BR112012023841B1 - CATALYTIC COMPOSITION AND PROCESS FOR OLEFIN CONVERSION - Google Patents

Description

(54) Title: CATALYTIC COMPOSITION AND OLEFIN CONVERSION PROCESS (51) lnt.CI .: B01J 23/00; B01J 23/887; C07C 253/26; B01J 35/00; B01J 37/03 (30) Unionist Priority: 23/03/2010 US 12 / 661,720 (73) Holder (s): INEOS USA LLC (72) Inventor (s): JAMES F. BRAZDIL; MARK A. TOFT; MICHAEL J. SEELY; CHARLES J. BESECKER; ROBERT A. GUSTAFERRO (85) National Phase Start Date: 20/09/2012

1/44 “Catalytic Composition and

Olefin Conversion Process ”

Descriptive Report

Related Order Reference

This Application relates to (i) US Patent Application No.

12 / 661,716, entitled “Process for Preparing Improved Mixed Metal Oxide Ammoxidatíon Catalysts”, deposited on March 23, 2010 by Brazdil et al. under Attorney Attorney No. 50031 and (ii) US Patent Application No. 12 / 661,705, entitled “Improved Mixed Metal Oxide

Ammoxidation Catalysts ”, filed on March 23, 2010 by Brazdil et al. under Attorney Attorney No. 50042, both filed on the same date as this Order and which are hereby incorporated by reference for all purposes.

Field of the Invention

The present invention relates to a friction resistant catalyst for use in amoxidizing an unsaturated hydrocarbon to the corresponding unsaturated nitrile. In particular, the present invention is directed to an improved catalytic composition for the amoxidation of propylene and / or isobutylene to acrylonitrile and / or methacrylonitrile, respectively.

Description of the State of the Art

Catalysts containing iron, bismuth and molybdenum oxides, promoted with suitable elements, have long been used for the conversion of propylene and / or isobutylene at elevated temperatures in the presence of ammonia and oxygen (usually in the form of air) to obtain acrylonitrile and / or methacrylonitrile. In particular, British patent 1436475; US Patents 4,766,232, 4,377,534,

2/44

4,040,978, 4,168,246, 5,223,469 and 4,863,891 are directed to bismuth-molybdenum-iron catalysts that can be promoted with Group II elements to produce acrylonitrile. In addition, US Patents 5,093,299. 5212,137. 5,658,842 and 5,834,394 are directed to catalysts promoted by bismuth-molybdenum exhibiting high yields in acrylonitrile.

In part, the present invention relates to supported friction resistant bismuth-molybdenum-iron catalysts promoted with cerium. It was found that the control of the relative amounts of iron and cerium impacts on the hardness of the catalyst. State-of-the-art catalysts were often characterized by low Ce to Fe rates (for example, below about 0.7) tending to produce softer catalysts less resistant to friction even when combined with a support material.

Summary of the Invention

The present invention is directed to a friction-resistant mixed metal oxide catalyst for amoxidation of propylene and / or isobutylene.

In one embodiment, the invention is directed to a catalytic composition comprising a complex of metal oxides where the relative proportions of the elements in said are represented by the following formula:

M012 Bi _a Feb A _c D _a E _e Ff G _g Ceh O _x where:

A is at least one element selected from the group consisting of sodium, potassium, rubidium and cesium; and

D is at least one element selected from the group consisting of

3/44 in nickel, cobalt, manganese, zinc, magnesium, calcium, strontium, cadmium and barium;

And it is at least one element selected from the group consisting of chromium, tungsten, boron, aluminum, gallium, indium, phosphorus, arsenic, antimony, vanadium and tellurium;

F is at least one element selected from the group consisting of a rare earth element, titanium, zirconium, hafnium, niobium, tantalum, aluminum, gallium, indium, thallium, silicon, germanium, and lead;

G is at least one element selected from the group consisting of 10 in silver, gold, ruthenium, rhodium, palladium, osmium, iridium, platinum and mercury;

and a, b, c, d, e, f, g, hen are, respectively, the atomic ratios of bismuth (Bi), iron (Fe), A, D, E, F, cerium (Ce) and oxygen (O ), in relation to 12 molybdenum atoms (Mo), where:

a is 0.05 to 7, b is 0.1 to 7, c is 0.01 to 5, d is 0.1 to 12, and is 0 to 5, f is 0 to 5, g is 0 to 0.2, h is 0.01 to 5, and n is the number of oxygen atoms required to satisfy

4/44 valence requirements of the other component elements present;

where 0.8 <h / b <5, and where the catalyst composition comprises a support selected from the group consisting of silica, alumina, zirconium, titania, or mixtures thereof, and where the support comprises between 30 and 70 weight percent of the catalyst composition.

The present invention is also directed to processes for the conversion of an olefin selected from the group consisting of propylene and isobutylene or mixtures thereof, acrylonitrile, and / or methacrylonitrile, and other by-product nitriles (i.e., compounds having the functional group “-CN”, such as acetonitrile and hydrogen cyanide) and mixtures thereof, by reaction in the vapor phase at an elevated temperature and pressure of said olefin with gas containing molecular oxygen and ammonia in the presence of a mixed metal oxide catalyst as described in previous paragraph.

Brief Description of Drawings

Figure 1 is a plot of the historical trend with respect to the development of the acrylonitrile catalyst showing the Yield on Acrylonitrile on the x axis and the Yield on Hydrogen Cyanide on the y axis. This plot illustrates that over time as

Yield on Acrylonitrile increased, the corresponding Yield on Hydrogen Cyanide decreased. The catalysts of the present invention do not fit this historical trend. The catalysts of the present invention produce an increase in Yield in Acrylonitrile without significant reduction in Yield in Hydrogen Cyanide as shown in the historical trend.

Figure 2 is an XRD diffraction pattern or XRD diffractogram of a catalyst within the scope of the present invention. This diffractogram illustrates an intense x-ray diffraction peak at 2Θ angle of 28 ± 0.3 degrees (with the intensity defined as “X”) and a diffraction peak

5/44 of intense x-ray at 2Θ angle of 26.5 ± 0.3 degrees (with the intensity defined as “Y”). The X / Y ratio is 0.97.

Figure 3 is a plot of the resistance to friction versus the Ce / Fe ratio in the catalyst. It was observed that the catalysts presenting the compositions described here and presenting a Ce / Fe ratio above or equal to 0.8 and below or equal to 5 tend to be more resistant in the fact that they present a lower friction loss as determined by a friction with submerged jet.

Detailed Description of the Invention

The present invention is a new catalyst comprising an unusual combination and proportion of promoters offering a better performance in the catalytic amoxidation of propylene, isobutylene or mixtures of these, to acrylonitrile, methacrylonitrile and mixtures thereof, respectively.

The catalyst.

The present invention is directed to a multicomponent mixed metal oxide catalytic composition for amoxidation comprising a complex of catalytic oxides where the elements and relative proportions in said catalytic composition are represented by the following formula:

Moi2 Bia Feb Ac Dj Eç Ff Gg Ceh Οχ where:

A is at least one element selected from the group consisting of sodium, potassium, rubidium and cesium; and

D is at least one element selected from the group consisting of nickel, cobalt, manganese, zinc, magnesium, calcium, strontium,

6/44 cadmium and barium;

And it is at least one element selected from the group consisting of chromium, tungsten, boron, aluminum, gallium, indium, phosphorus, arsenic, antimony, vanadium and tellurium;

At least one element selected from the group consisting of a rare earth element, titanium, zirconium, hafnium, niobium, tantalum, thallium, silicon, germanium, and lead;

G is at least one element selected from the group consisting of silver, gold, ruthenium, rhodium, palladium, osmium, iridium, platinum and mercury;

and a, b, c, d, e, f, g, hen are, respectively, the atomic ratios of bismuth (Bi), iron (Fe), A, D, E, F, cerium (Ce) and oxygen (O ), with respect to 12 molybdenum atoms (Mo), where a is 0.05 to 7, b is 0.1 to 7, c is 0.01 to 5, d is 0.1 to 12, e is 0 to 5, f is 0 to 5, g is 0 to 0.2 h is 0.01 to 5, and n is the number of oxygen atoms required to satisfy the valency requirements of the other component elements gifts.

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In one embodiment of the catalytic composition described above, 0.15 <(a + h) / d <1. In another embodiment of the catalytic composition described above, 0.8 <h / b <5. In yet another embodiment, the diffraction pattern of x-ray of the catalytic composition identified above presents x-ray diffraction peaks at 2Θ angle 28 ± 0.3 degrees and 2Θ angle 26.5 ± 0.3 degrees and if the ratio of the intensity of the x-ray diffraction peak more intense at 2Θ angle 28 ± 0.3 degrees for the intensity of the x-ray diffraction peak more intense at 2Θ angle 26.5 ± 0.3 degrees is defined as X / Y ,, so X / Y is greater or equal to 0.7. In other embodiments independent of the catalytic composition identified above: 0.2 <(a + h) / d <0.6; 0.3 <(a + h) / d <0.5; 1 <h / b <3; 1.5 <h / b <2; X / Y is greater than or equal to 0.8 .; and / or X / Y is greater than or equal to 0.90.

In the realization, (where 0.8 <h / b <5), “h / b” represents the ratio of cerium to iron in the catalyst and, for any catalyst formulation, this ratio is simply the moles of cerium (as represented by the subscript for cerium in the formula) divided by the moles of iron (as represented by the subscript for iron in the formula). It has been observed that the catalysts described by the above formula in which 0.8 <h / b <5 tend to be more resistant since they have less friction loss as determined by a submerged jet friction test.

In the realization, characterized by the x-ray diffraction pattern of the catalytic identified above, showing x-ray diffraction peaks at 2Θ angle 28 ± 0.3 degrees and 2Θ angle 26.5 ± 0.3 degrees and if the intensity ratio from the most intense x-ray diffraction peak at 2Θ angle 28 ± 0.3 degrees to the most intense x-ray diffraction peak at 2Θ angle 26.5 ± 0.3 degrees is defined as X / Y, , then, X / Y is greater than or equal to 0.7, it was observed that such catalysts produce a greater overall conversion in the amoxidation of propylene and / or isobutylene to nitriles (that is, compounds presenting the functional group

8/44 “-CN”, such as acrylonitrile, methacrylonitrile, acetonitrile and hydrogen cyanide.

As used here, the terms "catalytic composition" and "catalyst" are synonymous and used interchangeably.

As used here, a “rare earth element” means at least one of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, scandium and yttrium. As used here, "20" is synonymous with "2 theta".

The catalyst of the present invention can be used or supported or unsupported (i.e., the catalyst can comprise a support). Suitable supports are silica, alumina, zirconium, titania, or mixtures thereof. A support typically functions as a binder for the catalyst and results in a more resistant (i.e., more resistant to friction) catalyst. However, for commercial applications, an appropriate mixture of both the active phase (ie, the catalytic oxide complex described above) and the support is crucial to obtain acceptable activity and hardness (resistance to friction) for the catalyst. Typically, the support comprises between 40 and 60 weight percent of the supported catalyst. In one embodiment of this invention, the support can comprise as little as 30 weight percent of the supported catalyst. In another embodiment of this invention, the support can comprise as much as about 70 weight percent of the supported catalyst.

In one embodiment, the catalyst is supported using a silica sol. Typically, silica sols contain some sodium. In one embodiment, the silica sol contains less than 600 ppm of sodium. In another embodiment, the silica sol contains less than 200 ppm of sodium.

Typically, the average colloidal particle diameter of the silica sol is between about 15 nm and about 50 nm. In an achievement

9/44 of this invention, the average colloidal particle diameter of the silica sol is about 10 nm and can be as low as about 4 nm. In another embodiment of this invention, the average colloidal particle diameter of the silica sol is about 100 nm. In another embodiment of this invention, the average colloidal particle diameter of the silica sol is about 20 nm.

Preparation of the Catalyst.

In one embodiment, the elements in the catalyst composition identified above are combined together in an aqueous catalyst precursor slurry, the aqueous precursor sludge thus obtained is dried to form a catalyst precursor, and the catalyst precursor is calcined in order to form the catalyst. However, the unusual thing about the process of the present invention is as follows:

(i) combining, in an aqueous solution, compounds that are sources of

Bi and Ce, and optionally one or more of Na, K, Rb, Cs, Ca, a rare earth element, Pb, W and Y, in order to form a mixture (i.e., a first mixture), (ii) adding a molybdenum source compound to the mixture (ie, the first mixture) to react with the mixture and form a precipitate slurry, and (iii) combining the precipitate sludge with source compounds of the remaining elements and the remaining molybdenum in the catalyst so as to form the aqueous sludge of the catalyst precursor.

As used herein, the term "source compounds" means 25 compounds that contain and / or provide one or more of the metals for the mixed metal oxide catalyst composition. As used here, the terms "remaining elements" or "remaining elements in the catalyst" refer to those elements and the quantity of those

10/44 elements represented by “A”, “D”, “E”, “F” and “G” in the formula above, which were not included in the first mixture. In one embodiment, some elements can be part of both the first and the second mixture. In addition, as used here, "molybdenum remaining" or "molybdenum remaining in the catalyst" refers to the amount of molybdenum required in the finished catalyst that was not present (ie not included in the preparation of this) in the precipitate slurry. Finally, the sum of the amounts of molybdenum provided in the molybdenum source compounds added in (ii) and (iii) is equal to the total amount of molybdenum present in the catalyst.

In the preparation of the catalyst described here, the source compounds of the remaining elements and the remaining molybdenum which are combined with the precipitate slurry can be combined in any order or combination of such remaining elements and the remaining molybdenum. In one embodiment, a mixture of the source compounds of the remaining elements and the remaining molybdenum is combined with the precipitate slurry to form the aqueous catalyst precursor sludge. In another embodiment, (i) a mixture of the source compounds of the remaining elements is combined with the precipitate slurry, and (ii) the remaining molybdenum source compounds are added separately to the precipitate slurry to form the aqueous catalyst precursor sludge. . The order of addition is not critical. In another embodiment, the source compounds of the remaining elements and the remaining molybdenum are added individually (i.e., one by one) to the precipitate slurry.

In another embodiment, multiple mixtures (that is, more than one) of source compounds of the remaining elements and of the remaining molybdenum, where each mixture contains one or more of the source compounds of the remaining elements or of the remaining molybdenum, are added separately (i.e., one mixture at a time or multiple mixtures added simultaneously) to the precipitate slurry to form the aqueous catalyst precursor sludge. In yet another embodiment, a mixture of

11/44 source compounds of the remaining elements are combined with a molybdenum source compound and the resulting mixture is then added to the precipitate slurry to form the catalyst precursor sludge. In yet another embodiment, the support is silica (S1O2) and the silica is combined with a source compound for the remaining molybdenum before combining the remaining molybdenum with the precipitate slurry (ie, silica and a source compound for the remaining molybdenum are used). combined to form a mixture, and then this mixture is added to the precipitate slurry, individually or in combination with one or more source compounds of the remaining elements).

In the preparation of the catalyst described here, molybdenum is added both in the preparation of the precipitate slurry and in the preparation of the aqueous catalyst precursor sludge. At the atomic level, the minimum amount of molybdenum added to form the precipitate slurry is determined by the following relationship:

Mo = 1.5 (Bi + Ce) + 0.5 (Rb + Na + K + Cs) + (Ca) + 1.5 (sum of the atoms of the rare earth elements) + (Pb) + 3 ( W) + 1.5 (Y)

Where in the above list "Mo * is the number of molybdenum atoms to be added to the first mixture, and" Bi "," Ce "," Rb "," Na "," K "," Cs "," Ca ", "Pb", "W" and "Y" is the number of atoms of bismuth, cerium, rubidium, sodium, potassium, cesium, calcium, lead, tungsten and yttrium, respectively, present in the first mixture.

Typically, the amount of molybdenum added to the first mixture to form the sludge of precipitates is about 20 to 35% of the total molybdenum in the final catalyst. In one embodiment, a source compound for the remaining molybdenum present in the catalyst is added to the mixture of the source compounds of the remaining elements (ie, the second mixture) before combining the mixture of the remaining elements with the precipitate slurry to form the

12/44 catalyst precursor slurry. In other embodiments, a molybdenum source compound containing the remaining molybdenum present in the catalyst is added to the precipitate slurry or before, after or simultaneously with, the mixture of the source compounds of the remaining elements (ie the second mixture) in a manner forming the catalyst precursor slurry.

In the present preparation, the source compounds of Bi and Ce, and optionally one or more of Na, K, Rb, Cs, Ca, a rare earth element, Pb, W and Y, when combined in an aqueous solution to form a mix. In one embodiment, bismuth nitrate and optionally other metallic nitrates (ie, Na, K, Rb, Cs, Ca nitrates, a rare earth element, Pb, W and / or Y) are dissolved in an aqueous solution before ceric ammonium nitrate.

A molybdenum source compound is added to the mixture with 15 comprising bismuth and cerium (and optionally one or more of Na, K, Rb, Cs, Ca, a rare earth element, Pb, W and Y). In one embodiment, this molybdenum source compound is ammonium heptamolybdate dissolved in water. By adding the molybdenum source compound to the mixture comprising bismuth and cerium, a reaction will occur which results in a precipitate and the resulting mixture is the precipitate slurry.

The precipitate slurry is then combined with a mixture of the source compound of the remaining catalyst elements and a molybdenum source compound to form the aqueous catalyst precursor slurry. The mixture of source compounds from the remaining elements and a molybdenum source compound can be prepared by combining source compounds from the remaining elements in an aqueous solution (for example, the source compounds are combined in water) and then adding a source compound. of molybdenum. In one embodiment, this molybdenum source compound is ammonium heptamolybdate dissolved in water. When combining the precipitate mud

13/44 with the remaining elements / molybdenum mixture, the order of addition is not important, that is, the precipitate slurry can be added to the remaining elements / molybdenum mixture or the remaining elements / molybdenum mixture can be added to the sludge. precipitated. The aqueous sludge of catalyst precursor is maintained at an elevated temperature.

The amount of aqueous solvent in each of the mixtures and aqueous sludges described above may vary due to the solubilities of the source compounds combined to form the particular mixed metal oxide. The amount of aqueous solvent must be at least sufficient to produce a slurry or mixture of solids and liquids that is capable of being stirred.

In any case, the source compounds are preferably combined and / or reacted by a protocol that comprises mixing the source compounds during the combination and / or reaction step. The particular mixing mechanism is not critical, and may include, for example, mixing (for example, by stirring) the components during the reaction by any effective method. Such methods include, for example, shaking the contents of the vessel, for example, by shaking, beating or oscillating the vessel containing the components. Such methods also include, for example, agitation by the use of a stirring member located at least partially within the reaction vessel and a driving force coupled to the stirring member or reaction vessel in order to provide movement between the stirring member and the reaction vessel. The stirring member can be an axis driven and / or shaft supported stirring member. The actuation force can be directly coupled to the stirring member or it can be indirectly coupled to the stirring member (for example, by means of magnetic coupling). The mixture is in general preferably sufficient to mix the components to allow an efficient reaction between the components of the reaction medium in order to form a reaction medium

14/44 more homogeneous (for example, and resulting in a more homogeneous mixed metal oxide precursor) compared to an unmixed reaction. This results in a more efficient consumption of the starting materials and a more uniform mixed metal oxide product. Mixing the precipitate slurry during the reaction step also causes the precipitate to be formed in solution instead of on the sides of the rational vessel. More advantageously, the formation of the precipitate in solution allows the growth of the particle on all faces of the particle rather than limited to the exposed faces, when the growth occurs outside the reaction vessel wall.

A molybdenum source compound may include molybdenum (VI) oxide (ΜοΟβ), ammonium heptamolybdate or molybdic acid. The molybdenum source compound can be introduced from any molybdenum oxide such as dioxide, trioxide, pentoxide or heptaoxide.

However, it is preferable that a hydrolyzable or decomposable molybdenum salt is used as the source compound of molybdenum.

Typical source compounds for bismuth, cerium and remaining catalyst elements are nitrate salts of the metals. Such nitrate salts are readily available and easily soluble.

A bismuth source compound can include an oxide or a salt which, upon calcination, produces the oxide. Water-soluble salts that are easily dispersed, and which form stable oxides by heat treatment are preferred. In one embodiment, the source compound of bismuth is bismuth nitrate, Bi (NO3) 3.5H2O.

A cerium source compound can include an oxide or a salt which, upon calcination, produces the oxide. Water-soluble salts that are easily dispersed and form stable oxides by heat treatment are preferred. In one embodiment, the cerium source compound is ceric ammonium nitrate, (NH4) 2Ce (NO3) 615/44

An iron source compound can be obtained from any iron compound which, upon calcination, results in the oxide. As for the other elements, water-soluble salts are preferred because of the ease that they can be uniformly dispersed in the catalyst. The most preferred is ferric nitrate.

The source compounds for the remaining elements can be derived from any suitable source. For example, cobalt, nickel and magnesium can be introduced into the catalyst using nitrate salts. In addition, magnesium can be introduced into the catalyst as an insoluble carbonate or hydroxide which by heat treatment results in an oxide. Phosphorus can be introduced into the catalyst as an alkali metal salt or alkaline earth metal salt or ammonium salt, but it is preferably introduced as phosphoric acid.

The source compounds for the alkaline components of the catalyst can be introduced into the catalyst as an oxide or as a salt which by calcination produces the oxide.

Solvents, in addition to water, can be used to prepare the mixed metal oxides according to the invention include, but are not limited to, alcohols such as methanol, ethanol, propanol, diols (e.g. ethylene glycol, propylene glycol, etc. .), organic acids such as acetic acid, as well as other polar solvents known in the art. The metallic source compounds are at least partially soluble in the solvent.

As previously noted, the catalyst of the present invention can be used or supported or unsupported (i.e., the catalyst can comprise a support). Suitable supports are silica, alumina, zirconium, titania, or mixtures thereof. The point of addition of the support is not critical in the preparation of the catalyst. The support can be added at any time before the catalyst precursor slurry is dried. The support can be added at any time during or after the preparation of any mixture of elements, the precipitate slurry or the catalyst precursor sludge. In addition, support does not need to be added at a single point or stage, that is, support can be added at multiple points in preparation. In one embodiment, the support is combined with the other ingredients during the preparation of the aqueous catalyst precursor slurry. In one embodiment, the support is added to the precipitate slurry (i.e., after the precipitate sludge is prepared). In one embodiment, the support is combined with the molybdenum source compound before combining the molybdenum source compound with the source compounds of the remaining elements in the catalyst in order to form the "second mixture" mentioned above.

The catalyst precursor slurry is dried and denitrified (i.e., removal of nitrates) to produce the catalyst precursor. Preferably, the catalyst precursor slurry is spray dried and at a temperature between 110 ° C and 350 ° C as the dryer outlet temperature, preferably between 110 ° C and 250 ° C, more preferably between 110 ° C and 180 ° Ç. the denitrification temperature can vary from 100 ° C to 500 ° C, preferably 250 ° C to 450 ° C.

Finally, the dry catalyst precursor is calcined. In one embodiment, the calcination is carried out in air. In another embodiment, the calcination is carried out in an inert atmosphere, such as nitrogen.

Preferred calcination conditions include temperatures ranging from about 300 ° C to about 700 ° C, more preferably from about 350 ° C to about 650 ° C, and in some embodiments, the calcination can be at about 600 ° Ç.

The catalysts of the present invention can be prepared by any of the numerous catalyst preparation methods

17/44 known to those skilled in the art. In one embodiment, the components of the catalyst can be mixed with a support in the form of the sludge followed by drying or the components of the catalyst can be impregnated in silica or other supports.

Amoxidation Process:

The catalysts of the present invention are useful in amoxidation processes for the conversion of an oleine selected from the group consisting of propylene, isobutylene or mixtures thereof to acrylonitrile, methacrylonitrile and mixtures thereof, respectively, by reaction in vapor phase at a high temperature and pressure of said olefin with a gas containing molecular oxygen and ammonia in the presence of the catalyst. The catalysts of the present invention are also useful for the amoxidation of methanol to hydrogen cyanide and the amoxidation of ethanol to acetonitrile. In an embodiment employing the catalysts described here, methanol and / or ethanol can be co-fed in a process for the amoxidation of propylene, isobutylene or mixtures of these to acrylonitrile, methacrylonitrile or mixtures thereof, in order to increase the production of the co-products hydrogen cyanide and / or acetonitrile resulting from such a process.

Preferably, the amoxidation reaction is carried out in a fluidized bed although other types of reactors such as conveyor line reactors can be used. Fluidized bed reactors for the manufacture of acrylonitrile are well known in the art. For example, the reactor design shown in the US Patent

3,230,246, incorporated herein by reference, is adequate.

The conditions for the amoxidation reaction to occur are also well known in the state of the art as evidenced by US Patents 5,093,299, 4,863,891, 4,767,878 and 4,503,001, incorporated herein by reference. Typically, the amoxidation process is carried out

18/44 by contact of propylene or isobutylene in the presence of ammonia and oxygen with a fluidized bed catalyst at an elevated temperature to produce acrylonitrile or methacrylonitrile. Any source of oxygen can be used. For economic reasons, however, it is preferable to use air. The typical molar ratio of oxygen to olefin in the feed should range from 0.5: 1 to 4: 1, preferably from 1: 1 to 3: 1.

The molar ratio of ammonia to olefin in the feed in the reaction can vary between 0.5: 1 and 2: 1. There is actually no upper limit for the ammonia-olein ratio, however there is no reason to exceed 2: 1 for economic reasons. Feed ratios suitable for use with the catalyst of the present invention for the production of acrylonitrile from propylene are an ammonia to propylene ratio in the range of 0.9: 1 to 1.3: 1, and air to propylene ratio of 8.0: 1 to 12.0: 1. The catalyst of the present invention is capable of providing high yields of acrylonitrile at relatively low feed rates of ammonia to propylene from about 1: 1 to about 1.05: 1. These "low ammonia conditions" help to reduce unreacted ammonia in the reactor effluent, a condition known as "ammonia breakthrough", which subsequently helps to reduce process losses. Specifically, unreacted ammonia must be removed from the reactor effluent before recovery of acrylonitrile. Unreacted ammonia is typically removed by contacting the reactor effluent with sulfuric acid to obtain ammonium sulfate or by contacting the reactor effluent with acrylic acid to obtain ammonium acrylate, which in both cases results in a current of refuse to be treated and / or discarded.

The reaction is conducted at a temperature in the range of about 260 ° to 600 ° C, with preferred ranges from 310 ° to 500 ° C, especially preferred being 350 ° to 480 ° C. The contact time, although not critical, is generally in the range of 0.1 to 50 seconds, with preference for a contact time of 1 to 15 seconds.

19/44

The reaction products can be recovered and purified by any of the methods known to those skilled in the art. One such method involves washing the effluent gases from the reactor with cold water or an appropriate solvent to remove the reaction products and then purifying the reaction product by distillation.

The primary utility of the catalyst prepared by the process of the present invention is for the amoxidation of propylene to acrylonitrile. Other uses include amoxidation from propane to acrylonitrile and amoxidation from ethanol to acetonitrile. The catalyst prepared by the process of the present invention can also be used for the oxidation of propylene to acrylic acid. Such processes are typically two-stage processes, where propylene is converted in the presence of a catalyst primarily to acrolein in the first stage and acrolein is converted in the presence of a catalyst to primarily acrylic acid in the second stage. The catalyst described here is suitable for use in the first stage for the oxidation of propylene to acrolein.

Specific Achievements

In order to illustrate the present invention, catalysts prepared according to the present invention have been evaluated and compared under reaction conditions similar to similar catalysts prepared by prior art methods outside the scope of the present invention. These examples are provided for illustrative purposes only.

Catalysts featuring the composition of

Cso, iKo, iNÍ5Mg2Nao, o5Fei, 8Bio, 45Cei, iMoi2,55050,35 + 45% by weight of S1O2 were prepared by various preparation methods as described below and tested in a bench scale reactor for the propylene to acrylonitrile amoxidation . All tests were conducted in

20/44 a 40 cc fluidized bed reactor. Propylene was fed into the reactor at a rate of 0.06 WWH (i.e., propylene weight / catalyst weight / hour). The pressure inside the reactor was maintained at 10 psig.

The reaction temperature was 430 ° C. After a stabilization period of ~ 20 hours or more, samples of the reaction products were collected. The effluent from the reactor was collected in bubble washers containing a cold HCI solution. The output gas rate was measured with a soap film meter and the output gas composition was determined at the end of the run with the aid of a gas chromatograph equipped with a split column gas analyzer analyzef '). At the end of the recovery run, all the washing liquid was diluted to approximately 200 g with distilled water. A heavy amount of 2-butanone was used as an internal standard in an ~ 50 gram aliquot of the diluted solution. A 2 μΐ sample was analyzed in a GC equipped with a flame ionization detector and a Carbowax column. The amount of NH3 was determined by titrating the excess free HCI with a NaOH solution.

Comparative Example C1: Conventional Method

Reaction mixture A was prepared by heating 224 ml of deionized water to 65 ° C and then adding under stirring for 30 minutes ammonium heptamolybdate (203.75 g) to form a colorless solution. Silica sol (625 g, 32.5% silica by weight) was then added with stirring.

Reaction mixture B was prepared by heating 30 ml of deionized water to 55 ° C and then adding with stirring Fe (NO ₃ ) ₃ .9H ₂ O (66.9 g), Ni (NO ₃ ) ₂ . 6H ₂ 0 (133.7 g), Mg (NO ₃ ) ₂ .6H ₂ 0 (47.2 g), Bi (NO ₃ ) ₃ .5H ₂ O (20.1 g), CsNO ₃ (1.79 g), KNOs (0.93 g), and NaNO ₃ (0.39 g).

21/44

Then, 110.0 g of a 50% by weight aqueous solution of (NH4) 2Ce (NO3) 6 were added with stirring.

Reaction mixture B was then added to reaction mixture A with stirring to form the catalyst precursor slurry. The catalyst precursor slurry was left under stirring for one hour, while it was cooled to approximately 40 ° C. It was then homogenized in a mixer for 3 minutes at 5,000 rpm. The sludge was then spray dried in a dry spray at an inlet / outlet temperature of 325/140 ° C. The resulting powder hurts denitrified by heat treatment for 3 hours in air at 290 ° C, followed by an additional 3 hours at 425 ° C. The powder was then calcined in air at 560 ° C for 3 hours. The resulting calcined powder was then tested as a propylene amoxidation catalyst in a 40 cc micro-reactor. The test results are shown in Table 1.

Comparative Example C2; Prepared according to the US Patent

4,212,766 (that is, without Bi-Ce-Mo precipitate slurry formed as a separate step)

Reaction mixture A was prepared by heating 233 ml of deionized water to 65 ° C and then adding under stirring for 30 minutes ammonium heptamolybdate (212.1 g) to form a colorless solution. Silica sol (692 g, 32.5% silica by weight) was then added with stirring.

Reaction mixture B was prepared by heating 33 ml of deionized water to 55 ° C and then adding sequentially with stirring Fe (NO ₃ ) ₃ .9H ₂ O (73.6 g), Ni (NO ₃ ) ₂ .6H ₂ O (147.1 g), Mg (NO ₃ ) ₂ .6H ₂ O (51.9 g), CsNOs (1.97 g), KNO ₃ (1.02 g), NaN0 ₃ (0, 43 g), and 122.0 g of a 50% by weight aqueous solution of (NH4) ₂ Ce (NO ₃ ) ó.

Reaction mixture C was prepared by heating 152 ml of deionized water to 65 ° C and then adding under stirring for 30

22/44 minutes of ammonium heptamolybdate (12.1 g) in order to form a colorless solution.

The reaction mixture D was prepared by dissolving Bi (NO ₃ ) 3.5H ₂ O (22.1 g) in 160 g of a 10% by weight aqueous solution of HNO ₃ .

Reaction mixture E was prepared by adding with stirring reaction mixture B with reaction mixture A.

Reaction mixture F was prepared by adding reaction mixture D with reaction mixture C. This resulted in the precipitation of a colorless solid. Stirring was continued for 15 minutes while the temperature was maintained in the range of 50-55 ° C.

The reaction mixture F was then added to the reaction mixture E in order to form the final catalyst precursor slurry.

The catalyst precursor slurry was left under stirring for one hour while being cooled to approximately 40 ° C. It was then homogenized in a mixer for 3 minutes at 5,000 rpm. The sludge was then spray dried in a dry spray at an inlet / outlet temperature of 325/140 ° C. The resulting powder was denitrified by heat treatment for 3 hours in air at

290 ° C, followed by an additional 3 hours at 425 ° C. The powder was then calcined in air at 560 ° C for 3 hours. The resulting calcined powder was then tested as a propylene amoxidation catalyst in a 40 cc micro reactor. The test results are shown in Table 1.

Example 1: Prepared according to the Invention

Reaction mixture A was prepared by heating 198 ml of deionized water to 65 ° C and then adding under stirring for 30 minutes ammonium heptamolybdate (180.4 g) to form

23/44 a colorless solution. Silica sol (692 g, 32.5% silica by weight) was then added with stirring.

Reaction mixture B was prepared by heating 33 ml of deionized water to 55 ° C and then adding with stirring

Fe (NO ₃ ) ₃ .9H ₂ O (73.6 g), Ni (NO ₃ ) 2.6H ₂ O (147.1 g), and Mg (NO ₃ ) ₂ .6H ₂ O (51.9

g) ·

The reaction mixture C was prepared by heating 48 ml of deionized water to 65 ° C and then adding under stirring for 30 minutes ammonium heptamolybdate (43.75 g) to form a colorless solution.

Reaction mixture D was prepared by (i) heating 122.0 g of a 50% by weight aqueous solution of (NH4) 2Ce (NO ₃ ) õ to 55 ° C, and (ii) while the solution was under stirring and heating, Bi (NO ₃ ) ₃ .5H2O (22.1 g), CsNO ₃ (1.97 g), KNO ₃ (1.02 g), and NaNO ₃ (0.43 g) were added sequentially, resulting in a clear orange solution.

Reaction mixture E was prepared by adding stirring reaction mixture B to reaction mixture A.

Reaction mixture F was prepared by adding reaction mixture C to reaction mixture D. This resulted in the precipitation of an orange solid. The resulting mixture was the precipitate slurry. The stirring of reaction mixture F was maintained for 15 minutes while the temperature was maintained in the range of 50-55 ° C.

The reaction mixture F was then added to the reaction mixture E in order to form the final catalyst precursor slurry.

The catalyst precursor slurry was left under stirring for one hour while being cooled to approximately 40 ° C. It was then homogenized in a mixer for 3 minutes at 5,000

24/44 rpm. The sludge was then spray dried in a dry spray at an inlet / outlet temperature of 325/140 ° C. The resulting powder was denitrified by heat treatment for 3 hours in air at 290 ° C, followed by an additional 3 hours at 425 ° C. The powder was then calcined in air at 560 ° C for 3 hours. The resulting calcined powder was then tested as a propylene amoxidation catalyst in a 40 cc micro-reactor. The test results are shown in Table 1.

Example 2: Prepared according to the Invention

Reaction mixture A was prepared by heating 198 ml 10 of deionized water to 65 ° C and then adding under stirring for 30 minutes ammonium heptamolybdate (180.4 g) to form a colorless solution.

Reaction mixture B was prepared by heating 3 ml of deionized water to 55 ° C and then adding with stirring

Fe (NO ₃ ) ₃ .H ₂ O (73.6 g), Ni (NO ₃ ) 2.6H ₂ O (147.1 g), and Mg (NO ₃ ) ₂ .6H ₂ O (51.9

g) ·

The reaction mixture C was prepared by heating 48 ml of deionized water to 65 ° C and then adding under stirring for 30 minutes ammonium heptamolybdate (43.75 g) to form a colorless solution.

Reaction mixture D was prepared by (i) heating 122.0 g of a 50% by weight aqueous solution of (NH4) ₂ Ce (NO ₃ ) ô to 55 ° C, (ii) while the solution was under stirring and heating, sequential addition of Bi (NO ₃ ) ₃ .5H ₂ O (22.1 g), CsNO ₃ (1.97 g), KNO ₃ (1.02 g), and

NaNO ₃ (0.43 g), resulting in a light orange solution.

Reaction mixture E was prepared by adding stirring reaction mixture B to reaction mixture A.

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Reaction mixture F was prepared by (i) adding reaction mixture C to reaction mixture D, which resulted in the precipitation of an orange solid (this resulting mixture was then the precipitate sludge), (ii) stirring of the precipitate slurry was maintained for 15 minutes while the temperature was maintained in the range of 50-55 ° C, and (iii) addition with stirring of silica sol (692 g, 32.5% by weight of silica).

Reaction mixture E was then added to reaction mixture F to form the final catalyst precursor slurry.

The catalyst precursor slurry was left under stirring 10 for one hour while being cooled to approximately 40 ° C. It was then homogenized in a mixer for 3 minutes at 5,000 rpm. The sludge was then spray dried in a dry spray at an inlet / outlet temperature of 325/140 ° C. The resulting powder was denitrified by heat treatment for 3 hours in air at

290 ° C, followed by an additional 3 hours at 425 ° C. The powder was then calcined in air at 560 ° C for 3 hours. The resulting calcined powder was then tested as a propylene amoxidation catalyst in a 40 cc micro-reactor. The test results are shown in Table 1.

26/44

Table 1

Catalyst Comparison

Cso, iKo, iNÍ5Mg2Nao, 05Fei, 8Bio, 45Cei, iMoi2,5505o, 35 + 45% by weight of SiO2 Prepared by Different Methods

Example HOS C ₃ = Total Conv. Conv. for AN Conv. for HCN Conv. for AN and HCN Cl 160 96.3 80.4 5.2 85.6 C2 97 99.0 81.1 4.5 85.6 1 150 98.6 80.9 5.6 86.6 2 161 98.8 81.9 5.8 87.7

Grades:

1. All test catalyst compositions contained 55 wt% active phase and 45 wt% low 22 nm Na S1O2.

2. “HOS” is “current hours, that is, the amount of time the catalyst has been evaluated under the test conditions.

3. “C3 ⁼ Total Conv.” is the mol% per conversion passage of propylene to all products.

4. “Conv. the AN ”is the mol% per conversion passage from propylene to acrylonitrile.

5. “Conv. HCN ”is the mol% per conversion passage from propylene to 15 hydrogen cyanide.

6. “Conv. AN and HCN ”is the mol% per conversion passage from propylene to acrylonitrile and hydrogen cyanide.

27/44

As can be seen in Table 1, the catalyst compositions prepared by the method of the present invention, exhibit higher conversions to acrylonitrile and HCN when propylene was subjected to amoxidation on such a catalyst at elevated temperatures in the presence of ammonia and air compared to catalysts identical prepared by methods outside the scope of the present invention.

In order to illustrate the present invention, catalysts with compositions within the scope of the present invention (Examples 3 to 7) were prepared and evaluated and compared under similar reaction conditions with similar catalysts with compositions outside the scope of the present invention (Comparative Examples C3 to C7). These examples are provided by way of illustration only.

Comparative Example 3 - C-49MC Catalyst for Acrylonitrile

The test results and other data are shown in Table 2 for Catalyst C-49MC for Acrylonitrile. “C-49MC Catalyst” is the product designation for the commercial catalyst manufactured and marketed by INEOS USA LLC. The composition of the C49MC Catalyst is a trade secret of INEOS USA LLC. “C-49MC” is a trademark of INEOS USA LLC.

Comparative Example C4 NÍ7,5Mg3Fei, 8Rbo, i2Cro, iBio, 45Cei, iMoi5,85063,835 + 50% by weight 27 ppm

Na, S1O2 39 nm

Reaction mixture A was prepared by heating 225.1 ml of deionized water to 65 ° C and then adding under stirring for

30 minutes of ammonium heptamolybdate (204.6 g) in order to form a colorless solution. Silica sol (27 ppm Na, 39 nm average particle size, 595.2 g, 42 wt% silica) was then added with stirring.

28/44

Reaction mixture B was prepared by heating 32.2 ml of deionized water to 55 ° C and then adding with stirring Fe (NO ₃ ) ₃ .9H ₂ 0 (53.2 g), Ni (NO ₃ ) ₂ .6H ₂ 0 (159.5 g), Mg (NO ₃ ) ₂ .6H ₂ O (56.2 g), Bi (NO ₃ ) s.5H ₂ O (16 g), Cr (NO ₃ ) ₃ .9H ₂ O (2.9 g) and RbNOs (1.3 g).

88.2 g of a 50% by weight aqueous solution of (NH4) ₂ Ce (NO ₃ ) ô was added to solution B followed by the addition of this resulting mixture to solution A with mixing at ~ 55 ° C for one hour followed by if cooling to 40 ° C. The resulting catalyst slurry was then homogenized for 3 minutes at 5,000 rpm. The sludge was then spray dried in a dry spray at an inlet / outlet temperature of 325/140 ° C. The resulting powder was denitrified by heat treatment for 3 hours in air at 290 ° C, 3 hours in air at 425 ° C and then calcined in air at 560 ° C for 3 hours. The resulting calcined powder was then tested as a propylene amoxidation catalyst.

The test results are shown in Table 2.

Comparative Example C5 NÍT.sMgsFei.sRbo. ^ Cro.iBio ^ sCei.iMois.esOós.ess + 50% by weight of SiO ₂

Reaction mixture A was prepared by heating 191.1 ml of deionized water to 65 ° C and then adding under stirring for

30 minutes of ammonium heptamolybdate (173.8 g) in order to form a colorless solution. Silica sol (27 ppm Na, 39 nm average particle size, 595.2 g, 42 wt% silica) was then added with stirring.

Reaction mixture B was prepared by heating 32.1 ml of deionized water to 55 ° C and then adding with stirring Fe (NO ₃ ) 3.9H ₂ O (53.2 g), Ni (NO ₃ ) ₂ .6H ₂ O (159.5 g), Mg (NO ₃ ) ₂ .6H ₂ O (56.2 g) and Cr (NO ₃ ) ₃ .9H ₂ O (2.9 g).

Reaction mixture C was prepared by heating 33.9 ml of deionized water to 65 ° C and then adding under stirring for 30

29/44 minutes of ammonium heptamolybdate (30.8 g) in order to form a colorless solution.

Reaction mixture D was prepared by (i) heating 88.2 g of a 50% by weight aqueous solution of (NH4) 2Ce (NO3) to 55 ° C, and (ii) while the solution was under stirring and heating, sequential addition of Bi (NO3) 3 ^- 5H2O (16 g) and RbNCb (1.3 g) resulting in a light orange solution.

Reaction mixture E was prepared by adding stirring reaction mixture B to reaction mixture A.

Reaction mixture F was prepared by adding reaction mixture C to reaction mixture D. This resulted in the precipitation of an orange solid. The resulting mixture was the precipitate slurry. The stirring of reaction mixture F was maintained for 15 minutes while the temperature was maintained in the range of 50-55 ° C.

The reaction mixture F was then added to the reaction mixture

And in order to form the final catalyst precursor sludge.

The catalyst precursor slurry was left under stirring for one hour while being cooled to approximately 40 ° C. It was then homogenized in a mixer for 3 minutes at 5,000 rpm. The sludge was then spray dried in a dry spray at an inlet / outlet temperature of 325/140 ° C. The resulting powder was denitrified by heat treatment for 3 hours in air at 290 ° C, 3 hours in air at 425 ° C and then calcined in air at 560 ° C for 3 hours. The resulting calcined powder was then tested as a propylene amoxidation catalyst. The test results are shown in Table 2.

Comparative Example C6 NÍ5Mg2Fei, 8Rbo.i2Cro, iBio, 45Cei, iMoi2,35O4g, 835 + 50% S1O2

30/44

Reaction mixture A was prepared by heating 1619.7 ml of deionized water to 65 ° C and then adding under stirring for 30 minutes ammonium heptamolybdate (1472.5 g) to form a colorless solution. Silica sol (27 ppm Na, 39 nm average particle size, 5357.1 g, 42 wt% silica) was then added with stirring.

Reaction mixture B was prepared by heating 276.2 ml of deionized water to 55 ° C and then adding with stirring Fe (NO ₃ ) ₃ .9H ₂ O (608.6 g), Ni (NO ₃ ) ₂ .6H ₂ O (1216.8 g), Mg (NO ₃ ) ₂ .6H ₂ O (429.2 g) and Cr (NO ₃ ) ₃ -9H ₂ O (33.5 g).

The reaction mixture C was prepared by heating 387.7 ml of deionized water to 65 ° C and then adding under stirring for 30 minutes ammonium heptamolybdate (352.4 g) to form a colorless solution.

Reaction mixture D was prepared by (i) heating of

1009.4 g of a 50% by weight aqueous solution of (NH4) ₂ Ce (NO ₃ ) ô to 55 ° C, and (ii) while the solution was under stirring and heating, sequential addition of Bi (NO ₃ ) ₃ .5H ₂ O (182.7g) and RbN0 ₃ (14.8 g) resulting in a light orange solution.

Reaction mixture E was prepared by adding stirring reaction mixture B to reaction mixture A.

Reaction mixture F was prepared by adding reaction mixture C to reaction mixture D. This resulted in the precipitation of an orange solid. The resulting mixture was the precipitate slurry.

The stirring of reaction mixture F was maintained for 15 minutes while the temperature was maintained in the range of 50-55 ° C.

The reaction mixture F was then added to the reaction mixture E in order to form the final catalyst precursor slurry.

31/44

The catalyst precursor slurry was left under stirring for one hour while being cooled to approximately 40 ° C. It was then homogenized in a mixer for 3 minutes at 5,000 rpm. The sludge was then spray dried in a dry spray at an inlet / outlet temperature of 325/140 ° C. The resulting powder was denitrified by heat treatment for 3 hours in air at 290 ° C, 3 hours in air at 425 ° C and then calcined in air at 560 ° C for 3 hours. The resulting calcined powder was then tested as a propylene amoxidation catalyst. The test results are shown in the

Table 2.

Comparative Example C7 NÍ4Mg3Fei, 8Rbo.i92Cro, iBio, 45Cei, iMoi2,386049,979 + 50% by weight of S1O2

Reaction mixture A was prepared by heating 181.5 ml of deionized water to 65 ° C and then adding under stirring for

30 minutes of ammonium heptamolybdate (165 g) in order to form a clear colorless solution. Silica sol (90 ppm Na, 39.2 nm average particle size, 606.8 g, 41.2 wt% silica) was then added with stirring.

Reaction mixture B was prepared by heating 30.7 ml of deionized water to 55 ° C and then adding with stirring Fe (NO ₃ ) 3.9H ₂ O (68.2 g), Ni (NO ₃ ) ₂ .6H ₂ 0 (109.1 g), Mg (NO ₃ ) 2.6H ₂ O (72.1 g) and Cr (NO ₃ ) 3.9H ₂ O (3.8 g).

Reaction mixture C was prepared by heating 44.1 ml of deionized water to 65 ° C and then adding with stirring for 30 minutes ammonium heptamolybdate (40.1 g) to form a colorless solution.

Reaction mixture D was prepared by (i) heating 113.1 g of a 50% by weight aqueous solution of (NH ₄ ) 2Ce (NO3) 6 to 55 ° C, and (ii) while the solution was under stirring and heating, addition

32/44 sequential Βΐ (Νθ3) 3 · 5Η2θ (20.5 g) and RbNO3 (2.7 g) resulting in a light orange solution.

Reaction mixture E was prepared by adding stirring reaction mixture B to reaction mixture A.

Reaction mixture F was prepared by adding reaction mixture C to reaction mixture D. This resulted in the precipitation of an orange solid. The resulting mixture was the precipitate slurry. The stirring of reaction mixture F was maintained for 15 minutes while the temperature was maintained in the range of 50-55 ° C.

The reaction mixture F was then added to the reaction mixture

And in order to form the final catalyst precursor sludge.

The catalyst precursor slurry was left under stirring for one hour while being cooled to approximately 40 ° C. It was then homogenized in a mixer for 3 minutes at 5,000 rpm. The sludge was then spray dried in a dry spray at an inlet / outlet temperature of 325/140 ° C. The resulting powder was denitrified by heat treatment for 3 hours in air at 290 ° C, 3 hours in air at 425 ° C and then calcined in air at 560 ° C for 3 hours. The resulting calcined powder was then tested as a propylene amoxidation catalyst. The test results are shown in Table 2.

Example 3 - NÍ4Mg3Feo, 9Rbo, i92Cro, o5Bio, 72Cei, 76Moi2,80605i, 539 + 50% by weight of S1O2

Reaction mixture A was prepared by heating 154.5 ml of deionized water to 65 ° C and then adding under stirring for 30 minutes ammonium heptamolybdate (140.4 g) to form a colorless solution. Silica sol (27 ppm Na, 39 nm average particle size, 595.2 g, 42 wt% silica) was then added33 / 44 with stirring.

Reaction mixture B was prepared by heating 26.5 ml of deionized water to 55 ° C and then adding with stirring Fe (NO ₃ ) ₃ .9H ₂ O (32.2 g), Ni (NO ₃ ) ₂ .6H ₂ O (102.9 g), Mg (NO ₃ ) ₂ .6H ₂ O (68 g) and

Cr (NO ₃ ) ₃ .9H ₂ O (1.8 g).

Reaction mixture C was prepared by heating 65.5 ml of deionized water to 65 ° C and then adding under stirring for 30 minutes ammonium heptamolybdate (59.6 g) to form a colorless solution.

Reaction mixture D was prepared by (i) heating 170.6 g of a 50% by weight aqueous solution of (NH4) ₂ Ce (NO ₃ ) ô to 55 ° C, and (ii) while the solution was under stirring and heating, sequential addition of Bi (NO ₃ ) ₃ .5H ₂ O (30.9 g) and RbNO ₃ (2.5 g) resulting in a light orange solution.

Reaction mixture E was prepared by adding stirring reaction mixture B to reaction mixture A.

Reaction mixture F was prepared by adding reaction mixture C to reaction mixture D. This resulted in the precipitation of an orange solid. The resulting mixture was the precipitate slurry.

The stirring of reaction mixture F was maintained for 15 minutes while the temperature was maintained in the range of 50-55 ° C.

The reaction mixture F was then added to the reaction mixture E in order to form the final catalyst precursor slurry.

The catalyst precursor slurry was left under stirring for one hour while being cooled to approximately 40 ° C. It was then homogenized in a mixer for 3 minutes at 5,000 rpm. The sludge was then spray-dried in a

34/44 dry at an inlet / outlet temperature of 325/140 ° C. The resulting powder was denitrified by heat treatment for 3 hours in air at 290 ° C, 3 hours in air at 425 ° C and then calcined in air at 560 ° C for 3 hours. The resulting calcined powder was then tested as a propylene amoxidation catalyst. The test results are shown in Table 2.

Example 4 - NÍ4Mg ₃ Feo, 9Rbo, i9 ₂ Cro, o5Bio, 72Cei, 76Moi ₂₎ 335050, i ₂ 6 + 50% by weight of SiO ₂

Reaction Mixture A was prepared by heating 149.9 ml of deionized water to 65 ° C and then adding under stirring for 30 minutes ammonium heptamolybdate (136.3 g) to form a colorless solution. Silica sol (27 ppm Na, 39 nm average particle size, 595.2 g, 42 wt% silica) was then added with stirring.

Reaction mixture B was prepared by heating 27.1 ml of deionized water to 55 ° C and then adding with stirring Fe (NO ₃ ) 3.9H ₂ O (32.9 g), Ni (NO ₃ ) ₂ .6H ₂ O (105.4 g), Mg (NO ₃ ) ₂ .6H ₂ O (69.7 g) and Cr (NO ₃ ) ₃ .9H ₂ O (1.8 g).

Reaction mixture C was prepared by heating 67.1 ml of deionized water to 65 ° C and then adding under stirring for 30 minutes ammonium heptamolybdate (61 g) to form a colorless solution.

Reaction mixture D was prepared by (i) heating 174.8 g of a 50% by weight aqueous solution of (NH4) ₂ Ce (NO ₃ ) 6 to 55 ° C, and (ii) while the solution was under stirring and heating, sequential addition of Bi (NO ₃ ) ₃ .5H ₂ O (31.6 g) and RbNO ₃ (2.6 g) resulting in a light orange solution.

Reaction mixture E was prepared by adding with stirring the

35/44 reaction mixture B to reaction mixture A.

Reaction mixture F was prepared by adding reaction mixture C to reaction mixture D. This resulted in the precipitation of an orange solid. The resulting mixture was the precipitate slurry.

The stirring of reaction mixture F was maintained for 15 minutes while the temperature was maintained in the range of 50-55 ° C.

The reaction mixture F was then added to the reaction mixture E in order to form the final catalyst precursor slurry.

The catalyst precursor slurry was left under stirring 10 for one hour while being cooled to approximately 40 ° C. It was then homogenized in a mixer for 3 minutes at 5,000 rpm. The sludge was then spray dried in a dry spray at an inlet / outlet temperature of 325/140 ° C. The resulting powder was denitrified by heat treatment for 3 hours in air at

290 ° C, 3 hours in air at 425 ° C and then calcined in air at 560 ° C for 3 hours. The resulting calcined powder was then tested as a propylene amoxidation catalyst. The test results are shown in Table 2.

Example 5 - NÍ4,26Mg3,195Feo, 9Rbo, 192Cro, 05BÍo, 72Cei, 76MOl2,806051,994 +

50% by weight of SiO ₂

Reaction mixture A was prepared by heating 152.9 ml of deionized water to 65 ° C and then adding with stirring for 30 minutes ammonium heptamolybdate (139 g) to form a colorless solution. Silica sol (27 ppm Na, 39 nm average particle size, 595.2 g, 42 wt% silica) was then added with stirring.

Reaction mixture B was prepared by heating 27.4 ml of deionized water to 55 ° C and then adding with stirring

36/44

Fe (NO ₃ ) ₃ .9H ₂ O (31.8 g), Ni (NO ₃ ) ₂ .6H ₂ O (108.5 g), Mg (NO ₃ ) ₂ .6H ₂ O (71.7 g) and Cr (NO ₃ ) ₃ .9H ₂ O (1.8 g).

Reaction mixture C was prepared by heating 64.9 ml of deionized water to 65 ° C and then adding under stirring for 30 minutes ammonium heptamolybdate (59 g) to form a colorless solution.

Reaction mixture D was prepared by (i) heating 169 g of a 50% by weight aqueous solution of (NH4) ₂ Ce (NO ₃ ) δ to 55 ° C, and (ii) while the solution was under stirring and heating, sequential addition of Bi (NO ₃ ) ₃ .5H ₂ O (30.6 g) and RbNO ₃ (2.5 g) resulting in a light orange solution.

Reaction mixture E was prepared by adding stirring reaction mixture B to reaction mixture A.

Reaction mixture F was prepared by adding reaction mixture C to reaction mixture D. This resulted in the precipitation of an orange solid. The resulting mixture was the precipitate slurry. The stirring of reaction mixture F was maintained for 15 minutes while the temperature was maintained in the range of 50-55 ° C.

The reaction mixture F was then added to the reaction mixture 20 E in order to form the final catalyst precursor slurry.

The catalyst precursor slurry was left under stirring for one hour while being cooled to approximately 40 ° C. It was then homogenized in a mixer for 3 minutes at 5,000 rpm. The sludge was then spray dried in a dry spray at an inlet / outlet temperature of 325/140 ° C. The resulting powder was denitrified by heat treatment for 3 hours in air at 290 ° C, 3 hours in air at 425 ° C and then calcined in air at 560 ° C for 3 hours. The resulting calcined powder was then tested as a catalyst for

37/44 propox amoxidation. The test results are shown in Table 2.

Example 6 - Ni ₄ Mg ₃ Feo, 9Rbo, i92Cro, o5Bio, 72Cei, 76Moi2.50205o, 627 + 50% by weight of S1O2

Reaction mixture A was prepared by heating 1363.6 ml of deionized water to 65 ° C and then adding under stirring for 30 minutes ammonium heptamolybdate (1239.6 g) to form a colorless solution. Silica sol (90 ppm Na, 39 nm average particle size, 5461.2 g, 41.2 wt% silica) was then added with stirring.

Reaction mixture B was prepared by heating 241.9 ml of deionized water to 55 ° C and then adding with stirring Fe (NO ₃ ) ₃ .9H ₂ O (293.9 g), Ni (NO ₃ ) ₂ .6H ₂ O (940.2 g), Mg (NO ₃ ) ₂ .6H ₂ O (621.8 g) and Cr (NO ₃ ) ₃ .9H ₂ O (16.2 g).

The reaction mixture C was prepared by heating 599.1 ml of deionized water to 65 ° C and then adding under stirring for 30 minutes ammonium heptamolybdate (544.6 g) to form a colorless solution.

Reaction mixture D was prepared by (i) heating of

1 559.9 g of a 50% by weight aqueous solution of (NH ₄ ) 2Ce (NO ₃ ) ó for

55 ° C, and (ii) while the solution was under stirring and heating, sequential addition of Bi (NO ₃ ) ₃ .5H2O (282.3 g) and RbNO ₃ (22.9 g) resulting in a light orange solution.

Reaction mixture E was prepared by adding stirring reaction mixture B to reaction mixture A.

Reaction mixture F was prepared by adding reaction mixture C to reaction mixture D. This resulted in the precipitation of a

38/44 solid orange in color. The resulting mixture was the sludge of precipitates. The stirring of reaction mixture F was maintained for 15 minutes while the temperature was maintained in the range of 50-55 ° C.

The reaction mixture F was then added to the reaction mixture 5 E in order to form the final catalyst precursor slurry.

The catalyst precursor slurry was left under stirring for one hour while being cooled to approximately 40 ° C. It was then homogenized in a mixer for 3 minutes at 5,000 rpm. The sludge was then spray dried in a dry spray at an inlet / outlet temperature of 325/145 ° C. The resulting powder was denitrified by heat treatment for 3 hours in air at 290 ° C, 3 hours in air at 425 ° C and then calcined in air at 560 ° C for 3 hours. The resulting calcined powder was then tested as a propylene amoxidation catalyst. The test results are shown in the

Table 2.

Example 7 - NÍ4Mg3Feo, 9Rbo, i92Cro, o5Bio, 72Cei, 76Moi2,806 05i, 539 + 50% by weight of S1O2 22 nm

Reaction mixture A was prepared by heating 154.4 ml of deionized water to 65 ° C and then adding under stirring for

30 minutes of ammonium heptamolybdate (140.4 g) in order to form a colorless solution. Silica sol (568 ppm Na, 22 nm average particle size, 625 g, 40 wt% silica) was then added with stirring.

Reaction mixture B was prepared by heating 26.5 ml of deionized water to 55 ° C and then adding with stirring Fe (NO ₃ ) 3.9H ₂ O (32.2 g), Ni (NO ₃ ) ₂ .6H ₂ O (102.9 g), Mg (NO ₃ ) 2.6H ₂ O (68 g) and Cr (NO ₃ ) 3.9H ₂ O (1.8 g).

Reaction mixture C was prepared by heating 65.5 ml

39/44 of deionized water to 65 ° C and then adding under stirring for 30 minutes ammonium heptamolybdate (59.6 g) to form a colorless solution.

Reaction mixture D was prepared by (i) heating 170.65 g of a 50% by weight aqueous solution of (NH4) 2Ce (NO ₃ ) õ to 55 ° C, and (ii) while the solution was under stirring and heating, sequential addition of Bi (NO ₃ ) ₃ .5H2O (30.9 g) and RbNO ₃ (2.5 g) resulting in a light orange solution.

Reaction mixture E was prepared by adding with stirring reaction mixture B to reaction mixture A.

Reaction mixture F was prepared by adding reaction mixture C to reaction mixture D. This resulted in the precipitation of an orange solid. The resulting mixture was the precipitate slurry. The stirring of reaction mixture F was maintained for 15 minutes while the temperature was maintained in the range of 50-55 ° C.

The reaction mixture F was then added to the reaction mixture E in order to form the final catalyst precursor slurry.

The catalyst precursor slurry was left under stirring for one hour while being cooled to approximately 40 ° C.

It was then homogenized in a mixer for 3 minutes at 5,000 rpm. The sludge was then spray dried in a dry spray at an inlet / outlet temperature of 325/140 ° C. The resulting powder was denitrified by heat treatment for 3 hours in air at 290 ° C, 3 hours in air at 425 ° C and then calcined in air at 560 ° C for 3 hours. The resulting calcined powder was then tested as a propylene amoxidation catalyst. The test results are shown in Table 2.

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Table 2

Ex. No. Catalyst Reason X / V HOS % C ₃ = Conv. % Rend. AN % Know. AN % Rend. -CN C3 Catalyst C49MC 0.35 87.0 C4 NÍ7,5Mg3Fei _{> 8} Rbo, 12Cro ₎ lBIO _> 45Cei, lMOl5,85063,835 + 50% by weight 27 ppm Na, S1O2 39 nm 0.32 137 97.2 79.6 81.8 86.7 C5 NÍ7,5Mg3Fei, 8Rbo, 12Cro, lBÍo, 45Cei, lMOl5,85063,835 + 50% by weight 27 ppm Na, S1O2 39 nm 0.32 138 98.4 79.4 80.7 86.5 C6 NÍ5Mg2Fei, 8Rbo, i2Cro, iBio, 45Cei, iMoi2,35049,835 ⁺ 50% by weight 27 ppm Na, S1O2 39 nm 0.45 44 99.0 81.7 82.6 88.9 C7 NÍ4Mg3Fei, 8Rbo, 192Cro, lBÍo, 45Cei, lMOl2,386049,979 ⁺ 50% by weight 90 ppm Na, S1O2 39 nm 0.51 142 99.0 83.6 84.5 89.9 3 NUMSFeo, 9Rbo, 192Cro, 05BÍo, 72Cei, 76MOl2,806051,539 + 50% by weight 27 ppm Na, S1O2 39 nm 0.92 136 98.1 84.0 85.6 90.3 4 NÍ4Mg3Feo, 9Rbo, 192Cro, 05BÍo, 72Cei, 76Moi2,335050,126 + 50% by weight 27 ppm Na, S1O2 39 nm 0.93 113 99.7 82.2 82.5 89.1 5 N4,26Mg3 _; 195Feo, 9Rbo, 192Cro, 05Bío, 72Cei, 76MOl2,806051,994 + 50% by weight 27 ppm Na, S1O2 39 nm 0.85 142 98.6 82.4 83.6 89.2 6 NÍ4Mg3Feo, 9Rbo, 192Cro, 05BÍo, 72Cei, 76MOl2,502050,627 + 50% by weight 90 ppm Na, S1O2 39.2 nm 0.97 138 98.2 82.4 84.8 89.7 7 NÍ4Mg3Feo, 9Rbo, 192Cro, 05BÍo, 72Cei, 76Moi2,806051,539 + 50% by weight 568 ppm Na, S1O2 22 nm 1.25 148 99.7 82.2 82.4 89.7

Grades;

1. “X / Y ratio“ is the XRD X / Y intensity ratio as described here.

2. “HOS” is “current hours”.

3. “% C ₃ ⁼ Conv” is mol% per conversion passage of propylene to all products.

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4. “% Rend, AN” is the percentage yield in acrylonitrile.

5. “% AN Sei” is the percentage selectivity of acrylonitrile.

6. “% Income. -CN ”is the combined percentage yield of acrylonitrile, acetonitrile and hydrogen cyanide.

7. The catalysts here are described on a “M012” basis (ie, the Mo-12 subscript), to convert any of the above compositions to the '' M012 ”base, simply divide each subscript in the composition by the Mo subscript shown and then multiply by 12. For example, the composition of Example 3 of

NÍ4Mg3Feo, 9Rbo, i2Cro _> o5Bio, 72Cei, 76Moi2 ₎ 80605i, 539 is equivalent to NÍ3,748Mg2,8iiFeo, 843Rbo.i8oCro ₎ 047Bio, 675Cei, 65Moi2048,295 in the “M12” base.

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Table 3

Ex. No. Catalyst Reason CE / Fe test in Losses per Friction C4 NÍ7,5Mg3Fei, 8Rbo, 12Cro, lBÍo, 45Cei, lMOl5,85063,835 + 50% by weight 27 ppm Na, S1O2 39 nm 0.61 Not Measured C5 NÍ7,5Mg3Fei, 8Rbo, 12Cro, lBÍo, 45Cei, lMOl5,85063,835 + 50% by weight 27 ppm Na, S1O2 39 nm 0.61 Not Measured C6 NÍ5Mg2Fei, 8Rbo, i2Cro, iBio, 45Cei, iMoi2,35049,835 + 50% by weight 27 ppm Na, S1O2 39 nm 0.61 13.1 C7 NÍ4Mg3Fei, 8Rbo, 192Cro, lBÍo, 45Cei, lMoi2,386049,979 + 50% by weight 90 ppm Na, SiO ₂ 39 nm 0.61 10.3 3 NÍ4Mg3Feo, 9Rbo, 192Cro, 05BÍo, 72Cei, 76MOl ₂ , 806051,539 + 50% by weight 27 ppm Na, SiO ₂ 39 nm 1.95 6.2 4 NÍ4Mg3Feo, 9Rbo, i92Cro, o5Bio, 72Ce 1, 7oM 12,335050,126 + 50% by weight 27 ppm Na, S1O2 39 nm 1.95 7.2 5 NÍ4,26Mg3,195Feo, 9Rbo, 192Cro, 05BÍo, 72Cei, 76MOl2,806051,994 + 50% by weight 27 ppm Na, S1O2 39 nm 1.95 6.1 6 NÍ4Mg3Fe0,9Rb0,192Cr0,05BÍ0,72Cei, 76MOl2,502O50,627 + 50% by weight 90 ppm Na, S1O2 39.2 nm 1.95 7.1 7 Ni4Mg3Feo, 9Rbo, i92Cro, osBio, 72Ce 1jõM i2,806Os 1,539 + 50% by weight 568 ppm Na, S1O2 22 nm 1.95 4.9

Grades:

1. “Friction Loss Test” is the result of a friction test with a submerged jet and the numerical value is the percentage loss of catalyst for a period between 0 and 20 hrs. This is a measure of resistance

43/44 overall of the catalyst particle. Lower numerical friction values are desirable. Numerical friction values above about 8.0 are not preferred for commercial catalysts due to the higher rate of catalyst loss. The submerged jet is as described in the ASTM friction test standard.

As can be seen from Tables 2 and 3, the catalyst compositions as defined by the present invention (note the X / Y ratio) exhibit (i) greater overall conversion to acrylonitrile, acetonitrile and HCN when propylene was subjected to amoxidation on such a catalyst at elevated temperatures in the presence of ammonia and air and (ii) less friction losses (greater particle resistance), compared to similar catalysts outside the scope of the present invention.

Comparative Example C8 and Examples 8-11

Various catalyst formulations have been prepared by the techniques described here.

For such formulations, Table 4 illustrates that catalysts with Ce / Fe ratios less than about 0.7 exhibit poorer friction as opposed to catalysts with higher Ce / Fe ratios.

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Table 4

Ex. No. Catalyst Reason CE / Fe Results Friction 0-20 hours C8 NisMgsFei, 8Rbo, i2Cro, iBio, 45Ce ι, i Mo15,85049,835 + 50% by weight 27 ppm Na, SiO ₂ 39 nm 0.611 12.82 8 NisMgaF eo, 9Rbo, i2Cro, o5Bio, 45Ce ι, ι Mo 11,35045,835 + 50% by weight 27 ppm Na, SiO ₂ 39 nm 1,222 6.98 9 Ni4Mg3Feo.çRbo, i2Cro, o5Bio, 45Ce ι, ιΜο 11,375051,539 + 50% by weight 27 ppm Na, SiO ₂ 39 nm 1,956 6.32 10 NÍ4Mg3Feo, 9Rbo, 18Cro, 05BÍo, 58Cei, 75MOl ₂ , 575050,61 + 50% by weight 27 ppm Na, SiO ₂ 39 nm 1,944 6.35 11 NÍ4Mg3Feo, 9Rbo, i2Cro, o5Bio, 72Cei, 76Moi ₂ , 77051,395 + 50% by weight 27 ppm Na, SiO ₂ 39 nm 1,956 7.60

Although the above description and the above embodiments are typical for the practice of the present invention, it is evident that many alternatives, modifications and variations will be obvious to those skilled in the art in light of this description. Likewise, it is intended that such alternatives, modifications and variations are included and fall within the spirit and scope of the attached Claims.

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Claims (6)

Claims 1 - Catalytic Composition, characterized in that it comprises a complex of metal oxides, in which the relative proportions of the elements in said catalyst are represented by the following formula: M012 Bia Feb Ac D <i Ee Ff Gg Ceh, Ox where: A is at least one element selected from the group consisting of sodium, potassium, rubidium and cesium; and D is at least one element selected from the group consisting of nickel, cobalt, manganese, zinc, magnesium, calcium, strontium, cadmium and barium; And it is at least one element selected from the group consisting of chromium, tungsten, aluminum, boron, gallium, indium, phosphorus, arsenic, antimony, vanadium and tellurium; F is at least one element chosen from the group consisting of a rare earth element, titanium, zirconium, hafnium, niobium, tantalum, aluminum, gallium, indium, thallium, silicon, germanium and lead; G is at least one element selected from the group consisting of silver, gold, ruthenium, rhodium, palladium, osmium, iridium, platinum and mercury; and a, b, c, d, e, f, g, hen are, respectively, the atomic ratios of bismuth (Bi), iron (Fe), A, D, E, F, cerium (Ce) and oxygen (O ), with respect to 12 molybdenum atoms (Mo), where a is 0.05 to 7, 2/4 b is 0.1 to 7, c is 0.01 to 5, d is 0.1 to 12, and is 0 to 5, f is 0 to 5, g is 0 to 0 , 2, h is 0.01 to 5, and n is the number of oxygen atoms needed to satisfy the valency requirements of the other component elements present; where 0.8 <h / b <5 and where the catalyst composition comprises a support selected from the group consisting of silica, alumina, zirconium, titanium or mixtures thereof and where the support comprises between 30 and 70 weight percent of the catalyst composition. 2 - Catalytic composition, according to Claim 1, characterized in that 1 <h / b <3. Catalytic composition according to Claim 1, characterized in that 1.5 <h / b <2. 4 - Process for Conversion of Oleftna, selected from the group consisting of propylene, isobutylene or their mixtures, acrylonitrile, methacrylonitrile and their mixtures, respectively, by means of reaction in the vapor phase at a temperature and high pressure of said olefin with a gas containing molecular oxygen and ammonia in the presence 3/4 of a catalyst, in which the relative proportions of the elements in said catalyst are represented by the following formula: M012 Bia Feb A _c Da E _and Ff Gg Ceh O _x where: A is at least one element selected from the group consisting of sodium, potassium, rubidium and cesium; and D is at least one element selected from the group consisting of nickel, cobalt, manganese, zinc, magnesium, calcium, strontium, cadmium and barium; And it is at least one element selected from the group consisting of chromium, tungsten, aluminum, boron, gallium, indium, phosphorus, arsenic, antimony, vanadium and tellurium; F is at least one element chosen from the group consisting of a rare earth element, titanium, zirconium, hafnium, 15 niobium, tantalum, aluminum, gallium, indium, thallium, silicon, germanium and lead; G is at least one element selected from the group consisting of silver, gold, ruthenium, rhodium, palladium, osmium, iridium, platinum and mercury; and a, b, c, d, e, f, g, hen are, respectively, the atomic ratios of bismuth (Bi), iron (Fe), A, D, E, F, cerium (Ce) and oxygen ( O), with respect to 12 molybdenum atoms (Mo), where a is 0.05 to 7, b is 0.1 to 7, c is 0.01 to 5, 4/4 d is 0.1 to 12, f is 0 to 5, g is 0 to 0.2, h is 0.01 to 5 and n is the number of oxygen atoms needed to satisfy the valence of the other component elements present; where 0.8 <h / b <5 and where the catalyst composition comprises a support selected from the group consisting of silica, alumina, zirconium, titanium or mixtures thereof and where the support comprises between 30 and 70 per percent by weight of the catalyst composition. 5 - Olefin Conversion Process according to Claim 4, characterized in that 1 <h / b <3. 6 - Olefin Conversion Process according to Claim 4, characterized in that 1.5 <h / b <2. 1/3% Acrylonitrile Yield 2/3 XRD Diffractogram of Catalytic Composition Shown to Example 6 2 Theta (Degrees) Diffraction Angle O O O € » O O co O co O CÕ oo co uS d XI w * s 4 & hi £ _{Λ ο Ό} I ** 4 CL i S w 2 s ° OA υ ^M O O O O O co O O O O δ O co CM XP— Cl cS • wd 3/3 Ce / Fe «j · -> 4) Ό O O 2 * κ £ 6 <§ 3 «fal d 4) <S U T3 4>