Process for preparing cyclohexane from benzene and methylcyclopentane with upstream benzene hydrogenation

Patent metadata

Field	Value
Publication number	US-9873646-B2
Application number	US-201515305111-A
Country	US
Kind code	B2
Filing date	Apr 20, 2015
Priority date	Apr 22, 2014
Publication date	Jan 23, 2018
Grant date	Jan 23, 2018

Abstract

The present invention relates to a process for preparing cyclohexane from methylcyclopentane (MCP) and benzene. In the context of the present invention, MCP and benzene are constituents of a hydrocarbon mixture (HM1) additionally comprising dimethylpentanes (DMP), possibly cyclohexane and possibly at least one compound (low boiler) selected from acyclic C 5 -C 6 -alkanes and cyclopentane. First of all, benzene is converted in a hydrogenation step to cyclohexane (that present in the hydrocarbon mixture (HM2)), while MCP is isomerized in the presence of a catalyst, preferably of an acidic ionic liquid, to cyclohexane. After the hydrogenation but prior to the isomerization the dimethylpentanes (DMP) are removed, with initial removal of the cyclohexane present in the hydrocarbon mixture (HM2) together with DMP. This cyclohexane already present prior to the isomerization can be separated again from DMP in a downstream rectification step and isolated and/or recycled into the process for cyclohexane preparation. Between the DMP removal and MCP isomerization—if low boilers are present in the hydrocarbon mixture (HM1)—low boilers are, optionally removed. After the isomerization, the cyclohexane is isolated, optionally with return of unisomerized MCP and optionally of low boilers. Preferably, cyclohexane and/or low boilers are present in the hydrocarbon mixture (HM1), and so a low boiler removal is preferably conducted between the DMP removal from isomerization. It is additionally preferable that the removal of the cyclohexane from DMP is additionally conducted, meaning that the cyclohexane component which arises in the benzene hydrogenation and may be present in the starting mixture (HM1) is isolated and hence recovered.

First claim

The invention claimed is:

1. A process for preparing cyclohexane, comprising the following steps:
a) hydrogenating a hydrocarbon mixture (HM1), (HM1) comprising i) benzene, ii) methylcyclopentane (MCP), iii) dimethylpentanes (DMP), iv) possibly cyclohexane and v) possibly at least one compound selected from acyclic C 5 -alkanes, cyclopentane and acyclic C 6 -alkanes, to obtain a hydrocarbon mixture (HM2) having an elevated amount of cyclohexane compared to (HM1);
b) feeding the hydrocarbon mixture (HM2) into a rectification column (D1);
c) removing a stream (S1) comprising DMP and cyclohexane from the hydrocarbon mixture (HM2) via an outlet of the rectification column (D1), the outlet being below the feed to obtain the hydrocarbon mixture (HM2a) having a reduced amount of DMP compared to (HM2);
d) optionally removing at least one compound selected from acyclic C 5 -alkanes, cyclopentane and acyclic C 6 -alkanes from the hydrocarbon mixture (HM2a) in a rectification column (D3) to obtain the hydrocarbon mixture (HM2b) having a reduced amount of at least one compound selected from acyclic C 5 -alkanes, cyclopentane and acyclic C 6 -alkanes compared to (HM2a);
e) isomerizing the hydrocarbon mixture (HM2a) or optionally the hydrocarbon mixture (HM2b) in the presence of a catalyst to obtain a hydrocarbon mixture (HM3) having an elevated amount of cyclohexane compared to (HM2a) or, if appropriate, compared to (HM2b); and
f) isolating cyclohexane from the hydrocarbon mixture (HM3).

2. The process according to claim 1 , wherein, in step c), the outlet of the rectification column (D1) is at the bottom of(D1).

3. The process according to claim 1 , wherein, in step a), the hydrogenation of the hydrocarbon mixture (HM1) is performed in the presence of a catalyst comprising, as an active metal, at least one element of groups 8 to 10 of the Periodic Table of the Elements.

4. The process according to claim 1 , wherein, in step a), the hydrogenation of the hydrocarbon mixture (HM1) is performed in the presence of a catalyst comprising, as an active metal, nickel or ruthenium.

5. The process according to claim 1 , wherein the hydrocarbon mixture (HM2a) comprises at least 95% of the portion of MCP present in the hydrocarbon mixture (HM2), or the hydrocarbon mixture (HM2a) comprises at most 0.1% by weight (based on the total amount of MCP in (HM2a)) of DMP.

6. The process according to claim 1 , wherein the hydrocarbon mixture (HM2a) comprises at least 98% of the portion of MCP present in the hydrocarbon mixture (HM2), or the hydrocarbon mixture (HM2a) comprises at most 0.02% by weight (based on the total amount of MCP in (HM2a)) of DMP.

7. The process according to claim 1 , wherein the hydrocarbon mixture (HM2a) comprises at most 0.015% by weight (based on the total amount of MCP in (HM2a)) of 2,4-DMP.

8. The process according to claim 1 , wherein, in step a), the hydrocarbon mixture (HM1)
comprises cyclohexane as component iv) or
comprises at least one compound selected from acyclic C 5 -alkanes, cyclopentane and acyclic C 6 -alkanes as component v),
where, in the case that component b) is present in (HM1), step d) is necessarily conducted, and then, in step e), the hydrocarbon mixture (HM2b) is used rather than the hydrocarbon mixture (HM2a).

9. The process according to claim 1 , wherein the catalyst used in step e) is an acidic ionic liquid comprising, as a cation, an at least partly alkylated ammonium ion or a heterocyclic cation or, as an anion, a chloroaluminate ion having the composition Al n Cl (3n+1) where 1<n<2.5.

10. The process according to claim 1 , wherein,
i) in step f), cyclohexane is isolated in a purity of at least 98% by weight, or
ii) step f) is performed in a rectification column (D4), by removing a stream (LB2) comprising MCP and possibly acyclic C 5 -C 6 -alkanes from the hydrocarbon mixture (HM3) in (D4) and fully or partly recycling stream (LB2) to step d) or to step e).

11. The process according to claim 1 , wherein, in step f), cyclohexane is isolated in a purity of at least 99.5% by weight.

12. The process according to claim 1 , wherein the hydrocarbon mixture (HM3) comprising cyclohexane, MCP, possibly acyclic C 5 -C 6 -alkanes and possibly higher-boiling components than cyclohexane is fed into a rectification column (D4), and the majority of the MCP and, if present, of acyclic C 5 -C 6 -alkanes present in the feed to (D4) is removed from (D4) at a withdrawal point above the feed.

13. The process according to claim 12 , wherein the majority of the MCP and, if present, of acyclic C 5 -C 6 -alkanes present in the feed to (D4) is removed from (D4) via the top.

14. The process according to claim 10 , wherein cyclohexane is drawn off from the rectification column (D4) in a purity of at least 98% by weight via the bottom of (D4) or via a side draw from (D4) below the feed.

15. The process according to claim 14 , wherein cyclohexane is drawn off from the rectification column (D4) in a purity of at least 98% by weight via a vaporous side draw from (D4).

16. The process according to claim 14 , wherein the cyclohexane-enriched stream drawn off via the bottom of (D4) is introduced into a rectification column (D5), and a stream (S5) comprising higher-boiling components than cyclohexane is removed via the bottom of (D5) and cyclohexane is drawn off with a purity of at least 98% by weight, via a takeoff point above the feed to (D5).

17. The process according to claim 16 , wherein cyclohexane is drawn off with a purity of at least 99.5% by weight.

18. The process according to claim 16 , wherein cyclohexane is drawn off via the top of (D5).

19. The process according to claim 14 , wherein a cyclohexane-enriched stream is removed via the side draw from the rectification column (D4), the side draw being in the stripping section of (D4) or the cyclohexane-enriched stream from the side draw of (D4) being passed into an apparatus (D6) for further purification, in the form of a rectification column, and cyclohexane being obtained therein via a takeoff point above the feed of (D6) with a purity of at least 98% by weight.

20. The process according to claim 19 , wherein cyclohexane is obtained via the top of (D6).

21. The process according to claim 19 , wherein cyclohexane is obtained via a takeoff point above the feed of (D6) with a purity of at least 99.5%.

22. The process according to claim 10 , wherein the rectification column (D4) takes the form of a dividing wall column, the dividing wall is partly above the feed point, a draw point is in the region of the dividing wall and this draw point is used to withdraw a liquid cyclohexane stream having a purity of at least 98% by weight.

23. The process according to claim 22 , wherein the draw point is used to withdraw a liquid cyclohexane stream having a purity of at least 99.5% by weight.

24. The process according to claim 10 , wherein stream (LB2) is recycled to step d), stream (LB2) being introduced into the hydrocarbon mixture (HM2a) upstream of the rectification column (D3) in which step d) is performed.

25. The process according to claim 1 , wherein the stream (S1) removed from the hydrocarbon mixture (HM2) in step c) is introduced into a rectification apparatus (D2), cyclohexane being separated from DMP in (D2), and (D2) comprising an extractive rectification column or the cyclohexane-enriched stream drawn off from (D2) comprising at most 0.1% by weight.

2

Assignees

• Basf Se

Inventors

• Hübner Michael
• Schulz Lukas
• Czajka Pawel
• Gobin Oliver Christian
• Holub Nicole
• Pfeiffer Daniel
• Weickgenannt Andreas
• Porta Garcia Marta

Classifications

• C07C5/03 Primary

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

• C07C5/31

  changing the number of rings · CPC title

• C07C7/04

  by distillation · CPC title

• C07C2527/126

  Aluminium chloride · CPC title

• C07C5/10 Primary

  of aromatic six-membered rings · CPC title