JPH1133399A - Improved oxidizing catalyst based on vanadium-antimony oxide and preparation of ammoxidation catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an improving method for producing a hard and abrasion- resistant catalyst containing V and Sb in an oxide form (VSbOx). SOLUTION: A method for producing a catalyst having an experimental formula VSbm Aa Dd Ox is provided. Herein, A is Sn and/or Ti; D is selected from various metal elements; and m is 0.5-10; a is 0-10; d is 0-10; and x is a number of oxygen atoms necessary for satisfying a valency necessary condition of other element. This method includes a process for reacting VO(O2 )<+> in an aq. soln. with a first part of an Sb compd. containing Sb with a valency of 3<+> to reduce the average valency of V to below 5<+> and oxidizing Sb to a state of a valency of 5<+> , a process for removing water from such soln. to form a dry catalyst precursor and a process calcining the obtained dry precursor at predetermined temp. to form a catalyst. Herein, an improved point includes a process for adding the first part of the Sb compd. to at least partially reacting the same with peroxovanadium ions and thereafter adding at least the second part of the Sb compd.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to ammoxidation of C ₃ -C ₅ paraffinic hydrocarbons to the corresponding α, β-unsaturated nitriles, ammoxidation of propylene to acrylonitrile with NH ₃ and oxygen, methyl Useful for the production of cyanopyridine by ammoxidation of pyridine with NH ₃ and oxygen, the production of isophthalonitrile by ammoxidation of m-xylene with NH ₃ and oxygen, and the production of phthalic anhydride by the oxidation of o-xylene The present invention relates to a method for producing a VSbO _x based catalyst. In particular, the present invention relates to a process for preparing a VSbO _x based catalyst useful (preferably promoted with other metals) for the ammoxidation of propane to acrylonitrile.

[0002]

BACKGROUND OF THE INVENTION British Patent Nos. 1,336,135 and 1,336,1
No. 36, discloses the preparation of catalysts from V ₂ O ₅ slurry and Sb ₂ O ₅ slurry, these are mixed, dried and calcined. These catalysts are used to ammoxidize alkanes (eg, propane). U.S. Pat. No. 3,860,534 has a similar disclosure, but uses a calcined catalyst that has been washed with water prior to use to remove soluble vanadium compounds. In the above references, the dried and calcined material is relatively weak and has low abrasion resistance. More importantly, the dry material is a fine talcum powder-like material that cannot be spray dried to obtain microspheres large enough for a fluidized bed catalyst. is there.

[0003] US Patent No. 4,78, assigned to the assignee of the present application.
Nos. 4,979, 4,879,264 and 5,094,989 relate to specific preparation procedures of VSbO _x based catalysts useful in fluidized bed reactors (promoted with other metals) for the ammoxidation of propane to acrylonitrile. Although the processes disclosed in these patents produce good ammoxidation catalysts for use in this fluidized bed process, they can be improved.
The present invention relates to such improvements.

[0004]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide an improved method for producing a hard, wear-resistant catalyst containing V and Sb in oxide form (VSbO _x ).

It is another object of the present invention to provide a method for producing a microspherical catalyst containing V and Sb in oxide form.

[0006] In still another object of the present invention, the VSbO _x
The catalyst is promoted with various metals.

[0007] Other objects and aspects, features and advantages of the present invention will become apparent from a consideration of the accompanying disclosure and the appended claims.

[0008]

SUMMARY OF THE INVENTION To achieve the foregoing aspects, features and advantages of the present invention, there is provided a method of making a catalyst having the following empirical formula: VSb _m A _a D _d O _x Where A is Sn, Ti or a mixture thereof; D
Is Li, Mg, Na, Ca, Sr, Ba, Co, Fe, Cr, Ga, Ni, Z
n, Ge, Nb, Mo, W, Cu, Ti, Ta, Se, Bi, Ce, In, As,
Is at least one element selected from B, Al and Mn; and wherein m is 0.5 to 10;
D is from 0 to 10; x is the number of oxygen atoms needed to satisfy the valency requirements of the other elements.

The above method comprises reacting a monoperoxovanadium ion, VO (O ₂ ) ⁺ , in an aqueous solution with a first portion of an Sb-containing Sb compound having a valence of 3 ⁺ , reducing the average valence of the V to less than 5 ^+, and Sb
Oxidizing to a 5 ⁺ valence state; removing water from the solution to form a dried catalyst precursor; and drying the resulting dried precursor at a temperature in the range of 650 ° C to 950 ° C. Calcining to form a catalyst, wherein the improvement comprises adding a first portion of the Sb compound to at least partially react with the monoperoxovanadium ion and then reacting at least a portion of the Sb compound. Adding a second part.

In a preferred embodiment of the method of the present invention, the second part of the Sb compound is added after the first part of the Sb compound has completely reacted with the monoperoxovanadium ion.

In yet another preferred embodiment of the process of the present invention, the first and second parts of the Sb compound added to the catalyst are selected to be the same Sb compound.

In a further preferred embodiment of the method according to the invention, the first part and the second part of the Sb compound are selected from different compounds.

In yet another preferred embodiment of the present invention, the second part of the Sb compound is added before removing the water to form the dried catalyst precursor.

In another preferred embodiment of the present invention,
A second portion of the Sb compound is added following the step of removing the water to form the dried catalyst precursor.

In yet another preferred embodiment of the present invention, the second part of the Sb compound is added after calcining the dried precursor.

[0016] In yet another preferred embodiment of the present invention, the water is removed by spray drying at a temperature between about 110 ° C and 190 ° C.

Other objects, advantages and novel features of the invention will become apparent to those skilled in the art upon reviewing the following detailed description of the preferred embodiment of the invention.

[0018]

The method of the embodiment of the present invention includes a method of manufacturing a suitable VSbO _x based catalyst in the ammoxidation of propane to acrylonitrile. In particular, the method of the present invention comprises:
Comprising preparing a catalyst having the following empirical formula: VSb _m A _a D _d O _x where A is Sn, Ti or a mixture thereof; D
Is Li, Mg, Na, Ca, Sr, Ba, Co, Fe, Cr, Ga, Ni, Z
n, Ge, Nb, Mo, W, Cu, Ti, Ta, Se, Bi, Ce, In, As,
Is at least one element selected from B, Al and Mn; and wherein m is 0.5 to 10;
D is from 0 to 10; x is the number of oxygen atoms needed to satisfy the valency requirements of the other elements.

The above method comprises reacting VO (O ₂ ) ⁺ ions in an aqueous solution with a first portion of an Sb compound containing Sb in a 3 ⁺ valence state, whereby the average atom of the V ions is Reducing the valence to less than 5 ⁺ and oxidizing Sb to a 5 ⁺ valence state; removing water from the solution to form a dry catalyst precursor; and comprising the step of calcining at a maximum temperature ranging from 650 ° C. to 950 ° C., wherein the improvement, the VO (O ₂₎ said first portion ⁺
After at least partially reacting with the ions, a step of adding at least a second portion of the Sb compound is included.

Preferably, the calcination of the catalyst precursor is carried out at 70
It is carried out at a temperature between 0 ° C. and 875 ° C., most preferably 75
It is performed in the range of 0 ° C to 850 ° C.

In a further preferred embodiment, the water comprises
Temperatures between 110 ° C. and 190 ° C., particularly preferably between 115 ° C. and 1
Removed by spray drying at a temperature of 75 ° C, 10-200μ
, Particularly preferably in the range of 25 to 150μ.

The V compound to be reacted by the method of the present invention may be an inorganic or organic compound of V, but is usually an inorganic compound. Some of the lists of such compounds include:
An oxide of V (for example, V ₂ O ₅ , V ₇ O ₁₃ , VO, VO _{2 and the} like) can be given. For a more detailed listing of typical compounds used in practicing the present invention, see U.S. Pat.
See Nos. 979 and 4,879,264, the contents of which are incorporated herein by reference. Preferred V compounds used for reaction with hydrogen peroxide include one of its oxides, preferably, for cost reasons, the compound selected is V ₂ O ₅ . In the preparation of the catalyst of the present invention, the reactant of the antimony compound selected to react with VO (O ₂ ) ⁺ is also described in US Pat. Nos. 4,784,979 and 4,879,264, the contents of which are incorporated herein by reference. , Which is incorporated by reference). Some listings of these compounds include, for example, Sb ₂ O ₃ and Sb ₂
Sb oxides such as O _4, and halogenated antimony such as SbBr ₃ and SbCl _3. Suitable other antimony compounds for addition to the catalyst, the reaction product of Sb ₂ O ₃ were refluxed with nitric acid, antimony oxide sol, antimony metal,
And the hydrolysis products of the reaction of Sb ₂ O ₃ , SbCl ₃ and SbCl ₅ with water, or mixtures thereof.

If desired, the catalyst prepared according to the invention can be activated by contacting the catalyst with a hydroxy compound in liquid form, followed by drying the catalyst. The particular hydroxy compound selected typically includes isobutanol, cyclohexanol, cyclopentanol, and the like. See US Pat. No. 5,094,989, assigned to the assignee of the present invention, which is hereby incorporated by reference for further details on activation procedures suitable for the method of the present invention.

[0024]

The following examples are for illustrative purposes only and provide a detailed description of the method of the present invention.

Comparative Example A In a 2 liter beaker, V ₂
O ₅ powder 27.28G, consisting _{30% H 2 O 2 (100} ml) water (90
VSb _1.4 Sn _0.2 Ti _0.1
A catalyst having a composition of O _x was prepared. After the reaction of the V ₂ O ₅ powder was completed, Sb ₂ O ₃ (61.22 g) was added, followed by Ti
2.40 g of O ₂ powder (Degussa P-25) was added. The beaker was covered with a clockwork, the mixture was stirred and heated for about 3 hours. To the above dispersion was added 99.25 g of 9.11% by weight SnO ₂ sol (Nalco Chemical Co.). The mixture was stirred while heating in an uncovered beaker and the volume was reduced by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120 ° C. It was then calcined at 650 ° C. for 8 hours, cooled, then crushed and sieved to collect the 20-35 mesh particles. This part was calcined at 810 ° C. for 3 hours and then at 650 ° C. for another 3 hours.

The calcined catalyst is then placed in a coarse glass frit funnel and isobutanol is poured over the catalyst,
The catalyst was stirred in isobutanol to disperse it evenly at the bottom of the funnel, and then the isobutanol was passed through the funnel without suction, using about 6.25 ml of isobutanol per gram of catalyst. And contacted with isobutanol. This washing was performed three times in total. After passing the last isobutanol through the funnel, the catalyst was heated in an oven at 120 ° C. to remove any remaining isobutanol on the catalyst.

Using this catalyst, a 3/8 inch outer diameter titanium metal fixed bed reactor (this is a preheated leg)
leg) and immersed in a molten salt bath temperature controlled at 480 ° C.) to ammoxidize propane. The feed to this reactor consisted of propane, ammonia, oxygen, nitrogen and water in a ratio of 3 / 1.2 / 3/10/2. The results are shown in Table 1 below.

Comparative Example B In a 2 liter beaker, V ₂
O ₅ powder 27.28G, consisting _{30% H 2 O 2 (100} ml) water (90
VSb _1.4 Sn _0.2 Ti _0.1
A catalyst having a composition of O _x was prepared. After the reaction of the V ₂ O ₅ powder was completed, Sb ₂ O ₃ (61.22 g) was added, followed by Ti
2.40 g of O ₂ powder (Degussa P-25) was added. The beaker was covered with a clockwork, the mixture was stirred and heated for about 3 hours. To the above dispersion was added 99.25 g of 9.11% by weight SnO ₂ sol (Nalco Chemical Co.). The mixture was stirred while heating in an uncovered beaker and the volume was reduced by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120 ° C. It was then calcined at 650 ° C. for 8 hours, cooled, then crushed and sieved to collect the 20-35 mesh particles. This part was calcined at 810 ° C. for 3 hours and then at 650 ° C. for another 3 hours.

The catalyst was washed with refluxing isobutanol using a Soxhlet extractor.

Using this catalyst, a 3/8 inch outer diameter titanium metal fixed bed reactor (pre-heated legs, 48
The propane was ammoxidized using a bath immersed in a molten salt bath temperature controlled at 0 ° C. The feed to this reactor is
Propane, ammonia, oxygen in a ratio of 3 / 1.2 / 3/10/2,
It consisted of nitrogen and water. The results are shown in Table 1 below.

(Example 1) In a 2 liter beaker, V ₂
O ₅ powder 27.28G, consisting _{30% H 2 O 2 (100} ml) water (90
VSb _1.4 Sn _0.2 Ti _0.1
A catalyst having a composition of O _x was prepared. After the reaction of the V ₂ O ₅ powder was completed, Sb ₂ O ₃ (61.22 g) was added, followed by Ti
2.40 g of O ₂ powder (Degussa P-25) was added. The beaker was covered with a clockwork, the mixture was stirred and heated for about 3 hours. To the above dispersion was added 99.25 g of 9.11% by weight SnO ₂ sol (Nalco Chemical Co.). Concentrated nitric acid 2
In 50 ml, Sb ₂ O ₃ (4.37 g) was refluxed for about 3 hours. The mixture was filtered and the residue was washed with water to remove residual acid. Then, the obtained washed solid was added to the above-mentioned catalyst dispersion. The mixture was stirred while heating in an uncovered beaker and the volume was reduced by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120 ° C. Then it is 6
Calcined at 50 ° C. for 8 hours, cooled, then ground and sieved to collect the 20-35 mesh particles. This part was calcined at 810 ° C. for 3 hours, then at 650 ° C. for another 3 hours.
Time calcined.

The calcined catalyst was then placed in a coarse glass frit funnel and isobutanol was poured over the catalyst,
The catalyst was stirred in isobutanol to disperse it evenly at the bottom of the funnel, and then the isobutanol was passed through the funnel without suction, using about 6.25 ml of isobutanol per gram of catalyst. And contacted with isobutanol. This washing was performed three times in total. After passing the last isobutanol through the funnel, the catalyst was heated in an oven at 120 ° C. to remove any remaining isobutanol on the catalyst.

Using this catalyst, a 3/8 inch outer diameter titanium metal fixed bed reactor (pre-heated legs, 48
The propane was ammoxidized using a bath immersed in a molten salt bath temperature controlled at 0 ° C. The feed to this reactor is
Propane, ammonia, oxygen in a ratio of 3 / 1.2 / 3/10/2,
It consisted of nitrogen and water. The results are shown in Table 1 below.

(Example 2) In a 2 liter beaker, V ₂
O ₅ powder 27.28G, consisting _{30% H 2 O 2 (100} ml) water (90
VSb _1.4 Sn _0.2 Ti _0.1
A catalyst having a composition of O _x was prepared. After the reaction of the V ₂ O ₅ powder was completed, Sb ₂ O ₃ (61.22 g) was added, followed by Ti
2.40 g of O ₂ powder (Degussa P-25) was added. The beaker was covered with a clockwork, the mixture was stirred and heated for about 3 hours. To the above dispersion was added 99.25 g of 9.11% by weight SnO ₂ sol (Nalco Chemical Co.), followed by
b ₂ O ₃ (4.37 g) was added. The mixture was stirred while heating in an uncovered beaker and the volume was reduced by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120 ° C. It was then calcined at 650 ° C. for 8 hours, cooled, then crushed and sieved to collect the 20-35 mesh particles. This part was calcined at 810 ° C. for 3 hours and then at 650 ° C. for another 3 hours.

The calcined catalyst is then placed in a coarse glass frit funnel and isobutanol is poured over the catalyst,
The catalyst was stirred in isobutanol to disperse it evenly at the bottom of the funnel, and then the isobutanol was passed through the funnel without suction, using about 6.25 ml of isobutanol per gram of catalyst. And contacted with isobutanol. This washing was performed three times in total. After passing the last isobutanol through the funnel, the catalyst was heated in an oven at 120 ° C. to remove any remaining isobutanol on the catalyst.

Using this catalyst, a 3/8 inch outer diameter titanium metal fixed bed reactor (with a preheated leg,
Immersed in a molten salt bath temperature-controlled to 480 ° C)
Propane was ammoxidized. The feed to this reactor consisted of propane, ammonia, oxygen, nitrogen and water in a ratio of 3 / 1.2 / 3/10/2. The results are shown in Table 1 below.
Shown in

(Example 3) In a 2 liter beaker, V ₂
O ₅ powder 27.28G, consisting _{30% H 2 O 2 (100} ml) water (90
VSb _1.4 Sn _0.2 Ti _0.1
A catalyst having a composition of O _x was prepared. After the reaction of the V ₂ O ₅ powder was completed, Sb ₂ O ₃ (61.22 g) was added, followed by Ti
2.40 g of O ₂ powder (Degussa P-25) was added. The beaker was covered with a clockwork, the mixture was stirred and heated for about 3 hours. To the above dispersion was added 99.25 g of 9.11% by weight SnO ₂ sol (Nalco Chemical Co.), followed by
b ₂ O ₃ (8.75 g) was added. The mixture was stirred while heating in an uncovered beaker and the volume was reduced by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120 ° C. It was then calcined at 650 ° C. for 8 hours, cooled, then crushed and sieved to collect the 20-35 mesh particles. This part was calcined at 810 ° C. for 3 hours and then at 650 ° C. for another 3 hours.

The calcined catalyst was then placed in a coarse glass frit funnel and isobutanol was poured over the catalyst,
The catalyst was stirred in isobutanol to disperse it evenly at the bottom of the funnel, and then the isobutanol was passed through the funnel without suction, using about 6.25 ml of isobutanol per gram of catalyst. And contacted with isobutanol. This washing was performed three times in total. After passing the last isobutanol through the funnel, the catalyst was heated in an oven at 120 ° C. to remove any remaining isobutanol on the catalyst.

Using this catalyst, a 3/8 inch outer diameter titanium metal fixed bed reactor (with preheated legs,
Immersed in a molten salt bath temperature-controlled to 480 ° C)
Propane was ammoxidized. The feed to this reactor consisted of propane, ammonia, oxygen, nitrogen and water in a ratio of 3 / 1.2 / 3/10/2. The results are shown in Table 1 below.
Shown in

(Example 4) In a 2 liter beaker, V ₂
O ₅ powder 27.28G, consisting _{30% H 2 O 2 (100} ml) water (90
VSb _1.4 Sn _0.2 Ti _0.1
A catalyst having a composition of O _x was prepared. After the reaction of the V ₂ O ₅ powder was completed, Sb ₂ O ₃ (61.22 g) was added, followed by Ti
2.40 g of O ₂ powder (Degussa P-25) was added. The beaker was covered with a clockwork, the mixture was stirred and heated for about 3 hours. To the above dispersion was added 99.25 g of 9.11% by weight SnO ₂ sol (Nalco Chemical Co.), followed by
b ₂ O ₃ (13.12 g) was added. The mixture was stirred while heating in an uncovered beaker and the volume was reduced by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120 ° C. Then it is calcined at 650 ° C. for 8 hours, cooled and then ground,
The particles were sieved to collect the 20-35 mesh particles.
This part was calcined at 810 ° C. for 3 hours and then at 650 ° C. for another 3 hours.

The calcined catalyst was then placed in a coarse glass fritted funnel and isobutanol was poured over the catalyst,
The catalyst was stirred in isobutanol to disperse it evenly at the bottom of the funnel, and then the isobutanol was passed through the funnel without suction, using about 6.25 ml of isobutanol per gram of catalyst. And contacted with isobutanol. This washing was performed three times in total. After passing the last isobutanol through the funnel, the catalyst was heated in an oven at 120 ° C. to remove any remaining isobutanol on the catalyst.

Using this catalyst, a 3/8 inch outer diameter titanium metal fixed bed reactor (with preheated legs,
Immersed in a molten salt bath temperature-controlled to 480 ° C)
Propane was ammoxidized. The feed to this reactor consisted of propane, ammonia, oxygen, nitrogen and water in a ratio of 3 / 1.2 / 3/10/2. The results are shown in Table 1 below.
Shown in

(Example 5) In a 2 liter beaker, V ₂
O ₅ powder 27.28G, consisting _{30% H 2 O 2 (100} ml) water (90
VSb _1.3 Sn _0.2 Ti _0.1
A catalyst having a composition of O _x was prepared. After the reaction of the V ₂ O ₅ powder was completed, Sb ₂ O ₃ (56.85 g) was added, followed by Ti
2.40 g of O ₂ powder (Degussa P-25) was added. The beaker was covered with a clockwork, the mixture was stirred and heated for about 3 hours. To the above dispersion was added 99.25 g of 9.11% by weight SnO ₂ sol (Nalco Chemical Co.). Concentrated nitric acid 2
In 50 ml, Sb ₂ O ₃ (4.37 g) was refluxed for about 3 hours. The mixture was filtered and the residue was washed with water to remove residual acid. Then, the obtained washed solid was added to the above-mentioned catalyst dispersion. The mixture was stirred while heating in an uncovered beaker and the volume was reduced by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120 ° C. Then it is 6
Calcined at 50 ° C. for 8 hours, cooled, then ground and sieved to collect the 20-35 mesh particles. This part was calcined at 810 ° C. for 3 hours, then at 650 ° C. for another 3 hours.
Time calcined.

The calcined catalyst was then placed in a coarse glass frit funnel and isobutanol was poured over the catalyst,
The catalyst was stirred in isobutanol to disperse it evenly at the bottom of the funnel, and then the isobutanol was passed through the funnel without suction, using about 6.25 ml of isobutanol per gram of catalyst. And contacted with isobutanol. This washing was performed three times in total. After passing the last isobutanol through the funnel, the catalyst was heated in an oven at 120 ° C. to remove any remaining isobutanol on the catalyst.

Using this catalyst, a 3/8 inch outer diameter titanium metal fixed bed reactor (with preheated legs,
Immersed in a molten salt bath temperature-controlled to 480 ° C)
Propane was ammoxidized. The feed to this reactor consisted of propane, ammonia, oxygen, nitrogen and water in a ratio of 3 / 1.2 / 3/10/2. The results are shown in Table 1 below.
Shown in

(Example 6) In a 2 liter beaker, V ₂
O ₅ powder 27.28G, consisting _{30% H 2 O 2 (100} ml) water (90
VSb _1.3 Sn _0.2 Ti _0.1
A catalyst having a composition of O _x was prepared. After the reaction of the V ₂ O ₅ powder was completed, Sb ₂ O ₃ (56.85 g) was added, followed by Ti
2.40 g of O ₂ powder (Degussa P-25) was added. The beaker was covered with a clockwork, the mixture was stirred and heated for about 3 hours. To the above dispersion was added 99.25 g of 9.11% by weight SnO ₂ sol (Nalco Chemical Co.), followed by
b ₂ O ₃ (4.37 g) was added. The mixture was stirred while heating in an uncovered beaker and the volume was reduced by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120 ° C. It was then calcined at 650 ° C. for 8 hours, cooled, then crushed and sieved to collect the 20-35 mesh particles. This part was calcined at 810 ° C. for 3 hours, then at 600 ° C. for another 3 hours.

The calcined catalyst was then placed in a coarse glass frit funnel and isobutanol was poured over the catalyst,
The catalyst was stirred in isobutanol to disperse it evenly at the bottom of the funnel, and then the isobutanol was passed through the funnel without suction, using about 6.25 ml of isobutanol per gram of catalyst. And contacted with isobutanol. This washing was performed three times in total. After passing the last isobutanol through the funnel, the catalyst was heated in an oven at 120 ° C. to remove any remaining isobutanol on the catalyst.

Using this catalyst, a 3/8 inch outer diameter titanium metal fixed bed reactor (with preheated legs,
Immersed in a molten salt bath temperature-controlled to 480 ° C)
Propane was ammoxidized. The feed to this reactor consisted of propane, ammonia, oxygen, nitrogen and water in a ratio of 3 / 1.2 / 3/10/2. The results are shown in Table 1 below.
Shown in

Example 7 In a 2 liter beaker, V ₂
O ₅ powder 27.28G, consisting _{30% H 2 O 2 (100} ml) water (90
VSb _1.3 Sn _0.2 Ti _0.1
A catalyst having a composition of O _x was prepared. After the reaction of the V ₂ O ₅ powder was completed, Sb ₂ O ₃ (56.85 g) was added, followed by Ti
2.40 g of O ₂ powder (Degussa P-25) was added. The beaker was covered with a clockwork, the mixture was stirred and heated for about 3 hours. To the above dispersion was added 99.25 g of 9.11% by weight SnO ₂ sol (Nalco Chemical Co.), followed by
b ₂ O ₃ (4.37 g) was added. The mixture was stirred while heating in an uncovered beaker and the volume was reduced by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120 ° C. It was then calcined at 650 ° C. for 8 hours, cooled, then crushed and sieved to collect the 20-35 mesh particles. This part was calcined at 810 ° C. for 3 hours and then at 650 ° C. for another 3 hours.

The calcined catalyst was then placed in a coarse glass fritted funnel and isobutanol was poured over the catalyst,
The catalyst was stirred in isobutanol to disperse it evenly at the bottom of the funnel, and then the isobutanol was passed through the funnel without suction, using about 6.25 ml of isobutanol per gram of catalyst. And contacted with isobutanol. This washing was performed three times in total. After passing the last isobutanol through the funnel, the catalyst was heated in an oven at 120 ° C. to remove any remaining isobutanol on the catalyst.

Using this catalyst, a 3/8 inch outer diameter titanium metal fixed bed reactor (with preheated legs,
Immersed in a molten salt bath temperature-controlled to 480 ° C)
Propane was ammoxidized. The feed to this reactor consisted of propane, ammonia, oxygen, nitrogen and water in a ratio of 3 / 1.2 / 3/10/2. The results are shown in Table 2 below.
Shown in

Example 8 In a 2 liter beaker, V ₂
O ₅ powder 27.28G, consisting _{30% H 2 O 2 (100} ml) water (90
VSb _1.3 Sn _0.2 Ti _0.1
A catalyst having a composition of O _x was prepared. After the reaction of the V ₂ O ₅ powder was completed, Sb ₂ O ₃ (56.85 g) was added, followed by Ti
2.40 g of O ₂ powder (Degussa P-25) was added. The beaker was covered with a clockwork, the mixture was stirred and heated for about 3 hours. To the above dispersion was added 99.25 g of 9.11% by weight SnO ₂ sol (Nalco Chemical Co.), followed by
b ₂ O ₃ (8.75 g) was added. The mixture was stirred while heating in an uncovered beaker and the volume was reduced by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120 ° C. It was then calcined at 650 ° C. for 8 hours, cooled, then crushed and sieved to collect the 20-35 mesh particles. This part was calcined at 810 ° C. for 3 hours and then at 650 ° C. for another 3 hours.

The calcined catalyst was then placed in a coarse glass frit funnel and isobutanol was poured over the catalyst,
The catalyst was stirred in isobutanol to disperse it evenly at the bottom of the funnel, and then the isobutanol was passed through the funnel without suction, using about 6.25 ml of isobutanol per gram of catalyst. And contacted with isobutanol. This washing was performed three times in total. After passing the last isobutanol through the funnel, the catalyst was heated in an oven at 120 ° C. to remove any remaining isobutanol on the catalyst.

Using this catalyst, a 3/8 inch outer diameter titanium metal fixed bed reactor (with preheated legs,
Immersed in a molten salt bath temperature-controlled to 480 ° C)
Propane was ammoxidized. The feed to this reactor consisted of propane, ammonia, oxygen, nitrogen and water in a ratio of 3 / 1.2 / 3/10/2. The results are shown in Table 2 below.
Shown in

(Example 9) In a 2 liter beaker, V ₂
O ₅ powder 27.28G, consisting _{30% H 2 O 2 (100} ml) water (90
VSb _1.3 Sn _0.2 Ti _0.1
A catalyst having a composition of O _x was prepared. After the reaction of the V ₂ O ₅ powder was completed, Sb ₂ O ₃ (56.85 g) was added, followed by Ti
2.40 g of O ₂ powder (Degussa P-25) was added. The beaker was covered with a clockwork, the mixture was stirred and heated for about 3 hours. To the above dispersion was added 99.25 g of 9.11% by weight SnO ₂ sol (Nalco Chemical Co.), followed by
b ₂ O ₃ (13.12 g) was added. The mixture was stirred while heating in an uncovered beaker and the volume was reduced by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120 ° C. Then it is calcined at 650 ° C. for 8 hours, cooled and then ground,
The particles were sieved to collect the 20-35 mesh particles.
This part was calcined at 810 ° C. for 3 hours and then at 650 ° C. for another 3 hours.

The calcined catalyst was then placed in a coarse glass frit funnel and isobutanol was poured over the catalyst,
The catalyst was stirred in isobutanol to disperse it evenly at the bottom of the funnel, and then the isobutanol was passed through the funnel without suction, using about 6.25 ml of isobutanol per gram of catalyst. And contacted with isobutanol. This washing was performed three times in total. After passing the last isobutanol through the funnel, the catalyst was heated in an oven at 120 ° C. to remove any remaining isobutanol on the catalyst.

Using this catalyst, a 3/8 inch outer diameter titanium metal fixed bed reactor (with preheated legs,
Immersed in a molten salt bath temperature-controlled to 480 ° C)
Propane was ammoxidized. The feed to this reactor consisted of propane, ammonia, oxygen, nitrogen and water in a ratio of 3 / 1.2 / 3/10/2. The results are shown in Table 2 below.
Shown in

Example 10 In a 2 liter beaker,
By mixing 27.28 g of V ₂ O ₅ powder and a water (900 ml) solution containing 30% H ₂ O ₂ (100 ml), VSb _1.3 Sn _0.2 T
A catalyst having a composition of i _0.1 O _x was prepared. After the reaction of the V ₂ O ₅ powder was completed, Sb ₂ O ₃ (56.85 g) was added, followed by 2.40 g of TiO ₂ powder (Degussa P-25). The beaker was covered with a clockwork, the mixture was stirred and heated for about 3 hours. 9.11% by weight of the above dispersion
99.25 g of SnO ₂ sol (Nalco Chemical Co.) was added, followed by Sb ₂ O ₃ (4.37 g). The mixture was stirred while heating in an uncovered beaker and the volume was reduced by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120 ° C. It was then calcined at 650 ° C. for 8 hours, cooled, then crushed and sieved to collect the 20-35 mesh particles. A portion of this was calcined at 810 ° C. for 3 hours, then 700
Calcination at ℃ for a further 3 hours.

The calcined catalyst was then placed in a coarse glass fritted funnel and isobutanol was poured over the catalyst,
The catalyst was stirred in isobutanol to disperse it evenly at the bottom of the funnel, and then the isobutanol was passed through the funnel without suction, using about 6.25 ml of isobutanol per gram of catalyst. And contacted with isobutanol. This washing was performed three times in total. After passing the last isobutanol through the funnel, the catalyst was heated in an oven at 120 ° C. to remove any remaining isobutanol on the catalyst.

Using this catalyst, a 3/8 inch outer diameter titanium metal fixed bed reactor (with preheated legs,
Immersed in a molten salt bath temperature-controlled to 480 ° C)
Propane was ammoxidized. The feed to this reactor consisted of propane, ammonia, oxygen, nitrogen and water in a ratio of 3 / 1.2 / 3/10/2. The results are shown in Table 2 below.
Shown in

(Example 11) In a 2 liter beaker,
By mixing 27.28 g of V ₂ O ₅ powder and a water (900 ml) solution containing 30% H ₂ O ₂ (100 ml), VSb _1.3 Sn _0.2 T
A catalyst having a composition of i _0.1 O _x was prepared. After the reaction of the V ₂ O ₅ powder was completed, Sb ₂ O ₃ (56.85 g) was added, followed by 2.40 g of TiO ₂ powder (Degussa P-25). The beaker was covered with a clockwork, the mixture was stirred and heated for about 3 hours. 9.11% by weight of the above dispersion
99.25 g of SnO ₂ sol (Nalco Chemical Co.) was added, followed by Sb ₂ O ₄ (4.61 g). The mixture was stirred while heating in an uncovered beaker and the volume was reduced by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120 ° C. It was then calcined at 650 ° C. for 8 hours, cooled, then crushed and sieved to collect the 20-35 mesh particles. A portion of this was calcined at 810 ° C for 3 hours, then 650
Calcination at ℃ for a further 3 hours.

The calcined catalyst is then placed in a coarse glass frit funnel and isobutanol is poured over the catalyst,
The catalyst was stirred in isobutanol to disperse it evenly at the bottom of the funnel, and then the isobutanol was passed through the funnel without suction, using about 6.25 ml of isobutanol per gram of catalyst. And contacted with isobutanol. This washing was performed three times in total. After passing the last isobutanol through the funnel, the catalyst was heated in an oven at 120 ° C. to remove any remaining isobutanol on the catalyst.

Using this catalyst, a 3/8 inch outer diameter titanium metal fixed bed reactor, which had preheated legs,
Immersed in a molten salt bath temperature-controlled to 480 ° C)
Propane was ammoxidized. The feed to this reactor consisted of propane, ammonia, oxygen, nitrogen and water in a ratio of 3 / 1.2 / 3/10/2. The results are shown in Table 2 below.
Shown in

(Example 12) In a 2 liter beaker,
By mixing 27.28 g of V ₂ O ₅ powder and a water (900 ml) solution containing 30% H ₂ O ₂ (100 ml), VSb _1.3 Sn _0.2 T
A catalyst having a composition of i _0.1 O _x was prepared. After the reaction of the V ₂ O ₅ powder was completed, Sb ₂ O ₃ (56.85 g) was added, followed by 2.40 g of TiO ₂ powder (Degussa P-25). The beaker was covered with a clockwork, the mixture was stirred and heated for about 3 hours. 9.11% by weight of the above dispersion
99.25 g of SnO ₂ sol (Nalco Chemical Co.) was added.
Sb ₂ O ₃ (4.37 g) was heated in a hydrogen peroxide solution, dried, and then added to the catalyst dispersion described above. This mixture was stirred while heating in an uncovered beaker,
The volume was reduced by evaporation of the water. When the mixture could no longer be stirred, it was dried in an oven at 120 ° C. It was then calcined at 650 ° C. for 8 hours, cooled, then crushed and sieved to collect the 20-35 mesh particles. This part was calcined at 810 ° C. for 3 hours and then at 650 ° C. for another 3 hours.

The calcined catalyst was then placed in a coarse glass frit funnel and isobutanol was poured over the catalyst,
The catalyst was stirred in isobutanol to disperse it evenly at the bottom of the funnel, and then the isobutanol was passed through the funnel without suction, using about 6.25 ml of isobutanol per gram of catalyst. And contacted with isobutanol. This washing was performed three times in total. After passing the last isobutanol through the funnel, the catalyst was heated in an oven at 120 ° C. to remove any remaining isobutanol on the catalyst.

Using this catalyst, a 3/8 inch outer diameter titanium metal fixed bed reactor (with preheated legs,
Immersed in a molten salt bath temperature-controlled to 480 ° C)
Propane was ammoxidized. The feed to this reactor consisted of propane, ammonia, oxygen, nitrogen and water in a ratio of 3 / 1.2 / 3/10/2. The results are shown in Table 2 below.
Shown in

(Example 13) In a 2 liter beaker,
By mixing 27.28 g of V ₂ O ₅ powder and a water (900 ml) solution containing 30% H ₂ O ₂ (100 ml), VSb _1.3 Sn _0.2 T
A catalyst having a composition of i _0.1 O _x was prepared. After the reaction of the V ₂ O ₅ powder was completed, Sb ₂ O ₃ (56.85 g) was added, followed by 2.40 g of TiO ₂ powder (Degussa P-25). The beaker was covered with a clockwork, the mixture was stirred and heated for about 3 hours. 9.11% by weight of the above dispersion
99.25 g of SnO ₂ sol (Nalco Chemical Co.) was added. S
b ₂ O ₃ (4.37 g) was added to 100 ml of water and heated.
When mixing was stopped, a 50% hydrogen peroxide solution was added until a colloidal suspension without signs of particle settling was obtained. This colloidal suspension was then added to the catalyst dispersion described above. The mixture was stirred while heating in an uncovered beaker and the volume was reduced by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120 ° C. Then it is calcined at 650 ° C. for 8 hours, cooled, then crushed and sieved,
The 20-35 mesh particles were collected. Part of this, 810
C. for 3 hours and then for another 3 hours at 650.degree.

The calcined catalyst was then placed in a coarse glass frit funnel and isobutanol was poured over the catalyst,
The catalyst was stirred in isobutanol to disperse it evenly at the bottom of the funnel, and then the isobutanol was passed through the funnel without suction, using about 6.25 ml of isobutanol per gram of catalyst. And contacted with isobutanol. This washing was performed three times in total. After passing the last isobutanol through the funnel, the catalyst was heated in an oven at 120 ° C. to remove any remaining isobutanol on the catalyst.

Using this catalyst, a 3/8 inch outer diameter titanium metal fixed bed reactor (with preheated legs,
Immersed in a molten salt bath temperature-controlled to 480 ° C)
Propane was ammoxidized. The feed to this reactor consisted of propane, ammonia, oxygen, nitrogen and water in a ratio of 3 / 1.2 / 3/10/2. The results are shown in Table 2 below.
Shown in

(Example 14) In a 2 liter beaker,
By mixing 27.28 g of V ₂ O ₅ powder and a water (900 ml) solution containing 30% H ₂ O ₂ (100 ml), VSb _1.3 Sn _0.2 T
A catalyst having a composition of i _0.1 O _x was prepared. After the reaction of the V ₂ O ₅ powder was completed, Sb ₂ O ₃ (56.85 g) was added, followed by 2.40 g of TiO ₂ powder (Degussa P-25). The beaker was covered with a clockwork, the mixture was stirred and heated for about 3 hours. 9.11% by weight of the above dispersion
99.25 g of SnO ₂ sol (Nalco Chemical Co.) was added, followed by Sb ₂ O ₄ (4.61 g). The mixture was stirred while heating in an uncovered beaker and the volume was reduced by evaporation of water. When the mixture could no longer be stirred, it was dried in an oven at 120 ° C. It was then calcined at 650 ° C. for 8 hours, cooled, then crushed and sieved to collect the 20-35 mesh particles. This part was calcined at 810 ° C. for 3 hours.

The calcined catalyst was then placed in a coarse glass fritted funnel and isobutanol was poured over the catalyst,
The catalyst was stirred in isobutanol to disperse it evenly at the bottom of the funnel, and then the isobutanol was passed through the funnel without suction, using about 6.25 ml of isobutanol per gram of catalyst. And contacted with isobutanol. This washing was performed three times in total. After passing the last isobutanol through the funnel, the catalyst was heated in an oven at 120 ° C. to remove any remaining isobutanol on the catalyst.

7 g of the above-mentioned washed catalyst were added until the catalyst particles appeared to be uniformly coated with the Sb ₂ O ₃ powder.
In a ml flask, 0.3027 g of Sb ₂ O ₃ powder was physically mixed. The coated catalyst particles were then calcined at 650 ° C. for 3 hours.

The calcined catalyst was then placed in a coarse glass frit funnel and isobutanol was poured over the catalyst,
The catalyst was stirred in isobutanol to disperse it evenly at the bottom of the funnel, and then the isobutanol was passed through the funnel without suction, using about 6.25 ml of isobutanol per gram of catalyst. And contacted with isobutanol. This washing was performed three times in total. After passing the last isobutanol through the funnel, the catalyst was heated in an oven at 120 ° C. to remove any remaining isobutanol on the catalyst.

Using this catalyst, a 3/8 inch outer diameter titanium metal fixed bed reactor (with preheated legs,
Immersed in a molten salt bath temperature-controlled to 480 ° C)
Propane was ammoxidized. The feed to this reactor consisted of propane, ammonia, oxygen, nitrogen and water in a ratio of 3 / 1.2 / 3/10/2. The results are shown in Table 2 below.
Shown in

[0075]

[Table 1]

[0076]

[Table 2]

[0077]

According to the present invention, there is provided an improved method for producing a hard, abrasion resistant catalyst containing V and Sb in oxide form (VSbOx). Further, according to the present invention, there is provided a method for producing a microspherical catalyst containing V and Sb in an oxide form.

────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification symbol FI C07C 255/08 C07C 255/08 // C07B 61/00 300 C07B 61/00 300 (71) Applicant 595017584 200 Public Square, 39G BP Building, Cleveland and Ohio 44114, U.S.A. S. A. (72) Inventor Fernando A. P. Kabarkanti United States Ohio 44121, Saus Euclid, Belvoir Mews 1375 (72) Inventor Joseph P. Padresky United States Ohio 44333, Acron, W. Bus Road 4715

Claims (8)

[Claims] 1. A method for preparing a catalyst having the following empirical formula: VSb _m A _a D _d O _x, wherein A is Sn, Ti or a mixture thereof; D
Is Li, Mg, Na, Ca, Sr, Ba, Co, Fe, Cr, Ga, Ni, Z
n, Ge, Nb, Mo, W, Cu, Ti, Ta, Se, Bi, Ce, In, As,
Is at least one element selected from B, Al and Mn; and wherein m is 0.5 to 10;
D is 0-10; x is the number of oxygen atoms required to satisfy the valency requirements of the other elements;
Monoperoxovanadium ion in aqueous solution, VO (O ₂ ) ⁺
With a first portion of a Sb-containing Sb compound having a 3 ⁺ valence, thereby reducing the average valence of V to less than 5 ⁺ and reducing Sb to the 5 ⁺ valence state. Oxidizing to a temperature of 650 ° C .; removing water from the solution to form a dry catalyst precursor; and drying the resulting dry precursor at 650 ° C.
Calcining at a temperature in the range of 950950 ° C. to form a catalyst, wherein the improvement comprises adding a first portion of the Sb compound to at least partially combining the monoperoxovanadium ion with the monoperoxovanadium ion. Reacting, and then adding at least a second portion of the Sb compound. 2. The method of claim 1, wherein the second portion of the Sb compound is added after completely reacting the first portion of the Sb compound with the monoperoxovanadium ion. 3. The method of claim 1, wherein the first and second portions of the Sb compound added to the catalyst are selected to be the same Sb compound. 4. The method of claim 1, wherein the first and second portions of the Sb compound are selected from different compounds. 5. The method of claim 1, wherein the second portion of the Sb compound is added prior to removing the water to form the dried catalyst precursor.
The method of claim 1. 6. The method of claim 1, wherein a second portion of the Sb compound is added subsequent to removing the water to form the dried catalyst precursor. 7. The method of claim 1, wherein the second portion of the Sb compound is added after calcining the dried precursor. 8. The method of claim 1, wherein said water is removed by spray drying at a temperature between about 110 ° C. and 190 ° C.