Title of Invention	A PROCESS FOR THE PREPARATION OF CRYSTALLINE, VANADIUM SILICO-ALUMINOPHOSPHATE CATALYSTS USEFUL FOR ACID CATALYSED REACTIONS"
Abstract	A process for the preparation of crystalline vanadium-silico-alumino-phosphate catalyst useful for acid catalysed reactions which comprises mixing under constant stirring aqueous solutions of aluminium sulphate, tetralkyl ammonium bromide optionally with sodium chloride with aqueous solution of phosphoric acid and vanadium pentoxfde to obtain a mixture, adding sodium silicate to the above said mixture to obtain a slurry, maintaining the pH in the range of 5 to 12, heating the said slurry at a temperature in the range of 150-220°C for a period in the range of 24 to 80 hours, under autogenous pressure and under constant stirring, filtering the reaction mixture by known methods to obtain solid residue washing and drying the above said residue calcining the resultant residue at a temperature in the range of 500 to 550°C for a period of 5 to 15 hours to obtain vanadium-siiico alumino -phosphate catalyst.

Title of Invention

A PROCESS FOR THE PREPARATION OF CRYSTALLINE, VANADIUM SILICO-ALUMINOPHOSPHATE CATALYSTS USEFUL FOR ACID CATALYSED REACTIONS"

Abstract

A process for the preparation of crystalline vanadium-silico-alumino-phosphate catalyst useful for acid catalysed reactions which comprises mixing under constant stirring aqueous solutions of aluminium sulphate, tetralkyl ammonium bromide optionally with sodium chloride with aqueous solution of phosphoric acid and vanadium pentoxfde to obtain a mixture, adding sodium silicate to the above said mixture to obtain a slurry, maintaining the pH in the range of 5 to 12, heating the said slurry at a temperature in the range of 150-220°C for a period in the range of 24 to 80 hours, under autogenous pressure and under constant stirring, filtering the reaction mixture by known methods to obtain solid residue washing and drying the above said residue calcining the resultant residue at a temperature in the range of 500 to 550°C for a period of 5 to 15 hours to obtain vanadium-siiico alumino -phosphate catalyst.

Full Text	This invention relates to a process for the preparation of crystalline vanadium-silico-alumino-phosphate catalysts useful for acid catalysed reactions. We have described and claimed an ammoxidation processes for the preparation of 3-cyanopyridine, 4-cyanopyridine , benzonitrile and acetonitrile, selectively from 3-picoline, 4-picoline, toluene and ethanol with ammonia and air, respectively using the catalysts prepared by the present invention. The reaction of the feed is carried out over VSAPO catalysts prepared by the process of the present invention in to the temperature range of 300-450 C and at a weight hourly space velocity of 0.25 to 1 0"1 hr . The yields of the nitrites are in the range of 60 to 100%. The various silico-alumino-phosphates are reported in J. Am. Chem. Soc. 106, 6093 (1984) by using various templates. These molecular sieve catalysts are useful in acid catalysed reactions like n-butane cracking. With the variation of templates, the crystal structure, cage/pore dimension vary resulting into large number of molecular sieves. The silico-alumino-phosphates were synthesized using tri-n-propylamine, di-n- propylamine, tetramethylammonium salt. But these SAPOs are not modified to carry out oxidation and ammoxidation type of reactions. The object of the present invention is to provide a process for the preparation of VSAPO as-synthesized molecular sieves useful in the oxidation and ammoxidation of aliphatic alcohols, aromatic and hetero cyclic compounds. Molecular sieves are well- known shape selective catalysts. In the present invention, the high-boiling products are avoided due to the shape selectivity of the molecular sieves compared to non-zeolitic ammoxidation catalysts. The non-zeolitic ammoxidation catalysts are not shape -selective catalysts. Accordingly, the present invention provides a process for the preparation of crystalline vanadium-silico-alumino-phosphate catalyst useful for acid catalysed reactions which comprises mixing under constant stirring aqueous solutions of aluminium sulphate, tetralkyl ammonium bromide optionally with sodium chloride with aqueous solution of phosphoric acid and vanadium pentoxide to obtain a mixture, adding sodium silicate to the above said mixture to obtain a slurry, maintaining the pH in the range of 5 to 12, heating the said slurry at a temperature in the range of 150-220°C for a period in the range of 24 to 80 hours, under autogenous pressure and under constant stirring, filtering the reaction mixture by known methods to obtain solid residue washing and drying the above said residue calcining the resultant residue at a temperature in the range of 500 to 550°C for a period of 5 to 15 hours to obtain vanadium-silico alumino -phosphate catalyst. In an embodiment of the present invention the tetraalkyl ammonium bromide used may be such as tetrapropyl /butyl ammonium bromide. The catalysts are prepared in general in the following way. Basically in aluminophosphate molecular sieves the Al: P atomic ratio is 1:1. We have partially substituted phosphorus by silicon and vanadium. Aluminium also may be partially substituted by silicon and vanadium with the corresponding variation in the atomic ratio. Al, P and Si are expected to occupy tetrahedral positions in molecular sieves. The tetrahedral atoms are linked through oxygens to form preferably three-dimensional "rigid framework" of molecular sieve. The charges on the framework atoms are compensated by mobile and exchangeable cations like Na+ or template like TPA+ during the synthesis. Al2 (SO4)3, H3P04, V205, Na2SiO3 with or without NaCl and tetra-propyl ammonium bromide (TPA) or tetra-butyl ammonium bromide (TBA) used as a template are mixed in distilled water in the pH range of 5.0 to 12.0. The slurry is mixed at least 2 hrs at room temperature with constant stirring and the pH is adjusted by aqueous ammonia. The slurry was put into an auto clave preferably of 600 ml or 1 litre capacity, for autoclaving under autogeneous pressure in the temperature range of 150 to 220° C for 24 hrs to 80 hrs till complete crystallisation was achieved. The mixture was filtered and washed with distilled water. The solid catalyst was dried in oven at 120° C overnight. The organic template was removed by the activation of the catalyst at 500 - 550° C for 5-15 hrs. Then the calcined material was modified by promoters like Sb203 or oxides of the elements active as promoters in the respective reactions. The XRD patterns show 20 -80 % loss of crystallinity. The reactions were carried out in a tubular, down-flow, pyrex reactor with 20 mm internal diameter. The reaction mixture was fed from top using syringe pump (Sage Instruments, U.S. A) . The product was cooled by using ice-cooled water and collected at the bottom. The required number of ice-cooled traps were used to collect the total amount of products. The products were analysed by using SE-30 (5%) or OV-17 columns. The analysis was confirmed by mass spectra and GC- mass. The following examples are given to illustrate the process of the present invention, however, these should not be construed to limit the scope of the present invention. EXAMPLE -1 The VSAPO (TPA-A) was synthesized as follows. The solution A was prepared in 200 ml of distilled water by mixing 63.0 gms of AI2(S04) 3 16 H2O, 26.6 gms of tetrapropyl ammonium bromide, and 11.7 gms of sodium chloride. The solution B was prepared in 100 ml distilled water by adding 15.7 gms of H=PO4 and 18.2 gms of vanadium pentoxide. The solution C was prepared in 100 ml distilled water by mixing 11.4 gms of sodium silicate. Both the solutions are stirred well separately. The solution B is mixed to the solution of A drop wise with constant stirring. The mixture was stirred for 2 hrs, Then the solution C was mixed with the mixture (A + B) drop wise with constant stirring. After mixing the solutions, the pH was adjusted to 9.0 by adding aqueous ammonia. The slurry was stirred well for about 2 hrs at room temperature. The slurry was made 600 ml by adding the distilled water at 9 pH, The slurry was kept in 1- litre autoclave. The autoclaving was carried out at 200°C for 60 hrs.under autogeneous pressure of about 20 atms. The mixture was then filtered, washed with distilled water and dried in the oven at 120°C overnight. The novel and characteristic X— ray diffraction of the as-synthesized powdered sample was taken and given in Table 1. There was 70-80% loss of crystallinity after calcination > 400°C. TABLE -1 : X- rav diffraction pattern of VSAPO (TPA-A) (Table Removed) Fe Ka (x = 1 9399 A) radiation was used. The vanadium - silico-alumino phosphate catalyst was then calcined at 500°C for 5 hrs and at 420°C for 15 hrs. EXAMPLE-2 The VSAPO (TBA) was synthesized as follows. The solution A was prepared in 200 ml distilled water by mixing 25.2 gms of AI2(S04) 3 16 H20, 32.3 gms of tetrabutylammonium bromide. The solution B was prepared in 100 ml of distilled water by adding 9.8 gms of H3P04 and 18.2 gms of vanadium pentoxide. The solution C was prepared in 100 ml distilled water by adding 5.69 gms sodium silicate. The solution B was mixed to the solution A drop wise with constant stirring. The mixture was stirred for 2 hrs. Then the solution C was mixed with the mixture of (A + B) drop wise with constant stirring. After mixing the solutions, the pH was adjusted to 9.2 by adding aqueous ammonia.The slurry was stirred well for about 2 hrs at room temperature. The slurry was put in 600 ml autoclave. The hydro-thermal synthesis was carried out at 180°C for 24 hrs, under autogeneous pressure. The mixture was then filtered, washed with distilled water and dried in the oven at 120°C overnight. The charecteristic X— ray diffraction pattern of the powdered sample was taken. The catalyst vanadium - silico-alumino phosphate (TBA) is highly crystalline. The vanadium - silico-alumino phosphate, VSAPO(TBA)) catalyst was then calcined at 500°C for 5 hrs and at 420°C for 15 hrs. The catalyst vanadium - silica-alumina phosphate (TBA) is designated as VSAPO(TBA). EXAMPLE-3 The VSAPO -37 as synthesized as follow. The solution A was prepared in 200 ml of distilled water by mixing 31.5 gms of AI2(S04) 3 16 H20. 26.6 gms of tetrapropyl ammonium bromide and 0.77 gms of tetramethyl ammonium bromide. The solution B was prepared in 100 ml of distilled water by adding 9.8 gms of phosphoric acid and 9.1 gms of vanadium pentoxide.The solution C was prepared in 100 ml distilled water by mixing 11.4 gms of sodium silicate. Both the solutions are stirred well separately. The solution B is mixed to the solution of A drop Wise with constant stirring. The mixture was stiired for 2 hrs. Then the solution C was mixed with the mixture (A+B) drop wise with constant stirring. After mixing the solutions, the pH was adjusted to 6.8 by adding aqueous ammonia. The slurry was stirred well for about 2 hrs at room temperature. The slurry was made 600 ml by adding the distilled water at 6.8 pH. The slurry was kept in 1- litre autoclave. The autoclaving was carried out at 200°C for 60 hrs. under autogeneous pressure of about 20 atms. The mixture was then filtered, washed with distilled water dried in the oven at 120°C overnight. The novel and characteristic X- ray diffraction of the as- synthesized powdered sample was taken. There was 70 - 80 % loss of crystallinity after calcination > 400°C. EXAMPLE - 4 5 Weight percent of Sb203 ia mixed with vanadium - silico alumina phosphate VSAPO (TPA-A) in distilled water. The mixture stirred well for 2 hrs. The mixture is dried at 120°C over night and calcined at 400°C for about five hrs before use. The catalyst is composite Sb2O3 promoted VSAPO molecular sieve and designated Sb203 promoted (TPA -A). Advantages : The catalyst prepared by the present invention are useful in oxidation, ammoxidation, cracking and acid catalysed reaction such as in the preparation of cyanopyridines, benzonitriles and acetonitriles selectively from picolines, toluene & ethanol respectively in very high yield. We claim : 1. A process for the preparation of crystalline vanadium-silico-alumino- phosphate catalyst useful for acid catalysed reactions which comprises mixing under constant stirring aqueous solutions of aluminium sulphate, tetralkyl ammonium bromide optionally with sodium chloride with aqueous solution of phosphoric acid and vanadium pentoxide to obtain a mixture, adding sodium silicate to the above said mixture to obtain a slurry, maintaining the pH in the range of 5 to 12, heating the said slurry at a temperature in the range of 150- 220°C for a period in the range of 24 to 80 hours, under autogenous pressure and under constant stirring, filtering the reaction mixture by known methods to obtain solid residue washing and drying the above said residue calcining the resultant residue at a temperature in the range of 500 to 550°C for a period of 5 to 15 hours to obtain vanadium-silico alumino -phosphate catalyst. 2. A process as claimed in claim 1 wherein the tetraalkyl ammonium bromide used is tetrapropyl / butyl ammonium bromide . 3. A process for the preparation of crystalline vanadium-silico-alumino-phosphate catalyst useful for acid catalysed reactions substantially as herein described with reference to the examples .

Full Text

This invention relates to a process for the preparation of crystalline vanadium-silico-alumino-phosphate catalysts useful for acid catalysed reactions. We have described and claimed an ammoxidation processes for the preparation of 3-cyanopyridine, 4-cyanopyridine , benzonitrile and acetonitrile, selectively from 3-picoline, 4-picoline, toluene and ethanol with ammonia and air, respectively using the catalysts prepared by the present invention. The reaction of the feed is carried out over VSAPO catalysts prepared by the process of the present invention in to the temperature range of 300-450 C and at a weight hourly space velocity of 0.25 to 1 0"1 hr . The yields of the nitrites are in the range of 60 to 100%.
The various silico-alumino-phosphates are reported in J. Am. Chem. Soc. 106, 6093 (1984) by using various templates. These molecular sieve catalysts are useful in acid catalysed reactions like n-butane cracking. With the variation of templates, the crystal structure, cage/pore dimension vary resulting into large number of molecular sieves. The silico-alumino-phosphates were synthesized using tri-n-propylamine, di-n- propylamine, tetramethylammonium salt. But these SAPOs are not modified to carry out oxidation and ammoxidation type of reactions.
The object of the present invention is to provide a process for the preparation of VSAPO as-synthesized molecular
sieves useful in the oxidation and ammoxidation of aliphatic alcohols, aromatic and hetero cyclic compounds. Molecular sieves are well- known shape selective catalysts. In the present invention, the high-boiling products are avoided due to the shape selectivity of the molecular sieves compared to non-zeolitic ammoxidation catalysts. The non-zeolitic ammoxidation catalysts are not shape -selective catalysts.
Accordingly, the present invention provides a process for the preparation of crystalline vanadium-silico-alumino-phosphate catalyst useful for acid catalysed reactions which comprises mixing under constant stirring aqueous solutions of aluminium sulphate, tetralkyl ammonium bromide optionally with sodium chloride with aqueous solution of phosphoric acid and vanadium pentoxide to obtain a mixture, adding sodium silicate to the above said mixture to obtain a slurry, maintaining the pH in the range of 5 to 12, heating the said slurry at a temperature in the range of 150-220°C for a period in the range of 24 to 80 hours, under autogenous pressure and under constant stirring, filtering the reaction mixture by known methods to obtain solid residue washing and drying the above said residue calcining the resultant residue at a temperature in the range of 500 to 550°C for a period of 5 to 15 hours to obtain vanadium-silico alumino -phosphate catalyst.
In an embodiment of the present invention the tetraalkyl ammonium bromide used may be such as tetrapropyl /butyl ammonium bromide.
The catalysts are prepared in general in the following way. Basically in aluminophosphate molecular sieves the Al: P atomic ratio is 1:1. We have partially substituted phosphorus by silicon and vanadium. Aluminium also may be partially substituted by silicon and vanadium with the corresponding variation in the atomic ratio. Al, P and Si are expected to occupy tetrahedral positions in molecular sieves. The tetrahedral atoms are linked through oxygens to form preferably three-dimensional "rigid framework" of molecular sieve. The charges on the framework atoms are compensated by mobile and exchangeable cations like Na+ or template like TPA+ during the synthesis. Al2 (SO4)3, H3P04, V205, Na2SiO3 with or without NaCl and tetra-propyl ammonium bromide (TPA) or tetra-butyl ammonium bromide (TBA) used as a template are mixed in distilled water in the pH range of 5.0 to 12.0. The slurry is mixed at least 2 hrs at room temperature with constant stirring and the pH is adjusted by aqueous ammonia. The slurry was put into an auto clave preferably of 600 ml or 1 litre capacity, for autoclaving under autogeneous pressure in the temperature range of 150 to 220° C for 24 hrs to 80 hrs till complete crystallisation was achieved. The mixture was filtered and washed with distilled water. The solid catalyst was dried in oven at 120° C overnight. The organic template was removed by the activation of the catalyst at 500 - 550° C for 5-15 hrs. Then the calcined material was modified by promoters like Sb203 or oxides of the elements active as promoters in the respective reactions. The XRD patterns show 20 -80 % loss of crystallinity.
The reactions were carried out in a tubular, down-flow, pyrex reactor with 20 mm internal diameter. The reaction mixture was fed from top using syringe pump (Sage Instruments, U.S. A) . The product was cooled by using ice-cooled water and collected at the bottom. The required number of ice-cooled traps were used to collect the total amount of products. The products were analysed by using SE-30 (5%) or OV-17 columns. The analysis was confirmed by mass spectra and GC- mass.
The following examples are given to illustrate the process of the present invention, however, these should not be construed to limit the scope of the present invention.
EXAMPLE -1
The VSAPO (TPA-A) was synthesized as follows. The solution A was prepared in 200 ml of distilled water by mixing 63.0 gms of AI2(S04) 3 16 H2O, 26.6 gms of tetrapropyl ammonium bromide, and 11.7 gms of sodium chloride. The solution B was prepared in 100 ml distilled water by adding 15.7 gms of H=PO4 and 18.2 gms of vanadium pentoxide. The solution C was prepared in 100 ml distilled water by mixing 11.4 gms of sodium silicate. Both the solutions are stirred well separately. The solution B is mixed to the solution of A drop wise with constant stirring. The mixture was stirred for 2 hrs, Then the solution C was mixed with the mixture (A + B) drop wise with constant stirring. After mixing the solutions, the pH was adjusted to 9.0 by adding aqueous ammonia. The slurry was stirred well for about 2 hrs at room temperature. The slurry was made 600 ml by adding the distilled water at 9 pH, The slurry was kept in 1- litre autoclave. The autoclaving was carried out at 200°C for 60 hrs.under autogeneous pressure of about 20 atms. The mixture was then filtered, washed with distilled water and dried in the oven at 120°C overnight. The novel and characteristic X— ray diffraction of the as-synthesized powdered sample was taken and given in Table 1. There was 70-80% loss of crystallinity after calcination > 400°C.
TABLE -1 : X- rav diffraction pattern of VSAPO (TPA-A)
(Table Removed)
Fe Ka (x = 1 9399 A) radiation was used.
The vanadium - silico-alumino phosphate catalyst was then calcined at 500°C for 5 hrs and at 420°C for 15 hrs.
EXAMPLE-2
The VSAPO (TBA) was synthesized as follows. The solution A was prepared in 200 ml distilled water by mixing 25.2 gms of AI2(S04) 3 16 H20, 32.3 gms of tetrabutylammonium bromide. The solution B was prepared in 100 ml of distilled water by adding 9.8 gms of H3P04 and 18.2 gms of vanadium pentoxide. The solution C was prepared in 100 ml distilled water by adding 5.69 gms sodium silicate. The solution B was mixed to the solution A drop wise with constant stirring. The mixture was stirred for 2 hrs. Then the solution C was mixed with the mixture of (A + B) drop wise with constant stirring. After mixing the solutions, the pH was adjusted to 9.2 by adding aqueous ammonia.The slurry was stirred well for about 2 hrs at room temperature. The slurry was put in 600 ml autoclave. The hydro-thermal synthesis was carried out at 180°C for 24 hrs, under autogeneous pressure. The mixture was then filtered, washed with distilled water and dried in the oven at 120°C overnight. The charecteristic X— ray diffraction pattern of the powdered sample was taken.
The catalyst vanadium - silico-alumino phosphate (TBA) is highly crystalline. The vanadium - silico-alumino phosphate, VSAPO(TBA)) catalyst was then calcined at 500°C for 5 hrs and at 420°C for 15 hrs. The catalyst vanadium - silica-alumina phosphate (TBA) is designated as VSAPO(TBA).
EXAMPLE-3
The VSAPO -37 as synthesized as follow. The solution A was prepared in 200 ml of distilled water by mixing 31.5 gms of AI2(S04) 3 16 H20. 26.6 gms of tetrapropyl ammonium bromide and 0.77 gms of tetramethyl ammonium bromide. The solution B was prepared in 100 ml of distilled water by adding 9.8 gms of phosphoric acid and 9.1 gms of vanadium pentoxide.The solution C was prepared in 100 ml distilled water by mixing 11.4 gms of sodium silicate. Both the solutions are stirred well separately. The solution B is mixed to the solution of A drop Wise with constant stirring. The mixture was stiired for 2 hrs. Then the solution C was mixed with the mixture (A+B) drop wise with constant stirring. After mixing the solutions, the pH was adjusted to 6.8 by adding aqueous ammonia. The slurry was stirred well for about 2 hrs at room temperature. The slurry was made 600 ml by adding the distilled water at 6.8 pH. The slurry was kept in 1- litre autoclave. The autoclaving was carried out at 200°C for 60 hrs. under autogeneous pressure of about 20 atms. The mixture was then filtered, washed with distilled water dried in the oven at 120°C overnight. The novel and characteristic X- ray diffraction of the as- synthesized powdered sample was taken. There was 70 - 80 % loss of crystallinity after calcination > 400°C.
EXAMPLE - 4
5 Weight percent of Sb203 ia mixed with vanadium - silico alumina phosphate VSAPO (TPA-A) in distilled water. The mixture stirred well for 2 hrs. The mixture is dried at 120°C over night and calcined at 400°C for about five hrs before use. The catalyst is composite Sb2O3 promoted VSAPO molecular sieve and designated Sb203 promoted (TPA -A).
Advantages :
The catalyst prepared by the present invention are useful in oxidation, ammoxidation, cracking and acid catalysed reaction such as in the preparation of cyanopyridines, benzonitriles and acetonitriles selectively from picolines, toluene & ethanol respectively in very high yield.

We claim :
1. A process for the preparation of crystalline vanadium-silico-alumino-
phosphate catalyst useful for acid catalysed reactions which comprises mixing
under constant stirring aqueous solutions of aluminium sulphate, tetralkyl
ammonium bromide optionally with sodium chloride with aqueous solution of
phosphoric acid and vanadium pentoxide to obtain a mixture, adding sodium
silicate to the above said mixture to obtain a slurry, maintaining the pH in the
range of 5 to 12, heating the said slurry at a temperature in the range of 150-
220°C for a period in the range of 24 to 80 hours, under autogenous pressure
and under constant stirring, filtering the reaction mixture by known methods to
obtain solid residue washing and drying the above said residue calcining the
resultant residue at a temperature in the range of 500 to 550°C for a period of 5
to 15 hours to obtain vanadium-silico alumino -phosphate catalyst.
2. A process as claimed in claim 1 wherein the tetraalkyl ammonium
bromide used is tetrapropyl / butyl ammonium bromide .
3. A process for the preparation of crystalline vanadium-silico-alumino-phosphate
catalyst useful for acid catalysed reactions substantially as herein described with
reference to the examples .

Documents:

963-del-1995-abstract.pdf

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963-del-1995-correspondence-po.pdf

963-del-1995-description (complete).pdf

963-del-1995-form-1.pdf

963-del-1995-form-2.pdf

963-del-1995-form-4.pdf

963-del-1995-form-5.pdf

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Patent Number

190239

Indian Patent Application Number

963/DEL/1995

PG Journal Number

27/2003

Publication Date

05-Jul-2003

Grant Date

12-Mar-2004

Date of Filing

25-May-1995

Name of Patentee

COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH

Applicant Address

RAFI MARG, NEW DELHI-110001,INDIA

Inventors:

#	Inventor's Name	Inventor's Address
1	SHIVANAND JANARDAN KULKARNI	INDIAN INSTITUTE OF CHEMICAL TECHNOLOGY HYDERABAD 500 007,INDIA
2	SURESH FARSINAVIS	INDIAN INSTITUTE OF CHEMICAL TECHNOLOGY HYDERABAD 500 007,INDIA
3	REVUR RAMCHANDRA RAO	INDIAN INSTITUTE OF CHEMICAL TECHNOLOGY HYDERABAD 500 007,INDIA
4	GUDUR LAXMA REDDY	INDIAN INSTITUTE OF CHEMICAL TECHNOLOGY HYDERABAD 500 007,INDIA
5	PANJA KANTA RAO	INDIAN INSTITUTE OF CHEMICAL TECHNOLOGY HYDERABAD 500 007,INDIA
6	ALLA VENKAT RAMA RAO	INDIAN INSTITUTE OF CHEMICAL TECHNOLOGY HYDERABAD 500 007,INDIA

PCT International Classification Number

B01J 23/00

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA