Title of Invention	A PROCESS FOR THE PREPARATION OF A NOVEL CRYSTALLINE ZIRCONIUM CONTAINING ALUMINO-PHOSPHATE, ZR-APO-11
Abstract	A process for the preparation of porous crystalline zirconium contining alumino-phosphate molecular sieve: The present invention provides a process for the preparation of porous zirconium containing alumino-phosphate molecular sieve wherein zirconium is isomorphously substituted in the framework position of A1PO-11 structure (alumino-phosphate with AEL topology). The material prepared by the process of this invention is useful as a catalyst for hydroisomerstion of n-alkanes.

Title of Invention

A PROCESS FOR THE PREPARATION OF A NOVEL CRYSTALLINE ZIRCONIUM CONTAINING ALUMINO-PHOSPHATE, ZR-APO-11

Abstract

A process for the preparation of porous crystalline zirconium contining alumino-phosphate molecular sieve: The present invention provides a process for the preparation of porous zirconium containing alumino-phosphate molecular sieve wherein zirconium is isomorphously substituted in the framework position of A1PO-11 structure (alumino-phosphate with AEL topology). The material prepared by the process of this invention is useful as a catalyst for hydroisomerstion of n-alkanes.

Full Text	The present invention relates to a process for the preparation of a novel porous crystalline zirconium containing alumino-phosphate molecular sieve, designated as Zr-APO-11. More specifically it is related to the preparation of porous zirconium containing alumino-phosphate molecular sieve wherein zirconium is isomorphously substituted in the framework position of A1PO-11 structure (alumino-phosphate with AEL topology). The material prepared by the process of this invention is useful as a catalyst for hydroisomersation of n-alkanes. Crystalline alumino-phosphates with molecular sieve properties representing a new class of adsorbents are described in US patent No. 4,310,440. The properties of these molecular sieves are somewhat analogous to zeolite molecular sieves and therefore, they are useful as catalysts and catalyst supports in various chemical reactions, such as dehydration, isomerization, alkylation, various rearrangements, condensation and Diels-Alder cyclocondensation. Moreover A1PO-5 (alumino-phosphate with AFI topology) and A1PO-11 molecular sieves are also used as support for polymerization, oxidation, hydrogenation, reductive cleavage or hydration catalysts. The acid base properties of alumino-phosphate molecular sieves play an important role in catalytic reactions. By modifying the acid-base properties of alumino-phosphate, its catalytic activity can be controlled. The performance of such a catalyst is tailored by introducing metal ions in substitutional positions of different alumino-phosphate structures, which are known as Me-APO-n (Metal containing aluminp-phosphates). US patent Nos. 4 500 651, 4 544 143, 4 567 029 and EP patent No. 132 708, 158 976 describe the synthesis of different metal containing alumino-phosphates with 15 hetero-atoms such as Be, B, Mg, Si, Ga, Ge, As, Ti, Mn, Fe, Co, Zn, Cr and Vanadium. Another US patent No. 5374411 also describes the synthesis of crystalline alumino-phosphate composition having three-dimensional microporous crystal framework similar to large pore alumino-phosphate designated as VPI-5 as determined using XRD study. Metals such as Si, Mg, Zn, Sn, Zr, Ti, Co were incorporated in the oxide lattice. Adsorption study indicated usefulness of these. compositions as molecular sieves. In the prior art, Polish Pat. No. 291 460 describes a zirconium containing alumino-phosphate with A1PO-5 structure. The Zr-APO-5 material was synthesized hydrothermally using the reaction gel as Al2O3: P2O5 0.17 ZrO2: 1.3 Triethyl amine: 270 H2O. The materials were tested for its structure and adsorption properties. The product was crystalline with AlPO-11 structure and the zirconium content was in the range of 0.235-0.255, mole fraction of Al. The sorption capacity for water was higher than reference A1PO-5 sample and sorption of N2 was lower indicating framework incorporation of Zr ion in the sample. Silico-aluminophosphate, SAPO-11 a medium pore molecular sieve has been described in US patent 4,440,871 for highly selective isomerization of long-chain parafins. It has been used in a selective isomerization process for the manufacture of high viscosity index (HVI) lube oil from waxes (long-chain alkanes, Miller S.J; Stud. Surf. Sci. Catal. 1994, 84 C, 2319). European patent application No. 0146389 describes another type of crystalline silico-alumino-phosphate with, molecular sieve, ion exchange and catalytic properties especially in hydroisomerzation of n-alkanes. Hydroisomerzation of n-paraffins is of considerable interest because it plays an important role in petroleum industry to produce high-octane gasoline blending components and to increase the low temperature performance of diesel. These hydroisomerization reactions are carried out over bifunctional catalysts containing metal sites for hydrogenation/dehydrogenation and acidic sites for skeletal isomerization. However isomerization reactions are always accompanied by hydrocracking reactions, which lowers the yield of isomerized feed molecules. Medium pore molecular sieves catalysts with high acidic sites and with high shape selectivity have shown interesting results in hydroisomerization of n-alkanes. Synthesis of zirconium containing silico-aluminophosphate is described by P. Meriaudeau and coworkers in J. Chem. Soc. Faraday Trans., 1997, 93(23), 4201-4206 (designated as Zr-SAPO-11). The material was synthesized by hydrothermal process using pseudoboehmite, phosphoric acid and zirconium isopropoxide. The molar composition of the gel was Al2O3: P2O5: 0.1 SiO2: 0.1 ZrO2: 1 DPA: 50 H2O. The product obtained was SAPO-11 containing extra-framework zirconium species. The Zr-SAPO-11 exhibited similar activity for n-butane isomerization as SAPO-11 and higher isobutane selectivity, which was attributed to the presence of zirconium in the pores partially blocking the pores and not in the framework substitutional position. Despite all these Zr containing molecular sieves, a crystalline zirconium alumino-phosphate molecular sieve with A1PO-11 structre, wherein aluminum or phosphorous or a pair of Al and P is isomorphously substituted by zirconium in the AlPO-11 lattice and which does not contain any silicon or any other cation in the framework is not known in the prior art. Objective of the present invention is to provide a process for the preparation of crystalline zirconium containing aluminophosphate, Zr-APO-11 where the zirconium is in the aluminophosphate framework position. Accordingly, the present invention provides a process for the preparation of porous crystalline synthetic material having the formula Al2O3. xZrO2: yP2O5: zH2O where x is 0.005 to 0.2, y is 0.9 to 1.2, z is 20 to 50 and having AlPO-11 type structure characterized by an X-ray diffraction pattern as given below in Table 1. Table-1 (Table Removed) The 29 values may vary by ± 0.05° Relative Intensity: Vs: very strong, s: strong, m: medium and w: weak. Which comprises forming a gel by mixing a source of aluminium, phosphorous, zirconium and nitrogen containing base in the molar composition in the range of 0.5 - 1.5 R: Al2O3. .005 - 0.2 ZrO2: 0.9-1.2 P3O5: 20-50 H2O, where R represents nitrogen containing base, heating the gel for hydrothermal crystallization at 150 to 200 °C for 20 to 160 h, separating the product after hydrothermal crystallization, washing and drying by conventional methods, calcining at temperature in the range of 400-580 °C in air, and treating the calcined product with aqueous solution of platinum salt to obtain the product. In one of the embodiments of the present invention, the zirconium sources may be zirconium alkoxides such as zirconium tetrapropoxide, tetrabutoxide and other zirconium sources such as ZrOCl2 and ZrCl4, more preferably zirconium tetrapropoxide. In another embodiment, the noble metals used for loading may be platinum or palladium, more preferably platinum. In yet another embodiment the aluminium sources may be aluminium alkoxides and other aluminium source like psedoboehmite, more preferably aluminium tetrapropoxide. In another embodiment, the solvent used may be benzene, toluene or alcohol selected from solvent alcohols like, ethyl alcohol, propyl alcohol, butyl alcohol preferably isopropyl alcohol. The crystalline Zr-APO-11 material is characterized by x-ray powder diffraction, infrared spectroscopic and scanning electron microscopic examination. The most significant lines of the x-ray powder diffraction of the Zr-APO-11 sample taken on a Rigaku, D-MAX III VC model, with Ni filtered Cu K radiation along with the corresponding data for pure A1PO-11 are shown in table -1. The scanning electron micrographs of the materials by the process of the present invention were taken on JEOL JSM 5200 instrument. SEM photograph shows that the crystallite size distribution fall within the narrow range of 1 to 5 µm. Though the catalyst composite material provided by the present invention may be used directly as a catalyst, it is desirable in various applications to enhance the mechanical strength and ease of handling, they may be admixed with a suitable binder material and converting it into a suitable shape. Shapes may be cylindrical extrudates, spheres, etc. Silica, alumina, clay minerals such as bentonite, kaolinite or mixture thereof are suitable binder materials which impart improved mechanical strength to the Zr-APO-11 catalyst composite material. Zr-APO-11 and its composite material prepared by the process of the present invention is useful as a catalyst in various hydrocarbon conversion reactions such as 1) Oxidation of hydrocarbons or derivatives of hydrocarbons 2) Hydrogenation/dehydrogenation of hydrocarbons. 3) Conversion of dimethyl ether, and/or methanol or other lower molecular weight alcohols into hydrocarbons. 4) Disproportionation of aromatics i.e. toluenexylene etc. 5) Alkylation of benzene with ethanol or ethene and toluene with methanol. 6) Isomerization of aromatics and n-paraffins. 7) Reforming of hydrocarbons. 8) Oligomerization/Polymerization of the compound with olefinic or acetylenic bonds. 9) Cracking of n-paraffms. 10) Hydroisomerization of n-paraffms. The process of the present invention is further described by the following examples, which are illustrative only and should not be construed to limit the scope of the present invention, in any manner. Example 1 This example illustrates the preparation of Zr-APO-11 using hydrothermal gel with following molar compositions: 1DPA: lAl2O3: 0.1ZrO2: 0.90 P2O5: 50 H2O In this example the process for the preparation of ZrAPO-11 is described. 20.8 g. of aluminium isopropoxide and 50 g of isopropyl alcohol (IPA) were mixed together in a polypropylene beaker and stirred for two hours. 2.357g of zirconium propoxide (70 wt % in IP A) in 20g of IPA was added to the stirred solution. The mixture was heated under stirring at 60-70 °C for 2-3 h to remove excess of alcohol. 11.5 g of phosphoric acid (85 wt %) in 45g of water was added slowly to the above solution in ice cold conditions. Finally, a white gel obtained was stirred for another 1 h before the addition of 5.05g of dipropyl amine (DPA). The resulting gel was kept for hydrothermal crystallization at 180 °C for 90 to 120 h in a stainless steel autoclave. After the hydrothermal crystallization the sample was recovered by filtration, washed and dried at 100 °C in an oven. The sample was calcined at 560 °C in air for 8 to 10 h and the structure was characterized by X-ray diffraction pattern as shown in table -1 below. The calcined sample was treated with platinum solution to get different loadings of platinum before catalytic reaction. Table -1 (Table Removed) The 26 values may vary by ± 0.05° Relative Intensity: Vs: very strong, s: strong, m: medium and w: weak. Example 2 This example illustrates the use of hydrated alumina (Pseudoboehmite) as aluminium source instead of aluminium isopropoxide in the process for the preparation of Zr-APO-11. 7.28 g of hydrated alumina (70 %) and 2.357g of zirconium propoxide (70 wt % in IP A) in 20g of IPA was mixed together in a polypropylene beaker and stirred for two hours. 11.5 g of phosphoric acid (85 wt %) in 45g of water was added slowly to the above solution in ice cold conditions. Finally, a white gel obtained was stirred for another 1 h before the addition of 5.05g of dipropyl amine (DPA). The resulting gel was kept for hydrothermal crystallization at 180 °C for 90 to 120 h in a stainless steel autoclave. After the hydrothermal crystallization the sample was recovered by filtration, washed and dried at 100 °C in an oven. The sample was calcined at 560 °C in air for 8 to 10 h and the structure was characterized by X-ray diffraction. The calcined sample was treated with platinum solution to get different loadings of platinum before catalytic reaction. Example 3 In this example ZrOCl2 is used as zirconium source while the moler ratio of the precursor gel for the sample is same as in example-1.20.8 g. of aluminium isopropoxide and 50 g of isopropyl alcohol (IPA) were mixed together in a polypropylene beaker and stirred. The mixture was heated under stirring at 70 °C for 2-3 h to remove excess of alcohol. 1.61 g of ZrOCl2 in 10g of water added to the stirred solution. 11.5 g of phosphoric acid (85 wt %) in 35g of water was added slowly to the above solution in ice cold conditions. Finally, a white gel obtained was stirred for another 1 h before the addition of 5.05g of dipropyl amine (DPA). The resulting gel was kept for hydrothermal crystallization at 180 °C for 90 to 120 h in a stainless steel autoclave. After the hydrothermal crystallization the sample was recovered by filtration, washed and dried at 100 °C in an oven. The sample was calcined at 560 °C in air for 8 to 10 h and the structure was characterized by X-ray diffraction. The calcined sample was treated with platinum solution to get different loadings of platinum before catalytic reaction. Example4 This example illustrates the catalytic activity of the Zr-APO-11 in the hydroisomerization of n-hexane. The results of n-hexane hydroisomerization at different temperatures over Pt/Zr-APO-11 are presented in table -2 below. Table-2 (Table Removed) Conditions: WHSV= 1, H2/n-hexane = 4, time on stream lh. a: isomers of n-hexane such as 2,2 and 2, 3 Dimethyl butanes (DMB), 2- and 3- Methyl pentanes (MP) b: Moles of n-hexane isomerized / n-hexane cracked. The product mainly consists of isomerized products such as 2,2 and 2, 3 Dimethyl butanes (DMB), 2- and 3- Methyl pentanes (MP) and cracked (C1-C5) products. It is observed from the above table that the I/C is high in case of Zr-APO-11 samples along with negligible amounts of C6+ products. We Claim: 1 . A process for the preparation of microporous, crystalline Zirconium containing alumino-phosphate molecular sieve having the formula wherein x is 0.005 to 0.2, y is 0.9 to 1.2, z is 20 to 50 and having AIPO-11 (alumino - phosphate - 11) type structure having characteristic such as herein described , said process characterized in that forming a gel by mixing a source of aluminium selected from aluminium alkoxide , phosphoric acid , a source of zirconium selected from zirconium alkoxide and a nitrogen containing base such as herein described , heating the obtained gel for hydrothermal crystallization at 150° to 200°C for 20 to 160 h, separating the product by conventional filtration after hydrothermal crystallization, washing and drying by conventional methods such as herein described, calcining at temperature in the range of 400°-580°C in air, treating the calcined product with aqueous solution of platinum salt such as herein described to obtain the desired alumino-phosphate molecular sieve. 2. A process as claimed in claim 1 , wherein zirconium alkoxides used is selected from zirconium tetrapropoxide and other zirconium sources selected from ZrOCI2 and ZrCI4, more preferably zirconium tetrapropoxide. 3. A process as claimed in claims 1-2 wherein the aluminium alkoxides used is selected from aluminium tetrapropoxide, psedobohmite. 4. A process as claimed in claims 1 - 3 , wherein the solvents used is selected from benzene or toluene or alcohols having 2 to 5 number of carbon atoms, such as ethyl, propyl, butyl. 5. A process as claimed in claims 1-4, wherein the noble metal used for loading is selected from platinum or palladium. 6. A process as claimed in claims 1-5, the organic base used is di-n- propyl amine. 7. A process as claimed in claims 1-7, wherein the reaction temperature is preferably 160°C to 360°C. 8. A process for the preparation of porous crystalline zirconium containing alumino-phosphate molecular sieve substantially described herein with reference to example.

Full Text

The present invention relates to a process for the preparation of a novel porous crystalline zirconium containing alumino-phosphate molecular sieve, designated as Zr-APO-11. More specifically it is related to the preparation of porous zirconium containing alumino-phosphate molecular sieve wherein zirconium is isomorphously substituted in the framework position of A1PO-11 structure (alumino-phosphate with AEL topology). The material prepared by the process of this invention is useful as a catalyst for hydroisomersation of n-alkanes.
Crystalline alumino-phosphates with molecular sieve properties representing a new class of adsorbents are described in US patent No. 4,310,440. The properties of these molecular sieves are somewhat analogous to zeolite molecular sieves and therefore, they are useful as catalysts and catalyst supports in various chemical reactions, such as dehydration, isomerization, alkylation, various rearrangements, condensation and Diels-Alder cyclocondensation. Moreover A1PO-5 (alumino-phosphate with AFI topology) and A1PO-11 molecular sieves are also used as support for polymerization, oxidation, hydrogenation, reductive cleavage or hydration catalysts. The acid base properties of alumino-phosphate molecular sieves play an important role in catalytic reactions. By modifying the acid-base properties of alumino-phosphate, its catalytic activity can be controlled. The performance of such a catalyst is tailored by introducing metal ions in substitutional positions of different alumino-phosphate structures, which are known as Me-APO-n (Metal containing aluminp-phosphates). US patent Nos. 4 500 651, 4 544 143, 4 567 029 and EP patent No. 132 708, 158 976 describe the synthesis of different metal containing alumino-phosphates with 15 hetero-atoms such as Be, B, Mg, Si, Ga, Ge, As, Ti, Mn,
Fe, Co, Zn, Cr and Vanadium. Another US patent No. 5374411 also describes the synthesis of crystalline alumino-phosphate composition having three-dimensional microporous crystal framework similar to large pore alumino-phosphate designated as VPI-5 as determined using XRD study. Metals such as Si, Mg, Zn, Sn, Zr, Ti, Co were incorporated in the oxide lattice. Adsorption study indicated usefulness of these. compositions as molecular sieves.
In the prior art, Polish Pat. No. 291 460 describes a zirconium containing alumino-phosphate with A1PO-5 structure. The Zr-APO-5 material was synthesized hydrothermally using the reaction gel as Al2O3: P2O5 0.17 ZrO2: 1.3 Triethyl amine: 270 H2O. The materials were tested for its structure and adsorption properties. The product was crystalline with AlPO-11 structure and the zirconium content was in the range of 0.235-0.255, mole fraction of Al. The sorption capacity for water was higher than reference A1PO-5 sample and sorption of N2 was lower indicating framework incorporation of Zr ion in the sample.
Silico-aluminophosphate, SAPO-11 a medium pore molecular sieve has been described in US patent 4,440,871 for highly selective isomerization of long-chain parafins. It has been used in a selective isomerization process for the manufacture of high viscosity index (HVI) lube oil from waxes (long-chain alkanes, Miller S.J; Stud. Surf. Sci. Catal. 1994, 84 C, 2319). European patent application No. 0146389 describes another type of crystalline silico-alumino-phosphate with, molecular sieve, ion exchange and catalytic properties especially in hydroisomerzation of n-alkanes. Hydroisomerzation of n-paraffins is of considerable interest because it plays an important role in petroleum industry to produce high-octane gasoline blending
components and to increase the low temperature performance of diesel. These hydroisomerization reactions are carried out over bifunctional catalysts containing metal sites for hydrogenation/dehydrogenation and acidic sites for skeletal isomerization. However isomerization reactions are always accompanied by hydrocracking reactions, which lowers the yield of isomerized feed molecules. Medium pore molecular sieves catalysts with high acidic sites and with high shape selectivity have shown interesting results in hydroisomerization of n-alkanes.
Synthesis of zirconium containing silico-aluminophosphate is described by P. Meriaudeau and coworkers in J. Chem. Soc. Faraday Trans., 1997, 93(23), 4201-4206 (designated as Zr-SAPO-11). The material was synthesized by hydrothermal process using pseudoboehmite, phosphoric acid and zirconium isopropoxide. The molar composition of the gel was Al2O3: P2O5: 0.1 SiO2: 0.1 ZrO2: 1 DPA: 50 H2O. The product obtained was SAPO-11 containing extra-framework zirconium species. The Zr-SAPO-11 exhibited similar activity for n-butane isomerization as SAPO-11 and higher isobutane selectivity, which was attributed to the presence of zirconium in the pores partially blocking the pores and not in the framework substitutional position.
Despite all these Zr containing molecular sieves, a crystalline zirconium alumino-phosphate molecular sieve with A1PO-11 structre, wherein aluminum or phosphorous or a pair of Al and P is isomorphously substituted by zirconium in the AlPO-11 lattice and which does not contain any silicon or any other cation in the framework is not known in the prior art.
Objective of the present invention is to provide a process for the preparation of crystalline zirconium containing aluminophosphate, Zr-APO-11 where the zirconium is in the aluminophosphate framework position.
Accordingly, the present invention provides a process for the preparation of porous crystalline synthetic material having the formula
Al2O3. xZrO2: yP2O5: zH2O
where x is 0.005 to 0.2, y is 0.9 to 1.2, z is 20 to 50 and having AlPO-11 type structure characterized by an X-ray diffraction pattern as given below in Table 1.
Table-1
(Table Removed)
The 29 values may vary by ± 0.05°
Relative Intensity: Vs: very strong, s: strong, m: medium and w: weak.
Which comprises forming a gel by mixing a source of aluminium, phosphorous, zirconium and nitrogen containing base in the molar composition in the range of 0.5 - 1.5 R: Al2O3. .005 - 0.2 ZrO2: 0.9-1.2 P3O5: 20-50 H2O, where R represents nitrogen containing base, heating the gel for hydrothermal crystallization at 150 to 200 °C for 20 to 160 h, separating the product after hydrothermal crystallization, washing and drying by conventional methods, calcining at temperature in the range of 400-580 °C in air, and treating the calcined product with aqueous solution of platinum salt to obtain the product.
In one of the embodiments of the present invention, the zirconium sources may be zirconium alkoxides such as zirconium tetrapropoxide, tetrabutoxide and other zirconium sources such as ZrOCl2 and ZrCl4, more preferably zirconium tetrapropoxide.
In another embodiment, the noble metals used for loading may be platinum or palladium, more preferably platinum.
In yet another embodiment the aluminium sources may be aluminium alkoxides and other aluminium source like psedoboehmite, more preferably aluminium tetrapropoxide.
In another embodiment, the solvent used may be benzene, toluene or alcohol selected from solvent alcohols like, ethyl alcohol, propyl alcohol, butyl alcohol preferably isopropyl alcohol.
The crystalline Zr-APO-11 material is characterized by x-ray powder diffraction, infrared spectroscopic and scanning electron microscopic examination. The most significant lines of the x-ray powder diffraction of the Zr-APO-11 sample taken on a Rigaku, D-MAX III VC model, with Ni filtered Cu K radiation along with the corresponding data for pure A1PO-11 are shown in table -1.
The scanning electron micrographs of the materials by the process of the present invention were taken on JEOL JSM 5200 instrument. SEM photograph shows that the crystallite size distribution fall within the narrow range of 1 to 5 µm.
Though the catalyst composite material provided by the present invention may be used directly as a catalyst, it is desirable in various applications to enhance the mechanical strength and ease of handling, they may be admixed with a suitable binder material and converting it into a suitable shape. Shapes may be cylindrical extrudates, spheres, etc. Silica, alumina, clay minerals such as bentonite, kaolinite or mixture thereof are suitable binder materials which impart improved mechanical strength to the Zr-APO-11 catalyst composite material.
Zr-APO-11 and its composite material prepared by the process of the present invention is useful as a catalyst in various hydrocarbon conversion reactions such as 1)
Oxidation of hydrocarbons or derivatives of hydrocarbons 2) Hydrogenation/dehydrogenation of hydrocarbons. 3) Conversion of dimethyl ether, and/or methanol or other lower molecular weight alcohols into hydrocarbons. 4) Disproportionation of aromatics i.e. toluenexylene etc. 5) Alkylation of benzene with ethanol or ethene and toluene with methanol. 6) Isomerization of aromatics and n-paraffins. 7) Reforming of hydrocarbons. 8) Oligomerization/Polymerization of the compound with olefinic or acetylenic bonds. 9) Cracking of n-paraffms. 10) Hydroisomerization of n-paraffms.
The process of the present invention is further described by the following examples, which are illustrative only and should not be construed to limit the scope of the present invention, in any manner.
Example 1
This example illustrates the preparation of Zr-APO-11 using hydrothermal gel with following molar compositions: 1DPA: lAl2O3: 0.1ZrO2: 0.90 P2O5: 50 H2O In this example the process for the preparation of ZrAPO-11 is described. 20.8 g. of aluminium isopropoxide and 50 g of isopropyl alcohol (IPA) were mixed together in a polypropylene beaker and stirred for two hours. 2.357g of zirconium propoxide (70 wt % in IP A) in 20g of IPA was added to the stirred solution. The mixture was heated under stirring at 60-70 °C for 2-3 h to remove excess of alcohol. 11.5 g of phosphoric acid (85 wt %) in 45g of water was added slowly to the above solution in ice cold conditions. Finally, a white gel obtained was stirred for another 1 h before the addition of 5.05g of dipropyl amine (DPA). The resulting gel was kept for hydrothermal crystallization at 180 °C for 90 to 120 h in a stainless steel autoclave.
After the hydrothermal crystallization the sample was recovered by filtration, washed and dried at 100 °C in an oven. The sample was calcined at 560 °C in air for 8 to 10 h and the structure was characterized by X-ray diffraction pattern as shown in table -1 below. The calcined sample was treated with platinum solution to get different loadings of platinum before catalytic reaction.
Table -1

(Table Removed)
The 26 values may vary by ± 0.05°
Relative Intensity: Vs: very strong, s: strong, m: medium and w: weak.
Example 2
This example illustrates the use of hydrated alumina (Pseudoboehmite) as aluminium source instead of aluminium isopropoxide in the process for the preparation of Zr-APO-11. 7.28 g of hydrated alumina (70 %) and 2.357g of zirconium propoxide (70 wt % in IP A) in 20g of IPA was mixed together in a polypropylene beaker and stirred for two hours. 11.5 g of phosphoric acid (85 wt %) in 45g of water was added slowly to the above solution in ice cold conditions. Finally, a white gel obtained was stirred for another 1 h before the addition of 5.05g of dipropyl amine (DPA). The resulting gel was kept for hydrothermal crystallization at 180 °C for 90 to 120 h in a stainless steel autoclave. After the hydrothermal crystallization the sample was recovered by filtration, washed and dried at 100 °C in an oven. The sample was calcined at 560 °C in air for 8 to 10 h and the structure was characterized by X-ray diffraction. The calcined sample was treated with platinum solution to get different loadings of platinum before catalytic reaction.
Example 3
In this example ZrOCl2 is used as zirconium source while the moler ratio of the precursor gel for the sample is same as in example-1.20.8 g. of aluminium isopropoxide and 50 g of isopropyl alcohol (IPA) were mixed together in a polypropylene beaker and stirred. The mixture was heated under stirring at 70 °C for 2-3 h to remove excess of alcohol. 1.61 g of ZrOCl2 in 10g of water added to the stirred solution. 11.5 g of phosphoric acid (85 wt %) in 35g of water was added slowly to the above solution in ice cold conditions. Finally, a white gel obtained was stirred for another 1 h before the addition of 5.05g of dipropyl amine (DPA). The resulting gel was kept for hydrothermal crystallization at 180 °C for 90 to 120 h in a stainless steel autoclave. After the hydrothermal crystallization the sample was recovered by filtration, washed and dried at 100 °C in an oven. The sample was calcined at 560 °C in air for 8 to 10 h and the structure was characterized by X-ray diffraction. The calcined sample was treated with platinum solution to get different loadings of platinum before catalytic reaction.
Example4
This example illustrates the catalytic activity of the Zr-APO-11 in the hydroisomerization of n-hexane. The results of n-hexane hydroisomerization at different temperatures over Pt/Zr-APO-11 are presented in table -2 below.

Table-2
(Table Removed)
Conditions: WHSV= 1, H2/n-hexane = 4, time on stream lh.
a: isomers of n-hexane such as
2,2 and 2, 3 Dimethyl butanes (DMB), 2- and 3- Methyl pentanes (MP)
b: Moles of n-hexane isomerized / n-hexane cracked.
The product mainly consists of isomerized products such as 2,2 and 2, 3 Dimethyl butanes (DMB), 2- and 3- Methyl pentanes (MP) and cracked (C1-C5) products. It is observed from the above table that the I/C is high in case of Zr-APO-11 samples along with negligible amounts of C6+ products.

We Claim:
1 . A process for the preparation of microporous, crystalline Zirconium containing alumino-phosphate molecular sieve having the formula
wherein x is 0.005 to 0.2, y is 0.9 to 1.2, z is 20 to 50 and having AIPO-11 (alumino - phosphate - 11) type structure having characteristic such as herein described , said process characterized in that forming a gel by mixing a source of aluminium selected from aluminium alkoxide , phosphoric acid , a source of zirconium selected from zirconium alkoxide and a nitrogen containing base such as herein described , heating the obtained gel for hydrothermal crystallization at 150° to 200°C for 20 to 160 h, separating the product by conventional filtration after hydrothermal crystallization, washing and drying by conventional methods such as herein described, calcining at temperature in the range of 400°-580°C in air, treating the calcined product with aqueous solution of platinum salt such as herein described to obtain the desired alumino-phosphate molecular sieve.
2. A process as claimed in claim 1 , wherein zirconium alkoxides used is selected from zirconium tetrapropoxide and other zirconium sources selected from ZrOCI2 and ZrCI4, more preferably zirconium tetrapropoxide.
3. A process as claimed in claims 1-2 wherein the aluminium
alkoxides used is selected from aluminium tetrapropoxide,
psedobohmite.
4. A process as claimed in claims 1 - 3 , wherein the solvents used is
selected from benzene or toluene or alcohols having 2 to 5 number
of carbon atoms, such as ethyl, propyl, butyl.
5. A process as claimed in claims 1-4, wherein the noble metal used
for loading is selected from platinum or palladium.
6. A process as claimed in claims 1-5, the organic base used is di-n-
propyl amine.
7. A process as claimed in claims 1-7, wherein the reaction
temperature is preferably 160°C to 360°C.
8. A process for the preparation of porous crystalline zirconium
containing alumino-phosphate molecular sieve substantially
described herein with reference to example.

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Patent Number

217841

Indian Patent Application Number

130/DEL/2000

PG Journal Number

17/2008

Publication Date

25-Apr-2008

Grant Date

29-Mar-2008

Date of Filing

16-Feb-2000

Name of Patentee

COUNCIL OF SCIENTIFIC & INDUSTRIAL RESEARCH

Applicant Address

RAFI MARG, NEW DELHI- 110 001, INDIA

Inventors:

#	Inventor's Name	Inventor's Address
1	MOHAN KERABA DONGARE	NATIONAL CHEMICAL LABORATORY PUNE- 411008 MAHARASHTRA INDIA.
2	KANCHAN RAMCHANDRA KAMBLE	NATIONAL CHEMICAL LABORATORY PUNE- 411008 MAHARASHTRA INDIA.
3	DHANAJAY PRABHAKAR SABDE	NATIONAL CHEMICAL LABORATORY PUNE- 411008 MAHARASHTRA INDIA.
4	SOORYAKANT GANESH HEGDE	NATIONAL CHEMICAL LABORATORY PUNE- 411008 MAHARASHTRA INDIA.

PCT International Classification Number

B01J 21/06

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA