Process for obtaining high-purity 1-butene from C4 hydrocarbon mixtures

Patent metadata

Field	Value
Publication number	US-10774020-B2
Application number	US-201013144101-A
Country	US
Kind code	B2
Filing date	Jan 11, 2010
Priority date	Jan 13, 2009
Publication date	Sep 15, 2020
Grant date	Sep 15, 2020

Abstract

A process is described for obtaining high-purity 1-butene starting from C 4 hydrocarbon mixtures containing isobutene, n-butane, isobutane, 1,3-butadiene, 1-butene, 2-butenes and also optionally C 3 and C 5 hydrocarbons, comprising the following stages: conversion of isobutene effected in a double stage, wherein each stage consists of one or more reactors followed by a distillation column for the recovery of the reaction product; recovery of the excess alcohol; recovery of 1-butene using at least two distillation columns; characterised in that it also uses a further conversion stage, consisting of one or more reactors in series, for completing the isobutene removal.

First claim

The invention claimed is:

1. A process, comprising:
an initial conversion stage of converting isobutene from a FCC or stream cracking C4 hydrocarbon mixture comprising isobutene, n-butane, iso-butane, 1,3-butadiene, 1-butene, and a 2-butene by performing at least one of: etherifying the isobutene with an alcohol; dimerizing the isobutene in the presence of an alcohol; dimerizing the isobutene in the presence of water; and dimerizing the isobutene in the presence of an ether, wherein the initial conversion stage is conducted in two reaction steps, each reaction step occurring by (i) performing the converting in at least one reactor, optionally with intermediate cooling, and then immediately (ii) performing a single distillation in a distillation column that is separate from the at least one reactor and is suitable for recovery of an initial reaction product;
then, immediately following the initial conversion stage a further conversion stage of completely removing isobutene from the initial reaction product in a reactor or reactors in series, thereby producing a further reaction product comprising at least one oxygenated compound comprising dimethyl ether;
recovering excess alcohol if present in the initial reaction product or in the further reaction product;
removing the dimethyl ether and any other oxygenated compounds from the further reaction product produced in the further conversion stage, by distillation in a distillation column downstream therefrom; and
an additional stage of selectively hydrogenating a diene from the further reaction product in at least one reactor situated immediately upstream of a recovery stage that is performed by recovering 1-butene with at least a first distillation column having an outflow that is an inflow to a second distillation column,
thereby obtaining a high-purity 1-butene.

2. The process according to claim 1 , wherein the initial conversion stage of converting isobutene comprises etherifying the isobutene with a linear alcohol.

3. The process according to claim 1 , wherein the initial conversion stage of converting isobutene comprises selectively dimerizing the isobutene in the presence of a linear alcohol, a branched alcohol, an alkyl ether, or any combination thereof.

4. The process according to claim 3 , wherein the isobutene is selectively dimerized in the presence of a branched alcohol having a number of carbon atoms of from 3 to 6.

5. The process according to claim 3 , wherein the isobutene is selectively dimerized in the presence of an alkyl ether having a number of carbon atoms of from 5 to 10.

6. The process according to claim 1 , wherein the further conversion stage comprises reacting the isobutene with a linear alcohol.

7. The process according to claim 2 or 6 , wherein the linear alcohol has a number of carbon atoms of between 1 and 5.

8. The process according to claim 1 , wherein the further conversion stage comprises reacting the isobutene with water.

9. The process according to claim 1 , wherein the recovering of the excess alcohol comprises recovering the excess alcohol in two columns, of which a first column is a washing column with water.

10. The process according to claim 1 , wherein the recovering of the excess alcohol comprises recovering the excess alcohol in an absorption system with molecular sieves.

11. The process according to claim 1 , wherein the further conversion stage occurs before the recovery stage.

12. The process according to claim 1 , wherein the further conversion stage occurs before the recovering of the excess alcohol.

13. The process according to claim 1 , wherein the dimethyl ether and any other oxygenated compounds produced in the further conversion stage are removed with at least one distillation column situated downstream of the further conversion stage.

14. The process according to claim 1 , wherein the removing of the dimethyl ether and any other oxygenated compounds produced in the further conversion stage comprises feeding the distillation column with a C4 hydrocarbon stream comprising 2-butene and n-butane.

15. The process according to claim 1 , wherein the first distillation column of the recovery stage stabilizes the additional stage of selectively hydrogenating the diene.

16. The process according to claim 1 , further comprising:
a bond isomerization stage of bond isomerizing a stream comprising 2-butenes and n-butane, following the recovery stage.

17. The process according to claim 1 , further comprising:
a skeletal isomerization stage of skeletal isomerizing a stream comprising 2-butenes and n-butane, following the recovery stage.

18. The process according to claim 1 , wherein the first and second distillation columns of the recovery stage are thermally integrated.

19. The process according to claim 1 , further comprising:
providing a reboiler heat to one distillation column of the recovery stage from a total or partial condensation of a stream from the top of another distillation column of the recovery stage.

20. The process according to claim 1 , further comprising:
providing a reboiler heat to one distillation column of the recovery stage and to a distillation column for removal of heavy products in the further conversion stage from a total or partial condensation of a stream from the top of another distillation column of the recovery stage.

21. The process according to claim 9 or 18 , wherein the first and second distillation columns of the recovery stage are thermally integrated with an alcohol recovery column.

22. The process according to claim 21 , further comprising:
providing a partial or total condensation of a vapor from a top of the alcohol recovery column as a reboiler to the first and second distillation columns of the recovery stage.

23. The process according to claim 22 , further comprising:
providing a reboiler heat to the first and second distillation columns of the recovery stage by a total or partial condensation of the vapor from the top of the alcohol recovery column and from the first or the second distillation column of the recovery stage.

24. A process, comprising:
an initial conversion stage of converting isobutene from a FCC or stream cracking C4 hydrocarbon mixture comprising isobutene, n-butane, iso-butane, 1,3-butadiene, 1-butene, and a 2-butene by performing at least one of: etherifying the isobutene with an alcohol; dimerizing the isobutene in the presence of an alcohol; dimerizing the isobutene in the presence of water; and dimerizing the isobutene in the presence of an ether, wherein the initial conversion stage is conducted in two reaction steps, each reaction step occurring by (i) performing the converting in at least one reactor, optionally with intermediate cooling, and then immediately (ii) performing a single distillation in a distillation column that is separate from the at least one reactor and is suitable for recovery of an initial reaction product;
then, immediately following the initial conversion stage, a further conversion stage of completely removing isobutene from the initial reaction product in a reactor or reactors in series, thereby producing a further reaction product comprising at least one oxygenated compound comprising dimethyl ether;
recovering excess alcohol if present in the initial reaction product or in the further reaction product;
removing the dimethyl ether and any other oxygenated compounds from the further reaction product produced in the further conversion stage,

Assignees

• Di Girolamo Marco
• Brianti Maura
• Conte Massimo
• Saipem Spa

Inventors

• Di Girolamo Marco
• Brianti Maura
• Conte Massimo

Classifications

• C07C7/04 Primary

  by distillation · CPC title

• C07C7/00 Primary

  Purification; Separation; Use of additives (working-up undefined gaseous mixtures obtained by cracking hydrocarbon oils C10G70/00) · CPC title

• C07C7/177 Primary

  by selective oligomerisation or polymerisation of at least one compound of the mixture · CPC title

• C07C11/08

  with four carbon atoms · CPC title

• C07C41/06

  by addition of organic compounds only · CPC title