Method for preparing cyclododecene and synthesis device therefor

Patent metadata

Field	Value
Publication number	US-11608304-B2
Application number	US-201816958181-A
Country	US
Kind code	B2
Filing date	Oct 23, 2018
Priority date	Dec 28, 2017
Publication date	Mar 21, 2023
Grant date	Mar 21, 2023

Abstract

A method for preparing cyclododecene and a synthesis device therefor, of the present invention, remarkably increase the conversion ratio of cyclododecatriene and selectivity of cyclododecene, can minimize the costs required for equipment and processing, are practical, reduce processing time, and are industrially advantageous to mass production in comparison with a conventional method and device.

First claim

The invention claimed is:

1. A method for synthesizing cyclododecene, comprising a hydrogenation step of partially hydrogenating cyclododecatriene to synthesize cyclododecene,
wherein cyclododecatriene and hydrogen sequentially pass through a continuous stirred-tank reactor and a tubular reactor and react with each other in the continuous stirred-tank reactor and the tubular reactor to synthesize cyclododecene.

2. The method of claim 1 , wherein the following Expression 1 is satisfied,
1≤τ 1P /τ 1C ≤9  [Expression 1]

(in Expression 1, τ 1C is a residence time of a reactant or a product in the continuous stirred-tank reactor, and τ 1P is a residence time of a reactant or a product in the tubular reactor).

3. The method of claim 1 , wherein the continuous stirred-tank reactor is obtained by sequentially connecting a first continuous stirred-tank reactor and a second continuous stirred-tank reactor.

4. The method of claim 3 , wherein the following Expression 2 is satisfied,
0.1≤τ 2C /τ 1C ≤0.9

1≤τ 1P /τ 1C ≤9  [Expression 2]

(in Expression 2, τ 1C and τ 2C are a residence time of a reactant or a product in the first continuous stirred-tank reactor and a residence time of a reactant or a product in the second continuous stirred-tank reactor, respectively, and Tip is a residence time of a reactant or a product in the tubular reactor).

5. The method of claim 1 , wherein the cyclododecene is synthesized by hydrogenation to the cyclododecatriene in a solvent containing ethanol, and is synthesized by the reaction under a catalyst containing ruthenium chloride, triphenylphosphine, and formaldehyde.

6. The method of claim 5 , wherein a molar ratio of the ruthenium chloride to the triphenylphosphine is 1:110 to 130.

7. The method of claim 5 , wherein a molar ratio of the triphenylphosphine to the formaldehyde is 1:1.5 to 2.

8. The method of claim 5 , wherein in the hydrogenation step, a catalyst activator containing acetic acid is further used.

9. The method of claim 5 , wherein the catalyst is used in an amount of 1 to 7 parts by weight with respect to 100 parts by weight of the cyclododecatriene.

10. The method of claim 1 , wherein the reaction is performed at a pressure of 10 to 80 bar and a temperature of 130 to 170° C.

11. A device for synthesizing cyclododecene by partially hydrogenating cyclododecatriene, the device comprising:
a continuous stirred-tank reactor into which cyclododecatriene and hydrogen are introduced to synthesize cyclododecene; and
a tubular reactor into which the cyclododecene or a mixture including the cyclododecene is introduced from the continuous stirred-tank reactor to synthesize cyclododecene.

12. The device of claim 11 , wherein the following Expression 3 is satisfied,
1≤ V 1P /V 1C ≤9  [Expression 3]

(in Expression 3, V 1C is a volume of a reaction space of the continuous stirred-tank reactor, and V 1P is a volume of a reaction space of the tubular reactor).

13. A device for synthesizing cyclododecene by partially hydrogenating cyclododecatriene, the device comprising:
a first continuous stirred-tank reactor into which cyclododecatriene and hydrogen are introduced to synthesize cyclododecene;
a second continuous stirred-tank reactor into which the cyclododecene or a mixture including the cyclododecene is introduced from the first continuous stirred-tank reactor to synthesize cyclododecene; and
a tubular reactor into which the cyclododecene or a mixture including the cyclododecene is introduced from the second continuous stirred-tank reactor to synthesize cyclododecene.

14. The device of claim 13 , wherein the following Expression 4 is satisfied,
0.1≤ V 2C /V 1C ≤0.9

1≤ V 1P /V 1C ≤9  [Expression 4]

(in Expression 4, V 1C and V 2C are a volume of a reaction space of the first continuous stirred-tank reactor and a volume of a reaction space of the second continuous stirred-tank reactor, respectively, and V 1P is a volume of a reaction space of the tubular reactor).

15. The device of claim 13 , wherein first hydrogen is introduced into and reacted in the first continuous stirred-tank reactor, such that the cyclododecene is synthesized,
second hydrogen is introduced into and reacted in the second continuous stirred-tank reactor, such that the cyclododecene is synthesized, and
third hydrogen is introduced into and reacted in the tubular reactor, such that the cyclododecene is synthesized.

Assignees

• Hanwha Solutions Corp
• Hanwha Chemical Corp

Inventors

• Jang Namjin
• Song Kyuho
• Kim Youngjin
• Jeong Wook

Classifications

• C07C13/273

  with a twelve-membered ring · CPC title

• B01J31/02

  containing organic compounds or metal hydrides · CPC title

• C07C2523/46

  Ruthenium, rhodium, osmium or iridium · CPC title

• B01J27/13

  Platinum group metals · CPC title

• B01J19/0066 Primary

  Stirrers (mixing per se B01F) · CPC title