JPH0971567A - Production of 2-cyano-3-methylpyridine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound useful as a raw material for medicines, agricultural chemicals, especially antihistaminic agents from dimethylpyridine, ammonia and oxygen in the presence of a catalyst comprising a specific Fe,Sb,V,Cr-containing oxide composition in a gas phase. SOLUTION: A method for producing 2-cyano-3-methylpyridine comprises reacting (A) 2,3-dimethylpyridine with (C) ammonia and (D) oxygen in the presence of (B) an oxide composition of the formula: Fe10 Sba Vb Crc Xd Ye Of (X is at least one kind of element selected from Li, Na, K, Rb, Cs, La, Mg, Ca, Sr and Ba; Y is at least one kind of element selected from Ce, Ti, Zr, Nb, Ta, Mo, W, Mn, Re, Co, Ni, Cu, Ag, Zn, B, Al, Ge, Sn, Pb, P, Bi and Te; (a)-(f) are the atomic ratios of the elements, respectively, wherein when Fe=10, (a)=7-50, (b)=1-15, (c)=0.1-15, (d)=0-3, (e)=0-5, and (f) is a number corresponding to the oxide produced by binding the elements to each other).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to 2-cyano-3-
Regarding the method for producing methylpyridine, specifically, 2,3-dimethylpyridine is subjected to catalytic ammoxidation in the gas phase to give 2-cyano-
The present invention relates to a method for producing 3-methylpyridine. 2-Cyano-3-methylpyridine is a useful compound used as a raw material for medicines and agricultural chemicals, especially antihistamines.

[0002]

Various catalysts have been proposed as catalysts used for producing 2-cyano-3-methylpyridine by ammoxidation of 2,3-dimethylpyridine. For example,
Collect. Czeh. Chem. Commun.
28 , 55, 57 (1963) contains vanadium pentoxide.
A method using an alumina catalyst (yield 35%), Khim.
Farm. Zh. 1969, 3 (12) 42-3, a method using a catalyst containing vanadium pentoxide and molybdenum trioxide (yield 8.2%), Chem. Pharm. B
ull. 1974, 22 (10) 2402-6, there is a method using a chromium trioxide / alumina catalyst (yield 18%). Further, as an ammoxidation catalyst for synthesizing corresponding nitriles from an alkyl-substituted aromatic compound as a raw material, a catalyst containing antimony and tin (JP-A-63-1).
No. 0753), a catalyst containing vanadium, antimony and phosphorus (JP-A-63-72675), a catalyst containing vanadium and phosphorus (JP-A-63-152360).
No. 1). However, in these methods, the yield of 2-cyano-3-methylpyridine produced is low, the molar ratio of ammonia to the alkyl-substituted aromatic compound in the feed gas is high, or steam is allowed to coexist in the reaction system. However, there was a problem that had to be solved for industrial implementation.

[0003]

The object of the present invention is to:
The object of the present invention is to provide a method for producing 2-cyano-3-methylpyridine which can be industrially advantageously carried out in order to solve these problems in the prior art. Specifically, both activity and selectivity are good. And a method capable of stably producing 2-cyano-3-methylpyridine in high yield and for a long time by vapor-phase catalytic ammoxidation of 2,3-dimethylpyridine using a catalyst that is stable over time To provide.

[0004]

Means for Solving the Problems As a result of intensive studies for achieving the above object, the present inventors have found that a specific Fe.S
It has been found that the b.V.Cr-containing oxide composition exhibits excellent catalytic action for the reaction for producing 2-cyano-3-methylpyridine by ammoxidation of 2,3-dimethylpyridine. The present invention has been made based on such findings.

That is, the present invention is characterized in that 2,3-dimethylpyridine is reacted with ammonia and oxygen in the gas phase in the presence of an oxide composition represented by the following empirical formula (1). -Cyano-3-methylpyridine production method. Fe ₁₀ Sba Vb CrcXdYeOf (1) (In the formula, X is Li, Na, K, Rb, Cs, La, M
at least one element selected from the group consisting of g, Ca, Sr and Ba, Y is Ce, Ti, Zr, Nb, T
a, Mo, W, Mn, Re, Co, Ni, Cu, Ag,
Zn, B, Al, Ge, Sn, Pb, P, Bi and T
It shows at least one element selected from the group consisting of e, and the subscripts a, b, c, d, e and f represent the atomic ratio of each element, and when Fe = 10, a = 7 to 50, b = 1-1
5, c = 0.1 to 15, d = 0 to 3, e = 0 to 5, and f represents a number corresponding to an oxide formed by combining the above components. )

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. An important point in the gas phase reaction of 2,3-dimethylpyridine, ammonia and oxygen of the present invention lies in the catalyst used. The oxide composition represented by the above empirical formula (1) is used as the catalyst. Thereby, 2-cyano-3-methylpyridine can be effectively produced. In the above oxide composition, the X component effectively contributes to the selectivity and stability of 2-cyano-3-methylpyridine over time, and the Y component effectively contributes to the reaction rate and the catalyst physical properties. Further, the preferable atomic ratio of each component is a = 10 when Fe = 10.
30, b = 2 to 10, c = 0.3 to 12, d = 0 to 3,
e = 0-5.

Fe, Sb, V, which constitutes the catalyst of the present invention,
It is not clear what kind of complex oxide each component of Cr, X, Y and O forms in the constituent catalyst to contribute to the manifestation of the effect on the activity and selectivity. However, if the components of the catalyst and the atomic ratio of the components deviate from the range of the empirical formula, the desired 2-cyano-3-methylpyridine cannot be obtained at a high production yield, or the production yield decreases with time. Or the physical properties of the catalyst may deteriorate. Therefore, in the present catalyst, it is presumed that each component in the catalyst effectively constitutes its action, so that the components are closely related to each other. A particularly preferred catalyst composition is represented by the following empirical formula (2). Fe ₁₀ Sba Vb CrcXdYeOf (2) (wherein, X is at least one element selected from the group consisting of Li, Na, K, Cs, La and Mg, and Y is C
e, Mo, W, Mn, Co, Ni, Cu, Zn, B, A
At least one element selected from the group consisting of 1, P and Bi is shown, and the subscripts a, b, c, d, e and f represent the atomic ratio of each element, and when Fe = 10, a = 10 Three
0, b = 2 to 10, c = 0.3 to 12, d = 0 to 3, e
= 0 to 5, and f represents the number corresponding to the oxide formed by combining the above components. )

As a method for preparing the catalyst, any method known in the technical field of this kind such as a mixing method, a precipitation method, an impregnation method and the like can be used. Catalyst Raw Material The starting raw material for each component constituting the catalyst can be selected from many types such as metal, oxide, hydroxide, chloride and nitrate of each component. Also,
It is also possible to use a substance that can be converted into an oxide by subjecting it to a chemical treatment or a firing treatment. As the raw material of the iron component,
For example, metallic iron, ferrous oxide, ferric oxide, ferric oxide, iron nitrate, iron chloride, organic acid iron such as iron acetate and iron oxalate, and the like are used. As the raw material of the antimony component, for example, antimony trioxide, antimony tetraoxide, nitric oxide of metal antimony, mineral acid of antimony, organic acid salt, etc. are used. As the raw material of the vanadium component, for example, vanadium pentoxide, ammonium metavanadate, vanadyl oxalate, vanadium halides and the like are used. As the raw material of the chromium component, chromium nitrate, chromium oxalate, ammonium dichromate, chromium oxide, chromic anhydride, etc. are used. As the raw materials for the other X and Y components, oxides, hydroxides, chlorides, nitrates and the like of the respective elements are used.

Preparation of catalyst A catalyst can be prepared by mixing, coprecipitating or impregnating these catalyst raw materials so as to have a desired composition ratio, drying and then calcining. For example, in the case of producing a fixed bed catalyst, a slurry prepared from each component is dried, kneaded, and molded into a columnar shape or a spherical shape, which is heated at 200 ° C to 9 ° C.
00 ° C., preferably in the range of 400 ° C. to 850 ° C.
It can be produced by firing for 5 hours to 50 hours. Further, in the case of producing a fluidized bed catalyst, it can be produced by spray-drying a slurry prepared from each component by appropriate means to form fine particles, and calcining it at the temperature as described above. . In particular, a method is preferred in which an aqueous slurry containing crystalline iron antimonate and vanadium as components is prepared and then the slurry is dried and calcined (see JP-A-4-126548).

The catalyst can be used without a carrier, but may be supported on various carriers such as silica, alumina, silica-alumina, silica-titania, titania and zirconia. In that case, it is preferable to use a carrier of 5 to 95 wt% of the whole catalyst.

Reacting Raw Material The starting material of the present invention, 2,3-dimethylpyridine, may be not only pure but also containing a small amount of impurities. Ammonia for industrial use can be used. Air is usually preferably used as the oxygen source, but it may be diluted with nitrogen, steam, carbon dioxide gas or the like, or may be enriched with oxygen and used.

Reaction Method The reaction is carried out by supplying 2,3-dimethylpyridine, ammonia and oxygen to the reactor filled with the catalyst produced as described above. The reaction method may be either a fixed bed reaction or a fluidized bed reaction. From the viewpoint of strictly controlling the reaction temperature, the fluidized bed reaction is preferred.

The concentration of 2,3-dimethylpyridine in the gas supplied to the reactor is in the range of 0.3 to 10 vol%, preferably 0.5 to 7 vol%. Ammonia / 2,3
The molar ratio of dimethylpyridine is in the range of 0.7 to 15, preferably 1.0 to 10. Further, the molar ratio of oxygen / 2,3-dimethylpyridine is in the range of 2-10, preferably 2.5-7.

The reaction temperature is in the range of 250 to 500 ° C, preferably 300 to 460 ° C. The reaction pressure may be atmospheric pressure, pressurization, or depressurization, but 2 kg from around atmospheric pressure
A range of / cm ² is suitable. The contact time is 0.1 to 20 based on the gas volume at the reaction temperature and the reaction pressure.
Seconds, preferably 0.5-10 seconds.

[0015]

EXAMPLES The embodiments and effects of the present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Catalyst activity test method A catalyst was packed in a fluidized bed reactor having an inner diameter of a catalyst fluidized portion of 2.5 cm and a height of 40 cm, and 2,3-dimethylpyridine,
Ammonia and air were fed to the reactor in the following proportions. The reaction pressure is normal pressure. Supply gas composition (molar ratio) Oxygen (supplied as air): Ammonia: 2,3-Dimethylpyridine = 5.32: 7: 1

The conversion rate of 2,3-dimethylpyridine, the yield of 2-cyano-3-methylpyridine, the yield of 2,3-dicyanopyridine and the yield of 3-cyanopyridine in Examples and Comparative Examples are defined as follows.

Example 1 The empirical formula is Fe ₁₀ Sb ₂₀ V ₄ Cr ₅ Mg ₂ Co ₁ Mo _0.1.
A fluidized bed catalyst that was O _75.8 (SiO ₂ ) ₄₀ was prepared as follows. (I) Take 239.9 g of antimony trioxide powder. (II) Nitric acid (specific gravity 1.38) 355 ml and pure water 445 m
1 and 1 are mixed and heated, and 45.8 g of electrolytic iron powder is added little by little and dissolved therein. (III) Take 987 g of silica sol (SiO ₂ : 20 wt%). (III) and (I) are added to (II) in this order with good stirring, and the pH is adjusted to 2 with 15% aqueous ammonia. This slurry was heated at 100 ° C. for 3 hours while stirring. (IV) 164.0 g of chromium nitrate is dissolved in 500 ml of pure water. (V) Dissolve 42.1 g of magnesium nitrate in 100 ml of pure water. (VI) 23.9 g of cobalt nitrate is dissolved in 50 ml of pure water. (VII) Ammonium paramolybdate 1.4 g was added to pure water 5
Dissolve in 0 ml. (VIII) 38.4 g of ammonium metavanadate is added to 300 ml of pure water and heated, and 100 g of oxalic acid is added little by little and dissolved. To the slurry prepared above (IV), (V), (VI), (VII),
Add (VIII) and stir well. Such a slurry was spray-dried using a rotary disk type spray dryer. The fine spherical particles obtained are heated at 200 ° C. for 2 hours and then at 400 ° C. for 3 hours.
Fired for hours. The final baking was performed at 820 ° C. for 2 hours.

Example 2 The empirical formula is as follows: Fe ₁₀ Sb ₂₅ V ₇ Cr ₅ K _0.2 O _90.1 (Si
A fluidized bed catalyst with O ₂ ) ₈₀ was prepared as in Example 1. However, K was an aqueous potassium nitrate solution, and was added after (IV) into the heat-treated slurry. The final firing was 790 ° C. for 2 hours.

Example 3 The empirical formula is as follows: Fe ₁₀ Sb ₁₈ V _5.5 Cr ₇ O _75.2 (Si
A fluidized bed catalyst with O ₂ ) ₆₀ was prepared as in Example 1. However, the final firing was performed at 800 ° C. for 2 hours.

Example 4 The empirical formula is that Fe ₁₀ Sb ₁₅ V ₄ Cr ₅ Cs _0.1 Mn ₂ Ce
_A fluidized bed catalyst that is _0.5 O _67.3 (SiO ₂ ) ₅₅ is used in Example 1.
It was prepared in the same manner as described above. However, Cs was an aqueous solution of cesium nitrate, Mn was an aqueous solution of manganese nitrate, and Ce was an aqueous solution of cerium nitrate, which were added subsequently to (IV) in the heat treatment slurry. The final firing was 820 ° C. for 4 hours.

Example 5 The empirical formula is as follows: Fe ₁₀ Sb ₁₇ V _3.5 Cr ₄ La ₁ P _0.3 Mo
_A fluidized bed catalyst of _0.1 O _66.3 (SiO ₂ ) ₄₀ was used in Example 1.
It was prepared in the same manner as described above. However, La is an aqueous solution of lanthanum nitrate, P is phosphoric acid, and (I
V) and then sequentially added. The final firing was 820 ° C. for 2 hours.

Example 6 The empirical formula is as follows: Fe ₁₀ Sb ₁₅ V ₆ Cr ₃ Ni ₃ O _67.5 (Si
A fluidized bed catalyst with O ₂ ) ₅₀ was prepared as in Example 1. However, as the Ni, an aqueous solution of nickel nitrate was used, and Ni was sequentially added to the heat-treated slurry after (IV). The final firing was 800 ° C. for 2 hours.

Example 7 The empirical formula is that Fe ₁₀ Sb ₃₀ V ₁₀ Cr ₁₀ K _0.5 Al ₁ O
_A fluidized bed catalyst of _116.75 (SiO ₂ ) ₁₀₀ was prepared as in Example 1. However, K is an aqueous solution of potassium nitrate and Al is aluminum nitrate.
Was added subsequently to (IV). The final firing is 760
C. and 4 hours.

Example 8 The empirical formula is that Fe ₁₀ Sb ₂₀ V ₃ Cr ₈ Zn ₁ W _0.2 O _76.1
A fluidized bed catalyst of (SiO ₂ ) ₆₀ was prepared as in Example 1. However, an aqueous solution of zinc nitrate was used for Zn, and an aqueous solution of ammonium metatungstate was used for W, which was added subsequently to (IV) into the heat treatment slurry. The final firing was 800 ° C. for 2 hours.

Example 9 The empirical formula is Fe ₁₀ Sb ₁₇ V _2.5 Cr _5.5 Li _0.1 B _0.2
A fluidized bed catalyst of Cu _0.5 O _64.35 (SiO ₂ ) ₄₅ was prepared as in Example 1. However, Li was an aqueous solution of lithium nitrate, Cu was an aqueous solution of copper nitrate, and B was an aqueous solution of boric acid, which were sequentially added into the heat treatment slurry after (IV). The final firing was 810 ° C. for 2 hours.

Comparative Example 1 The empirical formula is Fe ₁₀ Sb ₂₀ V ₄ Mg ₂ Co ₁ Mo _0.1 O.
_A fluidized bed catalyst of _68.3 (SiO ₂ ) ₄₀ was prepared as in Example 1.

The catalyst composition and final calcination temperature of Examples 1 to 9 and Comparative Example 1 are shown in Table 1, and the activity test results are shown in Table 2.

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

According to the method of the present invention, specific Fe.S
By using the b.V.Cr-containing oxide composition as a catalyst, 2-cyano-3-methylpyridine can be produced in a high yield from 2,3-dimethylpyridine, ammonia and oxygen in a gas phase.

Claims (1)

[Claims] 1. 2-Cyano-3, which comprises reacting 2,3-dimethylpyridine with ammonia and oxygen in a gas phase in the presence of an oxide composition represented by the following empirical formula (1). -Method for producing methylpyridine. Fe ₁₀ Sba Vb CrcXdYeOf (1) (In the formula, X is Li, Na, K, Rb, Cs, La, M
at least one element selected from the group consisting of g, Ca, Sr and Ba, Y is Ce, Ti, Zr, Nb, T
a, Mo, W, Mn, Re, Co, Ni, Cu, Ag,
Zn, B, Al, Ge, Sn, Pb, P, Bi and T
It shows at least one element selected from the group consisting of e, and the subscripts a, b, c, d, e and f represent the atomic ratio of each element, and when Fe = 10, a = 7 to 50, b = 1-1
5, c = 0.1 to 15, d = 0 to 3, e = 0 to 5, and f represents a number corresponding to an oxide formed by combining the above components. )