JPH11114418A - Catalyst for gas-phase catalytic oxidation reaction of isobutane and manufacturing of alkene and/or oxygen-containing compound using this catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance heat resistance, degree of conversion and selectivity by using a catalyst composed of a composite oxide represented by a specific formula after its baking. SOLUTION: This catalyst is composed of a composite oxide represented by the formula: NbaMobSbcXdYeOf (wherein, Nb is niobium; Mo is molybdenum; Sb is antimony; O is oxygen;X is one or more kinds of element selected from the group of phosphor, arsenic, boron, silicon and germanium; Y is one or more kinds of element selected from the group of potassium, cesium, rubidium, calcium, magnesium, thallium, chromium, manganese, iron or the like; subscripts a, b, c, d and e represent the atomic ratio of each of elements; a is a value of at most 7 not including O, c is a value of at most 20 not including O and d and e are a value of at most 6 including O, when b=12; and f is a value to be determined depending upon the atomic value and the atomic ratio of each of elements). Alkene such as isobutylene and an oxygen-containing compound are manufactured using this catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a catalyst for the gas phase catalytic oxidation reaction of isobutane, and an alkene such as isobutylene, acetic acid, acrylic acid, methacrolein and methacrylic acid, and an alkane and oxygen containing isobutane obtained by using the catalyst. The present invention relates to a method for producing a compound.

[0002]

2. Description of the Related Art A method for producing methacrylic acid from isobutylene or tertiary butanol via methacrolein by two-step oxidation is well known and has already been industrialized. On the other hand, in recent years, there has been proposed a method for producing methacrolein and / or methacrylic acid from isobutane which has the same carbon skeleton and is inexpensive, although the reactivity is remarkably poor as compared with isobutylene or tertiary butanol. I have.

For example, Japanese Patent Application Laid-Open No. 62-132832 discloses that “isobutane and oxygen are alternately contacted with a catalyst containing a heteropolyacid containing molybdenum with phosphorus or arsenic as a central element, and methacrolein and / or methacrylic acid And Japanese Unexamined Patent Publication (Kokai) No. 2-42034 disclose "Ag, Z with heteropolyacid containing molybdenum and / or its salt with phosphorus and / or arsenic as the central element.
n, Cd, Ti, Zr, Nb, Ta, Cr, W, Mn,
Isobutane is contacted in the gas phase with a catalyst containing at least one selected from the group consisting of Fe, Co, Ni, Rh, Sn, Bi and Te as a catalyst constituent element, And a method for obtaining rhein and / or methacrylic acid. Japanese Patent Laid-Open No. 5-
178774 and JP-A-5-331085 disclose gas-phase catalytic oxidation of isobutane in the presence of a catalyst,
In producing methacrolein and / or methacrylic acid, a method characterized by using a composite oxide catalyst containing divanadyl pyrophosphate as a main component, and adding an additional metal element thereto to improve activity and selectivity, is used. It has been disclosed.

However, isobutane is less reactive than isobutylene and tertiary butanol,
Under the oxidation conditions of isobutylene and tertiary butanol, the conversion of isobutane is low. Therefore, a method of raising the oxidation reaction temperature to increase the conversion rate can be considered. However, the phosphorus-molybdenum-based Keggin-type heteropolyacid catalyst has a problem in heat resistance, and it is difficult to adopt a method of increasing the reaction temperature. On the other hand, when a composite oxide catalyst containing divanadyl pyrophosphate as a main component is used, a satisfactory selectivity improvement effect cannot always be obtained. Also, when preparing divanadyl pyrophosphate-based catalyst,
Generally, vanadium pentoxide is used as a vanadium raw material. However, vanadium pentoxide has a problem that it is not preferable in terms of hygiene because vanadium pentoxide is highly toxic.

[0005]

Under such circumstances, the present inventors have found that industrially useful isobutane is industrially useful by subjecting isobutane to gas-phase catalytic oxidation using molecular oxygen in the presence of a composite oxide catalyst. For the purpose of producing alkenes and / or oxygen-containing compounds such as isobutylene, acetic acid, acrylic acid, methacrolein, and methacrylic acid, as a result of diligent studies, niobium-molybdenum has been used as a catalyst for the gas phase catalytic oxidation reaction. When a composite oxide catalyst containing antimony as an essential component is used, it has been found that the catalyst has excellent heat resistance and is excellent in both conversion and selectivity, and has completed the present invention.

[0006]

That is, according to the present invention, after calcination, a general formula NbaMobSbcXdYeOf (where Nb is niobium, Mo is molybdenum, Sb is antimony,
O represents oxygen, X is at least one element selected from the group consisting of phosphorus, arsenic, boron, silicon, and germanium; Y is potassium, cesium, rubidium, calcium, magnesium, thallium, chromium, manganese, iron,
Cobalt, nickel, copper, silver, lead, bismuth, aluminum, gallium, indium, tin, zinc, lanthanum,
Cerium, yttrium, tungsten, tantalum, ruthenium, rhodium, palladium, platinum, iridium,
Osmium, rhenium, represents at least one element selected from the group consisting of hafnium, and subscripts a, b,
c, d and e represent the atomic ratio of each element, and when b = 12, a is a value of 7 or less not including 0, c is a value of 20 or less not including 0, and d and e include 0 6 represents a value of 6 or less, and f represents a value determined by the valence and atomic ratio of each element).

Further, the present invention relates to a process for producing an alkene and / or an oxygen-containing compound by subjecting isobutane to gas-phase catalytic oxidation using molecular oxygen in the presence of a catalyst, wherein the catalyst has the general formula NbaMobSbcXdYe as a catalyst.
Of (where Nb is niobium, Mo is molybdenum, Sb is antimony, O is oxygen, X is phosphorus, arsenic, boron,
At least one element selected from the group consisting of silicon, germanium, and Y is potassium, cesium, rubidium,
Calcium, magnesium, thallium, chromium, manganese, iron, cobalt, nickel, copper, silver, lead, bismuth,
Aluminum, gallium, indium, tin, zinc, lanthanum, cerium, yttrium, tungsten, tantalum, ruthenium, rhodium, palladium, platinum, iridium, osmium, rhenium, represents at least one element selected from the group consisting of hafnium, The subscripts a, b, c, d and e represent the atomic ratio of each element, and b = 1
When a is 2, a is a value of 7 or less not including 0, c is a value of 20 or less not including 0, d and e are values of 6 or less including 0, and f is a valence and an atom of each element. Indicates a value determined by the ratio. It is another object of the present invention to provide a method for producing an alkene and / or an oxygen-containing compound, which is a composite oxide catalyst represented by the formula (1).

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The feature of the present invention is that gaseous catalytic oxidation of isobutane using molecular oxygen, isobutylene, methacrolein,
In producing an alkene and / or an oxygen-containing compound such as methacrylic acid, a general formula NbaMo is used as an applied catalyst.
Nb-Mo-Sb represented by bSbcXdYeOf (the symbols in the formula are the same as above) is an essential component, that is, b = 1
When 2, a is 0 <a ≦ 7, preferably 0 <a ≦ 5, c
Is to provide a composite oxide having an atomic ratio of 0 <c ≦ 20, preferably 0 <c ≦ 12. In the present invention,
The lack of any of these catalyst compositions does not provide a satisfactory catalytic effect, mainly an improvement in selectivity.

The method for preparing the catalyst used in the present invention is not particularly limited. The catalyst can be prepared by various known methods. For example, a composite oxide catalyst composed of molybdenum, niobium, and antimony can be obtained by adding niobium pentoxide and antimony trioxide to an aqueous solution of ammonium paramolybdate, evaporating to dryness, and calcining to obtain a predetermined catalyst. it can. As a molybdenum raw material, molybdenum trioxide,
Molybdic acid, ammonium paramolybdate, sodium molybdate and the like can be used. Further, the catalyst constituting material of the present invention, including niobium, antimony and the elements represented by X and Y in the above general formula, is a compound which can be decomposed into an oxide in the course of preparing the catalyst, for example, an oxide, a hydroxide, It is used as a nitrate, ammonium salt, carbonate, chloride, organic acid salt, alkoxide, ammonium metal salt or the like. More specifically, as a niobium raw material,
As an antimony raw material such as niobium hydrogen oxalate, niobium pentoxide, niobium pentachloride, niobium ethoxide, etc., the X component is as antimony trioxide, antimony tetroxide, antimony pentoxide, antimony acetate, antimony sulfate, antimony ethoxide, etc. , Phosphoric acid, pyrophosphoric acid, polyphosphoric acid, arsenic acid, boric acid, ammonium borate, silicon dioxide,
As the Y component such as germanium dioxide, potassium nitrate, potassium chloride, potassium sulfate, cesium nitrate, cesium chloride, cesium sulfate, cesium hydroxide, rubidium nitrate, rubidium sulfate, calcium nitrate, calcium chloride, calcium sulfate, calcium oxide, magnesium nitrate , Magnesium chloride, magnesium sulfate, magnesium oxide, magnesium hydroxide, thallium nitrate, chromium nitrate, chromium acetate, chromium sulfate, chromium chloride, manganese lactate, manganese nitrate, manganese oxalate, manganese sulfate,
Iron nitrate, iron sulfate, iron ammonium oxalate, iron oxalate, cobalt acetate, cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt hydroxide, copper nitrate, copper chloride, copper sulfate,
Silver benzoate, silver nitrate, silver carbonate, silver chloride, silver oxide, bismuth acetate, bismuth nitrate, bismuth oxide, aluminum oxide, aluminum sulfate, aluminum nitrate, gallium chloride, gallium hydroxide, gallium nitrate, gallium oxide, indium chloride, nitric acid Indium, tin acetate, tin benzoate,
Tin chloride, tin formate, tin hydroxide, tin sulfate, tin oxalate, zinc nitrate, zinc chloride, zinc oxalate, zinc oxide, lanthanum carbonate, lanthanum chloride, lanthanum oxalate, lanthanum nitrate,
Lanthanum sulfate, cerium oxide, cerium acetate, cerium nitrate, yttrium nitrate, yttrium formate, yttrium carbonate, yttrium sulfate, tungsten oxide, tungstic acid, ammonium paratungstate, tantalum ethoxide, tantalum hydroxide, tantalum pentoxide, ruthenium chloride, Ruthenium oxide, ruthenium sulfate, rhodium chloride, rhodium oxide, rhodium sulfate, palladium chloride, palladium hydroxide, palladium nitrate, platinum chloride, iridium chloride, iridium oxide, osmium chloride, osmium oxide, rhenium chloride, rhenium oxide, hafnium chloride, oxidation Hafnium and the like. The elements represented by X and Y in the above general formula are not essential components, but the addition of arsenic, boron, germanium, lead, zinc, gallium, etc. improves selectivity, but does not include thallium, chromium, iron, cobalt, nickel, copper. , Silver, bismuth, tin, lanthanum, yttrium, palladium, platinum, osmium, rhenium, hafnium and the like can contribute to the improvement of the activity.

[0010] The catalyst can be used in a form supported and / or diluted and mixed on a carrier. As the carrier and / or diluent, for example, silica, alumina, silica-alumina, magnesia, titania, zeolite, zirconia,
Silicon-carbide and the like are mentioned, and there is no limitation on the amount of the carrier and the dilution mixture ratio of the diluent and the catalyst. The shape of the catalyst is not limited to tablets, rings, spheres, extruded products, and the like. The molding method can be performed by a known method such as compression molding, extrusion molding, spray drying granulation and the like.

The concentration of isobutane in the raw material gas used for the reaction is about 1 mol% to 85 mol%, preferably 3 mol% to 7 mol%.
0 mol%.

The molar ratio of molecular oxygen to isobutane is suitably from 0.05 to 4.0, preferably from 0.1 to 3.5. As a supply source of molecular oxygen, air, pure oxygen, oxygen-enriched air, or the like is used.

Although steam may be contained in the reaction raw material gas, steam is not always required.

The source gas may contain a noble gas, nitrogen, carbon monoxide, carbon dioxide or the like. Further, even if isobutylene is contained in the raw material, isobutylene is converted to methacrolein or methacrylic acid as in isobutane.

Unreacted isobutane can be used as fuel, but can also be recovered and recycled. Isobutylene and methacrolein can also be converted to methacrylic acid by collecting and recycling. When pure oxygen or oxygen-enriched air is used, it is preferable that unreacted oxygen is also collected and reused.

The reaction temperature can be selected within the range of 250 to 550 ° C., preferably 300 to 500 ° C. The reaction pressure can be selected from a wide range from reduced pressure to increased pressure.
0 kPa, preferably in the range of 100 to 200 kPa.

The method of the present invention can be carried out in any reaction mode such as a fixed bed, a moving bed, a fluidized bed and the like. When using the fixed bed method, there is no particular limitation on the space velocity, but if the space velocity is too low, productivity is reduced, which is industrially disadvantageous.
Conversely, if the space velocity is too high, the reaction activity will decrease, so the reaction temperature must be increased. Therefore, usually 400 to 5000 h ^-1 , preferably 600 to 200 h ^-1
0 is in the range of ^-1.

The produced alkenes and various oxygen-containing compounds can be separated and purified into respective products by operations such as extraction and distillation.

[0019]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. The conversion (%) and the selectivity (%) are represented by the following equations, respectively. Isobutane conversion (%) = (moles of reacted isobutane) ÷ (moles of supplied isobutane) × 100 Isobutylene selectivity (%) = (moles of generated isobutylene) ÷ (moles of reacted isobutane) × 100 methacrolein selectivity (%) = (mol number of generated methacrolein) ÷ (mol number of reacted isobutane) × 10
0 Selectivity of methacrylic acid (%) = (mol number of methacrylic acid generated) / (mol number of reacted isobutane) × 100 Selectivity of active ingredient (%) = (mol number of generated isobutylene + methacryloline generated) Number of moles of methacrylic acid generated) / (number of moles of reacted isobutane)
× 100 The reaction product was analyzed using gas chromatography.

Example 1 Niobium hydrogen oxalate @ Nb was added to 600 ml of ion-exchanged water.
(HC_TwoO_Four)_Five・ NH _TwoDissolve 102.37g of O
Then, a uniform solution was obtained (Solution A). Then, ion-exchanged water
Ammonium molybdate ｛(NH_Four)₆M
o₇O_{twenty four} ・ 4H_TwoAdd O｝ 53.10g and dissolve with stirring
After performing (solution B), the entire amount of solution B was poured into solution A, and triacid was further added.
Antimony hydride Sb_TwoO_ThreeWhile stirring 32.85g
Was added. Put this mixture in a 1 liter autoclave
After transfer and aging at 120 ° C for 17 hours, the resulting slurry
-Adjust the pH of the solution to approximately neutral using 25% aqueous ammonia.
It was adjusted. The slurry solution thus obtained is heated and stirred.
Concentrate to dryness with stirring, then dry at 120 ° C for 6 hours
And crushed and sieved to obtain 4 to 8 mesh particles.
Mo is fired at 600 ° C for 2 hours in a stream of air.₁₂Nb_4.5Sb
₉A catalyst having a composition of Ox was obtained. Obtained in this way
Pyrex glass reaction tube 15 mm in diameter with 6 g of catalyst
And then add isobutane / oxygen / nitrogen / steam
Source gas consisting of 40/20/40/0 (mol%)
At a reaction pressure of 152 kPa and a space velocity of 1000 /
When the oxidation reaction was examined under the conditions of hr, a reaction temperature of 42
At 1 ° C, the isobutane conversion was 2.7%.
Selectivity for methacrylic acid, methacrolein and methacrylic acid
They were 43.7%, 13.8% and 1.9%, respectively. reaction
Temperature (reactor wall temperature) between 400 ° C and 450 ° C in detail
As a result of the study, it was found that the
The selectivity was 50.6%.

Example 2 Niobium hydrogen oxalate @ Nb was added to 1200 ml of ion-exchanged water.
(HC ₂ O ₄ ) 5 · nH ₂ O｝ 204.7 g is dissolved,
A uniform solution was obtained (Solution A). Next, ion-exchanged water 15
Ammonium paramolybdate デ ン (NH ₄ ) ₆
After _{Mo 7 O 24 · 4H 2 O} } was added 105.84g was dissolved with stirring (B liquid), and the total amount injected solution B to solution A, and stirred for an additional antimony trioxide {Sb ₂ O _3} 65.61g While adding. The pH of the mixture was adjusted to about neutral by adding 25% aqueous ammonia. The slurry solution thus obtained was concentrated to dryness while heating and stirring, and further concentrated for 120 minutes.
C. for 3 hours, pulverized and sieved to obtain 4 to 8 mesh particles.
A catalyst having a composition of o ₁₂ Nb _4.5 Sb ₉ Ox was obtained. An oxidation reaction was carried out using this catalyst under the same conditions as in Example 1.
As a result, at a reaction temperature of 423 ° C., the isobutane conversion was 2.7%, and the selectivities to isobutylene, methacrolein and methacrylic acid were 35.3% and 18.9%, respectively.
0.4%. Reaction temperature (reactor wall temperature) 400 ° C
As a result of a detailed examination between -450 ° C, the selectivity to the active ingredient when the isobutane conversion was 5% was 46.5%.

Example 3 In the method of Example 2, niobium hydrogen oxalate @ Nb
(HC_TwoO_Four)_Five・ NH _TwoOther than changing the amount of O
In the same manner as in Example 2, Mo₁₂Nb_FourSb₉Ox composition
Was obtained. Using the same catalyst as in Example 1 using this catalyst
Oxidation reaction was carried out. As a result, the reaction temperature reached 424 ° C.
The isobutane conversion was 4.0%, isobutylene,
The selectivity to tacrolein and methacrylic acid was 2
5.4%, 17.2%, 1.9%. Reaction temperature
(Reactor wall temperature) Examine in detail between 400 ° C and 450 ° C
As a result, selection of active ingredient at isobutane conversion rate 5%
The rate was 42.5%.

Example 4 In the method of Example 2, niobium hydrogen oxalate @ Nb
(HC_TwoO_Four) 5 · nH _TwoOther than changing the amount of O
In the same manner as in Example 2, Mo₁₂Nb_ThreeSb₉Ox group
A catalyst having the following characteristics was obtained. Same as Example 1 using this catalyst
The oxidation reaction was performed under the conditions. As a result, the reaction temperature was 429 ° C.
3.9% isobutane conversion, isobutylene,
Selectivities for methacrolein and methacrylic acid are respectively
19.7%, 16.2% and 0.9%. Reaction temperature
(Reactor wall temperature) Examine in detail between 400 ° C and 450 ° C
As a result, selection of active ingredient at isobutane conversion rate 5%
The rate was 34.7%.

Example 5 The dried slurry obtained in Example 2 was treated with 60
It was baked at 0 ° C. for 2 hours. Using this catalyst, an oxidation reaction was carried out under the same conditions as in Example 1. At a reaction temperature of 406 ° C., the isobutane conversion was 4.4%, and the selectivity to isobutylene, methacrolein and methacrylic acid was 1 each.
4.4%, 18.2% and 3.4%. As a result of detailed examination of the reaction temperature (reactor wall temperature) between 350 ° C. and 425 ° C., the selectivity to the active ingredient when the isobutane conversion was 5% was 34.5%.

Example 6 In the method of Example 2, antimony trioxide @ Sb ₂ O
Except that the amount of ₃ % was changed, M
A catalyst having a composition of o ₁₂ Nb _4.5 Sb ₆ Ox was obtained. An oxidation reaction was performed using this catalyst under the same conditions as in Example 1.
As a result, at a reaction temperature of 429 ° C., the isobutane conversion was 3.6%, and the selectivities to isobutylene, methacrolein and methacrylic acid were 28.2% and 15.1%, respectively.
0.8%. Reaction temperature (reactor wall temperature) 400 ° C
As a result of a detailed examination between -450 ° C., the selectivity to the active ingredient at a conversion of isobutane of 5% was 38.1%.

Comparative Example 1 Niobium hydrogen oxalate Nb in 400 ml of ion-exchanged water
(HC_TwoO_Four)_Five・ NH _TwoAdd O｝ 68.33g and stir
After dissolution, oxalic acid with a vanadium concentration of 2 mol / l
75 ml of vanadyl aqueous solution was added to make a uniform solution (A
liquid). Anion of paramolybdate in 150 ml of ion-exchanged water
Monium ｛(NH_Four)₆Mo₇O_{twenty four}・ 4H _TwoO $ 10
After adding 5.95 g and dissolving with stirring (solution B), solution A was added to solution B
The whole amount was poured into the liquid to obtain a slurry solution. On the other hand, ion exchange
70% nitric acid / HNO in 100 ml of water _Three$ 67.59
g, tin acetate @ Sn (CH_ThreeCO_Two)_Two$ 35.55g
Was added to prepare a uniform aqueous solution (Solution C). Stir liquid C
The whole amount was poured into the slurry solution with stirring. Got
Add 25% aqueous ammonia to the slurry solution and adjust the pH to about
Adjusted to neutral. The slurry solution thus obtained is
The solution was concentrated to dryness while heating and stirring, and then pulverized and sieved to obtain 4 to 8
And obtained at 600 ° C. for 2 hours in a nitrogen stream.
Baked Mo ₁₂Nb_1.5V_ThreeSn_ThreeContact having composition of Ox
A medium was obtained. Using this catalyst, oxidation reaction was performed under the same conditions as in Example 1.
Responded. As a result, at a reaction temperature of 322 ° C.,
Butane conversion is 7.3%, isobutylene, methacrolein
Selectivity to methacrylic acid and 1.6%, respectively.
3.9% and 1.6%. Reaction temperature (reactor wall temperature
Degree) As a result of a detailed examination between 290 ° C and 350 ° C,
8.4% selectivity to active ingredients at 5% sobutane conversion
Met.

[0027] Comparative Example 2 Ion-exchanged water 1200ml to ammonium paramolybdate _{{((NH 4) 6 Mo} 7 O 24 · 4H 2 O)} 21
1.9 g was added thereto, and 300 ml of an aqueous vanadyl oxalate solution having a vanadium concentration of 1 mol / l was added to the solution obtained by stirring and dissolving. 25% aqueous ammonia was added to the mixture to adjust the pH to almost neutral. Then 120
The water was evaporated in a dryer at ℃. This is placed in a nitrogen stream 6
It was calcined at 00 ° C. for 3 hours to obtain a catalyst having a composition of Mo ₁₂ V ₃ Ox. Using this catalyst, isobutane / oxygen / nitrogen /
A raw material gas having a water vapor ratio (mol%) of 25/12/33/30 was supplied, and the oxidation reaction was examined under the conditions of a reaction pressure of 152 kPa and a space velocity of 1000 / hr.
At a reaction temperature of 353 ° C, the isobutane conversion was 5.0.
%, Selectivity to isobutylene, methacrolein and methacrylic acid were 6.7%, 3.1% and 0.7%, respectively. As a result of detailed examination of the reactor wall temperature between 310 and 350 ° C., the selectivity to the active ingredient when the conversion of isobutane was 5% was 10.5%.

Comparative Example 3 The slurry dried product obtained in Comparative Example 2 was
It was baked at 50 ° C. for 6 hours. An oxidation reaction was performed using this catalyst under the same conditions as in Comparative Example 1. As a result, the reaction temperature 291
At ° C., the isobutane conversion was 4.2% and the selectivities to isobutylene, methacrolein and methacrylic acid were 2.6%, 2.4% and 0.4%, respectively. As a result of a detailed study between 290 and 350 ° C. of the reactor wall temperature, the selectivity to the active ingredient was 5.3 when the conversion of isobutane was 5%.
%Met.

Comparative Example 4 Niobium hydrogen oxalate Nb in 300 ml of ion-exchanged water
(HC ₂ O ₄ ) ₅ · nH ₂ O｝ 58.87 g is dissolved,
A uniform solution was obtained (Solution A). On the other hand, ion-exchanged water 326
Ammonium metavanadate ｛NH ₄ VO ₃ ｍｌ1 ml
5.71 g, ammonium paramolybdate {((NH
_{4) 6 Mo 7 O 24 ·} 4H 2 O)} 78.90g, dissolved by stirring and held at 55 ° C. was added telluric acid {H ₆ TeO _6} 23.61g, was a uniform solution (B solution). The whole amount of the solution B was injected into the solution A to form a precipitate, thereby obtaining a slurry solution. The pH of the slurry solution was adjusted to approximately neutral by adding 25% aqueous ammonia. The slurry solution thus obtained was concentrated to dryness while being heated and stirred, and further dried at 120 ° C. for 18 hours, pulverized and sieved to obtain 4 to 8 mesh particles, which were placed in a nitrogen stream at 600 ° C. Baked for 2 hours at Mo ₁₂ Nb _1.4 V
A catalyst having a composition of _3.6 Te _2.8 Ox was obtained. Using this catalyst, an oxidation reaction was performed under the same conditions as in Comparative Example 1. As a result, at a reaction temperature of 354 ° C., the conversion of isobutane was 4.9%, and the selectivities of isobutylene, methacrolein and methacrylic acid were 4.3%, 13.9% and 1%, respectively.
1.8%. As a result of a detailed study of the reactor wall temperature between 330 and 400 ° C., the selectivity to the active ingredient when the conversion of isobutane was 5% was 30.0%.

Comparative Example 5 In 400 ml of ion-exchanged water, 27.8 g of hydroxylamine hydrochloride {NH ₂ OH.HCl}, 80% phosphoric acid @ H
_After dissolving 58.8 g of ₃ PO ₄ to form a uniform solution,
Heated to 80 ° C. with a hot stirrer. Was slowly added vanadium pentoxide {V ₂ O _5} 36.4g to this solution. Stirring was continued for about 6 hours after the completion of the addition of vanadium pentoxide, and dried in a dryer at 120 ° C. for 15 hours to evaporate water. The obtained dried product was calcined in air at 500 ° C. for 15 hours to obtain a catalyst having a composition of (VO) ₂ P ₂ O ₇ . 9 g of the catalyst obtained by the above method was charged into a 15 mm diameter Pyrex glass reaction tube, and the ratio (mol%) of isobutane / oxygen / nitrogen / water vapor was 47/36 /
The raw material gas consisting of 17/0 is supplied and the reaction pressure is 152 k.
When the oxidation reaction was performed under the conditions of Pa and a space velocity of 1000 / hr, at a reaction temperature of 367 ° C., the conversion of isobutane was 2.1%, and the selectivity to isobutylene, methacrolein and methacrylic acid was 1.7%, respectively. 6.%, 8.
9%.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 45/33 C07C 45/33 47/22 47/22 H 57/05 57/05

Claims (2)

[Claims] 1. After firing, the general formula NbaMobSbcX
dYeOf (where Nb is niobium, Mo is molybdenum,
Sb represents antimony, O represents oxygen, X represents phosphorus, arsenic,
At least one element selected from the group consisting of boron, silicon, germanium, and Y is potassium, cesium, rubidium, calcium, magnesium, thallium, chromium, manganese, iron, cobalt, nickel, copper, silver, lead,
Bismuth, aluminum, gallium, indium, tin, zinc, lanthanum, cerium, yttrium, tungsten, tantalum, ruthenium, rhodium, palladium, platinum, iridium, osmium, rhenium, at least one element selected from the group consisting of hafnium And the subscripts a, b, c, d, and e represent the atomic ratio of each element. When b = 12, a is a value of 7 or less not including 0, and c is a value of 20 or less not including 0. , D and e each represent a value of 6 or less including 0, and f represents a value determined by the valence and atomic ratio of each element). 2. An alkene and / or an isobutane is subjected to gas-phase catalytic oxidation using molecular oxygen in the presence of a catalyst.
Alternatively, in a method for producing an oxygen-containing compound, a catalyst represented by the general formula NbaMobSbcXdYeOf (where Nb
Is niobium, Mo is molybdenum, Sb is antimony, O is oxygen, X is at least one element selected from the group consisting of phosphorus, arsenic, boron, silicon, and germanium;
Y is potassium, cesium, rubidium, calcium, magnesium, thallium, chromium, manganese, iron, cobalt, nickel, copper, silver, lead, bismuth, aluminum,
Represents at least one element selected from the group consisting of gallium, indium, tin, zinc, lanthanum, cerium, yttrium, tungsten, tantalum, ruthenium, rhodium, palladium, platinum, iridium, osmium, rhenium, hafnium, and a subscript a, b, c, d and e represent the atomic ratio of each element, and when b = 12, a
Is a value of 7 or less not including 0, c is a value of 20 or less not including 0, d and e are values of 6 or less including 0, and f is a value determined by the valence and atomic ratio of each element. . )
A method for producing an alkene and / or an oxygen-containing compound, which is a composite oxide catalyst represented by the following formula: