Solvent-free green ammoximation process based on film distribution

Patent metadata

Field	Value
Publication number	US-10252985-B2
Application number	US-201516062630-A
Country	US
Kind code	B2
Filing date	Jul 31, 2015
Priority date	May 13, 2015
Publication date	Apr 9, 2019
Grant date	Apr 9, 2019

Abstract

The invention relates to a solvent-free green ammoximation process based on membrane distribution with a procedure as: adding TS-1 catalyst and ketone into a reactor in advance; setting the stirring speed and reaction temperature; after reaching the set temperature, adding a certain amount of ammonia and hydrogen peroxide into a reaction solution, wherein the hydrogen peroxide is fed in a way of using membrane as a distributor, the ammonia is fed in a continuous or semi-continuous manner; oxime is produced upon the reaction. The advantages of the invention include the mild reaction conditions, high reacting efficiency, simple operation and environmentally-friendly process. And there is no need to add any solvent during the reaction process. During the ammoximation reaction, both the conversion rate of the ketone and the selectivity of the oxime can be over 98.0%.

First claim

What is claimed is:

1. A solvent-free green ammoximation process based on a membrane distribution includes the following steps:
adding a TS-1 catalyst and a ketone into a reactor in advance, setting a stirring speed and a reaction temperature; and after reaching the set temperature,
adding hydrogen peroxide in a way of using membrane as a distributor, and
adding ammonia in a continuous or semi-continuous manner.

2. The solvent-free green ammoximation process according to claim 1 , characterized in that the ketone compound is cyclohexanone, butanone or acetone.

3. The solvent-free green ammoximation process according to claim 1 , characterized in that the ammonia is ammonium hydroxide or ammonia gas; and the mass concentration of the hydrogen peroxide is 25% to 99%.

4. The solvent-free green ammoximation process according to claim 1 , characterized in that the ratio of the mass of TS-1 catalyst over the molar of ketone is 9.0 g/mol to 20.0 g/mol; and the molar ratio of ketone to ammonia to hydrogen peroxide is 1.0:(1.3˜2.2):(1.1˜1.6).

5. The solvent-free green ammoximation process according to claim 1 , characterized in that the stirring speed is 600 rpm to 1,000 rpm.

6. The solvent-free green ammoximation process according to claim 1 , characterized in that the reaction temperature is 60° C. to 85° C.

7. The solvent-free green ammoximation process according to claim 1 , characterized in that a ceramic membrane is zirconia membrane, titania membrane, alumina membrane or silicon carbide membrane; and mean pore size of the membrane is 50 nm to 2,000 nm.

8. The solvent-free green ammoximation process according to claim 1 , characterized in that the membrane flux if 0.12 m 3 ·m −2 ·h −1 to 0.20 m 3 ·m −2 ·h −1 .

Assignees

• Nanjing University Of Technology

Inventors

• Xing Weihong
• Mao Honglin
• Chen Rizhi
• Shang Hongnian
• Xu Nanping

Classifications

• C07C249/04 Primary

  of oximes · CPC title

• C07C251/44

  with the carbon atom of at least one of the oxyimino groups being part of a ring other than a six-membered aromatic ring · CPC title

• B01J29/89

  Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium {(B01J29/005 takes precedence)} · CPC title

• C07C251/38

  to carbon atoms of a saturated carbon skeleton · CPC title

• B01J29/70

  of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 · CPC title