Title of Invention	AN IMPROVED PROCESS FOR THE PREPARATION OF A CATALYST SUITABLE FOR HYDROCARBON TRANSFORMATIONS
Abstract	The present invention provides a process for the preparation of a novel catalyst having formula (aM1 + bM2 + cM3)Ox : TiO2 : y (SiO2): suitable for hydrocarbon transformations where a, b and c represent the number of moles of the elements MI,M2 and M3 where M1 represents one or more of the ions from the gp. of hydrogen, lithium, sodium, potassium, rubidium and cesium, M1 represents one or more from the group II metals and M3 represents one or more metals from the group of platinum, palladium, rhenium, ruthenium, indium, and tin, prepared by ion exchange with the desired ions selected from M1 or M2 or both and further incorporation of one or more of the metals selected from M3, evaporating the water and converting it in a mechanically stable form.

Title of Invention

AN IMPROVED PROCESS FOR THE PREPARATION OF A CATALYST SUITABLE FOR HYDROCARBON TRANSFORMATIONS

Abstract

The present invention provides a process for the preparation of a novel catalyst having formula (aM1 + bM2 + cM3)Ox : TiO2 : y (SiO2): suitable for hydrocarbon transformations where a, b and c represent the number of moles of the elements MI,M2 and M3 where M1 represents one or more of the ions from the gp. of hydrogen, lithium, sodium, potassium, rubidium and cesium, M1 represents one or more from the group II metals and M3 represents one or more metals from the group of platinum, palladium, rhenium, ruthenium, indium, and tin, prepared by ion exchange with the desired ions selected from M1 or M2 or both and further incorporation of one or more of the metals selected from M3, evaporating the water and converting it in a mechanically stable form.

Full Text	This invention relates to an improved process for the preparation of a catalyst suitable for hydrocarbon transformations. More particularly, this invention relates to a process for the preparation of a modified titanosilicate molecular sieve material useful for hydrocarbon transformations, more particularly, for the reforming of light petroleum fraction into aromatics. Reforming processes are used in the industry to obtain high octane gasoline and aromatics from low octane straight run naphtha. The reforming process converts the alkane and cycloalkane components of naphtha into aromatics which have higher octane numbers than the parent hydrocarbons. When aromatics are the required final products, the aromatic rich product of the process called the reformate is extracted with a suitable solvent to separate the aromatics from the rest of the material called the raffiate. In the prior-art, most reforming catalysts are of the bifunctional type, being typically platinum supported on an acidic support such as alumina. Additionally, the metal may be promoted with one or more metals such as rhenium, iridium, tin or germanium. Besides, the acidity of the support alumina is usually enhanced with promoters such as chloride or fluoride ions. Often the catalysts contain platinum and the promoter metals each in the range of 0.2 to 0.8 wt%, besides a chloride (or fluoride) content of 0.5 to 1.5 wt%. The naphtha feed of the desired boiling range is usually contacted in admixture with hydrogen over these catalysts at temperatures in the range of 480 to 540°C and at pressures in the range of 4 to 20 atmospheres. Zeolites are aluminosilicates containing pores of uniform size of dimensions similar to those of some organic molecules. These are overly acidic in the protonic form and when used as support for platinum based reforming catalysts lead to excessive cracking and loss of liquid yield. However, the alkali metal exchanged forms of many large pore (diameter ~ 8A) zeolites have been used successfully as the support for platinum based reforming catalysts. For example, U.S. Pat. No. 3, 755, 486 discloses a process for the aromatization of C6 to C10 hydrocarbons over platinum supported on alkali ion exchanged faujasites. Subsequently, a number of disclosures (U.S. Pat. Nos. 4, 140, 320; 4, 448, 891; 4, 493, 901; 4, 619, 906 etc.) were made that platinum supported on alkali exchanged zeolite L made a good catalyst for the transformation of C6 to C9 alkanes to aromatics (Hughes and others, Proceedings of the 7th International Zeolite Conference, Tokyo, Japan, 1986, p. 725). Besides, it has been reported that the more basic the exchanged ion, the more active is the catalyst for the reaction (Besukhanova and others in J. Chem. Soc. Faraday Trans. I, Vol. 77, p. 1595, year 1981). However, one of the major limitations of the L-zeolite is that it is made up of linear unidirectional noninterconnected channels of about 7.4A diameter formed from linked cancrinite cages. Such an arrangement restricts the rapid diffusion of molecules through the pore system and hence causes rapid deactivation of the catalyst. Such a deactivation would have been less if the channels were interconnected (2 or 3 dimensional) or if they were larger in size. Engelhards Titano Silicate-ETS-10 (U.S. Pat. 4, 938, 939) is a wide pore molecular sieve whose framework structure is made up of corner sharing of oxygen atoms of [TiO6] octahedral units with [SiO4] tetrahedral units in such a way that each Ti-ion is linked to four Si-ions and two Ti-ions via O-ions. Details of its structure have been published by Anderson and others in Nature, Vol. 367, p. 347, year 1994. ETS-10 has a 2-dimensional pore system of interconnecting pores with a diameter of > 8A which is larger than that of L zeolite (pore diameter ~ 7A). The Si/Ti ratio of ETS-10 is 5 and with two cations charge balancing each Ti-ion, the overall ion- exchange capacity is similar to that of an aluminosilicate zeolite with a Si/AI ratio of 2.5. The typical Si/A/ ratio of zeolite L is 3, implying a lower ion-exchange capacity than ETS-10 and a consequent lower basicity than ETS-10 on exchange with cations. Besides, as the more basic ions such as rubidium and cesium are larger in size, a considerable amount of pore restriction takes place in zeolite L when exchanged with these ions further aggregating deactivation. The pore dimensions of ETS-10 being large (>8A) enables it to accommodate the large basic ions without any significant detriment to the movement of the reactants and products. The object of the present invention is to provide an improved process for the preparaiton of a novel catalyst composite material suitable for hydrocarbon transformations, a highly basic large pore titanosilicate containing a Group VIII transition metal suitable for use in the reforming of alkanes and cycloalkanes into aromatics. Accordingly, the present invention provides an improved process for the preparation of a catalyst composite material suitable for hydrocarbon transformations having a chemical composition in terms of mole rations of the oxides as given by the formula: (aM1 + bM1/M2 + cM3)Ox : TiO2: y (SiO2); where y is in the range of 2 to 10 and a, b and c represent the number of moles of the elements M1, M2 and M3, M1 represents one or more of the ions from hydrogen, lithium, sodium, potassium, rubidium and cesium, M2 represents one or more from the group II metals preferably magnesium, calcium barium and strontium and M3 represents one or more metals from the group, platinum, palladium, rhenium, ruthenium, iridium and tin and [(ax l) + (bx2) + (cxn)]>2, where n is the valency of the metal Ma and characterized by the x-ray diffraction pattern and infra red spectrum as herein described which comprises incorporating ion from M1 followed by metal from M1 or M2 or both in the range of 0 to 0.9 moles in a novel catalyst by conventional ion exchanging process, washing, filtering and drying by known methods then calcining at 400 to 500°C for 2 hours and further impregnating one or more of the metals from M3 in the range of 0 to 0.1 moles by known methods followed by drying to obtain the said improved catalyst composite material and converting it in a mechanically stable form such as extrudates, tablets, spheres or spray dried particles optionally using a binder. In an embodiment of the present invention, the binders used are selected from the group consisting of silica, alumina, bentonite, kaolinte, and mixture thereof. In yet an another embodiment of the present invention the SiO2 / Ti molar ratio may be preferably between 4 to 6. The univalent ions M1, the bivalent ions M2 and the variable valent ions M3 are present in such amounts that the molar sum of their valencies is equivalent to not less than 2 moles of an univalent ion; that is [(a x 1) + (b x 2) + (c x n)] > 2, where n is the valency of the metal M3. The moles of M2 (b) is in the range of 0 to 0.9 and the moles of M3 (c) in the range of 0.001 to 0.1 moles, the rest being M1. Y is in the range 2 to 10 preferably in the range 4 to 6 and x takes a value depending on the moles of M1, M2 and M3 and their valencies. The catalyst composite materials characterized by the x-ray diffraction pattern shown in Table 1 and the framework infrared spectrum shown in Table 2. Table 1 : X-ray diffraction pattern of the titanosilicate (ETS-10) (Table Removed) VS = Very strong; S = Strong; MS = Medium Strong; M = medium; W = weak; VW = Very Weak. Table 2 : Framework infrared vibration frequencies of the titanosilicate (Table Removed) VS = Very strong; S = Strong; MS = Medium strong; W = Weak; VW = Very weak. The present invention provides for the synthesis of the titanosilicate molecular sieves According to a preferred embodiment, the catalyst composite material is prepared by its ion exchange with the desired ions selected from MI or M2 or both and further incorporation of one or more of the metals from the group, platinum, palladium, rhenium, ruthenium, iridium and tin, evaporating the water at temperature ranging between 90 to 100°C for a period of 8-15 hrs to obtain the dry composite material and then converting in a mechanically stable form as extrudates, tablets, spheres or spray dried particles optionally using a binder. Examples of materials that can serve as binders include silica, alumina, bentonite, kaolinite and mixtures thereof. The incorporation of the metals from the group platinum, palladium, rhenium, ruthenium, iridium and tin can be carried out either after incorporation of the binder such as silica, alumina, bentonite, kaolinite and mixtures thereof and forming into a mechanically stable form or before such an operation. It is also possible that the above metals are introduced partly before and partly after the binder is incorporated. The present invention is illustrated with the following examples which should not be confirmed to limit the scope of the invention. Example 1 The prior art (Ind. Pat. 171483) method of preparation of the crystalline large pore titanosilicate [ETS-10(1)] will be described in this example, using the small pore titanosilicate (ETS-4) as seed (Example 1). Solution A comprising of 63 g of sodium silicate (28.6% SiO2, 8.82% Na2O, 62.58% H2O) and 20 g distilled water was kept stirring. Solution B was prepared by dissolving 8.4 g NaOH pellets in 58.84 g distilled water and added slowly to the above stirring solution A. The gel was allowed to stir for15 to 20 minutes. 54.4 g TiCI3 (15% solution in HCI) was added dropwise to the above stirred gel. The paste like blackish green material (C) was allowed to stir for half an hour. Finally 9.4 g KF.2H2O was added to the paste (C) and stirred for one hour to get paste (D). Finally 1.26 g titanosilicate seed of ETS-4 (prepared as described in example (1) was added to the paste D very slowly and stirred vigorously for another hour till homogeneous (pH = 10.8- 11.0) at room temperature and transferred to a stainless steel autoclave. Its composition in terms of moles of oxides was as follows : 3.7 Na2O : 0.95 K20 : Ti02: 5.71 SiO2: 171.4 H2O The autoclave was capped tightly and crystallization carried out at 170°C for 10 days. It was found that fully crystalline ETS-10 was not produced when crystallization was done for less than 10 days. The solid material recovered after 3 days was amorphous and had no ETS-10 phase in it. When crystallization was over, the autoclave was quenched in tap water and opened. The solid material was then separated from the mother liquor by suction filtration, washed with deionised water until the pH of the washings was about 11.5. The powder was then dried and identified ascrystalline titanosilicate having ETS-10 structure by means of X-ray diffraction, the X-ray diffraction pattern being similar to that reported in Ind. Pat. 171483. The chemical composition of the solid material in terms the mole ratio of oxides was found to be : 0.84 Na2O : 0.20 K2O : TiO2 : 5.68 SiO2 : 3.05 H2O Example 2 80 g distilled water was added to 52.5 g sodium silicate (28.6% Si02, 8.82% Na20, 62.58% H2O) and kept stirring (solution A). Solution (B) was prepared by dissolving 9.3 g NaOH pellets in 50.0 g distilled water and . added dropwise to the stirring solution (A). 32.75 g TiCI4 (25.42% TiCl4, 25.92% HCI and 48.66% H2O) was added to the above mixture (A+B). The colourless sticky material formed was kept stirring for one hour (C). 7.8 g potassium fluoride dihydrate dissolved in 36.68 g deionised water was added to (C) and stirred for one hour till free flowing homogeneous gel (pH = 10.8-11.0) at room temperature and then transferred to a stainless steel autoclave (Parr Instruments, USA). Its composition in terms of moles of oxides was as follows: 3.70 Na2O : 0.95 K20 : TiO2 : 5.71 Si02 : 171 H2O The crystallization was carried out at 200°C with a stirrer speed of 300 r.p.m for 14-16 hours. When crystallization was over the autoclave was quenched in water and opened. The solid material was then separated from the mother liquor by suction filtration, washed with deionised water until the pH of the washing was about 10.6-10.9. The powder was then dried in an air oven at 150°C and identified as crystalline titanosilicate having ETS-10 structure by means of X-ray diffraction, the X-ray diffraction being similar to that reported in Ind. Pat. 171483. The chemical composition of the solid material in terms of mole ratio of oxides was found to be : 0.83 Na2O : 0.18 K2O ; TiO2 : 5.1 SiO2 : 7.28 H2O Example 3 This example illustrates the process for preparing the ion-exchanged forms of the large pore titanosilicate synthesized following example 1. The crystalline material from example 1 was dried at 100°C for 10 hrs and converted into different ion-exchanged forms by exchanging thrice with the required metal substrate solutions (20 ml of 1M solution/g of the catalyst at 90°C for 3 hours). After washing, filtering and drying at 100°C (for 8 hours), the samples were calcined at 480°C for 2 hours. By this method, a number of metal (M) exchanged samples were prepared where M was lithium, sodium, potassium, rubidium, cesium, calcium and barium. Example 4 This example illustrates the procedure for incorporating platinum into the material prepared obtained from 3 10 grams of the sample prepared according to example 2 was soaked in 100 ml of a solution of tetraamine platinum (II) nitrate containing 0.1 g of the platinum salt and gently evaporated to dryness over a period of many hours at 60°C with gentle stirring. The material was further dried at 100°C for 8 hrs and calcined at 450°C for 2 hours. The Pt content was 0.4 wt%. Example 5 10 g of the sample prepared according to example 2 was soaked in 200 ml of a solution of palladium chloride Purisis containing 0.14 g of the palladium salt, gently evaporated on intermittant stirring to dryness over a period of 12-15 hours at 70°C. The matrial was further dried at 100°C for 8 hours and calcined at 450°C for two hours. The palladium was ~ 0.32 wt.%. Example 6 10 g of the sample prepared according to example 2 was soaked in 200 ml of a solution of Rhodium trichloride/Ruthenium trichloride /irridium trichloride or tin tetrachloride containing a 0.1 or 0.12 wt of the respective salt, gently evaporated on intermittant stirring to dryness over a period of 12-15 hours at 70°C. The matrial was further dried at 100°C for 8 hours and calcined at 450°C for two hours. The rhodium/ruthenium/irrridium or tinconetent was in the range of 0.2 to 0.3 wt.%. We Claim; 1. An improved process for the preparation of a catalyst composite material suitable for hydrocarbon transformations having a chemical composition in terms of mole ratios of the oxides as given by the formula: (aM1 + bM1/M2+ cM3)Ox: TiO2: y (SiO2); where y is in the range of 2 to 10 and a, b and c represent the number of moles of the elements M1, M2 and M3, M1 represents one or more of the ions from hydrogen, lithium, sodium, potassium, rubidium and cesium, M2 represents one or more from the group II metals preferably magnesium, calcium barium and strontium and M3 represents one or more metals from the group, platinum, palladium, rhenium, ruthenium, iridium and tin and [(ax l) + (bx2) + (cxn)]>2, where n is the valency of the metal M3 and characterized by the x-ray diffraction pattern and infra red spectrum as herein described which comprises incorporating ion from M1 followed by metal from M1 or M2 or both in the range of 0 to 0.9 moles in a novel catalyst by conventional ion exchanging process, washing, filtering and drying by known methods then calcining at 400 to 500°C for 2 hours and further impregnating one or more of the metals from M3 in the range of 0 to 0.1 moles by known methods followed by drying to obtain the said improved catalyst composite material and converting it in a mechanically stable form such as extrudates, tablets, spheres or spray dried particles optionally using a binder. 2. An improved process as claimed in claim 1, wherein the binders used optionally are selected from silica, alumina, bentonite, kaolinte and mixture thereof. 3. An improved process as claimed in claim 1, wherein the SiO2 / TiO2 molar ratio is preferably between 4 to 6. 4. An improved process for the preparation of a catalyst composite material suitable for hydrocarbon transformations substantially as herein described with reference to the examples.

Full Text

This invention relates to an improved process for the preparation of a catalyst suitable for hydrocarbon transformations. More particularly, this invention relates to a process for the preparation of a modified titanosilicate molecular sieve material useful for hydrocarbon transformations, more particularly, for the reforming of light petroleum fraction into aromatics.
Reforming processes are used in the industry to obtain high octane gasoline and aromatics from low octane straight run naphtha. The reforming process converts the alkane and cycloalkane components of naphtha into aromatics which have higher octane numbers than the parent hydrocarbons. When aromatics are the required final products, the aromatic rich product of the process called the reformate is extracted with a suitable solvent to separate the aromatics from the rest of the material called the raffiate. In the prior-art, most reforming catalysts are of the bifunctional type, being typically platinum supported on an acidic support such as alumina. Additionally, the metal may be promoted with one or more metals such as rhenium, iridium, tin or germanium. Besides, the acidity of the support alumina is usually enhanced with promoters such as chloride or fluoride ions. Often the catalysts contain platinum and the promoter metals each in the range of 0.2 to 0.8 wt%, besides a chloride (or fluoride) content of 0.5 to 1.5 wt%. The naphtha feed of the desired boiling range is usually contacted in admixture with hydrogen over these catalysts at temperatures in the range of 480 to 540°C and at pressures in the range of 4 to 20 atmospheres.
Zeolites are aluminosilicates containing pores of uniform size of dimensions similar to those of some organic molecules. These are overly acidic in the protonic form and when used as support for platinum based reforming catalysts lead to excessive cracking and loss of liquid yield. However, the alkali metal exchanged forms of many large pore (diameter ~ 8A) zeolites have been used successfully as the support for platinum based reforming catalysts. For example, U.S. Pat. No. 3, 755, 486 discloses a process for the aromatization of C6 to C10 hydrocarbons over platinum supported on alkali ion exchanged faujasites. Subsequently, a number of disclosures (U.S. Pat. Nos. 4, 140, 320; 4, 448, 891; 4, 493, 901; 4, 619, 906 etc.) were made that platinum supported on alkali exchanged zeolite L made a good catalyst for the transformation of C6 to C9 alkanes to aromatics (Hughes and others, Proceedings of the 7th International Zeolite Conference, Tokyo, Japan, 1986, p. 725). Besides, it has been reported that the more basic the exchanged ion, the more active is the catalyst for the reaction (Besukhanova and others in J. Chem. Soc. Faraday Trans. I, Vol. 77, p. 1595, year 1981). However, one of the major limitations of the L-zeolite is that it is made up of linear unidirectional noninterconnected channels of about 7.4A diameter formed from linked cancrinite cages. Such an arrangement restricts the rapid diffusion of molecules through the pore system and hence causes rapid deactivation of the catalyst. Such a deactivation would have been less if the channels were interconnected (2 or 3 dimensional) or if they were larger in size.
Engelhards Titano Silicate-ETS-10 (U.S. Pat. 4, 938, 939) is a wide pore molecular sieve whose framework structure is made up of corner sharing of oxygen atoms of [TiO6] octahedral units with [SiO4] tetrahedral units in such a way that each Ti-ion is linked to four Si-ions and two Ti-ions via O-ions. Details of its structure have been published by Anderson and others in Nature, Vol. 367, p. 347, year 1994. ETS-10 has a 2-dimensional pore system of interconnecting pores with a diameter of > 8A which is larger than that of L zeolite (pore diameter ~ 7A). The Si/Ti ratio of ETS-10 is 5 and with two cations charge balancing each Ti-ion, the overall ion- exchange capacity is similar to that of an aluminosilicate zeolite with a Si/AI ratio of 2.5. The typical Si/A/ ratio of zeolite L is 3, implying a lower ion-exchange capacity than ETS-10 and a consequent lower basicity than ETS-10 on exchange with cations. Besides, as the more basic ions such as rubidium and cesium are larger in size, a considerable amount of pore restriction takes place in zeolite L when exchanged with these ions further aggregating deactivation. The pore dimensions of ETS-10 being large (>8A) enables it to accommodate the large basic ions without any significant detriment to the movement of the reactants and products.
The object of the present invention is to provide an improved process for the preparaiton of a novel catalyst composite material suitable for hydrocarbon transformations, a highly basic large pore titanosilicate containing a Group VIII transition metal suitable for use in the reforming of alkanes and cycloalkanes into aromatics.
Accordingly, the present invention provides an improved process for the preparation of a catalyst composite material suitable for hydrocarbon transformations having a chemical composition in terms of mole rations of the oxides as given by the formula:
(aM1 + bM1/M2 + cM3)Ox : TiO2: y (SiO2);
where y is in the range of 2 to 10 and a, b and c represent the number of moles of the elements M1, M2 and M3, M1 represents one or more of the ions from hydrogen, lithium, sodium, potassium, rubidium and cesium, M2 represents one or more from the group II metals preferably magnesium, calcium barium and strontium and M3 represents one or more metals from the group, platinum, palladium, rhenium, ruthenium, iridium and tin and
[(ax l) + (bx2) + (cxn)]>2,
where n is the valency of the metal Ma and characterized by the x-ray diffraction pattern and infra red spectrum as herein described which comprises incorporating ion from M1 followed by metal from M1 or M2 or both in the range of 0 to 0.9 moles in a novel catalyst by conventional ion exchanging process, washing, filtering and drying by known methods then calcining at 400 to 500°C for 2 hours and further impregnating one or more of the metals from M3 in the range of 0 to 0.1 moles by known methods followed by drying to obtain the said improved catalyst composite material and converting it in a mechanically stable form such as extrudates, tablets, spheres or spray dried particles optionally using a binder. In an embodiment of the present invention, the binders used are selected from the group consisting of silica, alumina, bentonite, kaolinte, and mixture thereof.
In yet an another embodiment of the present invention the SiO2 / Ti molar ratio may be preferably between 4 to 6.
The univalent ions M1, the bivalent ions M2 and the variable valent ions M3 are present in such amounts that the molar sum of their valencies is equivalent to not less than 2 moles of an univalent ion; that is [(a x 1) + (b x 2) + (c x n)] > 2, where n is the valency of the metal M3. The moles of M2 (b) is in the range of 0 to 0.9 and the moles of M3 (c) in the range of 0.001 to 0.1 moles, the rest being M1.
Y is in the range 2 to 10 preferably in the range 4 to 6 and x takes a value depending on the moles of M1, M2 and M3 and their valencies. The catalyst composite materials characterized by the x-ray diffraction pattern shown in Table 1 and the framework infrared spectrum shown in Table 2. Table 1 : X-ray diffraction pattern of the titanosilicate (ETS-10)

(Table Removed)
VS = Very strong; S = Strong; MS = Medium Strong; M = medium; W = weak; VW = Very Weak.
Table 2 : Framework infrared vibration frequencies of the titanosilicate
(Table Removed)
VS = Very strong; S = Strong; MS = Medium strong; W = Weak; VW = Very weak.
The present invention provides for the synthesis of the titanosilicate
molecular sieves
According to a preferred embodiment, the catalyst composite material is prepared by its ion exchange with the desired ions selected from MI or M2 or both and further incorporation of one or more of the metals from the group, platinum, palladium, rhenium, ruthenium, iridium and tin, evaporating the water at temperature ranging between 90 to 100°C for a period of 8-15 hrs to obtain the dry composite material and then converting in a mechanically stable form as extrudates, tablets, spheres or spray dried particles optionally using a binder. Examples of materials that can serve as binders include silica, alumina, bentonite, kaolinite and mixtures thereof.
The incorporation of the metals from the group platinum, palladium, rhenium, ruthenium, iridium and tin can be carried out either after incorporation of the binder such as silica, alumina, bentonite, kaolinite and mixtures thereof and forming into a mechanically stable form or before such an operation. It is also possible that the above metals are introduced partly before and partly after the binder is incorporated.
The present invention is illustrated with the following examples which should not be confirmed to limit the scope of the invention.
Example 1
The prior art (Ind. Pat. 171483) method of preparation of the crystalline large pore titanosilicate [ETS-10(1)] will be described in this example, using the small pore titanosilicate (ETS-4) as seed (Example 1). Solution A comprising of 63 g of sodium silicate (28.6% SiO2, 8.82% Na2O, 62.58% H2O) and 20 g distilled water was kept stirring. Solution B was prepared by dissolving 8.4 g NaOH pellets in 58.84 g distilled water and added slowly to the above stirring solution A. The gel was allowed to stir for15 to 20 minutes. 54.4 g TiCI3 (15% solution in HCI) was added dropwise to the above stirred gel. The paste like blackish green material (C) was allowed to stir for half an hour. Finally 9.4 g KF.2H2O was added to the paste (C) and stirred for one hour to get paste (D). Finally 1.26 g titanosilicate seed of ETS-4 (prepared as described in example (1) was added to the paste D very slowly and stirred vigorously for another hour till homogeneous (pH = 10.8- 11.0) at room temperature and transferred to a stainless steel autoclave. Its composition in terms of moles of oxides was as follows :
3.7 Na2O : 0.95 K20 : Ti02: 5.71 SiO2: 171.4 H2O
The autoclave was capped tightly and crystallization carried out at 170°C for 10 days. It was found that fully crystalline ETS-10 was not produced when crystallization was done for less than 10 days. The solid material recovered after 3 days was amorphous and had no ETS-10 phase in it. When crystallization was over, the autoclave was quenched in tap
water and opened. The solid material was then separated from the mother liquor by suction filtration, washed with deionised water until the pH of the washings was about 11.5. The powder was then dried and identified ascrystalline titanosilicate having ETS-10 structure by means of X-ray diffraction, the X-ray diffraction pattern being similar to that reported in Ind. Pat. 171483.
The chemical composition of the solid material in terms the mole ratio of oxides was found to be :
0.84 Na2O : 0.20 K2O : TiO2 : 5.68 SiO2 : 3.05 H2O
Example 2
80 g distilled water was added to 52.5 g sodium silicate (28.6% Si02,
8.82% Na20, 62.58% H2O) and kept stirring (solution A). Solution (B) was
prepared by dissolving 9.3 g NaOH pellets in 50.0 g distilled water and .
added dropwise to the stirring solution (A). 32.75 g TiCI4 (25.42%
TiCl4, 25.92% HCI and 48.66% H2O) was added to the above mixture (A+B). The colourless sticky material formed was kept stirring for one hour (C). 7.8 g potassium fluoride dihydrate dissolved in 36.68 g deionised water was added to (C) and stirred for one hour till free flowing homogeneous gel (pH = 10.8-11.0) at room temperature and then transferred to a stainless steel autoclave (Parr Instruments, USA). Its composition in terms of moles of oxides was as follows:
3.70 Na2O : 0.95 K20 : TiO2 : 5.71 Si02 : 171 H2O
The crystallization was carried out at 200°C with a stirrer speed of 300 r.p.m for 14-16 hours. When crystallization was over the autoclave was
quenched in water and opened. The solid material was then separated from the mother liquor by suction filtration, washed with deionised water until the pH of the washing was about 10.6-10.9. The powder was then dried in an air oven at 150°C and identified as crystalline titanosilicate having ETS-10 structure by means of X-ray diffraction, the X-ray diffraction being similar to that reported in Ind. Pat. 171483. The chemical composition of the solid material in terms of mole ratio of oxides was found to be : 0.83 Na2O : 0.18 K2O ; TiO2 : 5.1 SiO2 : 7.28 H2O
Example 3
This example illustrates the process for preparing the ion-exchanged forms of the large pore titanosilicate synthesized following example 1.
The crystalline material from example 1 was dried at 100°C for 10 hrs and converted into different ion-exchanged forms by exchanging thrice with the required metal substrate solutions (20 ml of 1M solution/g of the catalyst at 90°C for 3 hours). After washing, filtering and drying at 100°C (for 8 hours), the samples were calcined at 480°C for 2 hours. By this method, a number of metal (M) exchanged samples were prepared where M was lithium, sodium, potassium, rubidium, cesium, calcium and barium.
Example 4
This example illustrates the procedure for incorporating platinum into the material prepared obtained from 3
10 grams of the sample prepared according to example 2 was soaked in 100 ml of a solution of tetraamine platinum (II) nitrate containing 0.1 g of the platinum salt and gently evaporated to dryness over a period of
many hours at 60°C with gentle stirring. The material was further dried at 100°C for 8 hrs and calcined at 450°C for 2 hours. The Pt content was 0.4 wt%.
Example 5
10 g of the sample prepared according to example 2 was soaked in 200 ml of a solution of palladium chloride Purisis containing 0.14 g of the palladium salt, gently evaporated on intermittant stirring to dryness over a period of 12-15 hours at 70°C. The matrial was further dried at 100°C for 8 hours and calcined at 450°C for two hours. The palladium was ~ 0.32 wt.%.
Example 6
10 g of the sample prepared according to example 2 was soaked in 200 ml of a solution of Rhodium trichloride/Ruthenium trichloride /irridium trichloride or tin tetrachloride containing a 0.1 or 0.12 wt of the respective salt, gently evaporated on intermittant stirring to dryness over a period of 12-15 hours at 70°C. The matrial was further dried at 100°C for 8 hours and calcined at 450°C for two hours. The rhodium/ruthenium/irrridium or tinconetent was in the range of 0.2 to 0.3 wt.%.

We Claim;
1. An improved process for the preparation of a catalyst composite material suitable
for hydrocarbon transformations having a chemical composition in terms of mole
ratios of the oxides as given by the formula:
(aM1 + bM1/M2+ cM3)Ox: TiO2: y (SiO2);
where y is in the range of 2 to 10 and a, b and c represent the number of moles of the elements M1, M2 and M3, M1 represents one or more of the ions from hydrogen, lithium, sodium, potassium, rubidium and cesium, M2 represents one or more from the group II metals preferably magnesium, calcium barium and strontium and M3 represents one or more metals from the group, platinum, palladium, rhenium, ruthenium, iridium and tin and
[(ax l) + (bx2) + (cxn)]>2,
where n is the valency of the metal M3 and characterized by the x-ray diffraction pattern and infra red spectrum as herein described which comprises incorporating ion from M1 followed by metal from M1 or M2 or both in the range of 0 to 0.9 moles in a novel catalyst by conventional ion exchanging process, washing, filtering and drying by known methods then calcining at 400 to 500°C for 2 hours and further impregnating one or more of the metals from M3 in the range of 0 to 0.1 moles by known methods followed by drying to obtain the said improved catalyst composite material and converting it in a mechanically stable form such as extrudates, tablets, spheres or spray dried particles optionally using a binder.
2. An improved process as claimed in claim 1, wherein the binders used optionally
are selected from silica, alumina, bentonite, kaolinte and mixture thereof.

3. An improved process as claimed in claim 1, wherein the SiO2 / TiO2 molar ratio is
preferably between 4 to 6.
4. An improved process for the preparation of a catalyst composite material suitable
for hydrocarbon transformations substantially as herein described with reference
to the examples.

Documents:

0729-del-2000-abstract.pdf

0729-del-2000-claims.pdf

0729-del-2000-correspondence-others.pdf

0729-del-2000-correspondence-po.pdf

0729-del-2000-description (complete).pdf

0729-del-2000-form-1.pdf

0729-del-2000-form-19.pdf

0729-del-2000-form-2.pdf

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Patent Number

232391

Indian Patent Application Number

729/DEL/2000

PG Journal Number

13/2009

Publication Date

27-Mar-2009

Grant Date

16-Mar-2009

Date of Filing

10-Aug-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	TAPAN KUMAR DAS	NATIONAL CHEMICAL LABORATORY, PUNE 411 008, MAHARASHTRA, INDIA.
2	ASHA JEEVAN CHANDWADKAR	NATIONAL CHEMICAL LABORATORY, PUNE 411 008, MAHARASHTRA, INDIA.
3	SUBRAMANIAN SIVASANKER	NATIONAL CHEMICAL LABORATORY, PUNE 411 008, MAHARASHTRA, INDIA.

PCT International Classification Number

B01J 29/00

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA