Indian Patents. 190178:"A PROCESS FOR PREPARATION OF AN IMPROVED AND ACTIVE CATALYST FOR USE IN THE PROCESSES OF OXIDATION AND AMMOXIDATION"

Title of Invention	"A PROCESS FOR PREPARATION OF AN IMPROVED AND ACTIVE CATALYST FOR USE IN THE PROCESSES OF OXIDATION AND AMMOXIDATION"
Abstract	Disclosed is a process comprising the heat treatment of certain V and Sb-containing catalysts at a lower temperature than the previous calcination temperature of the base catalyst to improve catalytic performance; the catalysts resulting from such process; and certain oxidation and ammoxidation reactions in the presence of such a catalyst.

Full Text	This invention relates to a process for preparation of an improved and active catalyst, particularly it relates to a process for preparation of an improved and active catalyst of formula VvSbmAaDdOx for use in the processes of oxidation and ammoxidation. It also relates to the catalyst so made. In another aspect the invention relates to the oxidation and ammoxidation of paraffins, olefins and aromatic compounds. Catalysts containing vanadium and antimony in oxide form, and usually containing tin or titanium, or both, as part of the metal oxide catalyst are normally calcined before using to catalyze the ammoxidation of paraffins, olefins and various aromatics; such calcination is above 750°C and activates the composition to make effective ammoxidation catalysts. It has now been found that such catalysts can be even further activated to increase the activity of conversion of the feedstock and the selectivity of conversion to a nitrile by the heat treatment of the catalyst previously activated by calcining at a temperature above 750°C, wherein the heat treatment is at an effective temperature at least 50°C below the highest calcination temperature. In a broad aspect of the method of the invention we have found that heat treating a catalyst calcined at a calcining temperature above 750°C at a temperature which is at least 500°C and at least 50°C below the calcining temperature is improved in its activity for converting the feed, such as propane or propylene to acrylonitrile. In a now preferred embodiment of the method for making an even more active catalyst, the catalyst which has been calcined at a temperature above 750°C and thereafter heat treated at the lower temperature, is contacted with a liquidbelieved to be a solvent for some minute quantity of a deleterious (generally well less than 1% of the composition) compound containing V and Sb in oxide form, and the bulk of the "solvent" separated from the catalyst. In this aspect of the invention there can be used various "solvents" that have been used to so treat such V and Sb catalysts in oxide form following calcination above 750°C. These include water, aqueous solutions of acids or bases, such as phosphoric, sulfuric and acetic acids and NH3 and NaOH solutions; and the hydroxy compounds of U.S. patent 5,094,989: cyclohexanol; cyclopentanol; a monohydroxy, acyclic hydrocarbon having 1-8 C atoms; and a dihydroxy, acyclic hydrocarbon having 2-4 carbon atoms. The catalyst to which the improved method applies contains the elements and relative amounts indicated by the formula: VvSbmA.DdOx wherein A when present is Sn and/or Ti; D when present is one or more of Li, Mg, Na, Ca, Sr, Ba, Co, Fe, Cr, Ga, Ni, Zn, Ge, Nb, Zr, Mo, W, Cu, Te, Ta, Se, Bi, Ce, In, As, B, Al and Mn; and wherein all of the elements of said formula except oxygen are present as cations, and v is 1 m is 0.5-10 a is up to 10 d is up to 10 x is determined by the oxidation state of the cations present In a more specific aspect of the invention the catalyst to which the method applies has the relation v + m + a > 0.5d. The process for improving the catalysts is most often applied to such foregoing catalysts wherein a is In the above formula the phrase "when present" means that A may be zero and that D may be zero. Thus, the catalysts can contain essentially only V and Sb. The highest calcination temperature of the catalysts above 7500C before the relatively low temperature heat treatment step of the process of the invention can be as high as 12000C, but is usually over 7500C and up to 10500C, most often up to 9500C. The present catalyst is useful for the oxidation and ammoxidation of paraffins, olefins and aromatic compounds in a reaction zone. In particular, in this aspect of the invention especially useful reactions include the ammoxidation of propane with NH3 and 02 to acrylonitrile, the ammoxidation of propylene with NH3 and 02 to acrylonitrile, the ammoxidation of a methyl pyridine with 02 and NH3 to the corresponding cyanopyridine, and the ammoxidation of m-xylene with 02 and NH3 to isophthalonitrile. Accordingly, the present invention relates to a process for preparation of an improved and active catalyst of formula VvSbmAaDdOx for use in the processes of oxidation and ammoxidation, wherein the process comprises following steps: a) calcination of a catalyst of the kind such as hereindescribed at a calcining temperature above 750°C to form a calcined catalyst in the manner such as hereindescribed, b) heat treating the calcined catalyst at an effective temperature, which is at least 50 C below the calcining temperature optionally contacting with a liquid of the kind such as hereindescribed to form an active catalyst in the manner such as hereindescribed, wherein the catalyst and the calcined catalyst of step-a) and the active catalyst of step-b) have the elements and relative amounts indicated by the formula: VvSbmAaDdOx wherein V represents vanadium; Sb represents antimony; A represents Sn and/or Ti; D represents one or more of Li, Mg, Na, Ca, Sr, Ba, Co, Fe, Cr, Ga, Ni, Zn, Ge, Nb, Zr, Mo, W, Cu, Te, Ta, Se, Bi, Ce, In, As, B, Al and Mn; O represents oxygen; and wherein all of the elements of said formula except oxygen are present as cations, and v is 1, m is 0.5 to 10, a is upto 10, d is upto 10, x is determined by the oxidation state of the cations present. The following specific examples are illustrative only and are not to be considered in any way limiting. Catalyst Example 1 27.42g of V205 powder was added to a solution consisting of 100 ml of 30% H202 in 900 ml of water in a 2 liter beaker. After the reaction of the V205 powder was complete, 61.22g of Sb203 and 2.40g of fumed Ti02 (Degussa P-25) powder were added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 89.52 g of 10.1% Sn02 sol (Nalco Chemical Co.) was added to the foregoing dispersion. The mixture was stirred in an uncovered beaker with heating in order to reduce the volume to 300 ml by evaporation of water. It was then dried in an oven at 120°C. Thereafter it was calcined for 8 hours at 650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst was calcined for 3 hours at 810°C. It was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glassfrit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. This was done a total of three times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst. The catalyst was then heat treated in an oven at 500°C for 3 hours according to the invention. The calcined catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, and then allowing the isobutanol to pass through the funnel without suction. This was done a total of two times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst. The catalyst was used to ammoxidize propane using a 3/8 inch O.D. titanium metal fixed bed reactor equipped with a preheat leg and immersed in a temperature controlled molten salt bath. 4.0 g of catalyst were placed in the reactor. Results of all ammoxidation runs are shown in Tables 1 and 2 as are the feed ratios and temperatures. Catalyst Example 2 27.42g of V205 powder was added to a solution consisting of 100 ml of 30% H202 in 900 ml of water in a 2 liter beaker. After the reaction of the V20j powder was complete, 61.22 g of Sb2O3,2.4 g of fumed Ti02 (Degussa P-25) powder were added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 89.52 g of 10.1% Sn02 sol (Nalco Chemical Co.) was added to the foregoing dispersion. The mixture was stirred, in an uncovered beaker with heating in order to reduce the volume to 300 ml by evaporation of water. It was then dried in an oven at 120°C. Thereafter it was calcined for 8 hours at 650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst wascalcined for 3 hours at 810°C. It was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. This was done a total of three times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst. The catalyst was then heat treated in an oven at 650°C for 3 hours according to the invention. The calcined catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, and then allowing the isobutanol to pass through the funnel without suction. This was done a total of two times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst. The catalyst was used to ammoxidize propane using a 3/8 inch O.D. titanium metal fixed bed reactor equipped with a preheat leg and immersed in a temperature controlled molten salt bath. 4.0 g of catalyst were placed in the reactor. Catalyst Example 3 27.42g of V2O5 powder was added to a solution consisting of 100 ml of 30% H202 in 900 ml of water in a 2 liter beaker. After the reaction of the V205 powder was complete, 61.22 g of Sb203 ,2.4g of fumed Ti02 (Degussa P-25) powder were added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 89.52 g of 10.1 % Sn02 sol (Nalco Chemical Co.) was added to the foregoing dispersion. The mixture was stirred in an uncovered beaker with heating in order to reduce the volume to 300 ml by evaporation of water. It was then dried in an oven at 120°C. Thereafter it was calcined for 8 hours at 650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst wascalcined for 3 hours at 810°C. It was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. This was done a total of three times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst. The catalyst was then heat treated in an oven at 650°C for 3 hours according to the invention. The calcined catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, and then allowing the isobutanol to pass through the funnel without suction. This was done a total of three times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst. The catalyst was used to ammoxidize propane using a 3/8 inch O.D. titanium metal fixed bed reactor equipped with a preheat leg and immersed in a temperature controlled molten salt bath. 4.5 g of catalyst were placed in the reactor. Comparative Catalyst Example A 27.42g of V205 powder was added to a solution consisting of 100 ml of 30% H202 in 900 ml of water in a 2 liter beaker. After the reaction of the V205 powder was complete, 61.22g of Sb203 and 2.40g of fumed Ti02 (Degussa P-25) powder were added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 89.52g of 10.1% Sn02 sol (Nalco Chemical Co.) was added to the foregoing dispersion. The mixture was stirred in an uncovered beaker with heating in order to reduce the volume to 300 ml by evaporation of water. It was then dried in an oven at 120°C. Thereafter it was calcined for 8 hours at650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst was calcined for 3 hours at 810°C. The calcined catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. This was done a total of three times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst. The catalyst was used to ammoxidize propane using a 3/8 inch O.D. titanium metal fixed bed reactor equipped with a preheat leg and immersed in a temperature controlled molten salt bath. 2.5g of catalyst were placed in the reactor. Results are summarized in Table 1. Catalyst Example 4 27.44g V205 was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. The mixture was stirred without heating for about 6 hours to produce a deep red sol/gel. It was then stirred overnight at room temperature. 61.26g Sb203 was then added and the resulting mixture was heated to boiling and allowed to boil with a watch glass covering the beaker for about 3 hours. Water was periodically added to the beaker to keep the mixture stirring and the volume of the mixture constant. During the heating the mixture turned green then gray then gray-black. At this point 84.56g of a 10.7 weight percent tin oxide sol and 2.4g of Ti02 were added and the mixture was evaporated to near dryness on the hot plate with constant stirring. The resulting paste was then dried at 120°C overnight. The dried material was heat treated at 650 °C for 8 hours then ground and screened and the 20-35 mesh particles were collected. A portion of the 20-35 mesh particles was heat treated at 810°C for 3 hours. A portion of the 810°C calcined particles was washed three times with isobutanol by using about 50ml of isobutanol per 8 grams of catalyst. The particles were placed in a coarse glass frit funnel, covered with isobutanol and the isobutanol was allowed to pass through the glass frit without suction. The resulting material was then placed in an oven at 120°C for several hours to remove residual isobutanol. The composition was then heat treated for 3 hours at 650°C. As will be seen by reference to Table 1, an improvement was effected in yield and selectivity by the later 650°C heat treatment, compared to and washed and heated as in Catalyst Comparative Catalyst Example B. Example 3. Comparative Catalyst Example B 27.44g V205 was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. The mixture was stirred without heating for about 6 hours to produce a deep red sol/gel. It was then stirred overnight at room temperature. 61.26g Sb203 was then added and the resulting mixture was heated to boiling and allowed to boil with a watch glass covering the beaker for about 3 hours. Water was periodically added to the beaker to keep the mixture stirring and the volume of the mixture constant. During the heating the mixture turned green then gray then gray-black. At this point 84.56g of a 10.7 weight percent tin oxide sol and 2.4g of Ti02 were added and the mixture was evaporated to near dryness on the hot plate with constant stirring. The resulting paste was then dried at 120°C overnight. The dried material was heat treated at 650°C for 8 hours then ground and screened and the 20-35 mesh particles were collected. A portion of the 20-35 mesh particles was heat treated at 810°C for 3 hours. A portion of the 810°C calcined particles was washed three times with isobutanol by using about 50ml of isobutanol per 8 grams of catalyst. The particles were placed in a coarse glass frit funnel, covered with isobutanol and the isobutanol was allowed to pass through the glass frit without suction. This was done three times. The resulting material was then placed in an oven at 120°C for several hours to remove residual isobutanol. Catalyst Example 5 27.44g V2O5 was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. The mixture was stirred without heating for about 6 hours to produce a deep red sol/gel. It was then stirred overnight at room temperature. 61.26g Sb203 was then added and the resulting mixture was heated to boiling and allowed to boil with a watch glass covering the beaker for about 3 hours. Water was periodically added to the beaker to keep the mixture stirring and the volume of the mixture constant. During the heating the mixture turned green then gray then gray-black. At this point 84.56g of a 10.7 weight percent tin oxide sol and 2.4g of Ti02 were added and the mixture was evaporated to near dryness on the hot plate with constant stirring. The resulting paste was then dried at 120°C overnight The dried material was heat treated at 650°C for 8 hours then ground and screened and the 20-35 mesh particles were collected. A portion of the 20-35 mesh particles was heat treated at 810°C for 3 hours. A portion of the 810°C calcined particles was heat treated according to the invention for 3 hours at 650°C and was washed with isobutanol by using about 50ml of isobutanol per 8 grams of catalyst. The particles were placed in a coarse glass frit funnel, covered with isobutanol and the isobutanol was allowed to pass through the glass frit without suction. This was done a total of three times. The resulting material was then placed in an oven at 120°C for several hours to remove residual isobutanol. It will be seen by reference to Table 1 that the post heat treatment for 3 hours at 650°C was an improvement in comparison to both comparative catalyst examples B and C. Comparative Catalyst Example C 27.44g V205 was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. The mixture was stirred without heating for about 6 hours to produce a deep red sol/gel. It was then stirred overnight at room temperature. 61.26g Sb203 was then added and the resulting mixture was heated to boiling and allowed to boil with a watch glass covering the beaker for about 3 hours. Water was periodically added to the beaker to keep the mixture stirring and the volume of the mixture constant. During the heating the mixture turned green then gray then gray-black. At this point 84.56g of a 10.7 weight percent tin oxide sol and 2.4g of Ti02 were added and the mixture was evaporated to hear dryness on the hot plate with constant stirring. The resulting paste was then dried at 120°C overnight. The dried material was heat treated at 650°C for 8 hours then ground and screenedand the 20-35 mesh particles were collected. A portion of the 20-35 mesh particles was calcined at 810°C for 3 hours. This was designated Comparative Catalyst Example C. Results of testing this catalyst in the ammoxidation of propane are shown in Table 1. Catalyst Example 6 27.44g V2O5 was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. The mixture was stirred without heating for about 6 hours to produce a deep red sol/gel. It was then stirred overnight at room temperature. 61.26g Sb203 was then added and the resulting mixture was heated to boiling and allowed to boil with a watch glass covering the beaker for about 3 hours. Water was periodically added to the beaker to keep the mixture stirring and the volume of the mixture constant. During the heating the mixture turned green then gray then gray-black. At this point 84.56g of a 10.7 weight percent tin oxide sol and 2.4g of Ti02 were added and the mixture was evaporated to near dryness on the hot plate with constant stirring. The resulting paste was then dried at 120°C overnight. The dried material was heat treated at 650°C for 8 hours then ground and screened and the 20-35 mesh particles were collected. A portion of the 20-35 mesh particles was calcined at 810°C for 3 hours and then heat treated according to the invention at 650°C for 3 hours. As will be seen in Table 1, there is an improvement in the yield and selectivity in the ammoxidation of propane brought about by the final lower temperature heat treatment at 650°C. Compare the results with the results when using Comparative Catalyst Example C. Catalyst Example 7 27.44g V205 powder was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. After the reaction of the V205 powder was complete, 61.26 g of Sb203 was added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 84.56 g of 10.7% Sn02 sol (Nalco Chemical Co.) and 2.40 g of Ti02 powder were added to the foregoing dispersion. The mixture was stirred in an uncovered beaker with heating in order to reduce the volume by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120°C. Thereafter it was calcined for 8 hours at 650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst was calcined for 3 hours at 810°C then heat treated at 650°C for an additional 3 hours. The calcined catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. This was done a total of three times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst. The catalyst was used to ammoxidize propane using a 3/8 inch O.D. titanium metal fixed bed reactor equipped with a preheat leg and immersed in a temperature controlled molten salt bath. 8.14 g of catalyst were placed in the reactor. Results are summarized in Table 1. Catalyst Example 8 27.29g V205 powder was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. After the reaction of the V205 powder was complete, 56.85 g of Sb203 was added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 42.25 g of 10.7% Sn02 sol (Nalco Chemical Co.) and 2.40 g of Ti02 powder were added to the foregoing dispersion. The mixture was stirred in an uncovered beaker with heating in order to reduce the volume by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120°C. Thereafter it was calcined for 8 hours at 650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst was calcined for 3 hours at 810°C then at 650°C for an additional 3 hours. The calcined catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glassfrit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. This was done a total of three times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst. The catalyst was used to ammoxidize propane using a 3/8 inch O.D. titanium metal fixed bed reactor equipped with a preheat leg and immersed in a temperature controlled molten salt bath. 8.285 g of catalyst were placed in the reactor. Results are summarized in Table 1. Catalyst Example 9 27.42g V205 powder was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. After the reaction of the V205 powder was complete, 61.22 g of Sb203 and 2.40 g of fumed Ti02 (Degussa P-25) powder were added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 84.50 g of 10.7% Sn02 sol (Nalco Chemical Co.) was added to the foregoing dispersion. The mixture was stirred in an uncovered beaker with heating in order to reduce the volume by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120°C. Thereafter it was calcined for 8 hours at 650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst was calcined for 3 hours at 810°C then at 650°C for an additional 3 hours. The calcined catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. This was done a total of three times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst. The catalyst was used to ammoxidize propane using a 3/8 inch O.D. titanium metal fixed bed reactor equipped with a preheat leg and immersed in a temperature controlled molten salt bath. 7.50 g of catalyst were placed in the reactor. Results are summarized in Table 1. Comparative Catalyst Example D 27.42g V205 powder was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. After the reaction of the V205 powder was complete, 61.22 g of Sb203 and 2.40 g of fumed Ti02 (Degussa P-25) powder were added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 84.50 g of 10.7% Sn02 sol (Nalco Chemical Co.) was added to the foregoing dispersion. The mixture was stirred in an uncovered beaker with heating in order to reduce the volume by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120°C. Thereafter it was calcined for 8 hours at 650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst was calcined for 3 hours at 810°C. The calcined catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. This was done a total of three times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120° C to remove the residual isobutanol on the catalyst. The catalyst was used to ammoxidize propane using a 3/8 inch O.D. titanium metal fixed bed reactor equipped with a preheat leg and immersed in a temperature controlled molten salt bath. 7.125 g of catalyst were placed in the reactor. Results are summarized in Table 1. Catalyst Example 10 27.29g V205 powder was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. After the reaction of the V205 powder was complete, 56.85 g of Sb203 was added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 84.51 g of 10.7% Sn02 sol (Nalco Chemical Co.) and 2.40 g of Ti02 powder were added to the foregoing dispersion. The mixture was stirred in an uncovered beaker with heating in order to reduce the volume by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120°C. Thereafter it was calcined for 8 hours at 650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst was calcined for 3 hours at 810°C then at 650°C for an additional 3 hours. The calcined catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. This was done a total of three times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst. The catalyst was used to ammoxidize propane using a 0.5 inch O.D. titanium metal fixed bed reactor equipped with a preheat leg and immersed in a temperature controlled fluidized sand bath. 8.151 g of catalyst were mixed with 4 ml of quartz chips (20-35 mesh particle size) and placed in the reactor. Results are summarized in Table 1. Catalyst Example 11 27.42g V205 powder was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. After the reaction of the V2O5 powder was complete, 61.22 g of Sb203 was added. Then 0.38 g of LiOH-H20 was added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 84.50 g of 10.7% Sn02 sol (Nalco Chemical Co.) and 2.40 g of Ti02 powder were added to the foregoing dispersion. The mixture was stirred in an uncovered beaker with heating in order to reduce the volume by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120°C. Thereafter it was calcined for 8 hours at 650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst was calcined for 3 hours at 810°C then at 650° C for an additional 3 hours. The calcined catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. This was done a total of three times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst. The catalyst was used to ammoxidize propane using a 3/8 inch O.D. titanium metal fixed bed reactor equipped with a preheat leg and immersed in a temperature controlled molten salt bath. Results are shown in Table 2, and can be compared to results shown using Comparative Catalyst Example E. Comparative Catalyst Example E 27.42g V2O5 powder was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. After the reaction of the V205 powder was complete, 61.22 g of Sb203 was added. Then 0.38 g of LiOH-H20 was added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 84.50 g of 10.7% Sn02 sol (Nalco Chemical Co.) and 2.40 g of Ti02 powder were added to the foregoing dispersion. The mixture was stirred in an uncovered beaker with heating in order to reduce the volume by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120°C. Thereafter it was calcined for 8 hours at 650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst was calcined for 3 hours at 810°C. The calcined catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst. Catalyst Example 12 27.42g V205 powder was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. After the reaction of the V2O5 powder was complete, 61.22 g of Sb203 was added. Then 0.13 g of LiOH-H20 was added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 84.50 g of 10.7% Sn02 sol (Nalco Chemical Co.) and 2.40 g of Ti02 powder were added to the foregoing dispersion. The mixture was stirred in an uncovered beaker with heating in order to reduce the volume by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120°C. Thereafter it was calcined for 8 hours at 650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst was calcined for 3 hours at 810°C then at 650°C for an additional 3 hours. The calcined catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. This was done a total of three times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst. The catalyst was used to ammoxidize propane using a 3/8 inch O.D. titanium metal fixed bed reactor equipped with a preheat leg and immersed in a temperature controlled molten salt bath. Results are shown in Table 2, and can be compared to results shown using Comparative Catalyst Example F. Comparative Catalyst Example F 27.42g V2O5 powder was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. After the reaction of the V205 powder was complete, 61.22 g of Sb203 was added. Then 0.13 g of LiOH-H20 was added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 84.50 g of 10.7% Sn02 sol (Nalco Chemical Co.) and 2.40 g of Ti02 powder were added to the foregoing dispersion. The mixture was stirred in an uncovered beaker with heating in order to reduce the volume by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120°C. Thereafter it was calcined for 8 hours at 650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst was calcined for 3 hours at 810°C. The calcined catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. This was done a total of four times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst. Catalyst Example 13 21.95g V205 powder was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. After the reaction of the V2O5 powder was complete, 49.01 g of Sb203 was added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 71.67 g of 10.7% Sn02 sol (Nalco Chemical Co.) and 1.92 g of Ti02 powder were added to the foregoing dispersion. 66.7 g silica sol (Nissan N-30); 30 weight percent silica, were then added. The mixture was stirred in an uncovered beaker with heating in order to reduce the volume by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120°C. Thereafter it was calcined for 8 hours at 650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst was calcined for 3 hours at 810°C then at 650°C for an additional 3 hours. The calcined catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. This was done a total of three times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst. The catalyst was used to ammoxidize propane using a 3/8 inch O.D. titanium metal fixed bed reactor equipped with a preheat leg and immersed in a temperature controlled molten salt bath. 3.0 g of catalyst were placed in the reactor. The results shown in Table 2 can be compared to the results using Comparative Catalyst Example G. Comparative Catalyst Example G 21.95g V205 powder was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. After the reaction of the V205 powder was complete, 49.01 g of Sb203 was added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 71.67 g of 10.7% Sn02 sol (Nalco Chemical Co.) and 1.92 g of Ti02 powder were added to the foregoing dispersion. 66.7 g silica sol (Nissan N-30); 30 weight percent silica, were then added. The mixture was stirred in an uncovered beaker with heating in order to reduce the volume by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120°C. Thereafter it was calcined for 8 hours at 650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst was calcined for 3 hours at 810°C. The calcined catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. This was done a total of three times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst. The catalyst was used to ammoxidize propane using a 3/8 inch O.D. titanium metal fixed bed reactor equipped with a preheat leg and immersed in a temperature controlled molten salt bath. 3.0 g of catalyst were placed in the reactor. Results are summarized in Table 2. Catalyst Example 14 27.42g V205 powder was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. After the reaction of the V205 powder was complete, 61.22 g of Sb203 was added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 43.89 g of 20.6% Sn02 sol (Nalco Chemical Co.) and 2.40 g of Ti02 powder were added to the foregoing dispersion. The mixture was stirred in an uncovered beaker with heating in order to reduce the volume by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120°C. Thereafter it was calcined for 8 hours at 650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst was calcined for 3 hours at 810°C then heat treated at 650°C for an additional 8 hours. The heat treated catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. This was done a total of three times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst. The catalyst was used to ammoxidize propane using a 3/8 inch O.D, titanium metal fixed bed reactor equipped with a preheat leg and immersed in a temperature controlled molten salt bath. 5 g of catalyst were placed in the reactor. Results are summarized in Table 2. (Table Removed) While the invention has been explained in relation to its preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. Therefore, it is to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims. WE CLAIM: 1. A process for preparation of an improved and active catalyst of formula VvSbmAaDdOx for use in the processes of oxidation and ammoxidation, wherein said process comprises following steps: a) calcination of a catalyst of the kind such as hereindescribed at a calcining temperature above 750°C to form a calcined catalyst in the manner such as hereindescribed, b) heat treating said calcined catalyst at an effective temperature, which is at least 50°C below the said calcining temperature optionally contacting with a liquid of the kind such as hereindescribed to form an active catalyst in the manner such as hereindescribed, wherein said catalyst and said calcined catalyst of step-a) and said active catalyst of step-b) have the elements and relative amounts indicated by the formula: VvSbmAaDdOx wherein V represents vanadium; Sb represents antimony; A represents Sn and/or Ti; D represents one or more of Li, Mg, Na, Ca, Sr, Ba, Co, Fe, Cr, Ga, Ni, Zn, Ge, Nb, Zr, Mo, W, Cu, Te, Ta, Se, Bi, Ce, In, As, B, Al and Mn; O represents oxygen; and wherein all of the elements of said formula except oxygen are present as cations, and v is 1, m is 0.5 to 10, a is up to 10, d is upto 10, x is determined by the oxidation state of the cations present. 2. A process as claimed in claim 1, wherein said liquid is selected from the group comprising water; aqueous solutions of acids or bases; cyclohexanol; cyclopentanol; a monohydroxy, acyclic hydrocarbon having 1-8 C atoms; and a dihydroxy, acyclic hydrocarbon having 2-4 C atoms 3. A process as claimed in claim 1 or 2, wherein v + m + a > 0.5d. 4. A process as claimed in any of the preceding claims, wherein a is 5. A process as claimed in any of the preceding claims, wherein said calcining temperature is preferably in the range of 750°C to 1200°C. 6. A process as claimed in any of the preceding claims, wherein said calcining temperature is more preferablyin the range of 7500C,1050°C. 7. A process as claimed in any of the preceding claims, wherein said calcining temperature is even more preferablyin the range of 7500C,950 C. 8. A process as claimed in any of the preceding claims, wherein said calcined catalyst is heat treated at a temperature which is at least 500°C. 9. A process for preparation of an improved and active catalyst of formula VvSbmAaDdOx substantially as herein described with reference to the accompanying examples.

Full Text

This invention relates to a process for preparation of an improved and active catalyst, particularly it relates to a process for preparation of an improved and active catalyst of formula VvSbmAaDdOx for use in the processes of oxidation and ammoxidation. It also relates to the catalyst so made. In another aspect the invention relates to the oxidation and ammoxidation of paraffins, olefins and aromatic compounds.
Catalysts containing vanadium and antimony in oxide form, and usually containing tin or titanium, or both, as part of the metal oxide catalyst are normally calcined before using to catalyze the ammoxidation of paraffins, olefins and various aromatics; such calcination is above 750°C and activates the composition to make effective ammoxidation catalysts.
It has now been found that such catalysts can be even further activated to increase the activity of conversion of the feedstock and the selectivity of conversion to a nitrile by the heat treatment of the catalyst previously activated by calcining at a temperature above 750°C, wherein the heat treatment is at an effective temperature at least 50°C below the highest calcination temperature.
In a broad aspect of the method of the invention we have found that heat treating a catalyst calcined at a calcining temperature above 750°C at a temperature which is at least 500°C and at least 50°C below the calcining temperature is improved in its activity for converting the feed, such as propane or propylene to acrylonitrile.
In a now preferred embodiment of the method for making an even more active catalyst, the catalyst which has been calcined at a temperature above 750°C and thereafter heat treated at the lower temperature, is contacted with a liquidbelieved to be a solvent for some minute quantity of a deleterious (generally well less than 1% of the composition) compound containing V and Sb in oxide form, and the bulk of the "solvent" separated from the catalyst.
In this aspect of the invention there can be used various "solvents" that have been used to so treat such V and Sb catalysts in oxide form following calcination above 750°C. These include water, aqueous solutions of acids or bases, such as phosphoric, sulfuric and acetic acids and NH3 and NaOH solutions; and the hydroxy compounds of U.S. patent 5,094,989: cyclohexanol; cyclopentanol; a monohydroxy, acyclic hydrocarbon having 1-8 C atoms; and a dihydroxy, acyclic hydrocarbon having 2-4 carbon atoms.
The catalyst to which the improved method applies contains the elements and relative amounts indicated by the formula:
VvSbmA.DdOx
wherein A when present is Sn and/or Ti;
D when present is one or more of Li, Mg, Na, Ca, Sr, Ba, Co, Fe, Cr, Ga, Ni, Zn, Ge, Nb, Zr, Mo, W, Cu, Te, Ta, Se, Bi, Ce, In, As, B, Al and Mn;
and wherein
all of the elements of said formula except oxygen are present as cations, and
v is 1
m is 0.5-10
a is up to 10
d is up to 10
x is determined by the oxidation state of the cations present
In a more specific aspect of the invention the catalyst to which the method applies has the relation
v + m + a > 0.5d.
The process for improving the catalysts is most often applied to such foregoing catalysts wherein a is In the above formula the phrase "when present" means that A may be zero and that D may be zero. Thus, the catalysts can contain essentially only V and Sb.
The highest calcination temperature of the catalysts above 7500C before the relatively low temperature heat treatment step of the process of the invention can be as high as 12000C, but is usually over 7500C and up to 10500C, most often up to 9500C.
The present catalyst is useful for the oxidation and ammoxidation of paraffins, olefins and aromatic compounds in a reaction zone. In particular, in this aspect of the invention especially useful reactions include the ammoxidation of propane with NH3 and 02 to acrylonitrile, the ammoxidation of propylene with NH3 and 02 to acrylonitrile, the ammoxidation of a methyl pyridine with 02 and NH3 to the corresponding cyanopyridine, and the ammoxidation of m-xylene with 02 and NH3 to isophthalonitrile.
Accordingly, the present invention relates to a process for preparation of an improved and active catalyst of formula VvSbmAaDdOx for use in the processes of oxidation and ammoxidation, wherein the process comprises following steps:
a) calcination of a catalyst of the kind such as hereindescribed at a calcining temperature above 750°C to form a calcined catalyst in the manner such as hereindescribed,
b) heat treating the calcined catalyst at an effective temperature, which is at least 50 C below the calcining temperature optionally contacting with a liquid of the kind such as hereindescribed to form an active catalyst in the manner such as hereindescribed,
wherein the catalyst and the calcined catalyst of step-a) and the active catalyst of step-b) have the elements and relative amounts indicated by the formula:
VvSbmAaDdOx
wherein
V represents vanadium;
Sb represents antimony;
A represents Sn and/or Ti;
D represents one or more of Li, Mg, Na, Ca, Sr, Ba, Co, Fe, Cr, Ga, Ni, Zn,
Ge, Nb, Zr, Mo, W, Cu, Te, Ta, Se, Bi, Ce, In, As, B, Al and Mn;
O represents oxygen;
and wherein
all of the elements of said formula except oxygen are present as cations, and
v is 1,
m is 0.5 to 10,
a is upto 10,
d is upto 10,
x is determined by the oxidation state of the cations present.
The following specific examples are illustrative only and are not to be considered in any way limiting.
Catalyst Example 1
27.42g of V205 powder was added to a solution consisting of 100 ml of 30% H202 in 900 ml of water in a 2 liter beaker. After the reaction of the V205 powder was complete, 61.22g of Sb203 and 2.40g of fumed Ti02 (Degussa P-25) powder were added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 89.52 g of 10.1% Sn02 sol (Nalco Chemical Co.) was added to the foregoing dispersion. The mixture was stirred in an uncovered beaker with heating in order to reduce the volume to 300 ml by evaporation of water. It was then dried in an oven at 120°C. Thereafter it was calcined for 8 hours at 650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst was calcined for 3 hours at 810°C. It was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glassfrit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. This was done a total of three times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst. The catalyst was then heat treated in an oven at 500°C for 3 hours according to the invention.
The calcined catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, and then allowing the isobutanol to pass through the funnel without suction. This was done a total of two times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst.
The catalyst was used to ammoxidize propane using a 3/8 inch O.D. titanium metal fixed bed reactor equipped with a preheat leg and immersed in a temperature controlled molten salt bath. 4.0 g of catalyst were placed in the reactor. Results of all ammoxidation runs are shown in Tables 1 and 2 as are the feed ratios and temperatures.
Catalyst Example 2 27.42g of V205 powder was added to a solution consisting of 100 ml of 30% H202 in 900 ml of water in a 2 liter beaker. After the reaction of the V20j powder was complete, 61.22 g of Sb2O3,2.4 g of fumed Ti02 (Degussa P-25) powder were added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 89.52 g of 10.1% Sn02 sol (Nalco Chemical Co.) was added to the foregoing dispersion. The mixture was stirred, in an uncovered beaker with heating in order to reduce the volume to 300 ml by evaporation of water. It was then dried in an oven at 120°C. Thereafter it was calcined for 8 hours at 650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst wascalcined for 3 hours at 810°C. It was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. This was done a total of three times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst. The catalyst was then heat treated in an oven at 650°C for 3 hours according to the invention.
The calcined catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, and then allowing the isobutanol to pass through the funnel without suction. This was done a total of two times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst.
The catalyst was used to ammoxidize propane using a 3/8 inch O.D. titanium metal fixed bed reactor equipped with a preheat leg and immersed in a temperature controlled molten salt bath. 4.0 g of catalyst were placed in the reactor.
Catalyst Example 3 27.42g of V2O5 powder was added to a solution consisting of 100 ml of 30% H202 in 900 ml of water in a 2 liter beaker. After the reaction of the V205 powder was complete, 61.22 g of Sb203 ,2.4g of fumed Ti02 (Degussa P-25) powder were added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 89.52 g of 10.1 % Sn02 sol (Nalco Chemical Co.) was added to the foregoing dispersion. The mixture was stirred in an uncovered beaker with heating in order to reduce the volume to 300 ml by evaporation of water. It was then dried in an oven at 120°C. Thereafter it was calcined for 8 hours at 650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst wascalcined for 3 hours at 810°C. It was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. This was done a total of three times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst. The catalyst was then heat treated in an oven at 650°C for 3 hours according to the invention.
The calcined catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, and then allowing the isobutanol to pass through the funnel without suction. This was done a total of three times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst.
The catalyst was used to ammoxidize propane using a 3/8 inch O.D. titanium metal fixed bed reactor equipped with a preheat leg and immersed in a temperature controlled molten salt bath. 4.5 g of catalyst were placed in the reactor.
Comparative Catalyst Example A 27.42g of V205 powder was added to a solution consisting of 100 ml of 30% H202 in 900 ml of water in a 2 liter beaker. After the reaction of the V205 powder was complete, 61.22g of Sb203 and 2.40g of fumed Ti02 (Degussa P-25) powder were added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 89.52g of 10.1% Sn02 sol (Nalco Chemical Co.) was added to the foregoing dispersion. The mixture was stirred in an uncovered beaker with heating in order to reduce the volume to 300 ml by evaporation of water. It was then dried in an oven at 120°C. Thereafter it was calcined for 8 hours at650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst was calcined for 3 hours at 810°C.
The calcined catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. This was done a total of three times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst.
The catalyst was used to ammoxidize propane using a 3/8 inch O.D. titanium metal fixed bed reactor equipped with a preheat leg and immersed in a temperature controlled molten salt bath. 2.5g of catalyst were placed in the reactor. Results are summarized in Table 1.
Catalyst Example 4 27.44g V205 was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. The mixture was stirred without heating for about 6 hours to produce a deep red sol/gel. It was then stirred overnight at room temperature. 61.26g Sb203 was then added and the resulting mixture was heated to boiling and allowed to boil with a watch glass covering the beaker for about 3 hours. Water was periodically added to the beaker to keep the mixture stirring and the volume of the mixture constant. During the heating the mixture turned green then gray then gray-black. At this point 84.56g of a 10.7 weight percent tin oxide sol and 2.4g of Ti02 were added and the mixture was evaporated to near dryness on the hot plate with constant stirring. The resulting paste was then dried at 120°C overnight. The dried material was heat treated at 650 °C for 8 hours then ground and screened and the 20-35 mesh particles were collected. A portion of the 20-35 mesh particles was heat treated at 810°C for 3 hours. A portion of the 810°C calcined particles was washed three times with isobutanol by using about 50ml of isobutanol per 8 grams of catalyst. The particles were placed in a coarse glass frit funnel, covered with
isobutanol and the isobutanol was allowed to pass through the glass frit without suction. The resulting material was then placed in an oven at 120°C for several hours to remove residual isobutanol. The composition was then heat treated for 3 hours at 650°C*. As will be seen by reference to Table 1, an improvement was
effected in yield and selectivity by the later 650°C heat treatment, compared to
* and washed and heated as in Catalyst Comparative Catalyst Example B. Example 3.
Comparative Catalyst Example B
27.44g V205 was added to a solution consisting of 100ml 30% H202
in 900ml of water in a 2 liter beaker. The mixture was stirred without heating for
about 6 hours to produce a deep red sol/gel. It was then stirred overnight at room
temperature. 61.26g Sb203 was then added and the resulting mixture was heated to
boiling and allowed to boil with a watch glass covering the beaker for about 3 hours.
Water was periodically added to the beaker to keep the mixture stirring and the
volume of the mixture constant. During the heating the mixture turned green then
gray then gray-black. At this point 84.56g of a 10.7 weight percent tin oxide sol and
2.4g of Ti02 were added and the mixture was evaporated to near dryness on the hot
plate with constant stirring. The resulting paste was then dried at 120°C overnight.
The dried material was heat treated at 650°C for 8 hours then ground and screened
and the 20-35 mesh particles were collected. A portion of the 20-35 mesh particles
was heat treated at 810°C for 3 hours. A portion of the 810°C calcined particles was
washed three times with isobutanol by using about 50ml of isobutanol per 8 grams
of catalyst. The particles were placed in a coarse glass frit funnel, covered with
isobutanol and the isobutanol was allowed to pass through the glass frit without
suction. This was done three times. The resulting material was then placed in an
oven at 120°C for several hours to remove residual isobutanol.
Catalyst Example 5
27.44g V2O5 was added to a solution consisting of 100ml 30% H202
in 900ml of water in a 2 liter beaker. The mixture was stirred without heating for
about 6 hours to produce a deep red sol/gel. It was then stirred overnight at room
temperature. 61.26g Sb203 was then added and the resulting mixture was heated to
boiling and allowed to boil with a watch glass covering the beaker for about 3 hours. Water was periodically added to the beaker to keep the mixture stirring and the volume of the mixture constant. During the heating the mixture turned green then gray then gray-black. At this point 84.56g of a 10.7 weight percent tin oxide sol and 2.4g of Ti02 were added and the mixture was evaporated to near dryness on the hot plate with constant stirring. The resulting paste was then dried at 120°C overnight The dried material was heat treated at 650°C for 8 hours then ground and screened and the 20-35 mesh particles were collected. A portion of the 20-35 mesh particles was heat treated at 810°C for 3 hours. A portion of the 810°C calcined particles was heat treated according to the invention for 3 hours at 650°C and was washed with isobutanol by using about 50ml of isobutanol per 8 grams of catalyst. The particles were placed in a coarse glass frit funnel, covered with isobutanol and the isobutanol was allowed to pass through the glass frit without suction. This was done a total of three times. The resulting material was then placed in an oven at 120°C for several hours to remove residual isobutanol.
It will be seen by reference to Table 1 that the post heat treatment for 3 hours at 650°C was an improvement in comparison to both comparative catalyst examples B and C.
Comparative Catalyst Example C 27.44g V205 was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. The mixture was stirred without heating for about 6 hours to produce a deep red sol/gel. It was then stirred overnight at room temperature. 61.26g Sb203 was then added and the resulting mixture was heated to boiling and allowed to boil with a watch glass covering the beaker for about 3 hours. Water was periodically added to the beaker to keep the mixture stirring and the volume of the mixture constant. During the heating the mixture turned green then gray then gray-black. At this point 84.56g of a 10.7 weight percent tin oxide sol and 2.4g of Ti02 were added and the mixture was evaporated to hear dryness on the hot plate with constant stirring. The resulting paste was then dried at 120°C overnight. The dried material was heat treated at 650°C for 8 hours then ground and screenedand the 20-35 mesh particles were collected. A portion of the 20-35 mesh particles was calcined at 810°C for 3 hours. This was designated Comparative Catalyst Example C. Results of testing this catalyst in the ammoxidation of propane are shown in Table 1.
Catalyst Example 6 27.44g V2O5 was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. The mixture was stirred without heating for about 6 hours to produce a deep red sol/gel. It was then stirred overnight at room temperature. 61.26g Sb203 was then added and the resulting mixture was heated to boiling and allowed to boil with a watch glass covering the beaker for about 3 hours. Water was periodically added to the beaker to keep the mixture stirring and the volume of the mixture constant. During the heating the mixture turned green then gray then gray-black. At this point 84.56g of a 10.7 weight percent tin oxide sol and 2.4g of Ti02 were added and the mixture was evaporated to near dryness on the hot plate with constant stirring. The resulting paste was then dried at 120°C overnight. The dried material was heat treated at 650°C for 8 hours then ground and screened and the 20-35 mesh particles were collected. A portion of the 20-35 mesh particles was calcined at 810°C for 3 hours and then heat treated according to the invention at 650°C for 3 hours. As will be seen in Table 1, there is an improvement in the yield and selectivity in the ammoxidation of propane brought about by the final lower temperature heat treatment at 650°C. Compare the results with the results when using Comparative Catalyst Example C.
Catalyst Example 7 27.44g V205 powder was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. After the reaction of the V205 powder was complete, 61.26 g of Sb203 was added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 84.56 g of 10.7% Sn02 sol (Nalco Chemical Co.) and 2.40 g of Ti02 powder were added to the foregoing dispersion. The mixture was stirred in an uncovered beaker with heating in order to reduce the volume by evaporation of water. When the mixture could no
longer be stirred, it was dried in an oven at 120°C. Thereafter it was calcined for 8 hours at 650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst was calcined for 3 hours at 810°C then heat treated at 650°C for an additional 3 hours.
The calcined catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. This was done a total of three times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst.
The catalyst was used to ammoxidize propane using a 3/8 inch O.D. titanium metal fixed bed reactor equipped with a preheat leg and immersed in a temperature controlled molten salt bath. 8.14 g of catalyst were placed in the reactor. Results are summarized in Table 1.
Catalyst Example 8 27.29g V205 powder was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. After the reaction of the V205 powder was complete, 56.85 g of Sb203 was added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 42.25 g of 10.7% Sn02 sol (Nalco Chemical Co.) and 2.40 g of Ti02 powder were added to the foregoing dispersion. The mixture was stirred in an uncovered beaker with heating in order to reduce the volume by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120°C. Thereafter it was calcined for 8 hours at 650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst was calcined for 3 hours at 810°C then at 650°C for an additional 3 hours.
The calcined catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glassfrit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. This was done a total of three times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst.
The catalyst was used to ammoxidize propane using a 3/8 inch O.D. titanium metal fixed bed reactor equipped with a preheat leg and immersed in a temperature controlled molten salt bath. 8.285 g of catalyst were placed in the reactor. Results are summarized in Table 1.
Catalyst Example 9 27.42g V205 powder was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. After the reaction of the V205 powder was complete, 61.22 g of Sb203 and 2.40 g of fumed Ti02 (Degussa P-25) powder were added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 84.50 g of 10.7% Sn02 sol (Nalco Chemical Co.) was added to the foregoing dispersion. The mixture was stirred in an uncovered beaker with heating in order to reduce the volume by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120°C. Thereafter it was calcined for 8 hours at 650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst was calcined for 3 hours at 810°C then at 650°C for an additional 3 hours.
The calcined catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. This was done a total of three times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst.
The catalyst was used to ammoxidize propane using a 3/8 inch O.D. titanium metal fixed bed reactor equipped with a preheat leg and immersed in a temperature controlled molten salt bath. 7.50 g of catalyst were placed in the reactor. Results are summarized in Table 1.
Comparative Catalyst Example D 27.42g V205 powder was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. After the reaction of the V205 powder was complete, 61.22 g of Sb203 and 2.40 g of fumed Ti02 (Degussa P-25) powder were added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 84.50 g of 10.7% Sn02 sol (Nalco Chemical Co.) was added to the foregoing dispersion. The mixture was stirred in an uncovered beaker with heating in order to reduce the volume by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120°C. Thereafter it was calcined for 8 hours at 650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst was calcined for 3 hours at 810°C.
The calcined catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. This was done a total of three times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120° C to remove the residual isobutanol on the catalyst.
The catalyst was used to ammoxidize propane using a 3/8 inch O.D. titanium metal fixed bed reactor equipped with a preheat leg and immersed in a temperature controlled molten salt bath. 7.125 g of catalyst were placed in the reactor. Results are summarized in Table 1.
Catalyst Example 10 27.29g V205 powder was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. After the reaction of the V205 powder was complete, 56.85 g of Sb203 was added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 84.51 g of 10.7% Sn02 sol (Nalco Chemical Co.) and 2.40 g of Ti02 powder were added to the foregoing dispersion. The mixture was stirred in an uncovered beaker with heating in order to reduce the volume by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120°C. Thereafter it was calcined for 8 hours at 650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst was calcined for 3 hours at 810°C then at 650°C for an additional 3 hours.
The calcined catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. This was done a total of three times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst.
The catalyst was used to ammoxidize propane using a 0.5 inch O.D. titanium metal fixed bed reactor equipped with a preheat leg and immersed in a temperature controlled fluidized sand bath. 8.151 g of catalyst were mixed with 4 ml of quartz chips (20-35 mesh particle size) and placed in the reactor. Results are summarized in Table 1.
Catalyst Example 11 27.42g V205 powder was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. After the reaction of the V2O5 powder was complete, 61.22 g of Sb203 was added. Then 0.38 g of LiOH-H20 was added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 84.50 g of 10.7% Sn02 sol (Nalco Chemical Co.) and 2.40 g of Ti02 powder were added to the foregoing dispersion. The mixture was stirred in an uncovered beaker with heating in order to reduce the volume by evaporation of water.

When the mixture could no longer be stirred, it was dried in an oven at 120°C. Thereafter it was calcined for 8 hours at 650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst was calcined for 3 hours at 810°C then at 650° C for an additional 3 hours.
The calcined catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. This was done a total of three times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst.
The catalyst was used to ammoxidize propane using a 3/8 inch O.D. titanium metal fixed bed reactor equipped with a preheat leg and immersed in a temperature controlled molten salt bath. Results are shown in Table 2, and can be compared to results shown using Comparative Catalyst Example E.
Comparative Catalyst Example E 27.42g V2O5 powder was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. After the reaction of the V205 powder was complete, 61.22 g of Sb203 was added. Then 0.38 g of LiOH-H20 was added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 84.50 g of 10.7% Sn02 sol (Nalco Chemical Co.) and 2.40 g of Ti02 powder were added to the foregoing dispersion. The mixture was stirred in an uncovered beaker with heating in order to reduce the volume by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120°C. Thereafter it was calcined for 8 hours at 650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst was calcined for 3 hours at 810°C.
The calcined catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the
isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst.
Catalyst Example 12 27.42g V205 powder was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. After the reaction of the V2O5 powder was complete, 61.22 g of Sb203 was added. Then 0.13 g of LiOH-H20 was added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 84.50 g of 10.7% Sn02 sol (Nalco Chemical Co.) and 2.40 g of Ti02 powder were added to the foregoing dispersion. The mixture was stirred in an uncovered beaker with heating in order to reduce the volume by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120°C. Thereafter it was calcined for 8 hours at 650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst was calcined for 3 hours at 810°C then at 650°C for an additional 3 hours.
The calcined catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. This was done a total of three times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst.
The catalyst was used to ammoxidize propane using a 3/8 inch O.D. titanium metal fixed bed reactor equipped with a preheat leg and immersed in a temperature controlled molten salt bath. Results are shown in Table 2, and can be compared to results shown using Comparative Catalyst Example F.
Comparative Catalyst Example F
27.42g V2O5 powder was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. After the reaction of the V205 powder was complete, 61.22 g of Sb203 was added. Then 0.13 g of LiOH-H20 was added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 84.50 g of 10.7% Sn02 sol (Nalco Chemical Co.) and 2.40 g of Ti02 powder were added to the foregoing dispersion. The mixture was stirred in an uncovered beaker with heating in order to reduce the volume by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120°C. Thereafter it was calcined for 8 hours at 650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst was calcined for 3 hours at 810°C.
The calcined catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. This was done a total of four times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst.
Catalyst Example 13
21.95g V205 powder was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. After the reaction of the V2O5 powder was complete, 49.01 g of Sb203 was added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 71.67 g of 10.7% Sn02 sol (Nalco Chemical Co.) and 1.92 g of Ti02 powder were added to the foregoing dispersion. 66.7 g silica sol (Nissan N-30); 30 weight percent silica, were then added. The mixture was stirred in an uncovered beaker with heating in order to reduce the volume by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120°C. Thereafter it was calcined for 8 hours at
650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst was calcined for 3 hours at 810°C then at 650°C for an additional 3 hours.
The calcined catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. This was done a total of three times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst.
The catalyst was used to ammoxidize propane using a 3/8 inch O.D. titanium metal fixed bed reactor equipped with a preheat leg and immersed in a temperature controlled molten salt bath. 3.0 g of catalyst were placed in the reactor. The results shown in Table 2 can be compared to the results using Comparative Catalyst Example G.
Comparative Catalyst Example G 21.95g V205 powder was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. After the reaction of the V205 powder was complete, 49.01 g of Sb203 was added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 71.67 g of 10.7% Sn02 sol (Nalco Chemical Co.) and 1.92 g of Ti02 powder were added to the foregoing dispersion. 66.7 g silica sol (Nissan N-30); 30 weight percent silica, were then added. The mixture was stirred in an uncovered beaker with heating in order to reduce the volume by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120°C. Thereafter it was calcined for 8 hours at 650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst was calcined for 3 hours at 810°C.
The calcined catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the
isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. This was done a total of three times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst.
The catalyst was used to ammoxidize propane using a 3/8 inch O.D. titanium metal fixed bed reactor equipped with a preheat leg and immersed in a temperature controlled molten salt bath. 3.0 g of catalyst were placed in the reactor. Results are summarized in Table 2.
Catalyst Example 14 27.42g V205 powder was added to a solution consisting of 100ml 30% H202 in 900ml of water in a 2 liter beaker. After the reaction of the V205 powder was complete, 61.22 g of Sb203 was added. The beaker was covered with a watch glass and the mixture was stirred and heated for about 3 hours. 43.89 g of 20.6% Sn02 sol (Nalco Chemical Co.) and 2.40 g of Ti02 powder were added to the foregoing dispersion. The mixture was stirred in an uncovered beaker with heating in order to reduce the volume by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120°C. Thereafter it was calcined for 8 hours at 650°C, cooled and then crushed and sieved to 20-35 mesh. A portion of this catalyst was calcined for 3 hours at 810°C then heat treated at 650°C for an additional 8 hours.
The heat treated catalyst was then contacted with isobutanol using about 6.25 ml of isobutanol per gram of catalyst by placing the catalyst in a coarse glass frit funnel, pouring the isobutanol over the catalyst, stirring the catalyst in the isobutanol in order to spread the catalyst evenly over the bottom of the funnel, then allowing the isobutanol to pass through the funnel without suction. This was done a total of three times. After the last of the isobutanol had passed through the funnel, the catalyst was heated in an oven at 120°C to remove the residual isobutanol on the catalyst.
The catalyst was used to ammoxidize propane using a 3/8 inch O.D, titanium metal fixed bed reactor equipped with a preheat leg and immersed in a temperature controlled molten salt bath. 5 g of catalyst were placed in the reactor. Results are summarized in Table 2.
(Table Removed)
While the invention has been explained in relation to its preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. Therefore, it is to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.

WE CLAIM:
1. A process for preparation of an improved and active catalyst of formula
VvSbmAaDdOx for use in the processes of oxidation and ammoxidation,
wherein said process comprises following steps:
a) calcination of a catalyst of the kind such as hereindescribed at a calcining temperature above 750°C to form a calcined catalyst in the manner such as hereindescribed,
b) heat treating said calcined catalyst at an effective temperature, which is at least 50°C below the said calcining temperature optionally contacting with a liquid of the kind such as hereindescribed to form an active catalyst in the manner such as hereindescribed,
wherein said catalyst and said calcined catalyst of step-a) and said active catalyst of step-b) have the elements and relative amounts indicated by the formula:
VvSbmAaDdOx wherein
V represents vanadium; Sb represents antimony; A represents Sn and/or Ti;
D represents one or more of Li, Mg, Na, Ca, Sr, Ba, Co, Fe, Cr, Ga, Ni, Zn, Ge, Nb, Zr, Mo, W, Cu, Te, Ta, Se, Bi, Ce, In, As, B, Al and Mn; O represents oxygen; and wherein all of the elements of said formula except oxygen are present as cations, and

v is 1,
m is 0.5 to 10,
a is up to 10,
d is upto 10,
x is determined by the oxidation state of the cations present.
2. A process as claimed in claim 1, wherein said liquid is selected from the group comprising water; aqueous solutions of acids or bases; cyclohexanol; cyclopentanol; a monohydroxy, acyclic hydrocarbon having 1-8 C atoms; and a dihydroxy, acyclic hydrocarbon having 2-4 C atoms
3. A process as claimed in claim 1 or 2, wherein v + m + a > 0.5d.
4. A process as claimed in any of the preceding claims, wherein a is 5. A process as claimed in any of the preceding claims, wherein said calcining temperature is preferably in the range of 750°C to 1200°C.
6. A process as claimed in any of the preceding claims, wherein said calcining temperature is more preferablyin the range of 7500C,1050°C.
7. A process as claimed in any of the preceding claims, wherein said calcining temperature is even more preferablyin the range of 7500C,950 C.
8. A process as claimed in any of the preceding claims, wherein said calcined catalyst is heat treated at a temperature which is at least 500°C.
9. A process for preparation of an improved and active catalyst of formula VvSbmAaDdOx substantially as herein described with reference to the accompanying examples.

Documents:

202-del-1995-abstract.pdf

202-del-1995-claims.pdf

202-del-1995-correspondence-others.pdf

202-del-1995-correspondence-po.pdf

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

202-del-1995-form-1.pdf

202-del-1995-form-13.pdf

202-del-1995-form-2.pdf

202-del-1995-form-3.pdf

202-del-1995-form-4.pdf

202-del-1995-form-9.pdf

202-del-1995-gpa.pdf

202-del-1995-pct-210.pdf

202-del-1995-petition-124.pdf

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Patent Number

190178

Indian Patent Application Number

202/DEL/1995

PG Journal Number

26/2003

Publication Date

28-Jun-2003

Grant Date

08-Dec-2006

Date of Filing

19-Feb-1995

Name of Patentee

BP AMERICA, INC.

Applicant Address

200 PUBLIC SQUARE, CLEVELAND, OHIO 44114, UNITED STATE OF AMERICA.

Inventors:

#	Inventor's Name	Inventor's Address
1	FERNANDO ANTONIO PESSOA CAVALCANTI	1375 BELVIOR, MEWS, SOUTH EUCLID, OHIO 44121, U.S.A.
2	JAMES FRANK BRAZDIL	422 MEDWAY ROAD, HIGHLAND HTS., 44143, U.S.A.
3	NOEL JEROME BREMER	3633 BY LANE, KENT, OHIO 44240, U.S.A.
4	LINDA CLAIRE BRAZDIL	422 MEDWAY ROAD, HIGHLAND HTS., OHIO 44143, U.S.A.

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