JP2988850B2 - Catalyst for producing unsaturated aldehyde and unsaturated carboxylic acid and method for producing unsaturated aldehyde and unsaturated carboxylic acid using the catalyst - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a catalyst for producing unsaturated aldehydes and unsaturated carboxylic acids and a method for producing unsaturated aldehydes and unsaturated carboxylic acids using the catalyst. Specifically, unsaturated aldehydes and unsaturated carboxylic acids are obtained from at least one compound selected from the group consisting of propylene, isobutylene, t-butanol and methyl-t-butyl ether by a gas phase catalytic oxidation reaction in a high yield and a long-term stable performance in an unsaturated aldehyde and unsaturated carboxylic acid. And a method for producing unsaturated aldehydes and unsaturated carboxylic acids using the catalyst.

[0002]

2. Description of the Related Art Various improved catalysts have been proposed for efficiently producing unsaturated aldehydes and unsaturated carboxylic acids by a gas phase catalytic oxidation reaction of propylene, isobutylene or the like. For example, Japanese Patent Application Laid-Open Nos. 50-13308 and 50
JP-A-47915 discloses a catalyst containing Mo, Bi, Fe, Sb and Ni and further containing at least one element of K, Rb and Cs as an essential component.
As described in US Pat. No. 6634, a catalyst containing Mo, Bi and Fe and further containing at least one element of Ni and Co as an essential component is described, most of the proposed catalysts are molybdenum, bismuth and It is mainly composed of iron.

[0003] The problem with these catalyst systems is that they are still considered to be inadequate in terms of not only the yield of unsaturated aldehydes and unsaturated carboxylic acids but also their lifetime. Molybdenum in the catalyst is easily scattered, which causes irreversible catalyst activity degradation. The above oxidation reaction is a very exothermic reaction, and considering that the molybdenum is scattered remarkably in the catalyst layer, particularly in a local abnormal high temperature zone called a hot spot, use of the catalyst at a high temperature should be avoided as much as possible. In addition, a catalyst that exhibits stable performance over a long period of time is desired. Especially in high-load operation aimed at high productivity, it is considered that the heat storage at the hot spot is considered to be larger, and that the period of use at high temperature is longer because catalyst deterioration is faster than normal reaction. Considering this, a catalyst that exhibits high activity and stable performance over a long period of time is indispensable.

On the other hand, acid strength (H ₀ ) (hereinafter sometimes simply referred to as “acid strength” or “H ₀ ”) is -11.93.
The following solid acids are usually called solid superacids. For example, "Catalyst" Vol. 31, No. 7 (1989) 512-51.
See page 8 for details. According to this document, superacids are defined as being more acidic than 100% sulfuric acid (H ₀ ≦ −1).
1.93), to be used under milder conditions compared to ordinary acid catalysts in reactions called acid catalysis such as hydrocarbon decomposition, isomerization, alkylation, polymerization, acylation, dehydration, and dehydrogenation. It is reported that can be. However, it has been found that such a superacid is effective in the gas phase catalytic oxidation reaction for producing the corresponding unsaturated aldehyde and unsaturated carboxylic acid from propylene, isobutylene and the like, especially in combination with a molybdenum-bismuth-iron catalyst. Not known at all.

[0005]

Accordingly, an object of the present invention is to provide a catalyst for producing unsaturated aldehydes and unsaturated carboxylic acids, which produces unsaturated aldehydes and unsaturated carboxylic acids in high yield.

Another object of the present invention is to provide a catalyst for producing unsaturated aldehydes and unsaturated carboxylic acids which has excellent catalyst life and enables stable operation for a long period of time.

Still another object of the present invention is to provide a catalyst for producing unsaturated aldehydes and unsaturated carboxylic acids which enables stable operation for a long period of time even under high load operation for the purpose of high productivity. is there.

Another object of the present invention is to provide a method for efficiently producing unsaturated aldehydes and unsaturated carboxylic acids using the above catalyst.

[0009]

As a catalyst for producing unsaturated aldehydes and unsaturated carboxylic acids, the present inventors have developed a composite oxide containing molybdenum, bismuth and iron as essential components and having an acid strength of -11.93 or less. It was found that the catalyst composition in combination with the solid acid of the present invention has high activity and excellent stability of the catalyst, and that the above object can be achieved by using this catalyst composition. The invention has been completed.

That is, the above objects are to oxidize at least one compound selected from the group consisting of propylene, isobutylene, t-butanol and methyl-t-butyl ether in the gas phase with molecular oxygen or a molecular oxygen-containing gas. A catalyst for producing unsaturated aldehydes and unsaturated carboxylic acids by propylene, isobutylene, t-butanol and / or methyl-t-butyl ether containing (A) molybdenum, bismuth and iron as essential components. Composite oxide for producing unsaturated aldehyde and unsaturated carboxylic acid by phase contact oxidation reaction and (B)
Acid strength (H ₀ ) of -11.93 or less (H ₀ ≦ -11.9)
This is achieved by the catalyst for producing unsaturated aldehyde and unsaturated carboxylic acid containing the solid acid of 3).

The present invention, component (A) is the general formula _{(1): Mo a W b} Bi in _{c Fe d A e B f C} g D h E i O x ( wherein, Mo is molybdenum, W is tungsten, Bi
Is bismuth, Fe is iron, A is at least one element selected from the group consisting of nickel and cobalt, B is at least one element selected from the group consisting of alkali metals and thallium, and C is at least one element selected from alkaline earth metals. A kind of element, D is phosphorus, tellurium, antimony,
At least one element selected from the group consisting of tin, cerium, lead, niobium, manganese, arsenic and zinc, E is at least one element selected from the group consisting of silicon, aluminum, titanium and zirconium, and O is oxygen , A, b, c, d, e, f, g, h,
i and x are Mo, W, Bi, Fe, A, B,
Represents the atomic ratio of C, D, E and O, and when a = 12,
b = 0 to 10, c = 0.1 to 10, d = 0.1 to 20,
e = 2 to 20, f = 0.001 to 10, g = 0 to 10,
h = 0 to 4, i = 0 to 30, and x is a value determined depending on the oxygen state of each element.) This shows a catalyst for producing unsaturated aldehydes and unsaturated carboxylic acids, which is a complex oxide represented by the following formula: Things. The present invention also provides a catalyst for producing unsaturated aldehydes and unsaturated carboxylic acids, wherein the component (B) is SO ₄ / a superacid of Group IV metal oxide of the periodic table. The present invention also provides a catalyst for producing an unsaturated aldehyde and an unsaturated carboxylic acid, wherein the Group IV metal of the periodic table is at least one selected from the group consisting of zirconium, titanium, tin and hafnium. The present invention also provides a catalyst for producing unsaturated aldehydes and unsaturated carboxylic acids wherein the component (B) is SO ₄ / iron oxide super strong acid. The present invention also provides a catalyst for producing unsaturated aldehydes and unsaturated carboxylic acids wherein the component (B) is SO ₄ / silicon oxide superacid. The present invention also provides a catalyst for producing unsaturated aldehydes and unsaturated carboxylic acids, wherein component (B) is a SO ₄ / aluminum oxide superacid. The present invention also provides a catalyst for producing unsaturated aldehydes and unsaturated carboxylic acids, wherein the component (B) is tungsten oxide, molybdenum oxide or tungsten-molybdenum composite oxide / zirconium oxide superacid. The present invention further provides an unsaturated aldehyde in which the component (B) is a tungsten oxide / tin oxide, titanium oxide, iron oxide, or a complex oxide superacid of at least two elements selected from the group consisting of tin, titanium and iron. And a catalyst for producing an unsaturated carboxylic acid. The present invention further provides a catalyst for producing unsaturated aldehydes and unsaturated carboxylic acids, wherein the component (B) is a phosphotungstic acid and / or a superacid of an alkali metal salt thereof. The present invention further provides a catalyst for producing unsaturated aldehydes and unsaturated carboxylic acids, wherein the ratio of component (B) to component (A) (as oxide) is 0.5 to 30% by weight.

[0012] The present invention also relates to a method of oxidizing at least one compound selected from the group consisting of propylene, isobutylene, t-butanol and methyl-t-butyl ether in the gas phase with molecular oxygen or a molecular oxygen-containing gas. In the gas phase catalytic oxidation reaction for producing a saturated aldehyde and an unsaturated carboxylic acid, the reaction is carried out in the presence of the catalyst for producing an unsaturated aldehyde and an unsaturated carboxylic acid described in any of the above. It is also achieved by a method for producing a saturated carboxylic acid.

[0013]

Hereinafter, the present invention will be described in detail.

Component (A): Component (A) includes propylene, isobutylene, t-butanol and methyl-t.
At least one selected from the group consisting of -butyl ether
As a catalyst for producing unsaturated aldehydes and unsaturated carboxylic acids by a gas phase catalytic oxidation reaction of various compounds, any of conventionally known composite oxide catalysts containing molybdenum, bismuth and iron as essential components can be used. Of these, the following general formula _{(1): Mo a W b} Bi c Fe d A e B f C g D h E i O x ( wherein, Mo is molybdenum, W is tungsten, Bi
Is bismuth, Fe is iron, A is at least one element selected from the group consisting of nickel and cobalt, B is at least one element selected from the group consisting of alkali metals and thallium, and C is at least one element selected from alkaline earth metals. A kind of element, D is phosphorus, tellurium, antimony,
At least one element selected from the group consisting of tin, cerium, lead, niobium, manganese, arsenic and zinc, E is at least one element selected from the group consisting of silicon, aluminum, titanium and zirconium, and O is oxygen , A, b, c, d, e, f, g, h,
i and x are Mo, W, Bi, Fe, A, B,
Represents the atomic ratio of C, D, E and O, and when a = 12,
b = 0 to 10, preferably 0.5 to 10, c = 0.1 to
10, preferably 0.2-6, d = 0.1-20, preferably 0.2-10, e = 2-20, preferably 3-1
5, f = 0.001 to 10, preferably 0.002 to
5, g = 0 to 10, preferably 0 to 5, h = 0 to 4, preferably 0 to 2, i = 0 to 30, preferably 0 to 15, and x is determined by the oxygen state of each element. A composite oxide represented by a numerical value) is preferably used.

The method for preparing these composite oxide catalysts is not particularly limited, and can be prepared by a conventionally known method. The type of the compound containing each element component as a starting material is not particularly limited, and any oxide containing each element component or a compound that generates an oxide by firing can be used. Examples of the compound that generates an oxide by firing include hydroxide, metal acid, nitrate, carbonate, ammonium salt, acetate, and formate. Compounds containing two or more of the above elemental components can also be used.

Usually, the required amount of the compound containing each elemental component as a starting material is appropriately dissolved in, for example, an aqueous medium, heated and stirred, evaporated to dryness, and further pulverized, if necessary, to achieve the intended purpose. The composite oxide catalyst of the component (A) is obtained.

Component (B): As the solid superacid as the component (B), as described in the above “catalyst”, a sulfuric acid-supported superacid and an oxide-supported superacid are known. Examples thereof include the following super strong acids (1) to (7).

(1) SO_Four/ Oxidation of Group IV metals in the periodic table
Here, as the Group IV metal of the periodic table, zirconium
, Titanium, tin and hafnium are preferably used.
It is. These can be used in combination. Representative example
As SO_Four/ Zirconium oxide, SO_Four/ Oxidation
Tan, SO_Four/ Tin oxide and SO_Four/ Hafnium oxide
Can be mentioned. And SO_Four/ Zr
O_Two, SO_Four/ TiO_Two, SO_Four/ SnO_TwoAnd SO
_Four/ HfO _TwoIt is expressed as These superacids are referred to above
Medium "and" Advances in Catalyst "
sis ", vol. 37, p. 182-191 (199
0), "Applied Catalysis", vo
l. 61, p. 1-25 (1990)
I have.

The method of preparing these superacids will be described by taking zirconium as an example. Zirconium hydroxide or amorphous zirconium oxide is brought into contact with a sulfate-containing solution, for example, sulfuric acid or an aqueous sulfuric acid solution, and then excess sulfate is added. After removing the containing solution and then drying, the solution is heated at a temperature of 350 to 800 ° C., preferably 400 to 700 ° C. for 1 to 10 hours, preferably 2 hours, in an atmosphere of an inert gas such as air or nitrogen.
By baking for about 8 hours, SO ₄ / zirconium oxide superacid is obtained. In the case of other metals, they can be similarly prepared using the respective hydroxides or amorphous oxides as raw materials.

It is generally considered that in the super-strong acid thus obtained, the sulfate group (SO ₄ ²⁻ ) is bound or supported on the metal oxide, and the above-mentioned “catalyst” and “Advances in Catalyst” are used.
Since “s” is also expressed as SO ₄ / metal oxide (MeO _x ), the super strong acid used in the present invention is also displayed according to such a display method.

(2) SO ₄ / iron oxide superacid This superacid is expressed as SO ₄ / Fe ₂ O _3, and is referred to as the above “catalyst”, “Advances in Catal”.
ysis ”and“ ChemistryLette ”
rs ", p. 1259-1260 (1979).

The super strong acid is obtained by contacting a hydroxide or an amorphous oxide of iron with a sulfate group-containing solution, for example, sulfuric acid or an aqueous sulfuric acid solution, and then removing excess sulfate group-containing solution.
Then, after drying, 350-800 ° C., preferably 400-6 ° C. in an inert gas atmosphere such as air or nitrogen gas.
It is obtained by firing at a temperature of 50 ° C. for 1 to 10 hours, preferably for about 2 to 8 hours.

(3) SO ₄ / Silicon Oxide Superacid This superacid is expressed as SO ₄ / SiO ₂ and is referred to as the “catalyst”, “Advances in Catalyst”.
sis ”and the like.

The superacid is dried by contacting the silica gel with a sulfur-containing compound, for example, sulfuryl chloride, and then drying it in an inert gas atmosphere such as air or nitrogen gas.
It is obtained by firing at a temperature of 00 to 600 ° C, preferably 350 to 500 ° C for 1 to 10 hours, preferably for about 2 to 8 hours.

(4) SO ₄ / aluminum oxide superacid This superacid is expressed as SO ₄ / Al ₂ O _3, and is referred to as the “catalyst”, “Advances in Catal”.
ysis ”and the like.

The super strong acid is obtained by contacting γ-alumina or aluminum hydroxide with a sulfate group-containing solution, for example, sulfuric acid or an aqueous sulfuric acid solution, removing excess sulfate group-containing solution, drying, and then drying with air or nitrogen. 350 to 800 ° C., preferably 400 ° C. in an inert gas atmosphere such as a gas.
It is obtained by firing at a temperature of about 700 ° C. for 1 to 10 hours, preferably about 2 to 8 hours.

(5) Tungsten oxide, molybdenum oxide or tungsten-molybdenum composite oxide / zirconium oxide superacid These superacids are WO ₃ / ZrO ₂ and MoO ₃ / ZrO.
₂ and WO ₃ -MoO ₃ / ZrO ₂ and are referred to above as “catalysts”, “Chemistry Letters”.
s "," Advances in Catalyst "
s "and" J. Chem. Soc., Chem. C. "
ommun. P. 1059-1060 (1988).

These super-strong acids are prepared by supporting a compound of tungsten and / or molybdenum on zirconium hydroxide or amorphous zirconium oxide, and then in an atmosphere of an inert gas such as air or nitrogen gas.
C., preferably at a temperature of 650 to 850 ° C. for 1 to 10 hours, preferably about 2 to 8 hours.

The loading amount of tungsten oxide, molybdenum oxide or tungsten-molybdenum composite oxide is usually 1 to 40% by weight of zirconium oxide, preferably 3 to 40%.
% By weight.

(6) Tungsten oxide / tin oxide, titanium oxide, iron oxide, or composite oxide superacid of at least two elements selected from the group consisting of tin, titanium and iron These superacids are WO ₃ / SnO ₂ , WO ₃ / Ti
O ₂ , WO ₃ / Fe ₂ O ₃ , WO ₃ / SnO ₂ —TiO
_{2, WO 3 / SnO 2 -Fe} 2 O 3, WO 3 / TiO 2
-Fe ₂ O ₃ and WO ₃ / SnO ₂ -TiO ₂ -Fe
₂ O _3, and in addition to the aforementioned “catalyst”, “St”
ud. Surf. Soc. Catal. ", Vol. 7
5, p. 2613-16 (1953).

These superacids include stannic hydroxide, amorphous stannic oxide, titanium hydroxide, amorphous titanium oxide,
A tungsten compound is supported on at least one compound selected from the group consisting of ferric hydroxide and amorphous ferric oxide, and then 650 to 1200 ° C. in an inert gas atmosphere such as air or nitrogen gas, preferably 650-1
It is obtained by firing at a temperature of 000 ° C. for 1 to 10 hours, preferably for about 2 to 8 hours.

The loading amount of tungsten oxide is usually 1 to 40% by weight, preferably 3 to 40% by weight of oxides such as tin oxide and titanium oxide.

(7) Phosphotungstic acid and / or its alkali metal salt superacid These superacids are H ₃ P ₁ W ₁₂ O ₄₀ and H _{3- x} A _x P ₁
W ₁₂ O ₄₀ (where A is an alkali metal (sodium, potassium, rubidium and cesium) and 0 <x <
3)). These superacids are described in Chem.
Tech. "November (1993), p. 28
-29.

These superacids are prepared by subjecting phosphotungstic acid or an alkali salt thereof to 350 to 500 ° C., preferably 380 to 45 ° C. in an atmosphere of air or an inert gas such as nitrogen gas.
It is obtained by firing at a temperature of 0 ° C. for 1 to 10 hours, preferably for about 2 to 8 hours.

As the component (B) of the present invention, various superacids as described above can be used in combination.

Some of the solid acids as the component (B) have an acid strength of -16.04 or less (H ₀ ≤-16.04), but a method for measuring an acid strength stronger than -16.04 Since has not yet been established, its value cannot be specified. However, the above superacids (1) to (7) all exhibit an acid strength higher than -11.93, and can be effectively used as the component (B) of the present invention.

Acid strength (H ₀ ): The acid strength in the present invention was measured by the following generally used method.

When the sample to be measured is white, the sample is immersed in benzene, a benzene solution containing an acid-base conversion indicator having a known pKa value is added thereto, and the change of the indicator of the sample surface to an acidic color is observed. The smallest value of the pKa at which the color changes to an acidic color is defined as the acid strength. The indicators used are as follows:

Indicator names (pKa): m-nitrotoluene (-12.0), p-nitrotoluene (-12.4),
p-nitrochlorobenzene (-12.7), m-nitrochlorobenzene (-13.2), 2,4-dinitrotoluene (-13.8), 2,4-dinitrofluorobenzene (-14.5), 1 , 3,5-trinitrobenzene (-16.0).

If the sample is colored, first place the sample in a container having a gas exhaust and introduction line, exhaust the air sufficiently, introduce ammonia gas, and adsorb ammonia to the sample. Let it. Next, the temperature was raised while exhausting the ammonia gas, the ammonia gas exhausted at each temperature was collected with liquid nitrogen, the amount of collected ammonia per sample weight was measured, and a sample having a known acid strength was separately measured. The acid strength is calculated based on the comparison with the calibration curve prepared in the above.

Catalyst: The catalyst of the present invention contains the above components (A) and (B). The ratio of component (B) to component (A) (as oxide) is usually 0.5 to 30% by weight.
And preferably 1 to 20% by weight. Component (B)
Is less than 0.5% by weight, a sufficient effect of addition cannot be obtained. On the other hand, when it exceeds 30% by weight, a decrease in the activity is observed.
The selectivity to unsaturated aldehydes and unsaturated carboxylic acids from isobutylene and the like decreases, and the selectivity to CO ₂ and CO increases. That is, when the component (B) is used alone,
The conversion of isobutylene and the like and the selectivity to unsaturated aldehydes and unsaturated carboxylic acids are low, and the reaction to CO ₂ and CO proceeds easily. Therefore, component (B) is not a preferable component to be used alone in the gas phase catalytic oxidation reaction or the like according to the present invention.

However, when the component (B) is contained in the component (A), the function of improving the activity of the component (A) and the selectivity to unsaturated aldehydes and unsaturated carboxylic acids from isobutylene and the like is improved. I found out. In particular, when the component (A) contains the component (B) in the above range, a remarkable effect as a cocatalyst is generated.

The catalyst of the present invention can be used alone, but can also be used by being supported on an inert carrier such as alumina, silica-alumina, silicon carbide, titanium oxide, magnesium oxide, and aluminum sponge. . At this time, inorganic fibers such as glass fibers and various whiskers which are generally well known as having an effect of improving the strength and the degree of powdering of the catalyst may be added. In addition, in order to control the physical properties of the catalyst with good reproducibility, ammonium nitrate, cellulose, starch, polyvinyl alcohol,
Additives commonly known as powder binders, such as stearic acid, can also be used.

The shape of the catalyst is not particularly limited, and may be any shape such as a pellet, a sphere, a column, a ring, and a tablet. Its average diameter is 1 to 1
5 mm, preferably 3 to 10 mm.

The method for preparing the catalyst containing the components (A) and (B) is not particularly limited, and can be prepared by any method. For example, a method of preparing powders of the respective components in advance and mixing the powders intimately using a ball mill or the like, a method of preparing the components (B ) Can be adopted.

In general, component (A) and component (B)
Is mixed sufficiently, and if necessary, water or the like is added as a molding aid to mold into a desired shape.
It is good to bake at a temperature of 00 to 600 ° C., preferably 350 to 550 ° C. for 1 to 10 hours, preferably 2 to 8 hours to use as a molded body.

Gas phase catalytic oxidation reaction: There are no particular restrictions on the apparatus, conditions, etc., for carrying out the gas phase catalytic oxidation reaction of the present invention. That is, regarding the reaction conditions, the reaction can be carried out under the conditions generally used for producing unsaturated aldehydes and unsaturated carboxylic acids by gas phase catalytic oxidation reaction.

For example, 1 to 10% by volume, preferably 2 to 8% by volume of at least one compound selected from the group consisting of propylene, isobutylene, t-butanol and methyl-t-butyl ether is used as a raw material gas. In the range of 1 to 10 times, preferably 1 to 8 times by volume, molecular oxygen and an inert gas as a diluent, for example, nitrogen, carbon dioxide, steam (especially, the use of steam suppresses the formation of A mixed gas of from 250 to 450 ° C., preferably 2 ° C.
300 to 5000 hr ^-1 (S) under a pressure of normal pressure to 10 atm, preferably normal pressure to 8 atm in a temperature range of 80 to 420 ° C.
TP), preferably 500-4000 hr ^-1 (STP)
What is necessary is just to make it contact and react with the catalyst of this invention at the space velocity of.

According to the process of the present invention, the unsaturated aldehydes and unsaturated carboxylic acids are acrolein and acrylic acid from propylene, methacrolein and methacrylic acid from isobutylene, methacrolein and methacrylic acid from t-butanol and methyl-t -Butyl ether gives methacrolein and methacrylic acid.

Action: The fact that a solid superacid, which is extremely effective in acid-catalyzed reactions, is active in oxidation reactions also includes the oxidation of butanes to CO and CO ₂ , the formation of acetaldehyde and acetone from ethylene, and the formation of cyclohexanone from cyclohexanol. It is surprising that it is not known until now that only an example is known and that it is also effective for an oxidation reaction such as a reaction for producing an unsaturated aldehyde and an unsaturated carboxylic acid.

Component (B) in the catalyst used in the present invention
Although the action of is not well understood, the strong acidity of the component (B) promotes the adsorption of the reactants such as propylene and isobutylene to the catalyst, so that the catalytic activity becomes high. Also, the component (B) has a high surface area. It is considered that it has excellent heat resistance and contributes to the stability of the composite oxide of the component (A). The present invention is not limited by such theoretical considerations.

[0052]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. The conversion, total selectivity and total single-stream yield are defined as follows.

[0053]

(Equation 1)

[0054]

(Equation 2)

[0055]

(Equation 3)

Example 1 Preparation of Catalyst Component (A) 1456 g of cobalt nitrate and 202 g of ferric nitrate were dissolved in 1 liter of ion-exchanged water. Also, bismuth nitrate 2
43 g was dissolved in a nitric acid aqueous solution consisting of 30 ml of concentrated nitric acid and 120 ml of ion-exchanged water.

Separately, 1059 g of ammonium paramolybdate and 265 g of ammonium paratungstate were added to 3 liters of heated ion-exchanged water and dissolved with stirring. The two separately prepared aqueous solutions were dropped and mixed into the obtained aqueous solution, and then an aqueous solution obtained by dissolving 39 g of cesium nitrate in 200 ml of ion-exchanged water was added.
203 g of silica sol having a concentration of% by weight was sequentially added and mixed.

The slurry thus obtained was heated and stirred, evaporated to dryness and then pulverized to obtain a molybdenum-tungsten-bismuth-iron composite oxide powder ("powder (A-
1) ").

Component (B) After 250 g of zirconium oxychloride was completely dissolved in ion-exchanged water, aqueous ammonia was gradually added with stirring to form zirconium hydroxide. The generated zirconium hydroxide was filtered, sufficiently washed with ion-exchanged water, and then dried at 100 ° C. for 24 hours. The dried hydroxide is spread on a funnel (filter paper), and separately prepared is poured over the hydroxide in ten portions while suctioning 0.25 molar sulfuric acid,
After sufficient suction to remove excess sulfate group solution, drying was performed. The dried sulfuric acid-treated product was calcined in an air stream at 500 ° C. for 3 hours to obtain an SO ₄ / ZrO ₂ super strong acid powder having a strong acidity of -14.5 (hereinafter referred to as “powder (B-1)”).

1,699 g of powder (A-1) (as oxide)
62.5 g of powder (B-1) (in terms of oxide) was added to the mixture, and after sufficient mixing, water was added as a molding aid to give an outer diameter of 6 mm.
After being formed into pellets having a length of 6.6 mm, the pellets were dried and then calcined at 500 ° C. for 6 hours in an air stream to obtain a catalyst (1). The ratio of the powder (B-1) to the powder (A-1) (as oxide) was 3.7% by weight. The elemental composition of this catalyst (1) was as follows in atomic ratio (atomic ratio excluding oxygen, the same applies hereinafter).

[0061] _{Mo 12 W 2 Bi 1 Fe 1} Co 10 Cs 0. 4 S
i _{1. 35} - were charged to (Zr _{1. 0} S _{0. 02)} oxidation catalyst (1) steel reactor 25.4mmφ a 1500 ml. 6% by volume of isobutylene, 13.2% by volume of oxygen, 10% by volume of steam and 70.
A mixed gas having a composition of 8% by volume was introduced, and the reaction temperature was 3
The oxidation reaction was performed at 30 ° C. and a space velocity of 1600 hr ⁻¹ (STP). Table 1 shows the results.

Comparative Example 1 Preparation of Catalyst A catalyst (2) was prepared in the same manner as in Example 1 except that only the powder (A-1) was used.

Oxidation reaction The oxidation reaction was carried out under the same reaction conditions as in Example 1 except that the catalyst (2) was used in place of the catalyst (1) and the reaction temperature was changed to 330 ° C. or 340 ° C. went. Table 1 shows the results.

Comparison between Example 1 and Comparative Example 1 shows that the catalyst (1) of the present invention has higher catalytic activity than the comparative catalyst (2) and shows the same catalytic activity at a lower temperature. I understand. Example 2 Preparation of Catalyst In Example 1, when powder (A-1) was prepared, 62.5 g (in terms of oxide) of powder (B-1) was added at the slurry stage, and then heated and stirred. Then, the mixture was evaporated to dryness, and water was added as a molding aid in the same manner as in Example 1 to obtain an outer diameter of 6 m.
m, pellets having a length of 6.6 mm, dried, and then calcined at 500 ° C. for 6 hours under air flow to obtain a catalyst (3)
I got The elemental composition and powder (A-
The ratio (in terms of oxide) of the powder (B-1) to 1) is
Same as catalyst (1).

Oxidation reaction An oxidation reaction was carried out in the same manner as in Example 1 except that the catalyst (3) was used instead of the catalyst (1).
Table 1 shows the results.

Example 3 Preparation of Catalyst In Example 1, powder (B-1) was added in advance to ion-exchanged water to which ammonium paramolybdate and ammonium metavanadate were added when powder (A-1) was prepared.
A catalyst (4) was obtained in the same manner as in Example 1 except that 5 g (in terms of oxide) was added. The element composition of the catalyst (4) and the ratio of the powder (B-1) to the powder (A-1) (as oxide) were the same as those of the catalyst (1).

Oxidation reaction An oxidation reaction was carried out in the same manner as in Example 1 except that the catalyst (4) was used instead of the catalyst (1).
Table 1 shows the results.

Example 4 In Example 2, the oxidation reaction was continued for 4000 hours, and the results after 4000 hours are shown in Table 1.

From the results shown in Table 1, the decrease in the activity after the oxidation reaction for 4000 hours is very small, and the decrease in the yield is almost negligible. The use of the catalyst (3) makes the oxidation reaction very stable over a long period. It was found that it was possible to continue.

Comparative Example 2 An oxidation reaction was carried out in the same manner as in Comparative Example 1, except that the reaction was carried out at a reaction temperature of 340 ° C. for 4000 hours. Table 1 shows the results.

Comparative Example 1 (reaction temperature 340 ° C.) and Comparative Example 2
It can be seen from the comparison with that that the catalyst (2) for comparison has a large decrease in activity and yield after a long-time reaction, and has a problem in stability.

Example 5 An oxidation reaction was carried out in the same manner as in Example 2 except that the reaction temperature and the space velocity were changed to 360 ° C. and 3000 hr ⁻¹ , respectively. Table 1 shows the results.

Comparative Example 3 An oxidation reaction was carried out in the same manner as in Example 5 except that the catalyst (2) was used instead of the catalyst (3).
Table 1 shows the results.

Comparison between Example 5 and Comparative Example 3 reveals that the catalyst (3) of the present invention is superior in activity and yield under high space velocity conditions as compared with the catalyst (2) for comparison. I understand.

Example 6 An oxidation reaction was carried out in the same manner as in Example 2 except that the proportions of isobutylene and nitrogen gas in the raw material gas were changed to 7.0% by volume and 69.8% by volume, respectively. Was. Table 1 shows the results.

Comparative Example 4 An oxidation reaction was carried out in the same manner as in Example 6, except that the catalyst (2) was used instead of the catalyst (3). Table 1 shows the results.

From a comparison between Example 6 and Comparative Example 4, it can be seen that the catalyst (3) of the present invention is excellent in both activity and yield even when the isobutylene concentration in the raw material gas is increased.

[0078]

[Table 1]

Example 7 An oxidation reaction was carried out in the same manner as in Example 2 except that t-butanol was used instead of isobutylene as the raw material gas. Table 2 shows the results.

Comparative Example 5 An oxidation reaction was carried out in the same manner as in Example 7, except that the catalyst (2) was used instead of the catalyst (3).
Table 2 shows the results.

[0081]

[Table 2]

Example 8 In Example 2, 5% by volume of methyl-t-butyl ether (MTBE), 13.2% by volume of oxygen,
A mixed gas consisting of 10% by volume of steam and 71.8% by volume of nitrogen was used.
Example 2 except that the temperature was changed to 000 hr ^-1 and 360 ° C.
An oxidation reaction was carried out in the same manner as described above. Table 3 shows the results.

Comparative Example 6 An oxidation reaction was carried out in the same manner as in Example 8, except that the catalyst (2) was used instead of the catalyst (3). Table 3 shows the results.

[0084]

[Table 3]

Example 9 Preparation of Catalyst In Example 2, the powder (B-
Catalyst (5) was prepared in exactly the same manner except that the addition ratio (in terms of oxide) of 1) was changed to 7.4% by weight. The element composition of this catalyst (5) was as follows in atomic ratio.

[0086] _{Mo 12 W 2 Bi 1 Fe 1} Co 10 Cs 0. 4 S
i _{1. 35} - In (Zr _{2. 0} S _{0. 04)} oxidation reaction in Example 1 while using the catalyst (5) in place of the catalyst (1) was subjected to the same oxidation reaction as in Example 1. Table 4 shows the results.

Example 10 Preparation of Catalyst In preparation of powder (B-1) in Example 1, powder was prepared except that titanium tetrachloride was used in place of zirconium oxychloride and the calcination temperature was changed to 520 ° C. By the same preparation method as in (B-1), SO ₄ / TiO ₂ having a strong acidity of -13.8 was used.
Super strong acid powder (referred to as “powder (B-10)”) was prepared. Hereinafter, a catalyst (6) was prepared in the same manner as in Example 2 except that the powder (B-10) was used instead of the powder (B-1). The element composition of this catalyst (6) was as follows in atomic ratio. The ratio of the powder (B-10) to the powder (A-1) (as oxide) is 2.4.
% By weight.

[0088] _{Mo 12 W 2 Bi 1 Fe 1} Co 10 Cs 0. 4 S
i _{1. 35} - In (Ti _{1. 0} S _{0. 02)} oxidation reaction in Example 1 while using the catalyst (6) in place of the catalyst (1) was subjected to oxidation reaction in the same manner as in Example 1 .
Table 4 shows the results.

Example 11 Preparation of Catalyst In preparing powder (B-1) in Example 1, the powder was changed except that stannic chloride was used instead of zirconium oxychloride and the calcination temperature was changed to 550 ° C. According to the same preparation method as that of the compound (B-1), SO ₄ / SnO _{2 having} a strong acidity of -14.5 was used.
Super strong acid powder (referred to as “powder (B-11)”) was prepared. Hereinafter, a catalyst (7) was prepared in the same manner as in Example 2 except that the powder (B-11) was used instead of the powder (B-1). The element composition of this catalyst (7) was as follows in atomic ratio. The ratio of the powder (B-11) to the powder (A-1) (as oxide) was 4.5.
% By weight.

[0090] _{Mo 12 W 2 Bi 1 Fe 1} Co 10 Cs 0. 4 S
i _{1. 35} - In (Sn _{1. 0} S _{0. 02)} oxidation reaction in Example 1 while using the catalyst (7) in place of the catalyst (1) was subjected to the same oxidation reaction as in Example 1. Table 4 shows the results.

Example 12 Preparation of Catalyst The powder (B-1) was prepared in the same manner as in Example 1 except that hafnium chloride was used instead of zirconium oxychloride and the calcination temperature was changed to 650 ° C. By the same preparation method as in B-1), SO ₄ / HfO having a strong acidity of -13.2 was used.
_2. Super strong acid powder (hereinafter referred to as “powder (B-12)”) was prepared. Hereinafter, a catalyst (8) was prepared in the same manner as in Example 2 except that the powder (B-12) was used instead of the powder (B-1). The element composition of this catalyst (8) was as follows in atomic ratio. The ratio of the powder (B-12) to the powder (A-1) (as oxide) was 6.2.
% By weight.

[0092] _{Mo 12 W 2 Bi 1 Fe 1} Co 10 Cs 0. 4 S
i _{1. 35} - In (Hf _{1. 0} S _{0. 02)} oxidation reaction in Example 1 while using the catalyst (8) in place of the catalyst (1) was subjected to the same oxidation reaction as in Example 1. Table 4 shows the results.

Example 13 Preparation of Catalyst A powder was prepared in the same manner as in the preparation of the powder (B-1) except that iron chloride was used instead of zirconium oxychloride in the preparation of the powder (B-1). To obtain an SO ₄ / Fe ₂ O ₃ super strong acid powder having a strong acidity of −12.7 (“powder (B-13)”).
Was prepared. Hereinafter, a catalyst (9) was prepared in the same manner as in Example 1 except that the powder (B-13) was used instead of the powder (B-1). The element composition of this catalyst (9) was as follows in atomic ratio. The ratio of the powder (B-13) to the powder (A-1) (as oxide) was 2.4% by weight.

[0094] _{Mo 12 W 2 Bi 1 Fe 1} Co 10 Cs 0. 4 S
i _{1. 35} - In (Fe _{1. 0} S _{0. 01)} oxidation reaction in Example 1 while using the catalyst (9) in place of the catalyst (1) was subjected to the same oxidation reaction as in Example 1. Table 4 shows the results.

Example 14 Preparation of Catalyst 100 g of ethyl silicate was dissolved in ion-exchanged water, a few drops of concentrated nitric acid were added, and the mixture was stirred to obtain silica gel. After drying the silica gel at 100 ° C., the silica gel is immersed in SO ₂ Cl ₂ and then calcined at 400 ° C. to obtain SO ₄ / S having a strong acidity of -12.7.
An iO ₂ super strong acid powder (hereinafter referred to as “powder (B-14)”) was obtained. Hereinafter, a catalyst (10) was prepared in the same manner as in Example 2 except that the powder (B-14) was used instead of the powder (B-1). The elemental composition of this catalyst (10) was as follows in atomic ratio. The powder (A-
The ratio of the powder (B-14) to 1) (as oxide) was 1.8% by weight.

[0096] _{Mo 12 W 2 Bi 1 Fe 1} Co 10 Cs 0. 4 S
i _{1. 35} - In (Si _{1. 0} S _{0. 02)} oxidation reaction in Example 1, the catalyst (10) in place of the catalyst (1)
An oxidation reaction was carried out in the same manner as in Example 1 except for using. Table 4 shows the results.

Example 15 Preparation of Catalyst After 5 N sulfuric acid was brought into contact with γ-alumina,
To obtain an SO ₄ / Al ₂ O ₃ super-strong acid powder having a strong acidity of -13.8 (hereinafter referred to as “powder (B-15)”). Hereinafter, a catalyst (11) was prepared in the same manner as in Example 2 except that the powder (B-15) was used instead of the powder (B-1). The element composition of this catalyst (11) was as follows in atomic ratio. The ratio of the powder (B-15) to the powder (A-1) (as oxide) was 1.6% by weight.

[0098] _{Mo 12 W 2 Bi 1 Fe 1} Co 10 Cs 0. 4 S
_{i 1. 35 - (Al 1. 0} S 0. 02) in the oxidation reaction of Example 1, a catalyst in place of the catalyst (1) (11)
An oxidation reaction was carried out in the same manner as in Example 1 except for using. Table 4 shows the results.

Example 16 Preparation of Catalyst The powder (B-1) of Example 1 was prepared by using an aqueous solution of ammonium metatungstate instead of the aqueous sulfuric acid solution and setting the calcination temperature to 800 ° C. the (B-1) and similar preparation method, the strong degree -13.8 WO ₃ / Zr
O ₂ super strong acid powder (referred to as “powder (B-16)”) was prepared. Hereinafter, a catalyst (12) was prepared in the same manner as in Example 2 except that the powder (B-16) was used instead of the powder (B-1). The elemental composition of this catalyst (12) was as follows in atomic ratio. The powder (A-
The ratio of the powder (B-16) to 1) (as oxide) was 4.6% by weight, and the amount of WO ₃ supported on ZrO ₂ was 28.2% by weight.

[0100] _{Mo 12 W 2 Bi 1 Fe 1} Co 10 Cs 0. 4 S
i _{1. 35} - In (Zr _{1. 0} W _{0. 15)} oxidation reaction in Example 1, a catalyst in place of the catalyst (1) (12)
An oxidation reaction was carried out in the same manner as in Example 1 except for using. Table 4 shows the results.

Example 17 Preparation of Catalyst In the preparation of the catalyst of Example 16, except that an aqueous solution of ammonium paramolybdate was used instead of the aqueous solution of ammonium metatungstate, a strong acidity of -12. No. 7 MoO ₃ / ZrO ₂ super strong acid powder (hereinafter referred to as “powder (B-17)”) was prepared. Hereinafter, in Example 2, instead of the powder (B-1), the powder (B-
Catalyst (1) was prepared in the same manner as in Example 2 except that 17) was used.
3) was prepared. The elemental composition of this catalyst (13) was as follows in atomic ratio. The ratio of the powder (B-17) to the powder (A-1) (as oxide) was 4.0% by weight.
And the amount of MoO ₃ supported on ZrO ₂ is 1
It was 1.7% by weight.

[0102] _{Mo 12 W 2 Bi 1 Fe 1} Co 10 Cs 0. 4 S
i _{1. 35} - In (Zr _{1. 0} Mo _{0. 10)} oxidation reaction in Example 1, a catalyst in place of the catalyst (1) (13)
An oxidation reaction was carried out in the same manner as in Example 1 except for using. Table 4 shows the results.

Example 18 Preparation of Catalyst In preparing the powder (B-1) of Example 1, an aqueous solution of ammonium metatungstate was used instead of the aqueous solution of sulfuric acid, instead of the dried zirconium hydroxide. And powder (B-1) except that the sintering temperature was 900 ° C.
WO ₃ / S with strong acidity of -12.0
An nO ₂ super strong acid powder (hereinafter referred to as “powder (B-18)”) was prepared. Hereinafter, a catalyst (14) was prepared in the same manner as in Example 2 except that the powder (B-18) was used instead of the powder (B-1). The element composition of this catalyst (14) was as follows in atomic ratio. The powder (A
Ratio of powder (B-18) to -1) (as oxide)
Was 5.3% by weight, and the amount of WO ₃ supported on SnO ₂ was 20.0% by weight.

[0104] _{Mo 12 W 2 Bi 1 Fe 1} Co 10 Cs 0. 4 S
_{i 1. 35 - (Sn 1. 0} W 0. 13) in the oxidation reaction of Example 1, a catalyst in place of the catalyst (1) (14)
An oxidation reaction was carried out in the same manner as in Example 1 except for using. Table 4 shows the results.

Example 19 Preparation of Catalyst In preparing the powder (B-18) of Example 18, dry titanium hydroxide was used in place of dry tin hydroxide, and the calcination temperature was 7
Except that the 00 ° C. in the same manner as preparation of the powder _{(B-18), WO 3} / TiO 2 super acid powder having acid strength -12.4 to (referred to as "powder (B-19)") Prepared. Hereinafter, in Example 2, instead of the powder (B-1), the powder (B-
Catalyst (1) was prepared in the same manner as in Example 2 except that 19) was used.
5) was prepared. The element composition of this catalyst (15) was as follows. In addition, powder (B-1) with respect to powder (A-1)
-19) is 3.1% by weight (as oxide).
The amount of WO ₃ supported on TiO ₂ was 31.9% by weight.
Met.

[0106] _{Mo 12 W 2 Bi 1 Fe 1} Co 10 Cs 0. 4 S
i _{1. 35} - In (Ti _{1. 0} W _{0. 11)} oxidation reaction in Example 1, the catalyst (15) in place of the catalyst (1)
An oxidation reaction was carried out in the same manner as in Example 1 except for using. Table 4 shows the results.

Example 20 Preparation of Catalyst In preparing the powder (B-18) of Example 18, dry iron hydroxide was used instead of dry tin hydroxide, and the calcination temperature was set to 700.
° C and a WO ₃ / Fe ₂ O ₃ super-strong acid powder having a strong acidity of -12.0 (hereinafter referred to as “powder (B-20)”) Was prepared. Hereinafter, in Example 2, instead of the powder (B-1), the powder (B-
Catalyst (1) was prepared in the same manner as in Example 2 except that 20) was used.
6) was prepared. The element composition of this catalyst (16) was as follows in atomic ratio. The ratio of powder (B-20) to powder (A-1) (as oxide) was 3.2% by weight.
The amount of WO ₃ supported on Fe ₂ O ₃ is 3
It was 7.8% by weight.

[0108] _{Mo 12 W 2 Bi 1 Fe 1} Co 10 Cs 0. 4 S
i _{1. 35} - In (Fe _{1. 0} W _{0. 13)} oxidation reaction in Example 1, a catalyst in place of the catalyst (1) (16)
An oxidation reaction was carried out in the same manner as in Example 1 except for using. Table 4 shows the results.

Example 21 Preparation of Catalyst Phosphotungstic acid was dissolved in ion-exchanged water, and cesium nitrate was added to an aqueous solution previously dissolved in ion-exchanged water.
A compound having the following composition (excluding oxygen) was prepared. _{Cs 2. 5 H 0. 5 P 1} W 12 phosphotungstic acid cesium salt super acid powder having a strong degree -12.4 This compound was calcined at 400 ° C. ( "Powder (B-
21))). Hereinafter, a catalyst (17) was prepared in the same manner as in Example 2 except that the powder (B-21) was used instead of the powder (B-1). The elemental composition of this catalyst (17) was as follows in atomic ratio. The ratio of the powder (B-21) to the powder (A-1) (as oxide) was 18.9% by weight.

[0110] _{Mo 12 W 2 Bi 1 Fe 1} Co 10 Cs 0. 4 S
i _{1. 35} - In _{(Cs 2. 5 H 0. 5 P} 1 W 12) 0. 2 oxidation reaction in Example 1, a catalyst in place of the catalyst (1) (17)
An oxidation reaction was carried out in the same manner as in Example 1 except for using. Table 4 shows the results.

Example 22 Preparation of Catalyst In preparing powder (A-1) of Example 1, nickel nitrate was used instead of cobalt nitrate, and phosphoric acid was added after ammonium paratungstate. The same procedure as in Example 1 was repeated except that rubidium nitrate was used instead of cesium nitrate, stannic oxide was added after rubidium nitrate, and aluminum nitrate was used instead of silica sol. Bismuth-iron composite oxide powder ("Powder (A-2
2) ").

To the powder (A-22), the powder (B-1) of Example 1 was added and mixed well, and then a catalyst (18) was prepared according to the method of Example 1. The elemental composition of this catalyst (18) was as follows in atomic ratio. The ratio of the powder (B-1) to the powder (A-22) (as oxide) was 3.4% by weight.

Mo ₁₂ W ₂ Bi ₃ Fe ₁ Ni ₇ Rb ₁ P _0.
2 Sn _{0. 5} Al ₁ - In (Zr _{1. 0} S _{0. 02)} oxidation reaction in Example 1, a catalyst in place of the catalyst (1) (18)
An oxidation reaction was carried out in the same manner as in Example 1 except for using. Table 4 shows the results.

Comparative Example 7 Preparation of Catalyst A catalyst (19) was prepared in the same manner as in Example 22, except that only the powder (A-22) was used.

Oxidation reaction In Example 22, the catalyst (1) was used instead of the catalyst (18).
An oxidation reaction was carried out in the same manner as in Example 22 except that 9) was used. Table 4 shows the results.

Example 23 Preparation of Catalyst In preparing powder (A-1) of Example 1, no ammonium paratungstate was used. Instead of cesium nitrate, potassium nitrate, lithium nitrate, magnesium nitrate and calcium nitrate were used. , Using titanium dioxide instead of silica sol, and finally using cerous nitrate and niobium pentoxide in the same manner as in Example 1 except that A powder (referred to as “powder (A-23)”) was prepared.

The powder of Example 1 (B-
After adding 1) and mixing well, a catalyst (20) was prepared according to the method of Example 1. The element composition of this catalyst (20) was as follows in atomic ratio. The powder (A-2)
The ratio of the powder (B-1) to 3) (as oxide) was 4.0% by weight.

[0118] _{Mo 12 Bi 1 Fe 1 Co 10} K 0. 5 Li 0. 2
_{Ca 0. 2 Mg 0. 2 Nb 0.} 5 Ce 1 Ti 1 - (Zr 1. 0 S
_0.02) in the oxidation reaction of Example 1, a catalyst in place of the catalyst (1) (20)
Example 1 was repeated except that the reaction temperature was changed to 340 ° C.
An oxidation reaction was carried out in the same manner as described above. Table 4 shows the results. Comparative Example 8 Preparation of Catalyst A catalyst (21) was prepared in the same manner as in Example 23 except that only the powder (A-23) was used.

Oxidation reaction In Example 23, the catalyst (2) was used instead of the catalyst (20).
An oxidation reaction was carried out in the same manner as in Example 23 except that 1) was used. Table 4 shows the results.

Example 24 Preparation of Catalyst In Example 1, no ammonium paratungstate was used, and instead of cesium nitrate, thallous nitrate and strontium nitrate were used, and then tellurium oxide, lead nitrate and zinc nitrate were used. A molybdenum-bismuth-iron composite oxide powder (hereinafter referred to as “powder (A-24)”) was prepared in the same manner as in Example 1 except that titanium oxide was used instead of silica sol.

The powder (B-24) of Example 1 was added to the powder (A-24).
After adding 1) and mixing well, a catalyst (22) was prepared according to the method of Example 1. The elemental composition of this catalyst (22) was as follows in atomic ratio. The powder (A-2)
The ratio of the powder (B-1) to 4) (as oxide) was 3.8% by weight.

[0122] _{Mo 12 Bi 1 Fe 3 Co 7} Tl 0. 7 Sr 0.
_{3 Te 0. 3 Pb 1 Zn 0.} 5 Ti 1 - In (Zr _{1. 0} S _{0. 02)} oxidation reaction in Example 1, a catalyst in place of the catalyst (1) (22)
Example 1 was repeated except that the reaction temperature was changed to 340 ° C.
An oxidation reaction was carried out in the same manner as described above. Table 4 shows the results. Comparative Example 9 Preparation of Catalyst A catalyst (23) was prepared in the same manner as in Example 24 except that only the powder (A-24) was used.

Oxidation reaction In Example 24, the catalyst (2) was used instead of the catalyst (22).
An oxidation reaction was carried out in the same manner as in Example 24 except that 3) was used. Table 4 shows the results.

Example 25 Preparation of Catalyst In preparing powder (A-1) of Example 1, potassium nitrate, barium nitrate and beryllium nitrate were used instead of cesium nitrate, and then antimony trioxide and manganese nitrate were used. And a molybdenum-tungsten-bismuth-iron-based composite oxide powder (referred to as "powder (A-25)") in the same manner as in Example 1 except that zirconium nitrate is used instead of silica sol. ) Was prepared.

To the powder (A-25), the powder (B-1) of Example 1 was added and mixed well, and then a catalyst (24) was obtained according to the method of Example 1. The element composition of this catalyst (24) was as follows in atomic ratio. The powder (A-2)
The ratio of the powder (B-1) to 5) (as oxide) was 3.9% by weight.

Mo₁₂W_{1. Five}Bi₁Fe_{1. Two}Co_FiveK_{1. 0}
Ba_{0. Two}Be_{0. Two}Sb₁Mn_{0. Five}Zr ₁− (Zr_{1. 0}S
_{0. 02}) Oxidation reaction In Example 1, the catalyst (24) was used instead of the catalyst (1).
An oxidation reaction was carried out in the same manner as in Example 1 except for using. Conclusion
The results are shown in Table 4.

Comparative Example 10 Preparation of Catalyst A catalyst (25) was prepared in the same manner as in Example 25 except that only the powder (A-25) was used.

Oxidation reaction In Example 25, the catalyst (2) was used in place of the catalyst (24).
An oxidation reaction was carried out in the same manner as in Example 25 except that 5) was used. Table 4 shows the results.

[0129]

[Table 4]

Example 26 Preparation of Catalyst A composite oxide powder ("powder (A-2)" having the following elemental composition (atomic ratio) was prepared by the same preparation method as in Example 1.
6))).

[0131] _{Mo 12 W 2 Bi 1 Fe 1} Co 4 K 0. 06 Si 1. 35 powder of Example 1 to the powder (A-26) (B- 1) was added and mixed well, It was molded into a columnar shape having an outer diameter of 6 mm and a length of 6.6 mm, and calcined at 450 ° C. for 6 hours in an air flow to obtain a catalyst (26). The element composition of this catalyst (26) was as follows in atomic ratio. The ratio of the powder (B-1) to the powder (A-26) (as oxide) was 4.3% by weight.

[0132] _{Mo 12 W 2 Bi 1 Fe 1} Co 4 K 0. 06 Si
_{1. 35 - (Zr 1. 0 S} 0. 02) an oxidation catalyst (26) 1500 ml was charged into a reactor as in Example 1, propylene 6 volume%, oxygen 12 volume%, water vapor 10 volume%, and nitrogen A mixed gas having a composition of 72% by volume was introduced, the reaction temperature was 300 ° C., and the space velocity was 2000 hr.
^-1 , the propylene conversion was 98.
5%, total selectivity to acrolein and acrylic acid and total single stream yield were 94.0% and 92.6%, respectively.

Comparative Example 11 Preparation of Catalyst A catalyst (27) was prepared in the same manner as in Example 26 except that the powder (B-1) was not added.

Oxidation reaction In Example 26, the catalyst (2) was used instead of the catalyst (26).
When an oxidation reaction was carried out in the same manner as in Example 26 except that 7) was used, the propylene conversion was 95.0%, the total selectivity to acrolein and acrylic acid, and the total single-stream yield were 93.8% and 93.8%, respectively. 89.1%.

[0135]

As described above, the catalyst for producing unsaturated aldehydes and unsaturated carboxylic acids according to the present invention comprises propylene, isobutylene, t-butanol and methyl-t-butanol.
(A) a catalyst for producing an unsaturated aldehyde and an unsaturated carboxylic acid by oxidizing at least one compound selected from the group consisting of butyl ether in a gas phase with molecular oxygen or a molecular oxygen-containing gas; Molybdenum, bismuth and iron as essential components, propylene,
Isobutylene, t-butanol and / or methyl-
Complex oxide for producing unsaturated aldehyde and unsaturated carboxylic acid by gas phase catalytic oxidation reaction of t-butyl ether and (B) acid strength (H ₀ ) of -11.93 or less (H ₀ ≦ −
11.93). Since the catalyst of the present invention maintains a high activity, it can produce unsaturated aldehydes and unsaturated carboxylic acids in high yield.

The catalyst of the present invention has an excellent catalyst life and maintains its excellent performance for a long time, so that unsaturated aldehydes and unsaturated carboxylic acids can be stably produced over a long period of time. Further, even after long use, the reaction for producing unsaturated aldehyde and unsaturated carboxylic acid can be continued at a high yield similar to that at the start of the reaction without significantly increasing the reaction temperature.

Since the catalyst of the present invention exhibits high activity even at a low temperature, the same yield can be obtained at a lower reaction temperature as compared with the conventional method.

Since the catalyst of the present invention does not decrease its catalytic performance even under high load operating conditions for the purpose of high productivity, it can stably convert unsaturated aldehydes and unsaturated carboxylic acids with high productivity over a long period of time. Can be manufactured.

According to the method of the present invention, unsaturated aldehydes and unsaturated carboxylic acids can be produced efficiently and industrially advantageously.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 45/35 C07C 45/35 45/37 45/37 47/22 47/22 AH 57/05 57/05 57/055 57 / 055 Z (72) Inventor Michio Tanimoto 992, Nishioki, Okihama-shi, Abashiri-ku, Himeji-shi, Hyogo Prefecture Inside Nippon Shokubai Catalysis Research Institute Co., Ltd. Inside the Catalyst Research Laboratory (56) References JP-A-4-295438 (JP, A) JP-A-4-217932 (JP, A) JP-A-6-71177 (JP, A) JP-A-2-42034 (JP, A A) JP-A-56-150436 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) B01J 27/055 B01J 23/88 B01J 27/057 B01J 27/192 C07C 27/00 340 C07C 45/35 C07C 45/37 C07C 47/22 C07C 57/05 C07C 57/055

Claims (12)

(57) [Claims] At least one compound selected from the group consisting of propylene, isobutylene, t-butanol and methyl-t-butyl ether is oxidized in the gas phase with molecular oxygen or a molecular oxygen-containing gas to produce an unsaturated aldehyde and A catalyst for producing an unsaturated carboxylic acid, wherein (A) a gas phase catalytic oxidation reaction of propylene, isobutylene, t-butanol and / or methyl-t-butyl ether, which contains molybdenum, bismuth and iron as essential components. Complex oxide for producing unsaturated aldehyde and unsaturated carboxylic acid and (B) acid strength (H ₀ ) of -1
A catalyst for producing unsaturated aldehydes and unsaturated carboxylic acids, comprising a solid acid of 1.93 or less (H ₀ ≦ -11.93). Wherein component (A) is the general formula _{(1): Mo a W b} Bi c Fe d A e B f C g D h E i O x ( wherein, Mo is molybdenum, W is tungsten, Bi
Is bismuth, Fe is iron, A is at least one element selected from the group consisting of nickel and cobalt, B is at least one element selected from the group consisting of alkali metals and thallium, and C is at least one element selected from alkaline earth metals. A kind of element, D is phosphorus, tellurium, antimony,
At least one element selected from the group consisting of tin, cerium, lead, niobium, manganese, arsenic and zinc, E is at least one element selected from the group consisting of silicon, aluminum, titanium and zirconium, and O is oxygen , A, b, c, d, e, f, g, h,
i and x are Mo, W, Bi, Fe, A, B,
Represents the atomic ratio of C, D, E and O, and when a = 12,
b = 0 to 10, c = 0.1 to 10, d = 0.1 to 20,
e = 2 to 20, f = 0.001 to 10, g = 0 to 10,
wherein h = 0 to 4, i = 0 to 30, and x is a value determined by the oxygen state of each element.) The unsaturated aldehyde and unsaturated carboxylic acid according to claim 1, Production catalyst. 3. The catalyst for producing an unsaturated aldehyde and unsaturated carboxylic acid according to claim 1, wherein the component (B) is SO ₄ / a superacid of a metal oxide of Group IV of the periodic table. 4. The group IV metal of the periodic table is zirconium,
The catalyst for producing an unsaturated aldehyde and an unsaturated carboxylic acid according to claim 3, which is at least one selected from the group consisting of titanium, tin and hafnium. 5. The catalyst for producing an unsaturated aldehyde and unsaturated carboxylic acid according to claim 1, wherein the component (B) is SO ₄ / iron oxide superacid. 6. The catalyst for producing unsaturated aldehydes and unsaturated carboxylic acids according to claim 1, wherein the component (B) is SO ₄ / silicon oxide superacid. 7. The catalyst for producing unsaturated aldehyde and unsaturated carboxylic acid according to claim 1, wherein the component (B) is SO ₄ / aluminum oxide superacid. 8. Component (B) is tungsten oxide, molybdenum oxide or tungsten-molybdenum composite oxide /
The catalyst for producing an unsaturated aldehyde and unsaturated carboxylic acid according to claim 1 or 2, which is a zirconium oxide superacid. 9. The composition according to claim 1, wherein the component (B) is tungsten oxide / tin oxide, titanium oxide, iron oxide, or a complex oxide superacid of at least two elements selected from the group consisting of tin, titanium and iron. Or the catalyst for producing an unsaturated aldehyde and an unsaturated carboxylic acid according to 2 above. 10. The catalyst for producing unsaturated aldehydes and unsaturated carboxylic acids according to claim 1, wherein the component (B) is phosphotungstic acid and / or a superacid of an alkali metal salt thereof. 11. The catalyst for producing an unsaturated aldehyde and unsaturated carboxylic acid according to claim 1, wherein the ratio of the component (B) to the component (A) (as oxide) is 0.5 to 30% by weight. . 12. An unsaturated aldehyde by oxidizing at least one compound selected from the group consisting of propylene, isobutylene, t-butanol and methyl-t-butyl ether with molecular oxygen or a molecular oxygen-containing gas in the gas phase. In the gas-phase catalytic oxidation reaction for producing an unsaturated carboxylic acid, the reaction is carried out in the presence of the catalyst for producing an unsaturated aldehyde and an unsaturated carboxylic acid according to any one of claims 1 to 11. A method for producing a saturated aldehyde and an unsaturated carboxylic acid.