Continuous preparation method of high-purity quadricyclane

Patent metadata

Field	Value
Publication number	US-9944574-B2
Application number	US-201414409448-A
Country	US
Kind code	B2
Filing date	May 23, 2014
Priority date	Feb 17, 2014
Publication date	Apr 17, 2018
Grant date	Apr 17, 2018

Abstract

The invention discloses a continuous process for producing high-pure quadricyclane, in which “a reaction-rectification integral process” or “a reaction followed by rectification process” may be employed. The two processes both use a novel composite catalyst which is obtained by loading an organic photo-sensitizer on a solid photocatalyst, and the composite catalyst has a high activity and a good stability. In the reaction-rectification integral process, the composite catalyst is used by being blended with rectification fillers or covering the rectification fillers, so as to achieve the integration of the reaction and the rectification. In the reaction followed by rectification process, the composite catalyst and the rectification fillers are placed separately from each other. The two processes achieve a relatively short residence time of reactants, produce highly-pure quadricyclane, and reduce the formation of cokes.

First claim

The invention claimed is:

1. A continuous process for producing highly-pure quadricyclane, comprising the following steps:
(a) a norbornadiene reactant is introduced into a reaction-rectification integral reactor; the reactor comprises a stainless steel cylinder in the outside, and a quartz tube is arranged inside of the reactor; an ultraviolet light source is arranged in the quartz tube, and rectification fillers and a composite catalyst are filled between the quartz tube and the stainless steel cylinder, wherein the rectification fillers are disorderly mixed with the composite catalyst in the particulate form, or the surface of the rectification fillers is covered with a layer of the composite catalyst; the introduced norbornadiene in a form of a liquid film or a gas-liquid mixture flows through the surface and inner channels of the composite catalyst so that a reaction is conducted to produce a reaction product comprising quadricyclane and cokes; and simultaneously,
(b) under the rectification action provided by the reaction-rectification integral reactor, the norbornadiene gradually moves toward the top of the reaction-rectification integral reactor and the reaction continues; unreacted norbornadiene leaves from the top and after being condensed, it returns the reaction-rectification integral reactor as the circulating reactant; the product quadricyclane and cokes can move toward the bottom of the reaction-rectification integral reactor under the action of rectification and are discharged from the bottom to a distiller in which the distillation is conducted; at last, the quadricyclane in the purity of more than 99.5% is produced on the top of the distiller, and the cokes are remained in the bottom of the distiller.

2. The process according to claim 1 , wherein said composite catalyst comprises:
a solid photocatalyst, which is selected from TiO 2 , Ti-MCM-41, Ti-SBA-15, ZnO, WO 3 , Ta 2 O 5 or SrTiO 3 ; and
an organic photo-sensitizer loaded on the surface or channels of the solid photocatalysts, the organic photo-sensitizer is selected from benzophenone, acetophenone, Michler's Ketone, tetraethyl Michler's Ketone or diethyl Michler's Ketone;
wherein the organic photo-sensitizer is present in an amount of 0.5 to 20% by weight of the solid photocatalyst.

3. The process according to claim 1 , wherein the process conditions in the reaction-rectification integral reactor are as follows: temperature on the top of the reactor ranges from 90 to 95° C.; temperature on the bottom of the reactor ranges from 100 to 105° C.; pressure is an atmospheric pressure; and reflux ratio ranges from 0.5 to 2.

4. The process according to claim 1 , wherein the process conditions in the distiller are as follows: temperature ranges from 60 to 65° C., and pressure ranges from 90 to 110 mBar, being gauge pressures.

5. A continuous process for producing highly-pure quadricyclane, comprising the following steps:
(a) a norbornadiene reactant is introduced into a reactor; the reactor comprises a stainless steel cylinder in the outside, and a quartz tube is arranged inside of the reactor; an ultraviolet light source is arranged in the quartz tube, and a composite catalyst is filled between the quartz tube and the stainless steel cylinder; the introduced norbornadiene flows through the surface and inner channels of the composite catalyst in a form of a liquid film so that a reaction is conducted to produce a reaction product comprising quadricyclane and cokes; and then
(b) all the materials are fed into a rectification column, and under the rectification action, unreacted norbornadiene, as the tops, leaves from the top of the rectification column and returns to the aforesaid reactor as the circulating reactant; the quadricyclane and cokes, as the bottoms, leave the rectification column; and then
(c) the aforesaid bottoms are fed into a distiller to conduct distillation; the quadricyclane in the purity of more than 99.5% is produced on the top of the distiller, and cokes are remained in the bottom of the distiller; wherein said composite catalyst comprises:
a solid photocatalyst, which is selected from TiO 2 , Ti-MCM-41, Ti-SBA-15, ZnO, WO 3 , Ta 2 O 5 or SrTiO 3 ; and
an organic photo-sensitizer loaded on the surface or channels of the solid photocatalyst, the organic photo-sensitizer is selected from benzophenone, acetophenone, Michler's Ketone, tetraethyl Michler's Ketone or diethyl Michler's Ketone;
wherein the organic photo-sensitizer is present in an amount of 0.5 to 20% by weight of the solid photocatalyst.

6. The process according to claim 5 , wherein the process conditions in the reactor are as follows: there are no specific requirements to the temperature, and the pressure is an atmospheric pressure.

7. The process according to claim 5 , wherein the process conditions in the rectification column are as follows: the height of the column is not lower than 100 cm; the temperature on the top of the column is from 90 to 95° C.; the temperature on the bottom of the column is from 100 to 105° C.; the pressure is an atmospheric pressure, and the reflux ratio ranges from 0.5 to 2.

8. The process according to claim 5 , wherein the process conditions in the distiller are as follows: the temperature ranges from 60 to 65° C., and the pressure ranges from 90 to 110 mBar, being gauge pressure.

Assignees

• Univ Tianjin

Inventors

• Zou Jijun
• Zhang Xiangwen
• Wang Li
• Wang Qingfa

Classifications

• C07C2523/30

  Tungsten · CPC title

• B01J19/123

  Ultraviolet light · CPC title

• B01J31/26

  containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 · CPC title

• B01J31/36

  of vanadium, niobium or tantalum · CPC title

• C07C2531/38

  of titanium, zirconium or hafnium · CPC title