Process for regeneration of titano silicate catalyst

• US 8,679,999 B2
• Filed: 01/31/2013
• Issued: 03/25/2014
• Est. Priority Date: 08/03/2010
• Status: Expired due to Fees

• Current Assignee: Aditya Birla Science & Technology Co., Ltd. (Aditya Birla Management Corp Pvt Ltd.)
• Original Assignee: Aditya Birla Science & Technology Co., Ltd. (Aditya Birla Management Corp Pvt Ltd.)
• Inventors: Kapoor, Bir, Kanagasabapathy, Subbareddy, Borle, Yogesh Laxman, Verma, Arati
• Primary Examiner(s): Oh, Taylor Victor
• Application Number:
  US13/755,689
• Publication Number:
  US 20130144075A1
• Time in Patent Office: 418 Days
• Field of Search: 502/33, 502/34, 549/531, 568/362
• US Class Current: 502/33
• CPC Class Codes: B01J 21/20 Regeneration or reactivation
• CPC Class Codes: B01J 29/89 Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium B01J29/005 takes precedence
• CPC Class Codes: B01J 29/90 Regeneration or reactivation
• CPC Class Codes: B01J 38/12 Treating with free oxygen-containing gas
• CPC Class Codes: B01J 38/48 Liquid treating or treating in liquid phase, e.g. dissolved or suspended
• CPC Class Codes: B01J 38/52 oxygen-containing
• CPC Class Codes: C07C 37/58 by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of molecular oxygen
• CPC Class Codes: C07D 301/12 with hydrogen peroxide or inorganic peroxides or peracids
• CPC Class Codes: C07D 303/08 with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
• CPC Class Codes: Y02P 20/584 Recycling of catalysts

Abstract

Titanosilicate catalyst is used in the oxidation reactions such as allylchloride epoxidation, phenol hydroxylation, Cyclohexanone ammoximation. During the reaction the catalyst is deactivated which further decrease in the efficiency of the oxidation reactions. The present invention provides a method for an efficient regeneration of catalyst titanosilicate catalyst at low temperature below 100° C. using a gaseous mixture containing ozone, without isolating the catalyst from the reactor system.

Claims

1. A process for activating a deactivated titano silicate catalyst, in a reactor, said process comprising the following steps;

i) washing the catalyst bed containing deactivated titano silicate at a temperature range of 20 to 40°

C., with a solvent selected from the group consisting of alcohol, ester, ketone, water and aqueous hydrogen peroxide;

ii) heating the reactor to a temperature in the range of 50°

C. to 100°

C., to provide a heated catalyst bed;

iii) reacting the heated catalyst in the catalyst bed, with ozone gas under exothermic conditions, said reaction being carried out by feeding a gaseous mixture containing air/oxygen and ozone having ozone content in the range of 2 to 10%, and monitoring the outlet stream of the gas coming out through said bed for ozone seepage, said reaction continued till the ozone content in the outlet stream is at least 0.2%, to provide a regenerated catalyst; and

iv) cooling the regenerated catalyst bed first by passing of air/oxygen gas through the said bed followed by washing of the said bed with a solvent selected from the group consisting of alcohol and water, to a temperature in the range of 20 to 40°

C.

2. The process as claimed in claim 1, wherein the steps (ii) and (iii) are repeated at least once, after cooling of the regenerated catalyst bed by air/oxygen gas in step (iv).

3. The process as claimed in claim 1, wherein the temperature of the heated catalyst bed in the step (ii) is raised to 80°

C.

4. The process as claimed in claim 1, wherein the solvent used in step (i) is an alcohol selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 1-butanol, 2-butanol, and ethylene glycol.

5. The process as claimed in claim 1, wherein the gaseous mixture in the step (iii), is fed to the catalyst bed over a period of 2 to 6 hrs.

6. An integrated process for the production of an oxidized product in an oxidation reaction employing titano silicate catalyst and hydrogen peroxide, said process being carried out in a reactor containing titano silicate catalyst bed and comprising the following steps:

A) performing oxidation reaction selected from the group consisting of allyl chloride epoxidation, phenol hydroxylation and cyclohexene ammoximation, in presence of hydrogen peroxide, to obtain an oxidized product;

B) monitoring the level of catalyst deactivation during the said oxidation reaction;

C) stopping the said reaction of step (A), when the level of catalyst deactivation in step B) shows catalyst weight loss of 8%;

D) activating the deactivated catalyst of step (C) in accordance with the process of claim 1, to obtain a regenerated catalyst;

E) resuming the said oxidation reaction of step (A) in the presence of regenerated catalyst of step (D), to provide an oxidized product.

7. The process as claimed in claim 1, wherein the reactor is selected from the group consisting of a fixed bed reactor and a tubular reactor.

8. The integrated process as claimed in claim 6, wherein the reactor is selected from the group consisting of a fixed bed reactor and a tubular reactor.

9. The integrated process as claimed in claim 6, wherein the oxidation reaction of step (A) is allylchloride epoxidation reaction.

10. The integrated process as claimed in claim 6, wherein the step (A) includes passing the reactants allylchloride, hydrogen peroxide and methanol through the catalyst bed containing titanosilicate to obtain epichlorohydrin as an oxidized product.

11. The integrated process as claimed in claim 6, wherein the step (C) of stopping the reaction includes stopping the flow of reactants through the catalyst bed.

12. The integrated process as claimed in claim 6, wherein the step (E) of resuming the reaction includes passing the reactants through the catalyst bed containing regenerated catalyst.

13. The integrated process as claimed in claim 6, wherein the oxidation reaction of step (A) is phenol hydroxylation reaction.

14. The integrated process as claimed in claim 6, wherein the oxidized product is an oxidized form of phenol.