Method for producing oxide catalyst for use in producing acrylonitrile or methacrylonitrile from propane or isobutane

Method for producing Oxide catalyst for use in the production of acrylontrile or methacrylontrile from propane or isobutane

Full description

Background of the invention:-

The present invention relates to a process for producing Oxide catalyst for use in the production of acrylontrile or methacrylontrile from propane or isobutane and, in particular, relating

The present invention is a process for producing an oxide catalyst for use in the production of acrylontrile or methacrylontrile from propane or isobutane by treatment with ammoxidation in the gaseous phase, wherein the oxide catalyst includes a compound oxide containing molybdenum (Mo), vanadium (V), antimony (Sb) and optionally element X . The process involves subjecting a slurry solution or slurry, in water and/or alcohol, of a raw material mixture including Mo, V, Sb and optionally X to a special oxidation treatment using an oxidizing gas and/or oxidizing liquid before subjecting the solution or slurry to subsequent drying and calcination. . When the resulting oxide catalyst is used in the process of the present invention in... Production of acrylontrile or methacrylontrile Not only can we produce the desired acrylontrile or methacrylontrile with high yield and yield over a long time frame, but also the damage of the catalyst has been stopped, so that the production of acrylontrile or methacrylontrile can be carried out stably for an extended period of time.

Recently, attention has been drawn to a technology for producing acrylontrile or methacrylontrile by gas-phase catalytic ammoxidation of propane or isobutane, as an alternative to gas-phase catalytic ammoxidation of propane or isobutane, and a number of proposals have been made depending on the catalyst used in propane or isobutane ammoxidation.

For example, an oxide catalyst is known to use a compound containing molybdenum (Mo), vanadium (V) and antimony (Sb) as a catalyst for use in the ammoxidation of propane or isobutane. Such an oxide catalyst compound is shown in, for example, unexamined and publicly available Japanese patent application specification numbers 257-2 (corresponding to US Patent No. 5,049,692), 148,212-5 (corresponding to US Patent No. 5,231,214 , 208136-5 (corresponding to European Patent No. 529,853), 227819-6, 2853272-6 (corresponding to US Patent No. 5,422,318), 144132-7, 232071-7, 57319-8 and 141401-8.

When the above-mentioned catalyst is used for the ammoxidation of propane or isobutane, the yield and time space yield of acrylontrile and methacrylontrile {hereinafter, often referred to as &acrylontrile (meth)&)} become high. However, this catalyst has a problem during acrylontrile (meth) production as the tellurium is evaporated from the catalyst, thus damaging the catalyst.

For this reason, as described below, oxide catalysts containing Mo,

V, Sb, and the oxide catalyst materials contain Sb, V, Mo, and Nb, each of which contains antimony instead of tellurium, which most likely evaporates from the catalyst.

For example, an oxide catalyst containing V, Mo,

Sb and Nb (where Nb is an optional component) in unexamined and open to the public Japanese patent application specification numbers 157241-9 (corresponding to US Patent No. 5,750,760) and 28862-10. This catalyst is produced using an aqueous solution containing a molybdenum compound. Vanadium compound, antimony compound, and optionally niobium compound. The process of producing the catalysts described in these documents includes mixing a pentavalent vanadium compound and a trivalent antimony compound for vanadium reduction, or mixing a hexavalent molybdenum compound and a trivalent antimony compound for molybdenum reduction; The resulting reaction mixture is mixed with compounds of other constituent elements, thus obtaining a mixture, and the mixture is dried

output, followed by calcination. Specifically, in these documents, the oxide catalyst is produced by a process that involves thermally resisting an aqueous paste containing a pentavalent vanadium compound and a trivalent antimony compound, followed by the addition of a lipdenium compound and a niobium compound, thus obtaining an aqueous mixture. The resulting aqueous mixture is optionally cooled and dried. aqueous mixture, followed by calcination.

When the catalyst produced in the above-mentioned process is used to produce acrylontrile (meth), acrylontrile (meth) can be produced with a relatively large yield. However, the time-space yield of acrylontrile (meth) [molar amount of acrylontrile (meth) formed (mu Mol.) / contact time (contact time) between the raw material and the catalyst (g.multidot.sec/ml times the weight of the catalyst (g)] is unhelpfully small from 0.11 to 0.22 [{mu.mol). /{(g.multidot.sec/ml).multidot.g.)].So, it becomes productive (meth)

A few acrylontrile per reactor. Also, when an attempt was made to increase the time-space yield of acrylontrile (meth) by using a high reaction temperature, the selectivity of acrylontrile (meth) was reduced, so that the yield of unexamined, open-to-public Japanese patent application specification number 293374-5 (corresponding to US patent No. 5, 094,989) describes an oxide catalyst that contains V and Sb as the main components, and also contains a small amount of Mo. However, when this catalyst is used in the production of acrylontrile (meth), not only is a large reaction temperature required, but also the acrylontrile (meth) product is

a little.

(1990) 515-525. New Developments in Selective Oxidation pp. mentions the results of the oxide treatment of propane, which was carried out using a catalyst containing supported alumina and a compound oxide containing V, Mo and Sb in molar ratios of 0.71/0.14/0.1, and according to this Document, the above-mentioned catalyst has the problem that not only the selectivity of (meth)acrylontrile is reduced but also the efficiency to perform the desired transformation.

US Patent No. 4,760,159 describes an Oxide catalyst containing Bismuth,

Vanadium and antimony as the main ingredients, and also contains a trace amount of vanadium. In any case, when this catalyst is used. In the production of acrylontrile (meth), a problem arises in that it not only requires a high temperature for the reaction, but also the yield of acrylontrile (meth) is low.

The oxide catalyst containing Mo--V--Sb or Mo--V-Sb--Nb also has the following problem. Amoxidized ammonia is converted to propane, as described in Applied Catalysis A General, Vol (1997) 143-172, 157. Oxide), and when the oxidation catalyst used on Mo--V--Sb or Mo--V-Sb--Nb is used in the ammonia treatment, the decomposition of ammonia to nitrogen occurs strongly (where the percentage of decomposed ammonia is

To form a large amount of nitrogen), so that the loss of ammonia is large.

General description of the invention

In this situation, the present inventors have carried out comprehensive and extensive studies to solve the aforementioned problem associated with the previous field. As a result, it has been unexpectedly found that during the production of Oxide catalyst including a compound oxide containing at least Molybdenum (Mo), Vanadium (V) and Antimony (Sb), when a solution or paste is made, in water and/or alcohol, of a raw material mixture containing... At least on the Mo compound, V compound and Sb compound for the specific oxidation treatment, then the oxidant mixture solution or paste is dried to obtain a dry formation catalyst, followed by calcination of the dry formation catalyst, and the Oxide catalyst can be obtained which is not affected by damage during acrylontrile production ( meth only (which is, unlikely for passivation), but is also effective in producing acrylontrile (meth) with high yield and time span over, which, therefore, can be used to produce acrylontrile (meth) effectively and efficiently for an extended period of time.

Also, it has also been unexpectedly found that when a base-treated oxide catalyst, which can be obtained by treating the above-mentioned oxide catalyst with an aqueous base solution, is used in the production of acrylontrile or (acrylontrile (meth) from propane or isobutane by oxide treatment in the gas phase, no Not only can we achieve the above-mentioned results, but it is also possible to prevent the decomposition of ammonia, which is one of the materials to produce acrylontrile (meth), into nitrogen, so that the usefulness of ammonia can be improved significantly.

The present invention has been completed, based on the new discovery of the previous one.

Accordingly, the main object of the present invention is to provide a method for producing an excellent oxide catalyst which is not only not susceptible to damage during the production of acrylontrile or acrylontrile (meth), but is also effective in producing acrylontrile or acrylontrile (meth) consistently with high yield and high time yield, which Therefore, they can be advantageously used to consistently produce sufficient acrylontrile or acrylontrile (meth) for an extended period of time.

A further object of the present invention is to provide a method for producing a pretreated oxide catalyst by treating the above-mentioned oxide catalyst with an aqueous base solution, wherein the base-treated oxide catalyst not only has the above-mentioned excellent effects, but is also capable of preventing the decomposition of ammonia into nitrogen; So that the usefulness of ammonia can be significantly improved.

Other objectives and advantages of the present invention will be apparent to those skilled in the art. From the following detailed description taken regarding the accessory elements.

Detailed description:-

As an essential aspect of the present invention, a method for producing an oxide catalyst for use in the production of acrylonitrile or acrylonitrile meth from propane or isobutane by gas-phase ammonia treatment is provided, including the oxide catalyst

Mo1.0 Va Sbb Xc On (I)

where:

X represents at least one element selected from a group consisting of niobium, tungsten,

Chromium, titanium, tantalium, zirconium, hafnium, manganese, ronium, iron, ruthenium,

Cobalt, rhodium, nickel, palladium, platinum, copper, silver, zinc, boron, gallium, indium, germanium, tin, tellurium, phosphorus, lead, bismuth, rare earth elements, and alkaline earth metals; And

c, b, a and n are, respectively, the atomic ratios of vanadium (V), antimony (Sb), X and oxygen (O), relative to molybdenum (Mo), where:

0.1.ltoreq.a.1toreq.1.0,

0.01.ltoreq.b.1toreq.0.6,

and 0.ltoreq.c.1toreq.1.0,

n is a number determined by and consistent with the valence requirements of the other elements present in the oxide of the compound with the formula (I), which involves the following steps from (1) to (5):

(1) Preparing a solution or liquid slurry from a raw material mixture in at least one aqueous medium selected from a group consisting of water and alcohol, and said raw material mixture includes a molybdenum compound (Mo), a vanadium compound (V), an antimony compound (Sb) and compound X. At least one is optionally selected from a group consisting of compounds of elements designated by

(2-a) treatment at 50 to 300 C in the presence of an oxidizing gas for an hour or more, and (2-b) treatment with an oxidizing liquid, thus obtaining a solution or liquid slurry of an oxidizing raw material mixture,

(3) Optionally adding at least one compound

(4) Drying the solution or liquid slurry of the aforementioned oxidizing raw material mixture resulting in step (2) or the solution or liquid slurry of the said oxidizing raw material mixture to which the aforementioned compound ) Calcination of the aforementioned dried catalyst-forming material, therefore, to obtain the Oxide catalyst, which includes an oxide compound with the formula (I).

For an easy understanding of the present invention, the necessary features and various embodiments of the present invention are listed below:

1- A process for producing Oxide catalyst for use in the production of acrylontrile or acrylontrile meth from propane or isobutane by treatment with oxide in the gas phase, and includes the oxide catalyst

Mo1.0 Va Sbb Xc On (I)

where:

X represents at least one element selected from a group consisting of niobium, tungsten,

Chromium, titanium, tantalum, zirconium, hafnium, manganese, ronium, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, zinc, boron, gallium, indium,

Germanium, tin, tellurium, phosphorus, lead, bismuth, rare earth elements, and alkaline earth metals; And

c, b, a and n are, respectively, the atomic ratios of vanadium (V), antimony (X), (Sb) and oxygen (O), relative to molybdenum (Mo), where:

0.1.ltoreq.a.1toreq.1.0,

0.01.ltoreq.b.1toreq.0.6,

and 0.ltoreq.c.1toreq.1.0,

n is a number determined by and consistent with the valence requirements of the other elements present in the oxide of the compound with the formula (I), which involves the following steps from (1) to (5):

(1) Preparing a solution or liquid slurry from a raw material mixture in at least one aqueous medium selected from a group consisting of water and alcohol, and said raw material mixture includes a molybdenum compound (Mo), a vanadium compound (V), an antimony compound (Sb) and compound X. At least one is optionally selected from a group consisting of compounds of elements designated by

(2-a) treatment at 50 to 300 C in the presence of an oxidizing gas for an hour or more, and (2-b) treatment with an oxidizing liquid, thus obtaining a solution or liquid slurry of an oxidizing raw material mixture,

(3) Optionally adding at least one compound

(4) Drying the solution or liquid slurry of the aforementioned oxidizing raw material mixture resulting in step (2) or the solution or liquid slurry of the said oxidizing raw material mixture to which the aforementioned compound ) Calcination of the aforementioned dried catalyst-forming material, therefore, to obtain the Oxide catalyst, which includes an oxide compound with the formula (I).

2- The process according to the previous paragraph 1, where the aforementioned oxidizing gas is at least one member selected from a group consisting of oxygen, air and nitrogen oxides.

3- The process in accordance with the previous paragraph 1 or 2, wherein the oxidizing liquid is an aqueous solution of at least one oxidizing compound selected from a group consisting of superoxide.

Hydrogen, nitric acid, and hypochlorous acid.

4- The process in accordance with the previous paragraph 3, where the amount of said oxidizing liquid is in the range from 0.01 to 2 molar ratio of at least one antimony oxidizing compound contained in a solution or liquid slurry of said raw material mixture prepared in step (1). 5- The process according to the previous paragraph 3 or 4, where the aforementioned oxidizing liquid is an aqueous solution of hydrogen peroxide.

6- The process according to any of the previous paragraphs 1 or 5, where the calcination process takes place in step (5) in an inert gas atmosphere that is largely devoid of molecular oxygen. 7- The process according to any of the previous paragraphs 1 or 6, where the calcination process takes place in step (5) at 400 to 700 degrees Celsius.

8- The process in accordance with any of the preceding paragraphs 1 or 7, which also includes the steps of (6) contacting the aforementioned oxide catalyst produced in step (5) with a base solution to obtain a contact mixture containing the oxide catalyst treated with a base, and (7) Separating and extracting the Oxide catalyst treated with the aforementioned base from the contact mixture. 9- The process according to the previous paragraph 8, where the aforementioned aqueous basic solution is an aqueous solution of at least one compound chosen from a group consisting of ammonia, alkaline earth metal hydroxide, alkaline earth metal hydroxide, alkaline metal carbonate, alkaline earth metal carbonate, metal salt. Alkali of an organic acid, alkaline earth metal salt, of an organic acid and an amine.

10- The process according to the previous paragraph 9, where the aforementioned aqueous basic solution is an aqueous solution of ammonia.

11- The process in accordance with any of the preceding paragraphs 8 to 10, which also includes step (8) for calcination of the oxide catalyst treated with the aforementioned base and extracted in step (7) from the contact mixture.

12- The process is in accordance with the previous paragraph 11, where the calcination process is performed in step (8) in

An inert gas atmosphere that is largely devoid of molecular oxygen.

13- The process is in accordance with the previous paragraph 11, where the calcination process is performed in step (8) at 400 to 700 degrees Celsius.

14- Oxide catalyst for use in the production of acrylontrile or methacrylontrile, which

It involves the reaction of propane or isobutane with ammonia and molecular oxygen in the gaseous phase in the presence of the oxidative catalyst produced by the process in any of paragraphs 1 to 13 above.

15- A process for producing oxide catalyst for use in producing acrylontrile or meth acrylontrile from propane or isobutane with ammonia and oxygen in the gaseous phase in the presence of the oxide catalyst in the previous paragraph 14.

Below, the present invention will be described in greater detail.

The oxide of the oxide catalytic compound produced by the process of the present invention has a composition represented by the following formula (I):

(Mo1.0 Va Sbb Xc On (I

where:

The Gallium, indium, germanium, tin, tellurium, phosphorus, lead, bismuth, rare earth elements, and alkaline earth metals; And

c, b, a and n are, respectively, the atomic ratios of vanadium (V), antimony (X), (Sb) and oxygen (O), relative to molybdenum (Mo), where:

0.1.ltoreq.a.ltoreq.1.0, 0.01.ltoreq.b.ltoreq.0.6, and 0.ltoreq.c.ltoreq.1.0,

n is a number determined by and consistent with the valence requirements of the other elements present in the oxide of the compound with the formula (I),

The preceding element Preferably, the atomic ratio (a) of vanadium (V) to Mo corresponds to the relationship: the most preferable

0.2.ltoreq.a.ltoreq.0.4 Preferably the atomic ratio (c) of .ltoreq.0.2, provided that, when the oxide of the aforementioned compound contains tellurium (Te), as element By preference

0.001.ltoreq.c'.ltoreq.0.03 0.001.ltoreq.c'.ltoreq.0.01 is particularly preferred.

Traditionally, an oxide catalyst containing V, Mo and Sb is produced by...

Includes:

- Preparation of a solution or paste of a raw material mixture containing a molybdenum compound (Mo), a vanadium compound (V) and an antimony compound (Sb);

- drying the solution or paste of the raw material mixture, thus obtaining a dry forming catalyst (drying step); And

- Calcination of the resulting dry forming catalyst (calcination step).

In contrast, an essential feature of the process of the present invention is that, in the process for producing an oxide catalyst comprising a compound oxide represented by the preceding formula (I) which includes at least V, Mo and Sb, a solution or paste in water and/or alcohol is subjected to a mixture A raw material containing at least a Mo compound, a V compound, and a Sb compound for special oxidizing treatment as described below prior to the drying step and subsequent calcination step, thereby significantly improving the oxidation of V, Mo, and Sb. Such a characteristic of the process of the present invention is preferred, as it is possible to produce an oxide catalyst that is not only not affected by damage during the production of acrylontrile (meth), but is also useful for producing acrylontrile (meth) effectively and efficiently with high productivity and high spatial productivity.

As mentioned previously, the process of the present invention includes the following steps: (1)

To (5):

(1) Preparation of a solution or paste in raw water containing a molybdenum (Mo) compound.

Vanadium compound (V), antimony compound (Sb) and optionally X;

(2) Exposing the solution or paste of the raw material mixture to a special oxidizing treatment, thus obtaining a solution or paste of the mixture:

(3) Optionally adding compound

(4) drying the solution or compound of the oxidizing feedstock mixture obtained in step (2) or step (3), optionally including compound

(5) Calcination of the aforementioned dried catalyst forming material in order to obtain an oxide catalyst that includes an oxide compound with the formula (I).

Below, the steps involved in the process of the present invention will be described in detail

Larger.

Step (1). Raw material mixture preparation step.

In step (1) of the process of the present invention, a raw material mixture comprising a molybdenum compound, a vanadium compound, an antimony compound and optionally at least one compound At least one liquid selected from a combination of water and alcohol to prepare a solution or paste for the raw material mixture.

As a liquid medium, from which at least one medium can be selected, a combination of water and alcohol can be used. Examples of alcohols used in the present invention include C1-4 alcohols and benzyl alcohol.

Below is the quantity of the liquid medium. There is no special limitation as long as the quantity of the liquid medium is sufficient to form a solution or paste from the raw material mixture. However, from the point of view of the solubility of the special raw material compounds of the element compounds and the promotion of the reactions that subsequently occur in the liquid medium; It is preferable to use 4 to 20 grams of liquid medium for every gram of molybdenum compound in the raw material mixture. When a mixture of water and alcohol is used as a liquid medium, the ratio of water to alcohol is chosen appropriately, taking into account the solubility of the compounds contained in the raw material mixture in water and alcohol.

In the process of the present invention for producing an oxide catalyst comprising a compound oxide,

The following compounds can be used as sources of components of the oxide catalyst.

Or examples of molybdenum sources include ammonium pentamolybdate, molybdenum oxides, molybdenum chlorides, molybdenum alkoxides and the like; Of these, hexavalent molybdate compounds, ammonium heptamolybdate are particularly preferred. Examples of vanadium sources include ammonium metavanadate, vanadium (V) oxide, vanadium oxychlorides, vanadium alkoxides, and the like. Among these are pentavalent vanadium compounds, preferably ammonium metavanadate, or vanadium (V) oxide in particular.

Examples of antimony sources include antimony(III) oxide, antimony(V) oxide,

Antimony chlorides, salts of antimony organic acids, such as antimony tartrate-like

that. Of these, trivalent antimony compounds, antimony(III) oxide is particularly preferred.

Examples of sources of elements When niobium and/or titanium are used as element X, an aqueous solution of their dicarboxylate is preferred. Regarding the source of niobium, it is preferable to use niobic acid. Niobic acid is a modified compound represented by the following formula: Nb2. O5.NH2O, also known as niobium hydroxide or modified niobium oxide. It is particularly preferable to use an aqueous solution containing niobium shown in:

Al 0895809 EP, which comprises water in which dicarboxylic acid is dissolved, a niobium compound, and optionally ammonia, wherein the molar ratio of dicarboxylic acid to niobium is in the range of 1 to 4, and the molar ratio of ammonia/niobium is 0 to 0.2 in the invention. Currently, however, the molar ratio of dicarboxylic acid to niobium can be greater than 4, as long as the molar ratio is 10 or less. In the niobium-containing aqueous solution used in the present invention, the preferred molar ratio of dicarboxylic acid to niobium is in the range from 2 to 6.

Oxalic acid is preferred, such as the aforementioned dicarboxylic acid.

The appropriate quantities of molydinium, a vanadium compound, an antimony compound, and an element

There is no special limitation regarding the method for preparing a solution or paste of a raw material mixture by combining the aforementioned liquid medium, a molybdenum compound, a vanadium compound, an antimony compound and an element X compound, as a compound of an optional component element. As specific examples of methods for preparing a raw material solution or paste mixture, the following methods can be mentioned. Where it is heated

An aqueous solution or paste containing a binary compound of ammonium metavanadate and antimony(III) oxide in an atmosphere of air to influence the reaction. It is preferable to heat the aqueous solution or paste to a temperature of 70 to 110 degrees Celsius. The aqueous solution or dough can be continued to be heated while water is added to the solution or dough to replace the water lost by evaporation or conducted under reflux conditions (boiling and returning the condensed vapor) using a reactor equipped with a condenser. It is preferable that the heating time be 3 hours or more, especially from 4 to 50 hours. A solution of vanadium (V) oxide in an aqueous solution of hydrogen peroxide or an aqueous solution of the aforementioned sources of vanadium other than ammonium metavanadate can be used. Vanadium (V) oxide can also be used as a source of vanadium, instead of ammonium metavanadate. It is possible to add ammonium heptamolybdate or an aqueous solution thereof to the aqueous solution or paste containing a mixture of a vanadium compound and an antimony compound, produced by the aforementioned method, thus obtaining an aqueous solution or paste of a raw material mixture containing a molybdenum compound, a vanadium compound and an antimony compound.

Alternatively, a raw material mixture solution or paste may be prepared by another method described below:

An aqueous solution or paste containing a binary mixture of hepta-molybdenum ammonium and antimony (III) oxide is heated to influence the reaction to obtain a reaction mixture, followed by adding a vanadium compound or an aqueous solution thereof to the reaction mixture, thus obtaining an aqueous solution or paste of a raw material mixture containing Molybdenum compound, vanadium compound and...

Antimony.

It is intended to prepare an aqueous solution or paste for a raw material mixture containing an element For example, element

An antimony compound (for example, a mixture of molybdenum hepta-ammonium and antimonyIII oxide), or the aforementioned aqueous solution or paste of a raw material mixture containing a molybdenum compound, a vanadium compound, and an antimony compound.

When alkoxide compounds are used as sources of molybdenum, vanadium and/or antimony, if water is used as a liquid medium, the alkoxide compounds can be unhelpfully hydrolyzed. Therefore, when alkoxide compounds are used as sources of molybdenum, vanadium and/or antimony, it is preferable to Alcohol is used as the liquid medium.

Step (2) Oxidation treatment step:-

In step (2) of the process of the present invention, the solution or paste of the raw material mixture prepared in the aforementioned manner is subjected to at least one oxidation treatment selected from a group of (2-a) heat treatment at 50 to 300°C in the presence of an oxidizing gas. for one hour or more, and (2-b) treated with oxidizing gas, thus obtaining a solution or paste of an oxidized raw material mixture.

First, it is explained below regarding oxidation treatment (2-a).

There is no special definition regarding oxidizing gas. However, it is preferable to use at least one organ that selects from a pool consisting of oxygen, air and nitrogen oxides. Hydrogen oxides mean nitrous oxide, nitrogen monoxide, nitrogen dioxide, and the like. It is preferable to use oxygen or air as an oxidizing gas. The air may be in the form of oxygen-rich air or air containing an oxidizing gas. The air has a body rich in oxygen.

The heat treatment temperature in oxidation treatment (2-A) is in the range from 50 to 300°C, preferably from 50 to 200°C, and more preferably from 70 to 110°C. The heat treatment time is 1 hour or more, preferably 3 hours or more, and most preferably 4 to 15 hours.

It is preferable that the heating (oxidation) treatment (2-A) of the raw material solution or mixture be carried out in the presence of the oxidizing gas using a device equipped with a reflux condenser, an autoclave or similar, under conditions such that the raw material mixture is not dried out as a result of evaporation of the liquid medium.

For example, heat treatment (2-a) can be performed in the following manner. The solution or paste of the raw material mixture is subjected to oxidation treatment in a device equipped with a reflux condenser by heating at 70 to 110 ° C in the presence of oxidizing gas. It is preferable to stir the solution or paste of the raw material mixture in an oxidizing gas atmosphere to increase the interface area between the solution or paste of the raw material mixture and the oxidizing gas, thus promoting oxidation. It is more preferable for the oxidizing gas to be blown into the solution or paste of the raw material mixture. When a reflux condenser is not used, it is preferable to add an appropriate amount of water so that drying of the raw material mixture does not occur. When an autoclave is used for heat treatment (2-A), heat treatment (2-A) can be performed in a manner that includes adding the solution or paste of the raw material mixture to the autoclave, introducing the oxidizing gas into the autoclave, and subjecting the solution or paste of the raw material mixture to oxidation treatment at 100 to 300 degree Celsius, or more. The temperature is preferably between 100 and 150 degrees Celsius. When alcohol is used as a liquid medium, heating can be performed at 50 to 150°C by means of a device equipped with a reflux condenser. Preferably, the heat treatment time should be two hours or more, and more preferably 4 to 15 hours.

Secondly, clarification is made regarding oxidation treatment (2-b).

There is no special specification regarding the oxidizing fluid. However, the oxidizing liquid is preferably an aqueous solution of at least one oxidizing compound selected from a group consisting of hydrogen peroxide, nitric acid, and hypochlorous acid. Of these, an aqueous solution of hydrogen peroxide (i.e., aqueous hydrogen peroxide) is preferred. There is no special limitation regarding the amount of oxidizing fluid used. However, the molar ratio of the oxidizing compound contained in the oxidizing liquid is:

The antimony contained in the solution or paste of the raw material mixture is preferably 0.01 to 2, and more preferably 0.1 to 1.

After adding the oxidizing liquid to the solution or paste to the raw material mixture, the resulting mixture can be stirred while cooling to a temperature such that the liquid medium does not solidify (for example, when water is used as the liquid medium, at 0 to 20 C), and at a temperature around room (for example, 20 to 30°C) or during heating at a temperature of 100°C or less. When the mixture is heated to a temperature above the boiling point of the liquid medium, oxidative treatment can be performed by means such as an autoclave. The oxidizing treatment time should preferably be 30 minutes or more, and more preferably 1 to 2 hours.

It is preferable to keep the solution or paste of the oxidized raw material mixture produced by oxidation treatment according to the aforementioned methods (2-A) and/or (2-B) in an inert gas atmosphere.

With regard to the process for preparing the oxide catalyst described in the unexamined and open Japanese patent application specification numbers 157241-9 and 28862-10 above, it is possible that, when the catalyst is produced under air, in the step of preparing the solution or paste of the mixture of the raw material comprising On Mo compounds, V compounds, Sb compounds, and optionally Nb compounds, some oxidation reaction may occur. However, in the previous documents, no special treatment was performed to improve the oxidation state of V, Mo and Sb.

On the other hand, in the present invention, the oxidation state of V, Mo and Sb contained in a solution or paste of the raw material mixture is greatly improved by subjecting the solution or paste containing the V, Mo and Sb complex to at least the aforementioned special oxidation treatment. Through this treatment, it becomes possible to obtain Oxide catalyst which is not only almost unaffected by damage during acrylontrile (meth) production, but is also effective for producing acrylontrile (meth) with high productivity and high time frame productivity. Step (3): The step of adding the compound of element X (as a compound of an optional component element).

In step (3), element compound X may optionally be added as an optional component compound to the solution or paste of the oxidized raw material mixture in plan (2). When a solution or paste of the raw material mixture containing an insufficient amount of the element compound is prepared in step (1), and an appropriate amount of the element compound Step (2) before the drying process mentioned below. While the raw material mixture given in the aforementioned step (1) contains an element or X, this has no effect on the effectiveness of the present invention.

Step (4). Drying step:-

In step (4) in the process of the present invention, the aforementioned solution or paste is dried from the oxidizing raw material mixture in order to obtain a dried catalytic initiator.

The solution or paste of the oxidized raw material mixture may be dried by a known method, such as spray drying or evaporation drying. Spray drying may be accomplished, for example, by spraying and heating a solution or paste of the oxidized raw material in a dryer. Spray drying may be accomplished by centrifugal separation, by a two-stage flow hose or by a high-pressure hose method. As a heating source for drying, it is preferable to use air which may be heated by steam, electric heater and the like. It is preferable that the temperature of the dryer at the entrance to the dryer section be between 150 and 300 degrees Celsius. Spray drying may also be performed in a familiar manner by spraying a solution or paste of the oxidized raw material mixture onto an iron plate that has been heated to a temperature of 100 to 300°C.

The solution or paste of the oxidizing raw material mixture may be evaporatively dried by heating it in a vessel, such as a beaker (glass beaker) at 100 to 300 C. Heating time varies depending

It depends on the composition or quantity of the solution or paste of the oxidizing raw material, but in general it is from 5 minutes to 20 hours, and preferably from 5 minutes to 3 hours.

The dried catalytic initiator may be obtained in powder form for the previously mentioned drying step.

Step (5). Thermal cracking step

In step (5) of the process of the present invention, the previously mentioned dried catalyst initiator is thermally cracked in order to obtain an oxidized catalyst containing an oxide component represented in Figure (1) previously.

Thermal cracking may be done in a known way, for example, work may be done

Using a furnace, for example a rotary kiln, tunnel or tube kiln, blast furnace or

Fluid inclusion furnace. In general, thermal cracking is carried out in an atmosphere of inert gas, such as nitrogen gas, under atmospheric pressure, which is essentially devoid of oxygen, preferably under a flow of inert gas, at a temperature of 400 to 700 C, and preferably 500 to 700 C. 550 to 650 m is more preferred. In general, the thermal cracking time is from 0.5 to 5 hours, and preferably 1 to 3 hours. It is preferable that the oxygen concentration in the previously mentioned empty gas be 1000 parts per million or less, and preferably 100 parts per million or less as measured by gas chromatography or by oxygen detection. Thermal cracking may be done in a repetitive manner. Prior to thermal cracking, the dried catalytic starter may be subjected to a first thermal crack in an atmosphere or under air vapor at 200 to 420 C, preferably 250 to 350 C for 10 minutes to 5 hours. The catalyst produced by thermal cracking may be subjected to another thermal cracking in an air atmosphere at a temperature of 200 to 400 C for a period of 5 minutes to 5 hours.

The resulting catalyst may be crushed by crushing and subjected to further thermal cracking.

When it is desired to produce a catalyst supported on silica, the addition of (silica colloid) may be made.

At any time in the previously mentioned steps (1) and (2). In general, the amount of silica is in the range from 20 to 60% by weight, and preferably 20 to 40% by weight, depending on the total weight of the catalyst and silica.

It is preferable to use silica colloid stabilized with ammonium ions to prevent gelatin formation. Preferably, the silica colloidal solution contains ammonium ions in sufficient quantity to maintain the pH of the silica colloidal at about 9.7.

It is preferable to use the oxide catalyst resulting from the process of the present invention, which includes the previously mentioned steps (1) to (5), to produce (such as) acrylontrile with a high yield and in a high time frame. However, when a base-treated oxide catalyst is used resulting from the process identical to another form of the present invention which also includes the steps of (6) contacting the aforementioned oxide catalyst with a base aqueous solution to obtain a contact mixture containing the base-treated oxide catalyst, and (7) Separating and extracting the aforementioned base-treated oxide catalyst from the contact mixture, and it has become possible to produce (meth) acrylontrile in an improved yield and in an improved time frame. In this way, it is noted that, by this embodiment, it is also possible to prevent the decomposition of ammonia, which is one of the materials producing (meth)acrylontrile, into nitrogen. The reason for obtaining these excellent effects has not yet been concluded. However, it is considered as follows: The oxide catalyst produced in step (5) contains undesired and inactive phases of component oxides, such as non-crystalline molybdenum oxide, and these inactive and undesirable phases of component oxides catalyze the combustion or decomposition of ammonia or (meth). acrylontrile. However, by treatment with a basic aqueous solution, undesirable inactive phases may be removed from the component oxides mentioned above, so as not only to prevent the resulting and time-space product of improved (meth)acrylontrile, but

The decomposition of ammonia into nitrogen is also prevented.

Here below, an explanation is made regarding the previously mentioned steps (6) and (7)

For treatment with a basic aqueous solution.

In step (6), the oxide catalyst is brought into contact with the base aqueous solution in order to obtain a contact mixture containing an oxide catalyst treated with a base.

Examples of basic substances present in a basic aqueous solution include ammonia, hydroxides, carbonates and salts of organic acids (for example, oxalates, acetates and stearates, from metallic minerals such as lithium, sodium, potassium, rubidium, cesium and the like, hydroxides, carbonates and salts of organic acids) For example, oxalates, acetates and stearates) of metallic earth minerals, such as beryllium, magnesium, calcium, strontium, barium and the like, and amines, such as ethylamine, methylamine and the like, especially aqueous ammonia. In general, the concentration of the basic substance in the basic aqueous solution is in the range from 0.1 to 30% by weight, and preferably from 1 to 10% by weight.

As examples of methods for contacting an oxide catalyst with a basic aqueous solution, a discontinuous process method and a flow process method may be cited.

When the intermittent process method is used, the oxide catalyst is suspended in a basic aqueous solution in a tank reactor to obtain a contact mixture in the form of a suspension. It is preferable that the weight ratio of the catalyst to the basic aqueous solution be in the range from 1 to 20% by weight. There is no special definition regarding the period during which the oxide catalyst is in contact with the basic aqueous solution. However, 2 hours or more is preferred, and 6 hours or more is preferable. It is preferable that the temperature of the basic aqueous solution be in the range from 0 to 100 °C. When aqueous ammonia is used as a basic aqueous solution, it is preferable that the temperature of the basic aqueous solution be in the range from 0 to 50 °C. To perform effective precise contact of the oxide catalyst with the basic aqueous solution, it is preferable to stir the contact mixture using a stirrer or blow gas into the contact mixture. There is no special definition regarding the previously mentioned gas. However, it is preferable to use a gas which does not change the basic aqueous solution into a neutral solution. Examples of these gases include air, nitrogen gas, and trace gases. As an example of a flow process method, a method may be given in which a basic aqueous solution is flowed through a stabilized layer formed by charging an oxide catalyst in a reactor.

In step (7), the base-treated oxide catalyst is separated and extracted from the contact mixture. Separation may be done by centrifugation, filtration using a filter paper or filter membrane, aeration (pouring from one container to another), and the like. It is preferable that the separated oxide catalyst extracted from the previously mentioned contact mixture be washed with water, followed by drying. Drying may be done after the previously mentioned treatment with basic aqueous solution, using a heated air dryer, a room with a constant temperature, or similar, at 100 to 150 C.

Also, in the process of the present invention, as step (8), it is detailed thermal cracking (the base-treated oxide catalyst extracted in the previously mentioned step (7). Thermal cracking may be performed after treatment with aqueous base solution after the same conditions as in the thermal cracking in the aforementioned step. Previously (5), thermal cracking may be carried out in an inert gas atmosphere, such as nitrogen gas or the like, which is essentially devoid of oxygen, preferably under an inert gas flow, at 400 to 700 C, and preferably 500 to 700 C. , preferably from 550 to 650 m.

The method involving pretreatment using basic aqueous brine in the previously mentioned steps (6) and (7) and subsequent thermal cracking in the previously mentioned step may be performed in a repeated manner in order to improve the yield and time space yield for (meth) acrylontrile.

Hereinafter, an explanation is made regarding the process of producing (meth)acrylontrile from propane or isobutane by adding ammonium oxide in the gas phase in the presence of an oxygen catalyst containing the oxide of the compound prepared by the process of the present invention.

The raw shipment mixture containing propane or isobutane and ammonia does not need to be highly pure but may be of commercial interest.

Examples of oxygen sources include air, oxygen-rich air, and pure oxygen. Also, this molecular oxygen source may be diluted with helium, aragon, nitrogen, carbon dioxide, steam or the like.

In general, the molar ratio of ammonia to propane or isobutane to add ammonium oxide may be in the range of 0.1 to 1.5, and preferably 0.2 to 1.2.

In general, the molar ratio of molecular oxygen to the propane or isobutane used to add ammonium oxide may be in the range from 0.2 to 6, and it is preferable to

From 0.4 to 4.

In general, the ammonium oxide addition pressure is in the range from 0.1 to 10

Air, preferably 1 to 3 air.

In general, the ammonium oxide addition temperature ranges from 350 to 600 C, and preferably from 380 to 470 C.

In general, the contact time (contact time) between the gaseous raw charge and the catalyst is in the range from 0.1 to 30 (Multidot.g. sec/ml), and preferably from 0.5 to 10 (Multidot.g. sec/ml).

In the process of the present invention, the contact time is determined according to the following formula:

Contact time (Multidot.g seconds/milli) ##EQU1 ## where:-

represents the weight (in grams) of the catalyst in the reactor,

F represents the flow rate (ml/s) of the feedstock mixture gas {as measured under conditions of normal temperature and normal pressure (0°C, 1 atm)} T represents the ammonium oxide addition reaction temperature (°C), and P represents the reaction pressure Addition of ammonium oxide (aerial).

The reaction of the present invention may be carried out in a conventional reactor, such as a fixed bed reactor,

Fluid bed reactor or moving bed reactor.

The reaction method used in the process of the present invention may be either a single pass method or a recirculation method.

The best way to conduct the interaction

Hereinafter, the present invention is described in greater detail by reference to the following examples and comparative examples, which are for illustrative purposes only and are not to be taken as a limitation of the scope of the present invention.

In the following and comparative examples, the conversion (%) of propane, the selectivity or responsiveness (%) of acrylonitrile, the yield (%) of acrylonitrile, and the time-space ratio [Multidot.g]/mu.mol sec/milli) are defined. g}] for acryllontrile and the ammonia decomposition rate (%), each one used to evaluate the results of adding ammonium oxide to propane, as follows:

##EQU2##

Example 1

Preparation of oxide catalyst

An oxide catalyst containing an oxide compound represented by the formula was prepared:

Mo1.0 V.0.33 Sb.0.17 Nb0.05 On where n is a specific number consistent with the valence requirements of the other elements present in the compound oxide in the previous formula, which uses the n shown in the formulas representing the resulting compound oxides in all of the following and comparative examples, as follows.

2.16 g of ammonium metavanadate (NH4 VO3) and 1.41 g of antimony oxide (Sb2O3) (III) were added to 80 g of water, and the resulting mixture was heated at 110 C for 24 hours under reflux, using an oil bath, under Atmospheric pressure while stirring. Then, to the resulting binary (double) mixture paste, 10 g of ammonium hepta molybdate [(NH4)6MO7O244H2O] was added to obtain a raw material mixture solution containing

Molybdenum (Mo), vanadium (V) and antimony (Sb). The resulting mixture was subjected to an oxidation treatment, whereby the solution was stirred for 4 hours, using a bath.

Water, in an atmosphere of air under atmospheric pressure while the solution temperature is maintained at 85°C, to obtain an oxidized raw material mixture solution. The resulting oxidant mixture solution was cooled to room temperature.

Separately, 0.50 g of niobic acid (Nb2O2, content: 76%) was dissolved

by weight) and 0.96 g of oxalic acid dihydrate (H2C2O42H2O) in 25 g

of water at 70°C, and the resulting solution was cooled to 30°C within 30 minutes) to obtain an aqueous solution containing niobium. The resulting aqueous solution containing niobium was added to the previously produced oxidized raw material mixture solution and stirred in air at 30°C for 30 minutes, to obtain an oxidized raw material mixture solution containing niobium.

The resulting solution of the oxidized raw material mixture containing niobium was subjected to spray drying, where the solution was sprayed on an iron plate sealed with Teflon heated to 140 °C, to obtain a dried fractionated catalytic initiator. 2.2 g of the resulting catalytic starter was subjected to heat treatment under air steam for 1 hour using a thermostat at 300 C.

The resulting catalytic starter was charged into a quartz tube with an inner diameter of 0.2 mm, and then it was thermally cracked at 600°C for two hours under nitrogen gas vapor at a flow rate of 350 m/min (mL means mL as measured under conditions of normal temperature and pressure, Named 0 m below 1 atmosphere, to obtain an oxide catalyst containing an oxide compound of the previous formula.

Regarding the oxygen concentration in the nitrogen gas used for thermal cracking, the measurement was made using an oxygen detection analyzer (type 306WA, manufactured and sold by Teledyne Analytical Instruments, USA). As a result, it was found that the oxygen concentration in nitrogen gas was 1 part per million. Ammonium oxide treatment of propane

Propane was treated with ammonium oxide in the presence of the previously generated oxide catalyst by a method described below.

0.3 g of the resulting catalyst was charged into a fixed-bed reaction tube with an inner diameter of 1 mm. In the reaction tube containing the catalyst, ammonium oxide treatment of propane was carried out under conditions such that the temperature (T) was 430°C and the flow rate (F) of the gaseous raw charge mixture (i.e., a gaseous mixture of propane, ammonia, molecular oxygen and helium) was 5, 5 ml/min, and the molar ratio [propane: ammonia: molecular oxygen: helium] in the gaseous raw charge mixture was 1: 1, 2: 2, 8: 12, the pressure (p) was 1 atmosphere, and the contact time was (contact time ) between the catalyst and the mortal raw charge mixture is 1.17 g. Multidot sec/ml The resulting gas reaction mixture was subjected to analysis by an actuated gas chromatograph (GC-14B, manufactured and sold by Shimadzu Corporation, Japan). The results of the previous ammonium oxide addition are shown in Table 1.

Example 2

Preparation of oxide catalyst

An oxide catalyst containing an oxide compound represented by the formula was prepared:

Mo V.0.33 Sb.0.17 Nb0.05 On

Essentially in a manner similar to Example 1, except that the solution of the raw material mixture was subjected to an oxidation treatment in which the solution was stirred for 6 hours, using a water bath, in air at atmospheric pressure while the temperature of the solution was maintained at 100°C, followed by cooling to Room temperature. Treating propane with ammonium oxide

Ammonium oxide treatment of propane was carried out in the presence of the previously produced oxide catalyst under the same conditions as in Example 1. The results of the ammonium oxide treatment are shown in Table 1.

Example 3

Preparation of oxide catalyst

An oxide catalyst was prepared containing a compound represented by the formula:

Mo V.0.33 Sb.0.17 Nb0.05 On

Essentially in a manner similar to Example 1, except that the solution of the raw material mixture was subjected to an ammonium oxide addition treatment in which the solution was stirred for 8 hours, using a water bath, in air at atmospheric pressure while the temperature of the solution was maintained at 75°C.

Treating propane with ammonium oxide

Ammonium oxide treatment of propane was carried out in the presence of the previously produced oxide catalyst under the same conditions as in Example 1. Except that the flow rate (F) of the raw charge mixture was increased to 4.3 ml/min and the contact time was increased to 1.50 g. Multidot sec/ml The results of adding ammonium oxide are shown in Table 1. Example 4

Preparation of oxide catalyst

An oxide catalyst containing an oxide compound represented by the formula was prepared:

Mo V.0.33 Sb.0.17 Nb0.05 On

Essentially in a manner similar to Example 1, except that the solution of the raw material mixture was subjected to an oxidation treatment in which the solution was stirred for 10 hours, using a water bath, in air at atmospheric pressure while the temperature of the solution was maintained at 95°C.

Treating propane with ammonium oxide

Ammonium oxide treatment of propane was carried out in the presence of the previously produced oxide catalyst under the same conditions as in Example 1. The results of the ammonium oxide treatment are shown in Table 1.

Example 5

Preparation of oxide catalyst

An oxide catalyst containing an oxide compound represented by the formula was prepared:

Mo V.0.33 Sb.0.17 Nb0.05 On

Essentially in a manner similar to Example 1, except that the raw material mixture solution was subjected to an oxidation treatment in which the solution was charged to a 500 ml autoclave with a Teflon liner on the inner wall and sealed together with air in the autoclave, followed by agitation at 150 °C under a pressure of 0. ,8 MPa for 2 hours.

Treating propane with ammonium oxide

Ammonium oxide treatment of propane was carried out in the presence of the previously produced oxide catalyst under the same conditions as in Example 1. Except that the flow rate (F) of the raw charge mixture was changed to 4.6 mS/min and the contact time was changed to 1.40 g. Multidot sec/ml The results of adding ammonium oxide are shown in Table 1.

Example 6

Preparation of oxide catalyst

An oxide catalyst was prepared containing a compound represented by the formula:

Mo V.0.33 Sb.0.17 Nb0.05 On

Essentially in a manner similar to Example 1, except that the raw material mixture solution was subjected to an oxidation treatment in which 0.8 g of 5% (w/w) aqueous hydrogen peroxide was added to the raw material mixture solution and stirred at 30°C under atmospheric pressure for 30 minutes. In the oxidation treatment (previously), the molar ratio of hydrogen peroxide (H2O2) present in the aqueous hydrogen peroxide used to the antimony (Sb) present in the solution of the raw material mixture (hereinafter, usually referred to in a simple way &molar ratio was 0.12 H2O2: Sb.

Treating propane with ammonium oxide

Ammonium oxide treatment of propane was carried out in the presence of the previously produced oxide catalyst under the same conditions as in Example 1. The results of the treatment with the addition of ammonium oxide are explained

In Table 1.

Example 7

Preparation of oxide catalyst

An oxide catalyst was prepared containing a compound represented by the formula:

Mo V.0.33 Sb.0.17 Nb0.05 On

Essentially in a manner similar to Example 6, except that the raw material mixture solution was subjected to an oxidation treatment in which 3.4 g of 5% (w/w) aqueous hydrogen peroxide was added to the raw material mixture solution at 30 C at atmospheric pressure for 1 hour. In the previous oxidation treatment, the molar ratio of H2O2: Sb was 0.25.

Treating propane with ammonium oxide

Ammonium oxide treatment of propane was carried out in the presence of the previously produced oxide catalyst under the same conditions as in Example 1. The treatment results with the addition of ammonium oxide are shown in Table 2.

Example 8

Preparation of oxide catalyst

An oxide catalyst was prepared containing a compound represented by the formula:

Mo V.0.33 Sb.0.17 Nb0.05 On

Essentially in a manner similar to Example 6, except that the raw material mixture solution was subjected to an oxidation treatment in which 2 g of 5% (w/w) aqueous hydrogen peroxide was added to the raw material mixture solution at 20 C at atmospheric pressure for 2 hours. In the previous oxidation treatment, the molar ratio of H2O2: Sb was 0.30.

Treating propane with ammonium oxide

Ammonium oxide treatment of propane was carried out in the presence of the previously produced oxide catalyst under the same conditions as in Example 1. The treatment results with the addition of ammonium oxide are shown in Table 2. Example 9

Preparation of oxide catalyst

An oxide catalyst was prepared containing a compound represented by the formula:

Mo V.0.33 Sb.0.17 Nb0.05 On

Essentially in a manner similar to Example 6, except that the raw material mixture solution was subjected to an oxidation treatment in which 5.5 g of aqueous hydrogen peroxide% (w/w) was added to the raw material mixture solution at 20 C under atmospheric pressure for 45 minutes. . In the previous oxidation treatment, the molar ratio of H2O2: Sb was 0.83. Treating propane with ammonium oxide

Ammonium oxide treatment of propane was carried out in the presence of the previously produced oxide catalyst under the same conditions as in Example 1. The treatment results with the addition of ammonium oxide are shown in Table 2.

Example 10

Preparation of oxide catalyst

An oxide catalyst was prepared containing a silica carrier supported by a complex oxide (silica carrier containing: 30% by weight related to silicon oxide SiO2, based on the total weight of the complex oxide and the silica carrier, in which the complex oxide is represented by the formula: -

Mo V.0.33 Sb.0.17 Nb0.05 On

as follows.

0.86 g ammonium methavanadate (NH4VO3) and 0.54 g ammonium oxide were added

antimony (Sb2O3)(III) to 50 g of water, and the resulting mixture was heated at 120 C for

8 hours under reflux, using an oil bath, in air under atmospheric pressure, with stirring. Then, to the resulting binary mixture paste, 5 g of ammonium heptamolybdate [NH4)6MO7O244H2O)] was added to obtain a raw material mixture solution containing

Molybdenum (Mo), vanadium (V) and antimony (Sb). The resulting raw material mixture solution was subjected to an oxidation treatment, whereby the solution was stirred for 4 hours, using a water bath, in an atmosphere of air under atmospheric pressure while the temperature of the solution was maintained at 80°C, in order to obtain an oxidized raw material mixture solution. The resulting oxidant mixture solution was cooled to 30°C, and then, 0.96 g of 30% (w/w) aqueous hydrogen peroxide was added to the resulting solution and stirred for 40 minutes, in order to perform another oxidation treatment. In the other oxidation treatment, the molar ratio [H2O2: Sb2] was 2.3. To the resulting oxidized raw material mixture solution, 7.89 g of silica colloid with a SiO2 content of 30% by weight was added while stirring, in order to obtain an oxidized raw material mixture solution containing silica.

Separately, 0.25 g of niobic acid (Nb2O5 content: 76%) was dissolved

(by weight) and 0.48 g of oxalic acid dihydrate (H2C2O4H2O) in 5 g of water at 70 C, and the resulting solution was cooled to 30 C, to obtain an aqueous solution containing niobium. The resulting aqueous solution containing niobium was added to the previously produced oxidized raw material mixture solution containing silica and stirred in air at 30 C for 30 minutes, in order to obtain the oxidized raw material mixture solution containing niobium and silica.

The resulting oxidized raw material mixture solution containing niobium and silica was subjected to spray drying, whereby the solution was sprayed on an iron plate covered with Teflon heated to 140 °C, in order to obtain a dried fractionated catalytic initiator. 2.2 g of the resulting catalytic starter was subjected to heating treatment under a stream of air for 1 hour using a thermostatic device at 300 C. The resulting catalytic initiator was charged into a diameter quartz tube

Inner 20 mm, and then thermally cracked at 600 C for two hours under a stream of nitrogen gas at a flow rate of 350 mL/min, in order to obtain an oxide catalyst contained on a silica carrier supported by the oxide compound of the previous formula.

Regarding the oxygen concentration in the nitrogen gas used for thermal cracking, the measurement was made with an oxygen detection analyzer (type 306 WA, manufactured and sold by Teledyne Analytical Instruments, USA) and as a result, the oxygen concentration in the nitrogen gas was found to be 1 ppm.

Ammonium oxide treatment of propane

Treatment of propane with ammonium oxide was carried out in the presence of the previously produced oxide catalyst containing a silica carrier supported by the compound oxide in a manner described below.

0.3 g of the resulting catalyst was charged into a fixed-bed reaction tube with an inner diameter of 4 mm. In the reaction tube containing the catalyst, ammonium oxide treatment of propane was carried out under conditions such that the temperature (T) was 430°C and the flow rate (F) of the gaseous crude charge mixture (i.e., a gaseous mixture of propane, ammonia, molecular oxygen and helium) was 5 ml. m/min, and the molar ratio [propane: ammonia: molecular oxygen: helium] in the gaseous raw charge mixture was 1: 0.95: 2.57: 10.65, the pressure (P) was 1 atmosphere, and the contact time (contact time) was Between the catalyst and the mortal raw charge mixture is 1.29 g. Multidot sec/ml The resulting gas reaction mixture was subjected to analysis by an actuated gas chromatograph (GC-14B, manufactured and sold by Shimadzu Corporation, Japan). The results of the previous ammonium oxide addition are shown in Table 2.

Example 11

Preparation of oxide catalyst

An oxide catalyst containing an oxide compound represented by the formula was prepared:

Mo1.0 V.0.33 Sb.0.13 Ti0.06 On

as follows.

5.48 g of ammonium metavanadate (NH4 VO3) and 2.96 g of antimony oxide (Sb2O3) (III) were added to 109.5 g of water, and the resulting mixture was heated at 100 C for 8 hours under reflux, using an oil bath. , under atmospheric pressure with stirring. Then, to the resulting binary (double) mixture paste, 27.47 g of ammonium hepta molybdate [NH4)6MO7O244H2O)] were added to obtain a raw material mixture solution containing

Molybdenum (Mo), vanadium (V) and antimony (Sb). The resulting raw material mixture solution was subjected to an oxidation treatment, in which the solution was stirred for 4 hours, using a water bath, in an atmosphere of air under atmospheric pressure while the temperature of the solution was maintained at 80°C, in order to obtain the oxidized raw material mixture solution. The resulting oxidant mixture solution was cooled to 30°C, and then, 0.96 g of 30% (w/w) aqueous hydrogen peroxide was added to the resulting solution and stirred for 40 minutes, in order to perform another oxidation treatment. In the other oxidation treatment, the molar ratio [H2O2 : Sb2] was 0.42.

Separately, 2.44 g of ammonium titanyl oxalate [NH4)2 TiO (C2O4)2] was dissolved in air at 30 C for 30 minutes, to obtain a titanium-containing oxidized feedstock mixture solution.

The resulting titanium-containing oxidized feedstock mixture was subjected to spray drying, in which the solution was sprayed onto a Teflon-sealed iron plate heated to 140 °C, in order to obtain a dried fractionated catalytic initiator. 3 g of the resulting catalytic starter was subjected to heat treatment under air flow for 1 hour using a thermostat at 300 C. The resulting catalyst starter was charged to a quartz tube with an inner diameter of 20 mm, and then it was thermally cracked at 600 C for two hours under a stream of nitrogen gas at a flow rate of 350 mSi/min, in order to obtain an oxide catalyst containing the oxide compound of the previous formula. Regarding the oxygen concentration in nitrogen gas for thermal cracking, the measurement was made using an oxygen detection analyzer (type 306WA,

Manufactured and sold by Teledyne Analytical Instruments USA). As a result, it was found that the oxygen concentration in nitrogen gas was 1 part per million. Ammonium oxide treatment of propane

Propane was treated with ammonium oxide in the presence of the previously produced oxide catalyst by a method described below.

1.5 g of the resulting catalyst was charged into a fixed bed reaction tube having an inner diameter of 9.5 mm. In the reaction tube containing the catalyst, ammonium oxide treatment of propane was carried out under conditions such that the temperature (T) was 430°C and the flow rate (F) of the gaseous raw charge mixture (i.e., a gaseous mixture of propane, ammonia, molecular oxygen and helium) was 23, 3 mN/min, and the molar ratio (propane: ammonia: molecular oxygen: helium] in the gaseous raw charge mixture was 1: 1.2: 2.7: 12.3, the pressure (P) was 1 atmosphere, and the contact time (contact time) between the catalyst and the gaseous raw charge mixture was 1.67 Multidot.g sec/ml. The resulting gas reaction mixture was subjected to analysis by an operating gas chromatograph (GC- 14B, manufactured and sold by Shimadzu Corporation, Japan). The results of the previous ammonium oxide addition are shown in Table 2.

Comparative example 1

Preparation of oxide catalyst

An oxide catalyst containing an oxide compound represented by the formula was prepared:

Mo1.0 V.0.33 Sb.0.17 Nb0.05 On

Essentially in a similar manner as in Example 1, except that the oxidation treatment of the raw material mixture solution was removed and instead, the solution was cooled to 30°C over 30 minutes using a water bath.

Treating propane with ammonium oxide

Ammonium oxide treatment of propane was performed in the presence of the previously produced oxide catalyst under the same conditions as in Example 1, except that the flow rate (F) of the charge mixture was changed.

The gaseous crude was reduced to 2.75 ml/min, and the contact time was changed to 2.33 g. Multidot sec/ml The results of adding ammonium oxide are shown in Table 2.

Comparative example 2

Preparation of oxide catalyst

An oxide catalyst containing a silica carrier supported by a complex oxide was prepared (silica carrier containing: 30% by weight related to silicon oxide SiO2, based on the total weight of the complex oxide and the silica carrier, in which the complex oxide is represented by the formula:

Mo V.0.26 Sb.0.13 Nb0.05 On

Essentially in the same manner as in Example 10, except that the treatment is not carried out by oxidizing the raw material mixture solution (by which the solution is heated in an air atmosphere), and instead, the raw material mixture solution is immediately cooled to 30°C, and no addition is made to Aqueous hydrogen oxide.

Treating propane with ammonium oxide

Ammonium oxide treatment of propane was carried out in the presence of the previously produced oxide catalyst containing a silica carrier supported by murk oxide under the same conditions as in Example 10. The results of the ammonium oxide treatment are shown in Table 2.

Comparative example 3

Preparation of oxide catalyst

An oxide catalyst containing an oxide compound represented by the formula was prepared:

Mo V.0.3 Sb.0.13 Ti0.06 On

Essentially in the same manner as in Example 10, except that the treatment is not carried out by oxidizing the raw material mixture solution (by which the solution is heated in an air atmosphere), and instead, the raw material mixture solution is immediately cooled to 30°C, and no addition is made to Aqueous hydrogen oxide.

Treating propane with ammonium oxide

Ammonium oxide treatment of propane was carried out in the presence of the previously produced oxide catalyst containing a silica carrier supported by murk oxide under the same conditions as in Example 11. The results of the ammonium oxide treatment are shown in Table 2.

Example 12

Preparation of oxide catalyst

An oxide catalyst containing an oxide compound represented by the formula was prepared:

Mo1.0 V.0.29 Sb.0.14 Nb0.06 On

as follows.

1.92 g of ammonium metavanadate (NH4 VO3) and 1.16 g of antimony (III) oxide (Sb2O3) were added to 80 g of water, and the resulting mixture was heated at 100 C for 8 hours under reflux, using an oil bath, under Atmospheric pressure while stirring. Then, to the resulting binary (double) mixture paste, 10 g of ammonium hepta molybdate [(NH4)6MO7O244H2O] was added to obtain a raw material mixture solution containing

Molydinium (Mo), vanadium (V) and antimony (Sb). The resulting raw material mixture solution was subjected to an oxidation treatment, in which the solution was stirred for 4 hours, using a water bath, in an atmosphere of air under atmospheric pressure while the temperature of the solution was maintained at 85°C, in order to obtain the oxidized raw material mixture solution. The resulting oxidant mixture solution was cooled to room temperature.

Separately, 0.60 g of niobic acid (Nb2O2, content: 76%) was dissolved

by weight) and 0.96 g of oxalic acid dihydrate (H2C2O42H2O) in 25 g

of water at 70 °C, and the resulting solution was cooled to 30 °C to obtain an aqueous solution containing niobium. The resulting aqueous solution containing niobium was added to the previously produced oxidized raw material mixture solution and stirred in air at 30°C for 30 minutes, to obtain an oxidized raw material mixture solution containing niobium.

The resulting oxidized feedstock mixture solution containing niobium was subjected to spray drying, where the solution was sprayed on an iron plate sealed with Teflon heated to 140 C, to obtain a dried fractionated catalytic initiator. 12 g of the resulting catalytic starter was subjected to heat treatment under air steam for 1 hour using a thermostat at 300 C. The resulting catalyst starter was charged to a quartz tube with an inner diameter of 20 mm, and then it was thermally cracked at 600 C for two hours under nitrogen gas steam at a flow rate of 350 mS/min in order to obtain an oxide catalyst containing the oxide compound of the previous formula.

Regarding the oxygen concentration in the nitrogen gas used for thermal cracking, the measurement was made using an oxygen detection analyzer (type 306WA, manufactured and sold by Teledyne Analytical Instalments, USA). As a result, it was found that the oxygen concentration in nitrogen gas was 1 part per million.

Ammonium oxide treatment of propane

Propane was treated with ammonium oxide in the presence of the previously generated oxide catalyst by a method described below.

0.3 g of the resulting catalyst was charged into a fixed-bed reaction tube with an inner diameter of 4 mm. In the reaction tube containing the catalyst, ammonium oxide treatment of propane was carried out under conditions such that the temperature (T) was 430°C and the flow rate (F) of the gaseous crude charge mixture (i.e., a gaseous mixture of propane, ammonia, molecular oxygen and helium) was 6 ml. m/min, and the molar ratio [propane: ammonia: molecular oxygen: helium] in the mortal crude charge mixture was 1:1.2:2.9:11.9, the pressure (P) was 1 atmosphere, and the contact time was (contact time ) between the catalyst and the mortal raw charge mixture is 1.17 g. Multidot sec/ml and the resulting gas reaction mixture was subjected to analysis by an operating gas chromatograph. The results of adding the previous ammonium oxide are shown in Table 3.

Example 13

Treatment of the oxide catalyst with a basic aqueous solution

3 g of the oxide catalyst produced in Example 12 is added to 50 g of 5%

by weight aqueous ammonia, and then, the resulting suspension was stirred in air at 25 °C under atmospheric pressure for 8 hours to obtain a suspension containing a base-treated oxide catalyst. The resulting suspension was subjected to absorption filtration to separate and remove aqueous ammonia from the base-treated oxide catalyst, and thus the base-treated oxide catalyst was extracted from the suspension. After filtration, the extracted catalyst was washed four times with 50 mL of purified water and dried in a thermostat at 200 C. The resulting catalyst starter was charged into a quartz tube with an inner diameter of 20 mm, and then thermally cracked at 550 C for two hours under a stream of nitrogen gas at a flow rate of 350 ml/min, to obtain a base-treated thermally cracked oxide catalyst. The nitrogen gas used in thermal cracking was the same as that used in thermal cracking in Example 12.

Ammonium oxide treatment of propane

An addition of ammonium oxide to propane was made in the presence of a previously produced base-treated thermally broken oxide catalyst under conditions as in Example 12.

The results of treatment with ammonium oxide to propane are shown in Table 3.

Example 13

Treatment of catalytic oxide with a basic aqueous solution

4.5 g of the oxide catalyst produced in Example 12 is added to 80 g of 5%

wt aqueous ammonia, and then, the resulting suspension was stirred in air at 25 °C under atmospheric pressure for 15 hours to obtain a suspension containing a base-treated oxide catalyst. The resulting suspension was subjected to absorption filtration to separate and remove aqueous ammonia from the base-treated oxide catalyst, and thus the base-treated oxide catalyst was extracted from the suspension. After filtration, the extracted catalyst was washed four times with 50 ml of...

Pure water, and dried in a thermostat at 200°C under a stream of air. The resulting catalyst starter was charged into a quartz tube with an inner diameter of 20 mm, and then thermally cracked at 550 C for two hours under a stream of nitrogen gas at a flow rate of 500 ml/min, to obtain a base-treated thermally cracked oxide catalyst. The nitrogen gas used in thermal cracking was the same as that used in thermal cracking in Example 12.

Ammonium oxide treatment of propane

An addition of ammonium oxide to propane was made in the presence of a previously produced base-treated thermally cracked oxide catalyst under conditions as in Example 12. Except that the flow rate (F) of the raw charge mixture was changed to 6.4 mL/min and the contact time was changed. 1 to 1.10 Multidot.g sec/mm. The results of ammonium oxide to propane treatment are shown in Table 3. Example 15

Preparation of catalytic oxide

A preserving oxide was prepared containing a compound oxide represented by the formula:

Mo V.0.31 Sb.0.14 Nb0.05 On

Essentially the same method as in Example 12, except that 2.05 g of ammonium metavanadate (NH4 VO3) was used, 1.16 g of antimony (III) oxide (Sb2O3) was used, and 0.50 g of niobic acid (Nb2O2, Content: 76% by weight).

Ammonium oxide treatment of propane

An addition of ammonium oxide to propane was made in the presence of the previously produced oxide catalyst under the same conditions as in Example 12. The results of the ammonium oxide treatment to propane are shown in Table 3.

Example 16

Treatment of the oxide catalyst with a basic aqueous solution

3 g of the resulting oxide catalyst was added in example 15 to 50 g of 10%

wt aqueous ammonia, and then, the resulting suspension was stirred in air at 25 C under atmospheric pressure for 6 hours, to obtain a suspension containing a base-treated oxide catalyst. The resulting suspension was subjected to filtration under absorption to separate and remove aqueous ammonia from the base-treated oxide catalyst, so that the base-treated oxide catalyst was extracted from the suspension. After filtration, the extracted catalyst was washed four times with 50 mM pure buffer, and dried in a thermostat at 200 °C under an air stream. All the dried catalyst was charged to a quartz tube with an inner diameter of 20 mm, and then thermally cracked at 550 C for two hours under a stream of nitrogen gas at a flow rate of 500 mN/min, to obtain a base-treated thermally cracked oxide catalyst. The nitrogen gas used in thermal cracking was the same as that used in thermal cracking in Example 12.

Ammonium oxide treatment of propane

An addition of ammonium oxide to propane was made in the presence of a previously produced base-treated thermally broken oxide catalyst under the same conditions as in Example 12. The results of the ammonium oxide treatment to propane are shown in Table 3.

Example 17

Treatment of the oxide catalyst with a basic aqueous solution

1.5 g of the resulting oxide catalyst was added in example 15 to 50 g of 2%

wt aqueous ammonia, and then, the resulting suspension was stirred in air at 25 C under atmospheric pressure for 6 hours, to obtain a suspension containing a base-treated oxide catalyst. The resulting suspension was subjected to filtration under absorption to separate and remove aqueous ammonia from the oxide catalyst treated with the base, so that the oxide catalyst treated with the base was extracted from

Commentator. After filtration, the extracted catalyst was washed four times with 50 mM pure buffer, and dried in a thermostat at 200 °C under an air stream. All the dried catalyst was charged to a quartz tube with an inner diameter of 20 mm, and then thermally cracked at 550 C for two hours under a stream of nitrogen gas at a flow rate of 350 mS/min, to obtain a base-treated thermally cracked oxide catalyst. The nitrogen gas used in thermal cracking was the same as that used in thermal cracking in Example 12.

Ammonium oxide treatment of propane

An addition of ammonium oxide to propane was made in the presence of a previously produced base-treated thermally cracked oxide catalyst under the same conditions as in Example 12. The results of the ammonium oxide treatment to propane are shown in Table 3. Example 18

Treatment of the oxide catalyst with a basic aqueous solution

1.5 g of thermally cracked and treated oxide catalyst was added to the resulting base in example 15 to 25 g of 10 wt% aqueous ammonia, and then, the resulting suspension was stirred in air at 25 C under atmospheric pressure for 8 hours, to obtain a suspension Contains double base treated oxide catalyst. The resulting suspension was subjected to filtration under absorption to separate and remove aqueous ammonia from the double-base treated oxide catalyst, so that the double-base treated oxide catalyst was extracted from the suspension. After filtration, the extracted catalyst was washed four times with 50 mM pure buffer, and dried in a thermostat at 200 °C under an air stream. All the dried catalyst was charged to a quartz tube with an inner diameter of 20 mm, and then thermally cracked at 550 C for two hours under a stream of nitrogen gas at a flow rate of 350 mS/min, to obtain a double-base treated thermally cracked oxide catalyst. The nitrogen gas used in thermal cracking was the same as that used in thermal cracking in Example 12.

Ammonium oxide treatment of propane

An addition of ammonium oxide to propane was made in the presence of a thermally cracked oxide catalyst treated with a double base produced under the same conditions as in Example 12. Except that the weight of the catalyst was changed to 0.1 g, the flow rate (F) of the gaseous raw charge mixture was set to 12 ml/min, and the contact time was changed to 0.58 multidot.g sec/ml. The results of adding ammonium oxide are shown in Table 3.

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Industrial applicability:-

When the oxide catalyst produced by the process of the present invention is used in the production of acrylontrile and acrylontrile, not only is spoilage of the catalyst prevented, but the desired acrylontrile or acrylontrile may also be produced with a high treatment yield and lead time. Thus, efficient and equivalent production of acrylontrile or methacrylontrile may be achieved in a consistent manner

for an extended period of time.

Also, when a base-treated oxide catalyst is used, which may be obtained by treating the above-mentioned oxide catalyst with a base aqueous solution, not only the above-mentioned excellent effects may be achieved but it also becomes possible to prevent the decomposition of ammonia, which is one of the materials for the production of acryllontrile or meth-acrylontrile. In order to significantly stimulate the use of ammonia.