP and, if present, of acyclic C5-C6-alkanes present in the feed to (D 4 ) is removed from (D 4 ) at a withdrawal point above the feed and recycled into or upstream of the isomerization in step a).

18. The process according to claim 17 , wherein cyclohexane is drawn off from the distillation column (D 4 ) in a purity of at least 98% by weight via the bottom of (D 4 ) or via a side draw from (D 4 ) below the feed.

19. The process according to claim 18 , wherein the cyclohexane-enriched stream drawn off via the bottom of (D 4 ) is introduced into a distillation column (D 5 ), and a stream (S 5 ) comprising higher-boiling components than cyclohexane is removed via the bottom of (D 5 ) and cyclohexane is drawn off with a purity of at least 98% by weight via a takeoff point above the feed to (D 5 ).

20. The process according to claim

Assignees

• Basf Se

Inventors

• Tschirschwitz Steffen
• Wissel-Stoll Kathrin
• Bürkle Jochen
• Kostova Albena
• Schmitt Markus
• Wloka Veronika
• Deuerlein Stephan
• Bosch Marco
• Oehlenschläger Steffen
• Schreiber Michael
• Averlant Gauthier Luc Maurice
• Joni Joni
• Prochazka Roman
• Bock Martin
• Kindler Alois
• Malkowsky Daniela
• Spuhl Katharina
• Bitterlich Stefan
• Pfeiffer Daniel

Classifications

• C07C2527/135

  Compounds comprising a halogen and titanum, zirconium, hafnium, germanium, tin or lead · CPC title

• C07C2527/125

  Compounds comprising a halogen and scandium, yttrium, aluminium, gallium, indium or thallium · CPC title

• C07C2527/11

  Hydrogen chloride · CPC title

• C07C2523/755

  Nickel · CPC title

• C07C2521/06

  Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof · CPC title