Title of Invention	A PROCESS FOR THE REGENERATION OF DEACTIVATED NOBLE METAL CATALYST FOR CYCLOHEXYLAMINE
Abstract	The invention relates to a process for the regeneration of a noble metal catalyst deactivated in the production of cyclohexylamine through hydrogenation of aniline in liquid phase batch process. The catalyst regenerated by die process of Ihe said invention showed selectivity of 86.75% to 91.88% to cyclohexylamine with an aniline conversion of 84.17 % to 84.50 % at 220° C and 16 kg/cm2 which is comparable to that of the fresh catalyst

Title of Invention

A PROCESS FOR THE REGENERATION OF DEACTIVATED NOBLE METAL CATALYST FOR CYCLOHEXYLAMINE

Abstract

The invention relates to a process for the regeneration of a noble metal catalyst deactivated in the production of cyclohexylamine through hydrogenation of aniline in liquid phase batch process. The catalyst regenerated by die process of Ihe said invention showed selectivity of 86.75% to 91.88% to cyclohexylamine with an aniline conversion of 84.17 % to 84.50 % at 220° C and 16 kg/cm2 which is comparable to that of the fresh catalyst

Full Text	FORM 2 THE PATENT ACT, 1970 (39 of 1970) & THE PATENT RULES, 2003 COMPLETE SPECIFICATION (See Section 10, Rule 13) 1. TITLE OF THE INVENTION : A Process for the Regeneration of Deactivated Noble Metal Catalyst for Cyclohexylamine. 2. APPLICANT® (a) Name: M/s. HINDUSTAN ORGANIC CHEMICALS LIMITED (b) Nationality: Indian (c) Address: Mr. A. S. Dfdolkar.CMD 81, Maharshi Karve Road, MUMBAI - 400 002, Maharashtra, India. 3. PREAMBLE TO THE DESCRIPTION : COMPLETE SPECIFICATION The following specification particularty describes the invention and the manner in which it is to be performed: PRIOR ART Cyclohexylamine is a useful intermediate for the manufacture of a variety of chemicals such as rubber vulcanizing additives, metal corrosion inhibiters, dyestuffs, agrochemicals, drugs etc. It can be produced from cyclohexanone, cyclohexanol or phenol in presence of ammonia and hydrogen (Japanese Unexamined Patent Publication No. 45-19897, No. 45-19898, No. 51-41627). An alternative method comprises of hydrogenating aniline with different catalysts viz. nickel, raney cobalt with cocatalysts like calcium oxide and sodium carbonate, palladium or ruthenium supported on alumina (US Patent No 4, 914, 239; Japanese Examined Patent Publication No. 45-28368; Japanese Unexamined Patent Publication No. 59-196843, and Unpublished Results to Hindustan Organic Chemicals Ltd., India). It is found mat these catalysts after prolonged use in the hydrogenation processes get deactivated and have to be discarded. However, by the process of the present invention, a ruthenium supported on alumina catalyst deactivated in the hydrogenation of aniline to produce cyclohexylamine in liquid phase batch process can be regenerated with a cyclohexylamine selectivity and aniline conversion comparable to that of the fresh catalyst. OBJECTIVE OF THE INVENTION The objective of the present invention is regeneration of a ruthenium supported on alumina catalyst, which gets deactivated in the liquid phase process, for reuse in the commercial production of cyclohexylamine from hydrogenation of aniline. The regenerated catalyst should be comparable in activity and selectivity to that of the fresh catalyst. SUMMARY OF THE INVENTION This invention relates to a process for the regeneration of an alumina supported ruthenium catalyst that has got deactivated in the liquid phase hydrogenation of aniline to produce cyclohexylamine. The said regeneration process consists of treating the deactivated catalyst with hydrochloric acid, removing the excess acid by filtration and subsequently washing with de-mineralized water, further washing with toluene, and drying the catalyst in two stages viz. at 15° to 30° C for 1 to 2 his and then 2 to 6 hrs at about 110° to 120° C. The regenerated catalyst exhibits selectivity of 86.75 % to 91.88 % to cyclohexylamine with an aniline conversion of 84.17 % to 84.50 % at 220° C and 16 kg/cm1 pressure. DESCRIPTION OF THE INVENTION The deactivated catalyst recovered from a commercial cyclohexylamine process consisting of hydrogenation of aniline in liquid phase is a finely divided powder of 37 micron to 95 micron size, having pore volume 0.29 ml/g to 0.35 ml/g, surface area of about 127 m2/g to 140 mVg and bulk density of about 1.0 g/ml to l.lg/ml with a ruthenium content of about 5% weight The said catalyst is regenerated by treating first with 10% hydrochloric acid solution at 15° to 30° C, then separating the catalyst from acid solution by filtration and subsequently washing with de-mineralized water. The catalyst is further washed with toluene and dried first at 15° to 30° C for 1 hr to 2 hrs and then at 110° to 120° C for 2 to 6 hrs. The regenerated catalyst exhibits a selectivity of 86.75 % to 91.88 % to cyclohexylamine with an aniline conversion of about 84.17 % to 84.57 % under standard process parameters viz 220 °C and 16 kg/cm2 pressure. The present invention is further described below by way of examples. However, theses examples are illustrative and should not be construed as limiting the scope of this invention. EXAMPLE-I 2.25 g of the fresh catalyst containing about 5% ruthenium on alumina in powder form of 30 micron to 90 micron size having pore volume of 0.42 ml/g, surface area of 149.4 m2/g, and bulk density of about 1.1 g/ml, and 300 ml aniline were charged in a 600 ml Parr reactor equipped with a stirrer, internal cooling coil, thermo-well, pressure gauge, safety rapture disc, automatic temperature controller and solenoid valve with a water flow connection to the internal cooling coil. The reactor was purged first with nitrogen and then with hydrogen. It was then pressurized with hydrogen to about 7 kg/cm2 and was heated to about 220 °C. The reactor pressure was then increased to about 16 kg/cm2 . The said pressure and temperature conditions were maintained for about 8 hrs. Under these conditions, the catalyst showed a selectivity of 95.41% to cyclohexylamine with an aniline conversion of about 93.34 %. EXAMPLE-H A deactivated catalyst, recovered from a commercial plant producing cyclohexylamine from aniline through hydrogenation in liquid phase batch process comprising of about 5% ruthenium on alumina powder of 37 micron to 95 micron size having pore volume of about 0.29 ml/g, surface area of about 127 m2/g and bulk density of about 1.05 g/ml, was evaluated as such, by the similar manner and process conditions as elaborated in example - I. Under these conditions, the deactivated catalyst showed a selectivity of about 88.65% to cyclohexylamine with an aniline conversion of about 40.36%. EXAMPLE - HI 10 g of the said deactivated catalyst as described in Example H, from a commercial cyclohexylamine plant, was added to 50 ml of 10% hydrochloric acid in a glass vessel and was constantly stirred for about 1 hr at 15° to 30° C. The catalyst was separated from the acid solution first by filtration and secondly by washing with 100 ml de-mineralized water. The catalyst was further washed with about 100 ml toluene and dried first at 15° to 30 ° C for 1 hr and secondly at about 110° to 120° C for 2 hrs. The regenerated catalyst wass evaluated by the similar manner and process conditions as elaborated in example - L The catalyst exhibited a selectivity of 91.88 % to cyclohexylamine with an aniline conversion of 84.50 % EXAMPLE-IV 5 kg of the said deactivated catalyst as described in Example - II was added to 30 liters of 10% hydrochloric acid in the glass vessel of a catalyst preparation unit equipped with a glass stirrer and was constantly stirred for 6 hrs at 15° to 30° C. The catalyst was separated from acid solution first by filtration and secondly by washing with 75 liters de-mineralized water. The catalyst was further washed with about 75 liters toluene and dried first at 15° to 30° C for 2 hrs and secondly at about 110° to 120° C for about 6 hrs. The regenerated catalyst was evaluated in a 1000 liters commercial reactor with a batch size of 500 liters aniline and 4 kg catalyst by the similar manner and process conditions as elaborated in Example - I. It exhibited a selectivity of 86.75 % to cyclohexylamine with an aniline conversion of about 84.17%. We claim: 1. A process for the regeneration of a deactivated noble metal catalyst recovered from a process producing cyclohexylamine through the hydrogenation of aniline in liquid phase by (i) treating it with hydrochloric acid; (ii) separating the acid by filtration; (iii) subsequently washing with de-mineralized water, (iv) further washing with toluene, and (v) drying the treated catalyst for reuse. 2. A process as claimed in Claim 1, wherein the noble metal is ruthenium supported on alumina powder. 3. A process as claimed in Claims 1 and 2, wherein the ruthenium content in the catalyst is 2.5% w to 7.5% w. 4. A process as claimed in Claim 1, wherein the deactivated ruthenium catalyst is treated with hydrochloric acid at 10° C to 50° C for 1 to 10 hrs. 5. A process as claimed in Claim 1, wherein the acid treated catalyst is washed first with de-mineralized water and secondly with toluene. 6. A process as claimed in Claim 1, wherein the washed catalyst is dried first at 10° to 50° C for 1 to 2 hrs and secondly at 10° to 130° C for 2 to 10 hrs. 7. A process as claimed in Claim 1, wherein it is preferably a batch process. 8. A complete process as claimed in Claims 1 to 7, for the regeneration of a deactivated noble metal catalyst recovered from a process producing cyclohexylamine from the hydrogenation of aniline in liquid phase as described herein with reference to the Examples I to IV.

Full Text

FORM 2
THE PATENT ACT, 1970
(39 of 1970)
&
THE PATENT RULES, 2003
COMPLETE SPECIFICATION
(See Section 10, Rule 13)
1. TITLE OF THE INVENTION : A Process for the Regeneration of
Deactivated Noble Metal Catalyst for Cyclohexylamine.

2. APPLICANT®
(a) Name: M/s. HINDUSTAN ORGANIC CHEMICALS LIMITED
(b) Nationality: Indian
(c) Address: Mr. A. S. Dfdolkar.CMD
81, Maharshi Karve Road, MUMBAI - 400 002,
Maharashtra, India.
3. PREAMBLE TO THE DESCRIPTION :
COMPLETE SPECIFICATION
The following specification particularty describes the invention and the manner in which it is to be performed:

PRIOR ART
Cyclohexylamine is a useful intermediate for the manufacture of a variety of chemicals such as rubber vulcanizing additives, metal corrosion inhibiters, dyestuffs, agrochemicals, drugs etc. It can be produced from cyclohexanone, cyclohexanol or phenol in presence of ammonia and hydrogen (Japanese Unexamined Patent Publication No. 45-19897, No. 45-19898, No. 51-41627). An alternative method comprises of hydrogenating aniline with different catalysts viz. nickel, raney cobalt with cocatalysts like calcium oxide and sodium carbonate, palladium or ruthenium supported on alumina (US Patent No 4, 914, 239; Japanese Examined Patent Publication No. 45-28368; Japanese Unexamined Patent Publication No. 59-196843, and Unpublished Results to Hindustan Organic Chemicals Ltd., India). It is found mat these catalysts after prolonged use in the hydrogenation processes get deactivated and have to be discarded. However, by the process of the present invention, a ruthenium supported on alumina catalyst deactivated in the hydrogenation of aniline to produce cyclohexylamine in liquid phase batch process can be regenerated with a cyclohexylamine selectivity and aniline conversion comparable to that of the fresh catalyst.
OBJECTIVE OF THE INVENTION
The objective of the present invention is regeneration of a ruthenium supported on alumina catalyst, which gets deactivated in the liquid phase process, for reuse in the commercial production of cyclohexylamine from hydrogenation of aniline. The regenerated catalyst should be comparable in activity and selectivity to that of the fresh catalyst.
SUMMARY OF THE INVENTION
This invention relates to a process for the regeneration of an alumina supported ruthenium catalyst that has got deactivated in the liquid phase hydrogenation of aniline to produce cyclohexylamine. The said regeneration process consists of treating the deactivated catalyst with hydrochloric acid, removing the excess acid by filtration and subsequently washing with de-mineralized water, further washing with

toluene, and drying the catalyst in two stages viz. at 15° to 30° C for 1 to 2 his and then 2 to 6 hrs at about 110° to 120° C. The regenerated catalyst exhibits selectivity of 86.75 % to 91.88 % to cyclohexylamine with an aniline conversion of 84.17 % to 84.50 % at 220° C and 16 kg/cm1 pressure.
DESCRIPTION OF THE INVENTION
The deactivated catalyst recovered from a commercial cyclohexylamine process consisting of hydrogenation of aniline in liquid phase is a finely divided powder of 37 micron to 95 micron size, having pore volume 0.29 ml/g to 0.35 ml/g, surface area of about 127 m2/g to 140 mVg and bulk density of about 1.0 g/ml to l.lg/ml with a ruthenium content of about 5% weight The said catalyst is regenerated by treating first with 10% hydrochloric acid solution at 15° to 30° C, then separating the catalyst from acid solution by filtration and subsequently washing with de-mineralized water. The catalyst is further washed with toluene and dried first at 15° to 30° C for 1 hr to 2 hrs and then at 110° to 120° C for 2 to 6 hrs. The regenerated catalyst exhibits a selectivity of 86.75 % to 91.88 % to cyclohexylamine with an aniline conversion of about 84.17 % to 84.57 % under standard process parameters viz 220 °C and 16 kg/cm2 pressure.
The present invention is further described below by way of examples. However, theses examples are illustrative and should not be construed as limiting the scope of this invention.
EXAMPLE-I
2.25 g of the fresh catalyst containing about 5% ruthenium on alumina in powder form of 30 micron to 90 micron size having pore volume of 0.42 ml/g, surface area of 149.4 m2/g, and bulk density of about 1.1 g/ml, and 300 ml aniline were charged in a 600 ml Parr reactor equipped with a stirrer, internal cooling coil, thermo-well, pressure gauge, safety rapture disc, automatic temperature controller and solenoid valve with a water flow connection to the internal cooling coil. The reactor was purged first with nitrogen and then with hydrogen. It was then pressurized with hydrogen to about 7 kg/cm2 and was heated to about 220 °C. The reactor pressure

was then increased to about 16 kg/cm2 . The said pressure and temperature conditions were maintained for about 8 hrs. Under these conditions, the catalyst showed a selectivity of 95.41% to cyclohexylamine with an aniline conversion of about 93.34 %.
EXAMPLE-H
A deactivated catalyst, recovered from a commercial plant producing cyclohexylamine from aniline through hydrogenation in liquid phase batch process comprising of about 5% ruthenium on alumina powder of 37 micron to 95 micron size having pore volume of about 0.29 ml/g, surface area of about 127 m2/g and bulk density of about 1.05 g/ml, was evaluated as such, by the similar manner and process conditions as elaborated in example - I. Under these conditions, the deactivated catalyst showed a selectivity of about 88.65% to cyclohexylamine with an aniline conversion of about 40.36%.
EXAMPLE - HI
10 g of the said deactivated catalyst as described in Example H, from a commercial cyclohexylamine plant, was added to 50 ml of 10% hydrochloric acid in a glass vessel and was constantly stirred for about 1 hr at 15° to 30° C. The catalyst was separated from the acid solution first by filtration and secondly by washing with 100 ml de-mineralized water. The catalyst was further washed with about 100 ml toluene and dried first at 15° to 30 ° C for 1 hr and secondly at about 110° to 120° C for 2 hrs. The regenerated catalyst wass evaluated by the similar manner and process conditions as elaborated in example - L The catalyst exhibited a selectivity of 91.88 % to cyclohexylamine with an aniline conversion of 84.50 %
EXAMPLE-IV
5 kg of the said deactivated catalyst as described in Example - II was added to 30 liters of 10% hydrochloric acid in the glass vessel of a catalyst preparation unit equipped with a glass stirrer and was constantly stirred for 6 hrs at 15° to 30° C. The catalyst was separated from acid solution first by filtration and secondly by washing

with 75 liters de-mineralized water. The catalyst was further washed with about 75 liters toluene and dried first at 15° to 30° C for 2 hrs and secondly at about 110° to 120° C for about 6 hrs. The regenerated catalyst was evaluated in a 1000 liters commercial reactor with a batch size of 500 liters aniline and 4 kg catalyst by the similar manner and process conditions as elaborated in Example - I. It exhibited a selectivity of 86.75 % to cyclohexylamine with an aniline conversion of about 84.17%.

We claim:
1. A process for the regeneration of a deactivated noble metal catalyst recovered from a process producing cyclohexylamine through the hydrogenation of aniline in liquid phase by (i) treating it with hydrochloric acid; (ii) separating the acid by filtration; (iii) subsequently washing with de-mineralized water, (iv) further washing with toluene, and (v) drying the treated catalyst for reuse.
2. A process as claimed in Claim 1, wherein the noble metal is ruthenium supported on alumina powder.
3. A process as claimed in Claims 1 and 2, wherein the ruthenium content in the catalyst is 2.5% w to 7.5% w.
4. A process as claimed in Claim 1, wherein the deactivated ruthenium catalyst is treated with hydrochloric acid at 10° C to 50° C for 1 to 10 hrs.
5. A process as claimed in Claim 1, wherein the acid treated catalyst is washed first with de-mineralized water and secondly with toluene.
6. A process as claimed in Claim 1, wherein the washed catalyst is dried first at 10° to 50° C for 1 to 2 hrs and secondly at 10° to 130° C for 2 to 10 hrs.
7. A process as claimed in Claim 1, wherein it is preferably a batch process.
8. A complete process as claimed in Claims 1 to 7, for the regeneration of a deactivated noble metal catalyst recovered from a process producing cyclohexylamine from the hydrogenation of aniline in liquid phase as described herein with reference to the Examples I to IV.

Documents:

1335-mum-2009-abstract.doc

1335-mum-2009-abstract.pdf

1335-MUM-2009-ANNEXURE B(SUBMISSION)-(17-7-2013).pdf

1335-MUM-2009-CLAIMS(AMENDED)-(17-7-2013).pdf

1335-MUM-2009-CLAIMS(AMENDED)-(22-2-2012).pdf

1335-mum-2009-claims.doc

1335-mum-2009-claims.pdf

1335-MUM-2009-CORRESPONDENCE(10-7-2009).pdf

1335-MUM-2009-CORRESPONDENCE(21-1-2013).pdf

1335-MUM-2009-CORRESPONDENCE(27-12-2012).pdf

1335-MUM-2009-CORRESPONDENCE(5-2-2013).pdf

1335-MUM-2009-CORRESPONDENCE(9-11-2012).pdf

1335-mum-2009-description(complete).doc

1335-mum-2009-description(complete).pdf

1335-mum-2009-form 1.pdf

1335-mum-2009-form 18.pdf

1335-mum-2009-form 2(title page).pdf

1335-mum-2009-form 2.doc

1335-mum-2009-form 2.pdf

1335-mum-2009-form 3.pdf

1335-mum-2009-form 5.pdf

1335-mum-2009-form 9.pdf

1335-MUM-2009-PUBLICATION REPORT(10-7-2009).pdf

1335-MUM-2009-REPLY TO EXAMINATION REPORT(22-2-2012).pdf

1335-MUM-2009-REPLY TO HEARING(17-7-2013).pdf

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Patent Number

256974

Indian Patent Application Number

1335/MUM/2009

PG Journal Number

34/2013

Publication Date

23-Aug-2013

Grant Date

21-Aug-2013

Date of Filing

02-Jun-2009

Name of Patentee

HINDUSTAN ORGANIC CHEMICALS LIMITED

Applicant Address

RASAYANI, DIST.RAIGAD,PIN-410 207,MAHARASHTRA, INDIA.

Inventors:

#	Inventor's Name	Inventor's Address
1	SHUKLA CHANDRA SHEKHAR	RASAYANI, DIST.RAIGAD, PIN-410207, MAHARASHTRA, INDIA.
2	SHINDE BAPURAO SIDRAM	RASAYANI, DIST.RAIGAD, PIN-410207, MAHARASHTRA, INDIA.
3	SATHE AMOD MADHUKAR	RASAYANI, DIST.RAIGAD, PIN-410207, MAHARASHTRA, INDIA.

PCT International Classification Number

B01J23/64

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA