Method for producing conjugated diene

Patent metadata

Field	Value
Publication number	US-10370309-B2
Application number	US-201715699666-A
Country	US
Kind code	B2
Filing date	Sep 8, 2017
Priority date	Mar 9, 2015
Publication date	Aug 6, 2019
Grant date	Aug 6, 2019

Abstract

The invention is concerned with a method for producing a conjugated diene including a reaction step of subjecting a raw material gas containing a monoolefin having a carbon atom number of 4 or more to an oxidative dehydrogenation reaction with a gas containing molecular oxygen in the presence of a catalyst, to obtain a reaction product gas containing a conjugated diene; and a cooling step of cooling the reaction product gas, wherein in the cooling step, a cooling agent is supplied into a cooling column and brought into contact with the reaction product gas; the cooling agent discharged from the cooling column is then cooled by a heat exchanger; a precipitate dissolved in the cooling agent is precipitated within the heat exchanger and recovered; and the cooling agent from which the precipitate has been recovered is circulated into the cooling column.

First claim

The invention claimed is:

1. A method for producing a conjugated diene, the method comprising:
subjecting a raw material gas comprising a monoolefin having a carbon number of 4 or more to an oxidative dehydrogenation reaction with a gas comprising molecular oxygen in the presence of a catalyst to obtain a reaction product gas comprising a conjugated diene; and
subjecting the reaction product gas to a cooling step;
wherein, in the cooling step, a cooling agent is supplied into a cooling column and is brought into contact with the reaction product gas,
the cooling agent discharged from the cooling column is then cooled by at least one heat exchanger,
a precipitate dissolved in the cooling agent is precipitated within the at least one heat exchanger and recovered, and
the cooling agent from which the precipitate has been recovered is circulated into the cooling column;
wherein the cooling agent is water;
wherein a liquid linear rate in the at least one heat exchanger for precipitating the precipitate is 1.0 m/sec or less;
wherein the cooling column comprises an upper zone and a lower zone which are separated by a chimney, and
the upper zone and the lower zone each comprise at least one tray; and
wherein, in the cooling column, the reaction product gas is introduced to the lower zone,
a mixture comprising a portion of the reaction product gas and the cooling agent is discharged from a bottom of the upper zone above the chimney,
the mixture is directed through the at least one heat exchanger to obtain a cooled mixture, and
the cooled mixture from which the precipitate has been recovered is directed to a top of the upper zone of the cooling column.

2. The method for producing a conjugated diene according to claim 1 , wherein the precipitate is 9-fluorenone.

3. The method for producing a conjugated diene according to claim 2 , wherein a concentration of 9-fluorenone in the cooling agent to be circulated into the cooling column is 30 ppm by weight or less.

4. The method for producing a conjugated diene according to claim 1 , wherein two or more of the at least one heat exchangers are provided.

5. The method for producing a conjugated diene according to claim 4 , wherein the two or more heat exchangers are arranged in at least either a parallel direction or a series direction.

6. The method for producing a conjugated diene according to claim 1 , wherein the raw material gas is a gas comprising:
1-butene, cis-2-butene, or tans-2-butene, each of which is obtained by dimerization of ethylene, or a mixture thereof;
a butene fraction which is produced through a dehydrogenation or oxidative dehydrogenation reaction of n-butane; or
a gas comprising a hydrocarbon having a carbon atom number of 4, which is obtained by performing fluid catalytic cracking of a fuel oil fraction.

7. A method for producing a conjugated diene, the method comprising:
subjecting a raw material gas comprising a monoolefin having a carbon atom number of 4 or more to an oxidative dehydrogenation with a gas comprising molecular oxygen in the presence of a catalyst to obtain a reaction product gas comprising a conjugated diene; and
subjecting the reaction product gas to a cooling stop;
wherein, in the cooling step, a cooling agent is supplied into a cooling column and is brought into contact with the reaction product gas,
the cooling agent discharged from the cooling column is then cooled by a condenser,
a precipitate precipitated by cooling is recovered by at least one separation apparatus, and
the cooling agent from which the precipitate has been recovered is circulated into the cooling column;
wherein the cooling agent is water;
wherein the condenser is heat exchanger, and a liquid linear rate in the condenser is faster than 1.0 m/sec;
wherein the cooling column comprises an upper zone and a lower zone which are separated by a chimney, and
the upper zone and the lower zone each comprise at least one tray; and
wherein, in the cooling column, the reaction product gas is introduced to the lower zone,
a mixture comprising a portion of the reaction product gas and the cooling agent is discharged from a bottom of the upper zone above the chimney,
the mixture is directed through the at least one separation apparatus to obtain a cooled mixture, and
the cooled mixture from which the precipitate has been recovered is directed to a top of the upper zone of the cooling column.

8. The method for producing a conjugated diene according to claim 7 , wherein the precipitate is 9-fluorenone.

9. The method for producing a conjugated diene according to claim 8 , wherein a concentration of 9-fluorenone in the cooling agent to be circulated into the cooling column is 30 ppm by weight or less.

10. The method for producing a conjugated diene according to claim 7 , wherein two or more of the at least one separation apparatus are provided.

11. The method for producing a conjugated diene according to claim 7 , wherein the raw material gas is a gas comprising:
1-butene, cis-2-butene, or tans-2-butene, each of which is obtained by dimerization of ethylene, or a mixture thereof;
a butene fraction which is produced through a dehydrogenation or oxidative dehydrogenation reaction of n-butane; or
a gas comprising containing a hydrocarbon having a carbon atom number of 4, which is obtained by performing fluid catalytic cracking of a fuel oil fraction.

12. A method for producing a conjugated diene the method comprising:
subjecting a raw material gas comprising a monoolefin having a carbon atom number of 4 or more to an oxidative dehydrogenation reaction with a gas comprising molecular oxygen in the presence of a catalyst, to obtain a reaction product gas comprising a conjugated diene; and
subjecting the reaction product gas to a cooling step;
wherein water is used as a cooling agent;
wherein, in the cooling step, the cooling agent is supplied into a cooling column and is brought into contact with the reaction product gas, and the cooling agent discharged from the cooling column is then cooled by at least one heat exchanger and circulated into the cooling column;
wherein the cooling column comprises an upper zone and a lower zone which are separated by a chimney, and
the upper zone and the lower zone each comprise at least one tray;
wherein, in the cooling column, the reaction product as is Introduced to the lower zone,
a mixture comprising a portion of the reaction product gas and the cooling agent is discharged from a bottom of the upper zone above the chimney,
the mixture is directed through the at least one heat exchanger and through at least one separation apparatus to obtain a cooled mixture, and
the cooled mixture from which the precipitate has been recovered is directed to a top of the upper zone of the cooling column; and
by regulating a liquid linear rate of the cooling agent passing through the at least one heat exchanger to 1.0 m/sec or less, 9-fluorenone is accumulated within the at least one heat exchanger, and the 9-fluorenone is separated from the cooling agent, or
by making a liquid linear rate of the cooling agent passing through the at least one heat exchanger faster than 1.0 m/sec to pass through the at least one heat exchanger, the 9-fluorenone is then separated from the cooling agent by the at least one separation apparatus.

13. The method for producing a conjugated diene according to claim 12 , wherein a concentration of 9-fluorenone in the cooling agent to be circulated into the cooling column is 30 ppm by weight or less.

14. The method for producing a conjugated diene according to claim 12 , wherein the raw material gas is a gas

Assignees

• Mitsubishi Chem Corp

Inventors

• Hinoishi Hiroki
• IWAKAI Kazuyuki
• Kameo Hiroshi

Classifications

• C07C7/11

  by absorption, i.e. purification or separation of gaseous hydrocarbons with the aid of liquids · CPC title

• C07C7/09

  by fractional condensation · CPC title

• C07C5/48 Primary

  with oxygen as an acceptor · CPC title

• C07B61/00

  Other general methods · CPC title

• B01J23/002

  Mixed oxides other than spinels, e.g. perovskite · CPC title