Title of Invention	NOVEL CHROMIUM AND MANGANESE MIXED OXIDE PILLARED CLAY AND A PROCESS FOR THE PREARATION THEREOF
Abstract	The present invention provides the preparation of a novel pillared material; chromium-manganese mixed oxide pillared clay. The first step of the present process involves the preparation of nonaqueous solution of chromium(lll) and manganese(lll) acetate complex in a fixed ratio. Pillared material was prepared by the ion-exchange process involving the pillaring agent and clay in stirring condition at a required temperature. The novel pillared clay material may be recovered by conventional methods well known to those skilled in the art. However, it is preferred that said pillared clay be washed and centrifuged with the solvent. The product thus obtained is thereafter dried using any method known to those of skill in the art such as oven, vacuum or freeze-drying. Further the dried material is calcined at 300 to 400°C preferably in an.

Title of Invention

NOVEL CHROMIUM AND MANGANESE MIXED OXIDE PILLARED CLAY AND A PROCESS FOR THE PREARATION THEREOF

Abstract

The present invention provides the preparation of a novel pillared material; chromium-manganese mixed oxide pillared clay. The first step of the present process involves the preparation of nonaqueous solution of chromium(lll) and manganese(lll) acetate complex in a fixed ratio. Pillared material was prepared by the ion-exchange process involving the pillaring agent and clay in stirring condition at a required temperature. The novel pillared clay material may be recovered by conventional methods well known to those skilled in the art. However, it is preferred that said pillared clay be washed and centrifuged with the solvent. The product thus obtained is thereafter dried using any method known to those of skill in the art such as oven, vacuum or freeze-drying. Further the dried material is calcined at 300 to 400°C preferably in an.

Full Text	Field of the invention This invention relates to a novel chromium and manganese mixed oxide pillared interlayer clay and a process for the preparation thereof. This invention particularly relates to a process for the insertion of catalytically active chromium and manganese mixed oxide as pillars into the interlayer space of natural clay. The product of this invention is useful as catalyst in heterogeneous catalytic reactions and as an adsorbent. Background of the invention Pillared clays as such and their preparations of pillared interlayer clays from natural smectite group of clays are well known to the scientific literature. Insertion of metal oxide pillars into the interlayer region of clay led to the development of a new class of porous solids, useful as catalyst and adsorbents. Mostly these interlayer pillared clays involved the reaction of clay with an aqueous solution of suitable polymeric species of metals such as aluminum, titanium, zirconium and chromium as illustrated in the US 4665045, US 4742033 and US 617404. Preparation of manganese oxide pillared clay from non-aqueous solution was described in Indian patent application no.1103/del/95. Further US 4855268 discloses that mixed oxide pillared clay can be prepared by ion exchange process involving aluminium hydroxyl polymer and another transition metal (Fe, Cr, Co or Cu) hydroxyl polymer as pillaring agents. However, there is an ever present need to develop new mixed oxide pillared inter layered clays that results in creating new materials for use as solid acid catalyst and an adsorbent. In particular it is of need to develop new material based on clay with different catalytically active metal oxide pillars with desired ratio for specific use. In this context no report is available in the literature on the preparation of chromium and manganese mixed oxide pillared clay. Due to the presence of variable oxidation state both chromium oxide and manganese oxide are used as excellent redox catalyst. Therefore this invention deals with the insertion of these two catalytically active oxides as pillar inside the clay layer so as to synthesize a novel porous catalytic material. Objectives of the invention The main object of this invention is to provide a process for preparation of chromium and manganese mixed oxide pillared interlayer clay, which obviates the drawbacks as detailed above. Another object of this invention is the insertion of chromium and manganese mixed oxide pillars in a desired ratio inside the clay layer. Yet another object of this invention is provides the application of acetate complex of the said metal ions as pillaring agents instead of pH dependent polyoxocationic spaces of the same. Yet another object of this invention is to maintain the porous structure of the material at least up to 40CTC with the help of stable oxide pillars. Summary of the invention Accordingly the present invention provides a novel chromium and manganese mixed oxide pillared interlayer clay. In an embodiment of the present invention the mixed metals oxide pillared interlayer clay obtained has the following characteristics: i) basal spacing in the rage of 16-18A0, ii) BET surface area in the rage of 270-290m2/g when calcined at a temperature of about 400°C. The invention further provides a process for the preparation of chromium and manganese mixed oxide pillared interlayer clay, the said process comprising the steps of: (i) preparing a cationic acetate complex of manganese from manganese salt and potassium permanganate in acetic acid medium, (ii) preparing a cationic acetate complex of chromium from chromium salt and acetic anhydride in a non aqueous medium, (iii) dissolving the above said prepared complexes of manganese and chromium in a non aqueous solvent with chromium to manganese ratio in the range of 0.06 to 16.5 and total metals to solvent ratio in the range of 0.025 to 0.175 to form the pillaring agents in solution, (iv) preparing sodium exchanged clay by ion exchange process with sodium chloride and water solution under stirring condition, (v) adding the above said sodium exchanged clay obtained in step (iv) to the mixed metal complex pillaring solution obtained in step (iii) and stirring the resultant solution mixture, at a temperature in the range of 30 to 80°C, for a period of 30 min to 3h, (vi) filtering the above said solution mixture followed by washing and drying at about 40 °C to obtain the pillared material and calcining the resultant dried pillared material in an inert atmosphere, at a temperature in the range of 200 to 500 degree C to obtain the desired chromium and manganese mixed oxide pillared interlayer clay material. In an embodiment of the present invention the non aqueous solvent used in step (ii) is methanol. In yet another embodiment the non aqueous solvent used in step (iii) is selected from methanol and glacial acetic caid.. In yet another embodiment the clay used in step (iv) is synthetic or natural (montmorillonite, bentonite or saponite) smectite group of clay with layered structure containing ion exchangeable cations in the interlayer space. In yet another embodiment the concentration of pillaring agents used is in range of 5 to 35mmol/g of clay, preferably 15 to 35mmol/g of clay. In yet another embodiment the molar ratio of manganese(lll) to chromium(lll) concentration in pillaring solution is in the range of 0.06 to 16.5, preferably from 0.75 to 16.5. In still another embodiment the temperature used for the calcination of pillared material in step (vi) is in the range of 300 to 500°C. Detailed description of the invention The clays employed in the present invention are dioctahedral and trioctahedral smectites having layered structures. The natural abundance and commercial availability of these clays make them an inexpensive alternative starting material for catalyst preparation. The present method employed consists of considerable modifications to the process disclosed in US 4855268 and 4968652 for the preparation of mixed oxide pillared clay, which involves the preparation of hydrolyzed solution of metal ions mostly in water at a fixed pH. The present invention provides the preparation of a novel pillared material; chromium-manganese mixed oxide pillared clay. The first step of the present process involves the preparation of nonaqueous solution of chromium(lll) and manganese(lll) acetate complex in a fixed ratio. Pillared material was prepared by the ion-exchange process involving the pillaring agent and clay in stirring condition at a required temperature. The novel pillared clay material may be recovered by conventional methods well known to those skilled in the art. However, it is preferred that said pillared clay be washed and centrifuged with the solvent. The product thus obtained is thereafter dried using any method known to those of skill in the art such as oven, vacuum or freeze-drying. Further the dried material is calcined at 300 to 400°C preferably in an inert atmosphere. The following examples are given by way of illustration and should not be construed to limit the scope of the invention. Sodium exchanged clay was prepared by the ion exchange of clay with the aqueous solution of sodium chloride for 1h at 30°C. Obtained material is filtered washed and dried at 100°C and kept for use as the starting material. Trinuclear acetate complexes of chromium(lll) and manganese (III) were prepared according to the reported methods and used as pillaring agents. The following examples are given by the way of illustration and therefore should not be construed to limit the scope of the invention. Example-1 Trinuclear acetate complexes of chromium and manganese were dissolved in the 500ml non aqueous solvent (methanol) maintaining the chromium to manganese molar ratio of 1:1 and total metal ion to clay ratio of 30mmol/g of clay in the solution. In the above solution 5g of sodium exchanged clay was suspended for 3h in a stirring condition at 40°C. Resulting pillared material was filtered, washed and dried under vacuum at 40°C. Obtained material was calcined at 400°C for 2h to get the final mixed oxide pillared clay. Above pillared material still maintains the basal spacing of 16.9A having the Brunauer-Emmet-Teller (BET) surface area of 270m2/g. Chromium to manganese ratio was found to be 0.36 in the 400°C calcined product. Example-2 Trinuclear acetate complexes of chromium and manganese were dissolved in the 500ml non aqueous solvent (methanol) maintaining the chromium to manganese molar ratio of 25:5 and total metal ion to clay ratio of 30mmol/g of clay in the solution. In the above solution 5g of sodium exchanged clay was suspended for 3h in a stirring condition at 75°C. Resulting pillared material was filtered, washed and dried under vacuum at 40'C. Obtained material was calcined at 400°C for 2h to get the final mixed oxide pillared clay. Above pillared material still maintains the basal spacing of17.2A having the BET surface area of 280m2/g. Chromium to manganese ratio was found to be 0.66 in the 400°C calcined product. Example-3 Trinuclear acetate complexes of chromium and manganese were dissolved in the 500ml non aqueous solvent (methanol) maintaining the chromium to manganese molar ratio of 25:5 and total metal ion to clay ratio of 35mmol/g of clay in the solution. In the above solution 5g of sodium exchanged clay was suspended for 3h in a stirring condition at 75°C. Resulting pillared material was filtered, washed and dried under vacuum at 40"C. Obtained material was calcined at 400"C for 2h to get the final mixed oxide pillared clay. Prepared material maintains the basal spacing of 17.4 A having the BET surface area of 285m2/g. Chromium to manganese ratio was found to be 0.82 in the 400°C calcined product. The main advantages of the present invention are: 1. Preparation of thermally stable chromium-manganese mixed oxide pillared clay using trinuclear acetate complexes of chromium and manganese as of pillaring agents. 2. Ratio of chromium to manganese in the pillared material can be varied as per required. 3. Pillared material maintains the BET surface area of 275m2/g after 400°C calcinations. 4. Novel material useful as catalyst due to the presence of both chromium oxide and manganese oxide as pillars. 5. Useful as both acid as well as redox catalyst for organic reactions. We Claim 1. A novel chromium and manganese mixed oxide pillared interlayer clay. 2. A mixed metals oxide pillared interlayer clay as claimed in claim 1 has the following characteristics: i) basal spacing in the rage of 16-1 ~AO, ii) BET surface area in the rage of 270-290m2/g when calcined at a temperature of 400°C. 3. A process for preparation of chromium and manganese mixed oxide pillared interlayer clay as claimed in claim 1, comprising the steps of: (i) preparing a cationic acetate complex of manganese from manganese salt and potassium permanganate in acetic acid medium, (ii) preparing a cationic acetate complex of chromium from chromium salt and acetic anhydride in a non aqueous medium, (iii) dissolving the above said prepared complexes of manganese and chromium in a non aqueous solvent with chromium to manganese ratio in the range of 0.06 to 16.5 and total metals to solvent ratio in the range of 0.025 to 0.175 to form the pillaring agents in solution, (iv) preparing sodium exchanged clay by ion exchange process with sodium chloride and water solution under stirring condition, (v) adding the above said sodium exchanged clay obtained in step (iv) to the mixed metal complex pillaring solution obtained in step (iii) and stirring the resultant solution mixture, at a temperature in the range of 30 to 80°c, for a period of 30 min to 3h, (vi) filtering the above said solution mixture followed by washing and drying at about 40 OC to obtain the pillared material and calcining the resultant dried pillared material in an inert atmosphere, at a temperature in the range of 200 to 500 degree C to obtain the desired chromium and manganese mixed oxide pillared interlayer clay material. 4. A process as claimed in claim 3, wherein the non aqueous solvent used in step (ii) is methanol. 5. A process as claimed in claim 3, wherein the non aqueous solvent used in step (iii) is selected from methanol and glacial acetic caid.. 6. A process as claimed in claim 3, wherein clay used in step (iv) is synthetic or natural (montmorillonite, bentonite or saponite) smectite group of clay with layered structure containing ion exchangeable cations in the interlayer space. 7. A process as claimed in claim 3, wherein the concentration of pillaring agents used is in range of 5 to 35mmollg of clay, preferably 15 to 35mmollg of clay. 8. A process as claimed in claim 3, wherein the molar ratio of manganese(l1l) to chromium(lll) concentration in pillaring solution is in the range of 0.06 to 16.5, preferably from 0.75 to 16.5. 9. A process as claimed in claim 3, wherein the temperature used for the calcination of pillared material in step (vi) is in the range of 300 to 500'~.

Full Text

Field of the invention
This invention relates to a novel chromium and manganese mixed oxide pillared interlayer clay and a process for the preparation thereof. This invention particularly relates to a process for the insertion of catalytically active chromium and manganese mixed oxide as pillars into the interlayer space of natural clay. The product of this invention is useful as catalyst in heterogeneous catalytic reactions and as an adsorbent. Background of the invention
Pillared clays as such and their preparations of pillared interlayer clays from natural smectite group of clays are well known to the scientific literature. Insertion of metal oxide pillars into the interlayer region of clay led to the development of a new class of porous solids, useful as catalyst and adsorbents. Mostly these interlayer pillared clays involved the reaction of clay with an aqueous solution of suitable polymeric species of metals such as aluminum, titanium, zirconium and chromium as illustrated in the US 4665045, US 4742033 and US 617404. Preparation of manganese oxide pillared clay from non-aqueous solution was described in Indian patent application no.1103/del/95. Further US 4855268 discloses that mixed oxide pillared clay can be prepared by ion exchange process involving aluminium hydroxyl polymer and another transition metal (Fe, Cr, Co or Cu) hydroxyl polymer as pillaring agents. However, there is an ever present need to develop new mixed oxide pillared inter layered clays that results in creating new materials for use as solid acid catalyst and an adsorbent. In particular it is of need to develop new material based on clay with different catalytically active metal oxide pillars with desired ratio for specific use. In this context no report is available in the literature on the preparation of chromium and manganese mixed oxide pillared clay. Due to the presence of variable oxidation state both chromium oxide and manganese oxide are used as excellent redox catalyst. Therefore this invention deals with the insertion of these two catalytically active oxides as pillar inside the clay layer so as to synthesize a novel porous catalytic material. Objectives of the invention
The main object of this invention is to provide a process for preparation of chromium and manganese mixed oxide pillared interlayer clay, which obviates the drawbacks as detailed above.
Another object of this invention is the insertion of chromium and manganese mixed oxide pillars in a desired ratio inside the clay layer.
Yet another object of this invention is provides the application of acetate complex of the said metal ions as pillaring agents instead of pH dependent polyoxocationic spaces of the same.
Yet another object of this invention is to maintain the porous structure of the material at least up to 40CTC with the help of stable oxide pillars.
Summary of the invention
Accordingly the present invention provides a novel chromium and
manganese mixed oxide pillared interlayer clay.
In an embodiment of the present invention the mixed metals oxide pillared
interlayer clay obtained has the following characteristics: i) basal spacing in the rage of 16-18A0, ii) BET surface area in the rage of 270-290m2/g when calcined at a
temperature of about 400°C. The invention further provides a process for the preparation of chromium
and manganese mixed oxide pillared interlayer clay, the said process comprising
the steps of:
(i) preparing a cationic acetate complex of manganese from manganese
salt and potassium permanganate in acetic acid medium,
(ii) preparing a cationic acetate complex of chromium from chromium salt
and acetic anhydride in a non aqueous medium,
(iii) dissolving the above said prepared complexes of manganese and
chromium in a non aqueous solvent with chromium to manganese ratio in
the range of 0.06 to 16.5 and total metals to solvent ratio in the range of
0.025 to 0.175 to form the pillaring agents in solution,
(iv) preparing sodium exchanged clay by ion exchange process with
sodium chloride and water solution under stirring condition,
(v) adding the above said sodium exchanged clay obtained in step (iv) to
the mixed metal complex pillaring solution obtained in step (iii) and stirring
the resultant solution mixture, at a temperature in the range of 30 to 80°C,
for a period of 30 min to 3h,
(vi) filtering the above said solution mixture followed by washing and drying
at about 40 °C to obtain the pillared material and calcining the resultant
dried pillared material in an inert atmosphere, at a temperature in the
range of 200 to 500 degree C to obtain the desired chromium and
manganese mixed oxide pillared interlayer clay material.
In an embodiment of the present invention the non aqueous solvent used in
step (ii) is methanol.
In yet another embodiment the non aqueous solvent used in step (iii) is
selected from methanol and glacial acetic caid..
In yet another embodiment the clay used in step (iv) is synthetic or natural
(montmorillonite, bentonite or saponite) smectite group of clay with layered
structure containing ion exchangeable cations in the interlayer space.
In yet another embodiment the concentration of pillaring agents used is in
range of 5 to 35mmol/g of clay, preferably 15 to 35mmol/g of clay.
In yet another embodiment the molar ratio of manganese(lll) to
chromium(lll) concentration in pillaring solution is in the range of 0.06 to 16.5,
preferably from 0.75 to 16.5.
In still another embodiment the temperature used for the calcination of
pillared material in step (vi) is in the range of 300 to 500°C.
Detailed description of the invention
The clays employed in the present invention are dioctahedral and trioctahedral smectites having layered structures. The natural abundance and commercial availability of these clays make them an inexpensive alternative starting material for catalyst preparation.
The present method employed consists of considerable modifications to the process disclosed in US 4855268 and 4968652 for the preparation of mixed oxide pillared clay, which involves the preparation of hydrolyzed solution of metal ions mostly in water at a fixed pH. The present invention provides the preparation of a novel pillared material; chromium-manganese mixed oxide pillared clay. The first step of the present process involves the preparation of nonaqueous solution of chromium(lll) and manganese(lll) acetate complex in a fixed ratio. Pillared material was prepared by the ion-exchange process involving the pillaring agent
and clay in stirring condition at a required temperature. The novel pillared clay material may be recovered by conventional methods well known to those skilled in the art. However, it is preferred that said pillared clay be washed and centrifuged with the solvent. The product thus obtained is thereafter dried using any method known to those of skill in the art such as oven, vacuum or freeze-drying. Further the dried material is calcined at 300 to 400°C preferably in an inert atmosphere.
The following examples are given by way of illustration and should not be construed to limit the scope of the invention.
Sodium exchanged clay was prepared by the ion exchange of clay with the aqueous solution of sodium chloride for 1h at 30°C. Obtained material is filtered washed and dried at 100°C and kept for use as the starting material. Trinuclear acetate complexes of chromium(lll) and manganese (III) were prepared according to the reported methods and used as pillaring agents.
The following examples are given by the way of illustration and therefore should not be construed to limit the scope of the invention.
Example-1
Trinuclear acetate complexes of chromium and manganese were dissolved in the 500ml non aqueous solvent (methanol) maintaining the chromium to manganese molar ratio of 1:1 and total metal ion to clay ratio of 30mmol/g of clay in the solution. In the above solution 5g of sodium exchanged clay was suspended for 3h in a stirring condition at 40°C. Resulting pillared material was filtered, washed and dried under vacuum at 40°C. Obtained material was calcined at 400°C for 2h to get the final mixed oxide pillared clay. Above pillared material still maintains the basal spacing of 16.9A having the Brunauer-Emmet-Teller (BET) surface area of 270m2/g. Chromium to manganese ratio was found to be 0.36 in the 400°C calcined product.
Example-2
Trinuclear acetate complexes of chromium and manganese were dissolved in the 500ml non aqueous solvent (methanol) maintaining the chromium to manganese molar ratio of 25:5 and total metal ion to clay ratio of 30mmol/g of clay in the
solution. In the above solution 5g of sodium exchanged clay was suspended for 3h in a stirring condition at 75°C. Resulting pillared material was filtered, washed and dried under vacuum at 40'C. Obtained material was calcined at 400°C for 2h to get the final mixed oxide pillared clay. Above pillared material still maintains the basal spacing of17.2A having the BET surface area of 280m2/g. Chromium to manganese ratio was found to be 0.66 in the 400°C calcined product.
Example-3
Trinuclear acetate complexes of chromium and manganese were dissolved in the 500ml non aqueous solvent (methanol) maintaining the chromium to manganese molar ratio of 25:5 and total metal ion to clay ratio of 35mmol/g of clay in the solution. In the above solution 5g of sodium exchanged clay was suspended for 3h in a stirring condition at 75°C. Resulting pillared material was filtered, washed and dried under vacuum at 40"C. Obtained material was calcined at 400"C for 2h to get the final mixed oxide pillared clay. Prepared material maintains the basal spacing of 17.4 A having the BET surface area of 285m2/g. Chromium to manganese ratio was found to be 0.82 in the 400°C calcined product.
The main advantages of the present invention are:
1. Preparation of thermally stable chromium-manganese mixed oxide pillared
clay using trinuclear acetate complexes of chromium and manganese as of
pillaring agents.
2. Ratio of chromium to manganese in the pillared material can be varied as
per required.
3. Pillared material maintains the BET surface area of 275m2/g after 400°C
calcinations.
4. Novel material useful as catalyst due to the presence of both chromium
oxide and manganese oxide as pillars.
5. Useful as both acid as well as redox catalyst for organic reactions.

We Claim
1. A novel chromium and manganese mixed oxide pillared interlayer clay.
2. A mixed metals oxide pillared interlayer clay as claimed in claim 1 has the
following characteristics:
i) basal spacing in the rage of 16-1 ~AO,
ii) BET surface area in the rage of 270-290m2/g when calcined at a
temperature of 400°C.
3. A process for preparation of chromium and manganese mixed oxide pillared
interlayer clay as claimed in claim 1, comprising the steps of:
(i) preparing a cationic acetate complex of manganese from manganese salt
and potassium permanganate in acetic acid medium,
(ii) preparing a cationic acetate complex of chromium from chromium salt and
acetic anhydride in a non aqueous medium,
(iii) dissolving the above said prepared complexes of manganese and
chromium in a non aqueous solvent with chromium to manganese ratio in the
range of 0.06 to 16.5 and total metals to solvent ratio in the range of 0.025 to
0.175 to form the pillaring agents in solution,
(iv) preparing sodium exchanged clay by ion exchange process with sodium
chloride and water solution under stirring condition,
(v) adding the above said sodium exchanged clay obtained in step (iv) to the
mixed metal complex pillaring solution obtained in step (iii) and stirring the
resultant solution mixture, at a temperature in the range of 30 to 80°c, for a
period of 30 min to 3h,
(vi) filtering the above said solution mixture followed by washing and drying at
about 40 OC to obtain the pillared material and calcining the resultant dried
pillared material in an inert atmosphere, at a temperature in the range of 200
to 500 degree C to obtain the desired chromium and manganese mixed oxide
pillared interlayer clay material.
4. A process as claimed in claim 3, wherein the non aqueous solvent used in
step (ii) is methanol.
5. A process as claimed in claim 3, wherein the non aqueous solvent used in
step (iii) is selected from methanol and glacial acetic caid..
6. A process as claimed in claim 3, wherein clay used in step (iv) is synthetic or
natural (montmorillonite, bentonite or saponite) smectite group of clay with
layered structure containing ion exchangeable cations in the interlayer space.
7. A process as claimed in claim 3, wherein the concentration of pillaring agents
used is in range of 5 to 35mmollg of clay, preferably 15 to 35mmollg of clay.
8. A process as claimed in claim 3, wherein the molar ratio of manganese(l1l) to
chromium(lll) concentration in pillaring solution is in the range of 0.06 to 16.5,
preferably from 0.75 to 16.5.
9. A process as claimed in claim 3, wherein the temperature used for the
calcination of pillared material in step (vi) is in the range of 300 to 500'~.

Documents:

652-del-2006-Abstract-(03-04-2013).pdf

652-del-2006-abstract.pdf

652-del-2006-Claims-(03-04-2013).pdf

652-del-2006-claims.pdf

652-del-2006-correspondence-others 1.pdf

652-del-2006-Correspondence-Others-(03-04-2013).pdf

652-del-2006-correspondence-others.pdf

652-del-2006-description (complete).pdf

652-del-2006-form-1.pdf

652-del-2006-form-18.pdf

652-del-2006-form-2.pdf

652-del-2006-Form-3-(03-04-2013).pdf

652-del-2006-form-3.pdf

652-del-2006-form-5.pdf

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Patent Number

257386

Indian Patent Application Number

652/DEL/2006

PG Journal Number

40/2013

Publication Date

04-Oct-2013

Grant Date

28-Sep-2013

Date of Filing

10-Mar-2006

Name of Patentee

COUNCIL OF SCIENTIFIC & INDUSTRIAL RESEARCH

Applicant Address

ANUSANDHAN BHWAN, RAFI MARG, NEW DELHI-110001, INDIA.

Inventors:

#	Inventor's Name	Inventor's Address
1	TRILOCHAN MISHRA	NATIONAL METALURGICAL LABORATORY, JAMSHEDPUR-830117, JHARKHAND, INDIA.

PCT International Classification Number

B01J 29/04

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA