Metal complex catalyst, preparation method thereof, and use thereof in preparing D,L-menthol

Patent metadata

Field	Value
Publication number	US-10058849-B2
Application number	US-201615565593-A
Country	US
Kind code	B2
Filing date	May 10, 2016
Priority date	May 21, 2015
Publication date	Aug 28, 2018
Grant date	Aug 28, 2018

Abstract

The present invention discloses a metal complex catalyst, its preparing method and its application in preparing D,L-menthol, the metal complex catalyst includes weight percent elements as follows: 70-85% of Ni, 8-10% of Al, 5-10% of V, and 2-10% of Co. When this metal complex catalyst is applied in preparing D,L-menthol through thymol hydrogenation, it has the characteristics of high reaction activity and quick racemization of chiral compound. Meanwhile, a certain kind of alkali added in isomerization is the key to reducing light constituent byproduct. The whole process comes in good reaction selectivity, simple preparing technology, low production cost, and environment-friendly synthetic route.

First claim

The invention claimed is:

1. A metal complex catalyst comprising the following elements of weight percentages:

Ni
70-85% 

Al
8-10%

V
5-10%

Co
 2-10%.

2. The method for preparing metal complex catalyst according to claim 1 , comprising the following steps:
(1) treating Ni—Al alloy with a dilute sodium hydroxide solution, then water-washing the treated Ni—Al alloy until neutral;
the mass percent concentration of the dilute sodium hydroxide solution is 3˜8%;
(2) adding the Ni—Al alloy treated in Step (1) batch by batch into the concentrated sodium hydroxide solution for reaction, after the reaction being completed, keeping the reaction solution static and then washing to obtain intermediate;
the mass percent concentration of the concentrated sodium hydroxide solution is 15˜25%;
(3) adding vanadium nitrate solution and cobalt nitrate solution to the intermediate obtained in Step (2) for replacement reaction, after the reaction being completed, the metal complex catalyst is obtained through post-treatment.

3. The method for preparing metal complex catalyst according to claim 2 , wherein: in Step (1), the weight percent content of Ni in the Ni—Al alloy is 50%˜60%, the weight percent content of Al is 40%˜50%.

4. The method for preparing metal complex catalyst according to claim 2 , wherein: in Step (1), the mass percent concentration of the dilute sodium hydroxide solution is 5%; the treatment temperature is 20˜25° C., and the treatment duration is 1˜3 hours.

5. The method for preparing metal complex catalyst according to claim 2 , wherein: in Step (2), the mass percent concentration of the concentrated sodium hydroxide solution is 20%; the reaction temperature is 10˜25° C., and the reaction duration is 8˜12 hours.

6. The method for preparing metal complex catalyst according to claim 2 , wherein: in Step (3), the concentration of vanadium nitrate is 1˜2 mol/L, that of cobalt nitrate is 0.5˜1 mol/L;
the molar ratio of vanadium nitrate to the Ni in the Ni—Al alloy is 1:8˜15; and
the molar ratio of cobalt nitrate to the Ni in the Ni—Al alloy is 1:30˜40.

7. A method for preparing D,L-menthol, comprising the following steps:
(1) under the effect of the metal complex catalyst in claim 1 and hydrogen, thymol going through hydrogenation reaction, rectifying the produced hydrogenation product to obtain the D,L-menthol and residual fraction;
(2) under the effect of the metal complex catalyst in claim 1 and hydrogen, the residual fraction obtained in Step (1) further going through isomerization reaction, rectifying the produced isomerization product to obtain D,L-menthol.

8. The method for preparing D,L-menthol according to claim 7 , wherein: in Step (1), the pressure of hydrogenation reaction is 2˜8 Mpa, and the temperature of that is 120˜220° C.

9. The method for preparing D,L-menthol according to claim 7 , wherein: in Step (2), the pressure of isomerization reaction is 2˜3 Mpa, and the temperature of that is 80˜120° C.;
the isomerization reaction is conducted under the catalysis of alkaline, and the weight ratio of alkaline to material is 1:10˜30.

10. A method for preparing D,L-menthol, comprising the following steps:
under the effect of the metal complex catalyst in claim 1 and hydrogen, the material containing menthol isomer going through isomerization reaction, the produced isomerization product being rectified to obtain D,L-menthol.

Assignees

• Zhejiang Nhu Co Ltd
• Univ Zhejiang
• Shandong Nhu Pharmaceutical Co Ltd

Inventors

• Yu Ming
• Yuan Jintao
• Yu Haidong
• Shao Weikang
• Zhang Yuhong

Classifications

• B01J2523/31

  Aluminium · CPC title

• C22C19/03

  based on nickel · CPC title

• B01J2523/55

  Vanadium · CPC title

• B01J25/02

  Raney nickel · CPC title

• C07C29/20

  in a non-condensed rings substituted with hydroxy groups · CPC title