JPH07289902A - Production of catalyst for synthesizing unsaturated aldehyde and unsaturated carboxylic acid - Google Patents

Abstract

PURPOSE:To produce an industrial catalyst high in reproducibility for advantageously producing corresponding unsaturated aldehyde and unsaturated carboxylic acid from propylene and isobutylene. CONSTITUTION:In a catalyst containing at least Mo, Bi and Fe used in the synthesis of corresponding unsaturated aldehyde and unsaturated carboxylic acid by the vapor phase catalytic oxidation of propylene, isobutylene and tertiary butyl alcohol or methyl tertiary butyl ether using molecular oxygen, a mixed soln. or aq. slurry containing catalyst components is finely pulverized to be aged at 100-200 deg.C and, subsequently, the aged particles are dried, baked and heat-treated.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to propylene, isobutylene, tertiary butyl alcohol (hereinafter abbreviated as TBA) or methyl tertiary butyl ether (hereinafter MTB).
Abbreviated as E. The method for producing an industrial catalyst for use in synthesizing a corresponding unsaturated aldehyde and unsaturated carboxylic acid by gas-phase catalytic oxidation of) with molecular oxygen, and an unsaturated aldehyde and an unsaturated catalyst using the catalyst. It relates to a method for producing a saturated carboxylic acid.

[0002]

2. Description of the Related Art Conventionally, a catalyst used in the vapor phase catalytic oxidation of propylene to produce acrolein and acrylic acid, and a vapor phase catalytic oxidation of isobutylene, TBA or MTBE to produce methacrolein and methacrylic acid. Many proposals have been made for catalysts used in.

However, the catalysts known so far are
It is difficult to say that the catalyst performance including the catalyst activity is sufficient, and it is the current situation that development of a catalyst production method that solves these problems and is excellent in reproducibility is desired.

[0004]

DISCLOSURE OF THE INVENTION The present invention is directed to a novel reproducible process for producing industrial catalysts which advantageously produces the corresponding unsaturated aldehyde and unsaturated carboxylic acid from propylene, isobutylene, TBA or MTBE, respectively. And a method for producing an unsaturated aldehyde and an unsaturated carboxylic acid using the obtained catalyst.

[0005]

The present invention is directed to propylene,
Isobutylene, tertiary butyl alcohol or methyl tertiary butyl ether is subjected to gas phase catalytic oxidation using molecular oxygen, and at least molybdenum and bismuth used for synthesizing the corresponding unsaturated aldehyde and unsaturated carboxylic acid, respectively. In a catalyst containing iron and iron, the mixed solution containing the catalyst components or the aqueous slurry is atomized, and then 100
Aging at ˜200 ° C., followed by drying and calcination, and heat treatment, and a process for producing a catalyst for synthesizing unsaturated aldehyde and unsaturated carboxylic acid, and using such a catalyst, propylene, isobutylene, and tertiary Butyl alcohol or methyl tertiary butyl ether is subjected to gas phase catalytic oxidation using molecular oxygen to synthesize an unsaturated aldehyde and an unsaturated carboxylic acid corresponding to the unsaturated aldehyde and unsaturated carboxylic acid, respectively. It is in the manufacturing method.

In the present invention, a mixed solution containing a catalyst component or an aqueous slurry is atomized, and then 100 to 200 ° C.
It is important to age, preferably at 120 to 180 ° C., then dry and bake, and heat treat. By carrying out such an operation, it becomes possible to improve the catalytic performance including the catalytic activity and to prepare the desired catalyst with good reproducibility.

In the present invention, as a method for atomizing a mixed solution or an aqueous slurry containing a catalyst component, it is practical to use a means having excellent atomization efficiency such as a homogenizer and ultrasonic waves. As the time for this atomization processing,
Although it depends on the atomization ability, it is preferably several seconds to several tens of minutes.

According to the present invention, the average particle size of the mixed solution or the aqueous slurry containing the catalyst component by the atomization treatment is 0.1 to 100 μm, preferably 0.5 to 50 μm.
It is a degree.

In the present invention, a mixed solution or an aqueous slurry containing the above-mentioned atomized catalyst component is aged in a temperature range of 100 to 200 ° C. When aged at a temperature of less than 100 ° C., It is not preferable because the improvement of the catalyst performance is small and it is difficult to obtain the intended effect of the present invention, and when the temperature exceeds 200 ° C., the design and structure of the industrial catalyst production apparatus becomes complicated and it becomes unpractical.

In the present invention, 100 to 200 of a mixed solution or an aqueous slurry containing the above-mentioned atomized catalyst component is used.
As a method of aging at ° C, a method generally performed using an autoclave can be mentioned.

In carrying out the present invention, this
The time for aging at 0 to 200 ° C. is 1 to 120 minutes, preferably 10 to 90 minutes.

In the present invention, the mixed solution or aqueous slurry containing the aged catalyst component is dried and then calcined. Drying is performed at a temperature in the range of 60 to 150 ° C. The calcination conditions are not particularly limited, and known conditions can be applied. Usually, the calcination is performed at a temperature of 200 to 400 ° C., and the calcination time is appropriately selected depending on the target catalyst. The fired product is then shaped.

The shaping method and shape are not particularly limited,
Using a general powder molding machine such as a tablet molding machine, an extrusion molding machine, or a rolling granulator, it is molded into any shape such as a spherical shape, a ring shape, a cylindrical shape, or a star shape. It can also be used by supporting it on a carrier.

The catalyst thus shaped is then heat treated. In the present invention, these processing conditions are not particularly limited, and known processing conditions can be applied. Usually, the heat treatment is performed at 300 to 600 ° C.

The present invention has the general formula Mo _a Bi _b Fe _c A _d X _e Y _f Z _g Si _h O _i (wherein Mo, Bi, Fe, Si and O are molybdenum, bismuth, iron, silicon and oxygen, respectively). Where A is cobalt and / or nickel, X is chromium, lead, manganese,
At least one element selected from the group consisting of calcium, magnesium, niobium, silver, barium, tin, tantalum and zinc, Y is a group consisting of phosphorus, boron, sulfur, selenium, tellurium, cerium, tungsten, antimony and titanium. At least one element selected from the group Z is at least one element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium and thallium. a, b, c, d, e, f, g, h and i represent the atomic ratio of each element, and when a = 12, b = 0.
01-3, c = 0.01-5, d = 1-12, e = 0
8, f = 0 to 5, g = 0.001 to 2, h = 0 to 20 and i is the number of oxygen atoms required to satisfy the valence of each component. It is preferable to use it for a catalyst having a composition represented by (4).

In the present invention, the method for producing a mixed solution or an aqueous slurry containing a catalyst component does not need to be limited to a special method, and is well known in the art as long as the components are not unevenly distributed. Evaporation to dryness, precipitation,
Various methods such as an oxide mixing method can be used.

As the raw material for the catalyst component, a combination of oxides, sulfates, nitrates, carbonates, hydroxides, ammonium salts, halides and the like of each element can be used. For example, as a molybdenum raw material, ammonium paramolybdate, molybdenum trioxide, or the like can be used.

When molding the present catalyst, conventionally known additives, for example, organic compounds such as polyvinyl alcohol and carboxymethyl cellulose may be further added. Inorganic compounds such as graphite and diatomaceous earth, and inorganic fibers such as glass fibers, ceramic fibers and carbon fibers may be added.

As the carrier used for carrying, silica, alumina, silica-alumina, magnesia, titania or the like can be used. Furthermore, the catalyst of the present invention can be used after diluting it with an inert carrier such as silica, alumina, silica-alumina, magnesia, titania, and silicon carbide.

The catalyst of the present invention is used in the case where molecular oxygen is added to propylene, isobutylene, TBA or MTBE as a raw material and the gas phase catalytic oxidation is carried out in the presence of the catalyst. In carrying out the gas phase catalytic oxidation reaction, the molar ratio of propylene, isobutylene, TBA or MTBE to oxygen is 1: 0.
The range of 5 to 3 is preferable.

The raw material gas is preferably diluted with an inert gas before use. Although it is economical to use air as the oxygen source, pure oxygen-enriched air can be used if desired.

The reaction pressure is preferably from normal pressure to several atmospheres.
The reaction temperature can be selected in the range of 200 to 450 ° C. Particularly, the range of 250 to 400 ° C is preferable.

[0023]

EXAMPLES The production examples of the catalyst according to the present invention and the reaction examples using the same are described below together with comparative examples. In the description, “part” means part by weight. Analysis was by gas chromatography.

Raw material olefin, T in Examples and Comparative Examples
The reaction rate of BA or MTBE, and the selectivity of the unsaturated aldehyde and unsaturated carboxylic acid formed are defined as follows.

[0025]

[Equation 1]

[Equation 2]

[Equation 3]

Example 1 500 parts of ammonium paramolybdate in 1000 parts of water
Parts, 6.2 parts of ammonium paratungstate, 1.4 parts of potassium nitrate, 20.6 parts of antimony trioxide and 49.5 parts of bismuth trioxide were added and stirred with heating (A-1).
liquid). Separately, to 1000 parts of pure water, 133.5 parts of ferric nitrate,
7.0 parts of zinc nitrate and 281.6 parts of cobalt nitrate were sequentially added and dissolved (Liquid B-1). Liquid B-1 was added to liquid A-1 to form a slurry, which was then atomized for 5 minutes with a homogenizer, then transferred to an autoclave and stirred at 150 ° C.
It was aged for 30 minutes. Then most of the water was evaporated.

After drying the obtained cake-like substance at 120 ° C., it was calcined in an air atmosphere at 300 ° C. for 1 hour and crushed,
It was pressure molded. After that, heat treatment was again performed at 500 ° C. for 6 hours in an air atmosphere.

The composition of the elements other than oxygen of the catalyst thus obtained (hereinafter the same) is Mo ₁₂ W _0.1 Bi _0.9 Fe.
_{It was 1.4} Sb _0.6 Co _4.1 Zn _0.1 K _0.06 .

A stainless steel reaction tube was filled with this catalyst,
Propylene 5%, oxygen 12%, steam 10% and nitrogen 7
3% (volume%) of the raw material mixed gas was passed through the catalyst layer with a contact time of 3.6 seconds to react at 310 ° C. As a result, the propylene reaction rate was 99.6% and the acrolein selectivity was 9
The selectivity was 1.0% and the selectivity of acrylic acid was 6.7%.

Comparative Example 1 Preparation of a catalyst and reaction of a raw material mixed gas were carried out in the same manner as in Example 1 except that the aging temperature was 80 ° C. as a result,
The reaction rate of propylene was 98.9%, the selectivity of acrolein was 89.2%, and the selectivity of acrylic acid was 6.5%.

Comparative Example 2 Preparation of a catalyst and reaction of a raw material mixed gas were carried out in the same manner as in Example 1 except that atomization by a homogenizer was not carried out. As a result, the reactivity of propylene was 98.6%, the selectivity of acrolein was 89.6%, and the selectivity of acrylic acid was 6.2%.

Example 2 Ammonium paramolybdate 500 was added to 1000 parts of water.
Parts, 6.2 parts of ammonium paratungstate, 23.0 parts of cesium nitrate, 27.5 parts of antimony trioxide and 33.0 parts of bismuth trioxide were added and heated and stirred (A-2.
liquid). Separately, 1000 parts of pure water and 181.2 parts of ferric nitrate,
Nickel nitrate 151.0 parts, magnesium nitrate 48.4
And 322.8 parts of cobalt nitrate were sequentially added and dissolved (Liquid B-2). Solution B-2 was added to solution A-2 to form a slurry, which was then atomized with a homogenizer for 10 minutes.
The solution was transferred to an autoclave and aged at 150 ° C. for 30 minutes with stirring. Then most of the water was evaporated.

After drying the obtained cake-like substance at 120 ° C., it was calcined in an air atmosphere at 300 ° C. for 1 hour and crushed,
It was pressure molded. After that, heat treatment was again performed at 500 ° C. for 6 hours in an air atmosphere.

The composition of elements other than oxygen in the catalyst thus obtained was Mo ₁₂ W _0.1 Bi _0.6 Fe _1.9 Sb _0.8 Ni.
_{It was 2.2} Co _4.7 Cs _0.5 Mg _0.8 .

A stainless steel reaction tube was filled with this catalyst,
A raw material mixed gas of 5% isobutylene, 12% oxygen, 10% steam and 73% nitrogen (volume%) was passed through the catalyst layer at a contact time of 3.6 seconds and reacted at 340 ° C. as a result,
The conversion of isobutylene was 98.4%, the selectivity of methacrolein was 90.4%, and the selectivity of methacrylic acid was 3.5%.

Comparative Example 3 Preparation of a catalyst and reaction of a raw material mixed gas were carried out in the same manner as in Example 2 except that the aging temperature was 80 ° C. as a result,
The conversion of isobutylene was 97.7%, the selectivity of methacrolein was 89.1%, and the selectivity of methacrylic acid was 3.0%.

Comparative Example 4 Preparation of a catalyst and reaction of a raw material mixed gas were carried out in the same manner as in Example 2 except that atomization by a homogenizer was not carried out. As a result, the reaction rate of isobutylene is 98.1%,
The selectivity of methacrolein was 89.3% and the selectivity of methacrylic acid was 3.2%.

Example 3 Using the catalyst of Example 2, the raw material was changed to TBA and the reaction was carried out in the same manner as in Example 2. As a result, TB
A reaction rate of 100%, methacrolein selectivity of 87.9
%, And the selectivity of methacrylic acid was 3.1%.

Comparative Example 5 Using the catalyst of Comparative Example 2, the raw material was changed to TBA and the reaction was carried out in the same manner as in Comparative Example 2. As a result, TB
A reaction rate of 100%, methacrolein selectivity of 86.2
%, And the selectivity of methacrylic acid was 2.8%.

[0040]

EFFECTS OF THE INVENTION The present invention has the above-mentioned constitution so that propylene, isobutylene, TBA or MTBE can be obtained.
It is possible to produce a highly reproducible catalyst that advantageously produces the corresponding unsaturated aldehyde and unsaturated carboxylic acid, respectively, and use it to produce the desired unsaturated aldehyde and unsaturated carboxylic acid advantageously. It has an excellent effect such as being able to

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Claims (2)

[Claims] 1. When synthesizing a corresponding unsaturated aldehyde or unsaturated carboxylic acid by subjecting propylene, isobutylene, tertiary butyl alcohol or methyl tertiary butyl ether to gas phase catalytic oxidation using molecular oxygen. In the used catalyst containing at least molybdenum, bismuth and iron, a mixed solution containing a catalyst component or an aqueous slurry is atomized, then aged at 100 to 200 ° C., then dried and baked, and heat treated. Method for producing catalyst for synthesizing unsaturated aldehyde and unsaturated carboxylic acid. 2. The catalyst according to claim 1, wherein propylene, isobutylene, tertiary butyl alcohol or methyl tertiary butyl ether is subjected to gas phase catalytic oxidation with molecular oxygen, and an unsaturated aldehyde corresponding to each is obtained. And a method for producing an unsaturated aldehyde and an unsaturated carboxylic acid, which comprises synthesizing an unsaturated carboxylic acid.