JPH044048A - Production of catalyst for synthesizing unsaturated aldehyde and unsaturated acid - Google Patents

Abstract

PURPOSE:To obtain a catalyst of high activity and high selectivity by performing the pre- or post-calcination under specified conditions at a constant temp. for a certain time and adding starch or the like by a specified proportion to the calcined material. CONSTITUTION:An soln. or slurry containing molybdenum compd. and bismuth compd. is dried, precalcined, molded or made to deposit on a carrier, and then postcalcined. The pre- or post-calcination is carried out in a gas atmosphere containing 0-30vol.% oxygen molecules at 250-600 deg.C for 1-10 hours. Or 0.5-10 pts.wt. starch or polymethylmethacrylate is added to 100 pts.wt. of the pre- calcined material, which is then molded or made to deposit on a carrier. The obtd. catalyst is suitable for synthesis of acrolein and acrylic acid, or methacrolein and methacrylic acid from propylene, isobutylene or tertiary butanol.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a catalyst for the synthesis of unsaturated aldehydes and unsaturated acids,
That is, the present invention relates to a method for producing a catalyst used when synthesizing acrolein and acrylic acid or methacrolein and methacrylic acid by subjecting propylene, isobutylene, or tertiary butanol to gas phase catalytic oxidation with molecular oxygen.

[Prior Art] Many methods have been proposed for producing catalysts for the synthesis of unsaturated aldehydes and unsaturated acids. Taking the case where isobutylene or tertiary butanol is used as a raw material, for example, Japanese Patent Application Laid-Open No. Many proposals have been made, such as JP-A No. 6028824 and JP-A-63-122642. Furthermore, although there is a report in JP-A-58-98143 that the formability of the catalyst is improved by the addition of nitrogen-containing organic compounds such as aniline, methylamine, and formamide, it is generally Further improvements are desired from an industrial standpoint in terms of catalyst performance such as acid selectivity and catalyst life.

[Problems to be Solved by the Invention] The present invention aims to provide a novel method for producing a catalyst for advantageously synthesizing acrolein and acrylic acid or methacrolein and methacrylic acid from propylene, isobutylene, or tertiary butanol. .

[Means for Solving the Problems] The present invention comprises drying a mixed solution or aqueous slurry in which a molybdenum compound and a bismuth compound are mixed, and then performing pre-baking,
In a production method in which a catalyst is obtained by molding or supporting the obtained pre-calcined product on a carrier and post-calcining the obtained molded body or carrier, in at least one of the pre-calcination and post-calcination steps, molecular 1 at a temperature in the range of 250 to 600°C in a gas atmosphere containing 0 to 30% by volume of oxygen.
Heat treated for ~10 hours, and added 0.5~l of starch, polymethyl methacrylate, ammonium nitrate, and/or methyl cellulose to 100 parts by weight of the pre-fired product.
This is a method for producing a catalyst for synthesizing unsaturated aldehydes and unsaturated acids, which comprises adding and mixing O (preferably 1 to 5 parts by weight) and then molding or supporting on a carrier.

The catalyst obtained by the method of the present invention has the general formula % (where A is nickel and/or cobalt, X is sodium, potassium, rubidium, cesium and/or thallium, Y is magnesium, zinc, manganese, lead and/or or tin, Z represents phosphorus, boron, antimony, silicon, sulfur, titanium, tellurium and/or tungsten, a, b.

C, d, e, f, g and h represent the atomic ratio of each element,
When a=12, b=o, old~3, c=0.5~4, d=
1~12, e=0.01~2, f=0~10, g=Q~
10, and h is the number of oxygen atoms necessary to satisfy the valences of each component.

According to the method of the present invention, it is possible to produce a catalyst with good reproducibility that has a long catalyst life and provides a high yield of the desired product.

In the present invention, raw materials for elements that are catalyst components include:
Although not particularly limited, oxides or chlorides, sulfates, nitrates, carbonates, ammonium salts, or mixtures thereof, which can be converted into oxides by ignition, are usually used.

In the present invention, heat treatment is performed at 250 to 600°C for 1 to 10 hours in a gas atmosphere containing 0 to 30% by volume of molecular oxygen in either the first firing or the second firing. It is preferable that both or one of the firing and the post-stage firing be performed at 450° C. or higher. If the first stage firing and the second stage firing are performed at a temperature lower than 450°C, an effective catalyst for the reaction may not be obtained.

In the present invention, the method for shaping the fired product obtained by the pre-stage firing is not particularly limited, but
Generally known molding methods include, for example, molding methods using a tablet press, an extrusion molding machine, a transfer granulator, and the like. At this time, moldability can be improved by adding and mixing 0.5 to 5 parts by weight of graphite to 100 parts by weight of the pre-fired product and molding the resulting mixture.

In the present invention, based on 100 parts by weight of the pre-fired product,
0.5 to IO parts by weight of starch, polymethyl methacrylate, ammonium nitrate and/or methylcellulose (
After addition and mixing (preferably 1 to 5 parts by weight), it is molded or supported on a carrier. At this time, if the amount of starch, polymethyl methacrylate, ammonium nitrate and/or methyl cellulose added is less than 0.5 part by weight based on 100 parts by weight of the pre-fired product, no effect of the addition will be exhibited. On the other hand, if the amount exceeds 10 parts by weight, calcination tends to occur during the subsequent calcination, and starch, polymethyl methacrylate, ammonium nitrate and/or methylcellulose are lost by volatilization, resulting in a weakening of the mechanical strength of the catalyst. , cannot be used as an industrial catalyst.

Using the catalyst obtained by the method of the present invention, propylene,
When producing acrolein and acrylic acid or methacrolein and methacrylic acid by gas phase catalytic oxidation of isobutylene or tertiary butanol with molecular oxygen, the molar ratio of propylene, isobutylene or tertiary butanol to oxygen is 1:0. 5 to 3 is preferred. raw material propylene,
It is preferable to use isobutylene or tertiary butanol after diluting it with an inert gas. The molecular oxygen used for oxidation may be pure oxygen gas or air, but air is industrially advantageous.

The reaction pressure used is normal pressure to diffused pressure.

The reaction temperature is preferably in the range of 200 to 450°C, and the reaction can be carried out in either a fluidized bed or a fixed bed.

[Effect of the Invention 1] By using the catalyst produced by the method of the present invention, acrolein and acrylic acid or methacrolein and methacrylic acid can be advantageously obtained from propylene, isobutylene or tertiary butanol.

[Example] In the following Examples and Comparative Examples, parts mean parts by weight, and the analysis was performed by gas chromatography. Further, the reaction rate of propylene, inbutylene or tertiary butanol as a reaction raw material, and the selectivity of the unsaturated aldehyde and unsaturated acid produced are defined as follows.

Reaction rate of raw materials (%) Selectivity of unsaturated aldehyde (%) Selectivity of unsaturated acid c%) Example 1 500 parts of ammonium paramolybdate in 1000 parts of pure water
1 part and 25.1 parts of thallium nitrate were added and heated and stirred (A
liquid). Separately, 30 parts of concentrated nitric acid was added to 100 parts of pure water, and then 114.5 parts of bismuth nitrate was dissolved. To this were sequentially added 286.0 parts of ferric nitrate, 274.5 parts of nickel nitrate, 274.7 parts of cobalt nitrate, and 1200 parts of pure water, and stirred well until completely dissolved (solution B). After adding Solution B to Solution A to form a slurry, 34.4 parts of antimony trioxide was added and stirred with heating.

The obtained slurry material was dried at 130°C, and then pre-baked at 300°C for 2 hours in an air atmosphere.

After pulverizing this pre-fired product, 2 parts of starch and 2 parts of graphite were added and mixed to 100 parts of the pre-fired product,
After adding pure water to make a slurry, it was dried, crushed, and formed into pellets. The molded body was post-baked at 500° C. for 3 hours in an air atmosphere. The composition of the catalyst thus produced is expressed by the following formula.

Mo+Ji+FezNi4Con TI2 o4sb+
Since the atomic ratio of oh oxygen is a value naturally determined by the valences of other elements, it will be omitted below.

This catalyst was packed in a stainless steel reaction tube, and a raw material mixed gas containing 5% inbutylene, 12% oxygen, 10% water vapor, and 73% nitrogen (volume %) was passed through the catalyst layer for a contact time of 3.6 seconds. The reaction was carried out at ℃. As a result, the reaction rate of isobutylene was 90.5%, and the selectivity of methacrolein was 86.2%.
%, and the selectivity for methacrylic acid was 3.3%.

Comparative Example 1 A catalyst having the same composition as in Example 1 was produced in the same manner as in Example 1, except that starch was not added to the pre-calcined product. When a reaction was carried out using this catalyst under the same reaction conditions as in Example 1, the reaction rate of inbutylene was 90.0%, the selectivity of methacrolein was 84.7%, and the selectivity of methacrylic acid was 3.0%.
It was 2%.

Example 2 500 parts of ammonium paramolybdate in 1000 parts of pure water
parts, cesium nitrate 13.8 parts and potassium nitrate 7.2 parts
(Liquid A) Separately, 30 parts of concentrated nitric acid was added to 100 parts of pure water, and then 57.2 parts of bismuth nitrate was dissolved therein. To this, 286,0 parts of ferric nitrate, 2 parts of nickel nitrate
74.5 parts, cobalt nitrate 206.0 parts, magnesium nitrate 60.5 parts, 85% phosphorus M2.2 parts, and pure water 120 parts
0 parts were added one after another and stirred well until completely dissolved (B
liquid). After adding Solution B to Solution A to form a slurry, 34.4 parts of antimony trioxide was added and stirred with heating.

The resulting slurry material was dried at 130°C, and then pre-calcined for 2 hours at 300°C in a gas atmosphere consisting of 5% oxygen and 95% nitrogen (volume %).

After pulverizing this pre-fired product, 1.5 parts of polymethyl methacrylate and 2 parts of graphite were added and mixed to 100 parts of the pre-fired product, pure water was added to make a slurry, and the slurry was dried, pulverized, and It was formed into a shape. The molded body was post-baked at 500° C. for 3 hours in an air atmosphere. The composition of the catalyst thus produced is expressed by the following formula.

Mo+ 28IO, 5Fe3N14cOJo, 3C3
O, aMg+Po, oasb When a reaction was carried out using this catalyst under the same reaction conditions as in Example 1, the reaction rate of inbutylene was 91.0% and the selectivity of methacrolein was 86.
．． The selectivity for methacrylic acid was 5.5%.

Comparative Example 2 A catalyst having the same composition as in Example 2 was produced in the same manner as in Example 2, except that polymethyl methacrylate was not added to the pre-calcined product. When a reaction was carried out using this catalyst under the same reaction conditions as in Example 1, the reaction rate of isobutylene was 90.
．． The selectivity for methacrolein was 86.5%, and the selectivity for methacrylic acid was 5.5%.

Example 3 A reaction was carried out under the same reaction conditions as in Example 1, except that the catalyst of Example 2 was used and tertiary butanol was used as a raw material. 80.2%, selectivity for methacrylic acid4.
It was 5%.

Comparative Example 3 A reaction was carried out under the same reaction conditions as in Example 1, except that the catalyst of Comparative Example 2 was used and tertiary butanol was used as a raw material. The reaction rate of tertiary butanol was 100%, and methacrolein was selected. rate 79.5%, selectivity of methacrylic acid 4.2
%Met.

Example 4 500 parts of ammonium paramolybdate in 1000 parts of pure water
18.5 parts of ammonium paratungstate, 13.8 parts of cesium nitrate, and 7.0 parts of rubidium nitrate were added and stirred with heating (Liquid A). Separately, 30 parts of concentrated nitric acid in 100 parts of pure water
114.5 parts of bismuth nitrate were dissolved.

To this, 286.0 parts of ferric nitrate and 480 parts of cobalt nitrate.
7 parts of zinc nitrate, 70.2 parts of zinc nitrate, and 1200 parts of pure water were sequentially added and stirred well until completely dissolved (solution B). After adding liquid B to liquid A to make a slurry, antimony trioxide 34
．． 4 parts were added and the mixture was heated and stirred.

The resulting slurry material was dried at 130° C., and then pre-calcined at 300° C. for 2 hours in a gas atmosphere consisting of 10% oxygen and 90% nitrogen (volume %).

After pulverizing this pre-fired product, 3 parts of methylcellulose and 2 parts of graphite were added and mixed to 100 parts of the pre-fired product, pure water was added to make a slurry, and the slurry was dried and pulverized.
It was formed into a ring shape.

The molded body was post-baked at 500° C. for 3 hours in an air atmosphere. The composition of the catalyst thus produced is expressed by the following formula.

MOtJz+FezCoyRbo, *C8a, xZ
n+sb+Wo, s Using this catalyst, a reaction was carried out under the same reaction conditions as in Example 1, and the reaction rate of isobutylene was 96.0%, the selectivity of methacrolein was 87.7%,
The selectivity of methacrylic acid was 4.9%.

Comparative Example 4 A catalyst having the same composition as in Example 4 was produced in the same manner as in Example 4, except that methyl cellulose was not added to the pre-calcined product. When a reaction was carried out using this catalyst under the same reaction conditions as in Example 1, the reaction rate of isobutylene was 95.2%,
The selectivity for methacrolein was 87.2% and the selectivity for methacrylic acid was 4.8%.

Example 5 A reaction was carried out using the catalyst of Example 4 under the same reaction conditions as in Example 1 except that tertiary butanol was used as a raw material, and the reaction rate of tertiary butanol was 100% and the selectivity of methacrolein. The selectivity for methacrylic acid was 86.9% and 3.1%.

Comparative Example 5 A reaction was carried out using the catalyst of Comparative Example 4 under the same reaction conditions as in Example 1 except that tertiary butanol was used as a raw material, and the reaction rate of tertiary butanol was 100% and the selectivity of methacrolein was The selectivity for methacrylic acid was 85.7% and 2.8%.

Example 6 50 ammonium paramolybdate in 1000 parts of pure water
0 parts, 18.5 parts of ammonium paratungstate, and 18.4 parts of cesium nitrate were added and stirred with heating (Liquid A).

Separately, 30 parts of concentrated nitric acid was added to 100 parts of pure water, and then 114.5 parts of bismuth nitrate was dissolved. Add this to ferric nitrate 190
．． 7 parts, cobalt nitrate 528, 7 parts, manganese nitrate 6.
8 parts, 141.8 parts of 10% silica sol and 1000 parts of pure water
were added one by one and stirred well until completely dissolved (solution B). After adding Solution B to Solution A to form a slurry, 34.4 parts of antimony trioxide was added and stirred with heating.

After drying the obtained slurry material at 130'C,
Preliminary firing was performed at 500° C. for 2 hours in an air atmosphere.

After pulverizing the pre-fired product, 2.5 parts of starch and 2 parts of graphite were added and mixed to 100 parts of the pre-fired product, pure water was added to form a slurry, and the slurry was dried, crushed, and formed into pellets.

The molded body was post-baked at 400° C. for 5 hours in an air atmosphere. The composition of the catalyst thus produced is expressed by the following formula.

MO+Ji+Fe2C0y, ycso, nMna,
+Sb+Sl+Wo3 This catalyst was packed into a stainless steel reaction tube and mixed with 5% isobutylene, 12% oxygen, and 10% water vapor.
% and nitrogen at 73% (volume %) was passed through the catalyst layer for a contact time of 3.6 seconds, and reacted at 350°C.

As a result, the reaction rate of isobutylene was 95.1%, the selectivity of methacrolein was 87.1%, and the selectivity of methacrylic acid was 4.
It was 1%.

Comparative Example 6 A catalyst having the same composition as in Example 6 was produced in the same manner as in Example 6, except that starch was not added to the pre-calcined product. When a reaction was carried out using this catalyst under the same reaction conditions as in Example 6, the reaction rate for isobutylene was 93.2%, the selectivity for methacrolein was 87.6%, and the selectivity for methacrylic acid was 4.
It was 0%.

Example 7 A reaction was carried out using the catalyst of Example 6 under the same reaction conditions as in Example 6, except that tertiary butanol was used as a raw material, and the reaction rate of tertiary butanol was 100% and the selectivity of methacrolein. The selectivity for methacrylic acid was 84.6% and 30%.

Comparative Example 7 A reaction was carried out using the catalyst of Comparative Example 6 under the same reaction conditions as in Example 6, except that tertiary butanol was used as a raw material, and the reaction rate of tertiary butanol was 100% and the selectivity of methacrolein. The selectivity for methacrylic acid was 84.0% and 2.5%.

Example 8 500 parts of ammonium rosemolybdate in 1000 parts of pure water
1, 6.2 parts of ammonium paratungstate and 23.0 parts of cesium nitrate were added and stirred with heating (Liquid A). Separately, 30 parts of concentrated nitric acid was added to 100 parts of pure water to make it homogeneous, and then 57.2 parts of bismuth nitrate was added and dissolved. Add to this 238.4 parts of ferric nitrate, 549.3 parts of cobalt nitrate, and 1 part of pure water.
200 parts were added one after another and stirred well until completely dissolved (solution B). After adding liquid B to liquid A to form a slurry, 34.4 parts of antimony dioxide and 4.4 parts of porium # were added and stirred with heating.

The obtained slurry material was dried at 130°C, and then pre-baked at 300°C for 2 hours in an air atmosphere.

After pulverizing the pre-fired product, 2 parts of ammonium nitrate was added and mixed to 100 parts of the pre-fired product, pure water was added to form a slurry, and this slurry was supported on porous amorphous silica-alumina.

The above-mentioned support was post-baked at 500° C. for 3 hours in a gas atmosphere consisting of 10% oxygen and 90% nitrogen (volume %). The composition of the catalyst thus produced except for the carrier and oxygen is represented by the following formula.

MO+Jlo, 5Fei, 5cOscso, 5s
bJo, +Bo, s Using this catalyst, a reaction was carried out under the same reaction conditions as in Example 1, and the reaction rate of isobutylene was 93.0% and the selectivity of methacrolein was 83.9%.
, the selectivity for methacrylic acid was 3.7%.

Comparative Example 8 A catalyst having the same composition as in Example 8 was produced in the same manner as in Example 8, except that ammonium nitrate was not added to the pre-calcined product. When a reaction was carried out using this catalyst under the same reaction conditions as in Example 1, the reaction rate of isobutylene was 91.6%,
The selectivity for methacrolein was 83.8% and the selectivity for methacrylic acid was 3.5%.

Example 9 A reaction was carried out using the catalyst of Example 8 under the same reaction conditions as in Example 1 except that secondary butanol was used as a raw material, and the reaction rate of tertiary butanol was 100% and the selectivity of methacrolein was The selectivity for methacrylic acid was 79.2% and 3.5%.

Comparative Example 9 A reaction was carried out using the catalyst of Comparative Example 8 under the same reaction conditions as in Example 1, except that tertiary butanol was used as a raw material, and the reaction rate of tertiary butanol was 100% and the selectivity of methacrolein. The selectivity for methacrylic acid was 78.0% and 3.2%.

Example 10 500 parts of ammonium paramolybdate in 1000 parts of pure water
and 18.4 parts of cesium nitrate were added and stirred with heating (A
liquid). Separately, 30 parts of concentrated nitric acid was added to 100 parts of pure water, and then 91.6 parts of bismuth nitrate and 167 parts of bismuth sulfate were dissolved. To this, 286.0 parts of ferric nitrate, 4 parts of cobalt nitrate
80.7 parts, magnesium nitrate 60.5 parts and pure water 12
Add 00 parts one by one until completely dissolved (stir).
B liquid). After adding Solution B to Solution A to form a slurry, 34.4 parts of antimony trioxide was added and stirred with heating.

The obtained slurry-like material was spray-dried using a spray dryer, and then pre-baked at 300° C. for 2 hours in an air atmosphere.

2 parts of methylcellulose and 2 parts of graphite were added to and mixed with 100 parts of this pre-fired product, and then formed into a pellet shape.

The molded body was post-baked at 500° C. for 3 hours in an air atmosphere. The composition of the catalyst thus produced is expressed by the following formula.

MO+J1+FesCOyC3o4Mg+sb+so,
z This catalyst was packed into a stainless steel reaction tube and mixed with 5% isobutylene, 12% oxygen, 10% water vapor and 73% nitrogen (
% by volume) was passed through the catalyst layer for a contact time of 3.6 seconds, and reacted at 355°C. As a result, the reaction rate of isobutylene was 92.1%, and the selectivity of methacrolein was 8.
The selectivity for methacrylic acid was 4.8%.

Comparative Example 10 A catalyst having the same composition as in Example 10 was produced in the same manner as in Example 10, except that methylcellulose was not added to the pre-calcined product in Example 1O. When a reaction was carried out using this catalyst under the same reaction conditions as in Example 10, the reaction rate of isobutylene was 90.
The selectivity for methacrolein was 86.6%, and the selectivity for methacrylic acid was 4.8%.

Example 11 500 parts of ammonium paramolybdate in 1000 parts of pure water
18.5 parts of ammonium paratungstate and 18.4 parts of cesium nitrate were added and stirred with heating (Liquid A). Separately, 30 parts of concentrated nitric acid was added to 100 parts of pure water, and then 57.2 parts of bismuth nitrate was dissolved. In this, ferric nitrate 238.4
parts, cobalt nitrate 274.7 parts, nickel nitrate 205 parts
9 parts, zinc nitrate 35.1 parts, magnesium nitrate 30.3 parts
and 1,200 parts of pure water were sequentially added thereto and stirred well until completely dissolved (Liquid B). After adding Solution B to Solution A to form a slurry, 34.4 parts of antimony trioxide was added and stirred with heating.

The obtained slurry material was dried at 130°C, and then pre-baked at 300°C for 2 hours in an air atmosphere.

After pulverizing this pre-fired product, 2 parts of polymethyl methacrylate and 2 parts of graphite are added to 100 parts of the pre-fired product.
After addition and mixing, the mixture was molded into pellets.

The molded body was post-baked at 500° C. for 3 hours in an air atmosphere. The composition of the catalyst thus produced is expressed by the following formula.

MO+Jlo, 5Fez, 5cOJlicsa,
nano, sMgo, ssb+Wa, 3 Using this catalyst, a reaction was carried out under the same reaction conditions as in Example 10, and the reaction rate of isobutylene was 96.1%, the selectivity of methacrolein was 86.9%, and the selectivity of methacrylic acid was 96.1%. Selection rate 4,8
%Met.

Comparative Example 11 A catalyst having the same composition as in Example 11 was produced in the same manner as in Example 11, except that polymethyl methacrylate was not added to the pre-calcined product. When a reaction was carried out using this catalyst under the same reaction conditions as in Example 10, the reaction rate of isobutylene was 95.1%, the selectivity of methacrolein was 86.2%, and the selectivity of methacrylic acid was 4.8%. Ta.

Example 12 500 parts of ammonium paramolybdate in 1000 parts of pure water
and 18.9 parts of thallium nitrate were added and heated and stirred (A
liquid). Separately, 30 parts of concentrated nitric acid was added to 100 parts of pure water, and then 57.2 parts of bismuth nitrate was dissolved. In this, ferric nitrate 2
38.4 parts of cobalt nitrate, 274.7 parts of nickel nitrate, 7.8 parts of lead nitrate, 6.8 parts of manganese nitrate, and 1200 parts of pure water were added in sequence and stirred well until completely dissolved ( Solution B), after adding Solution B to Solution A to make a slurry, 34.4 parts of antimony trioxide and tellurium #27
．． 1 part was added and the mixture was heated and stirred.

The obtained slurry material was dried at 130°C, and then pre-baked at 300°C for 2 hours in an air atmosphere.

After pulverizing the pre-fired product, 1 part of methyl cellulose, 145 parts of polymethyl methacrylate and 2 parts of graphite were added and mixed to 100 parts of the pre-fired product, and after adding pure water, it was extruded into a clover shape. The molded body was post-baked at 500° C. for 3 hours in an air atmosphere. The composition of the catalyst thus produced is expressed by the following formula.

Mo+Jio, sFe*, 5Co4Nis, s
Tj2 o, sMno, +Pbo, +Sb+Te
a, s When a reaction was carried out using this catalyst under the same reaction conditions as in Example 10, the reaction rate of isobutylene was 91.7%, the selectivity of methacrolein was 87.3%, and the selectivity of methacrylic acid was 4. It was 3%.

Comparative Example 12 Example 12 except that methyl cellulose and polymethyl methacrylate were not added to the pre-fired product in Example 12.
A catalyst with the same composition was produced in the same manner as above. When a reaction was carried out using this catalyst under the same reaction conditions as in Example 10, the reaction rate of inbutylene was 90.5%, the selectivity of methacrolein was 87.1%, and the selectivity of methacrylic acid was 4.1%. there were.

Comparative Example 13 A catalyst having the same composition as in Example 12 was produced in the same manner as in Example 12, except that the temperature of the post-stage calcination was changed to 300°C. When a reaction was carried out using this catalyst under the same reaction conditions as in Example 10, the reaction rate of isobutylene was 93.0%.
The selectivity for methacrolein was 84.8%, and the selectivity for methacrylic acid was 3.0%.

Example 13 500 parts of ammonium rosemolybdate in 1000 parts of pure water
and 13.9 parts of rubidium nitrate were added and stirred with heating (
A liquid). Separately, after adding 30 parts of concentrated nitric acid to 100 parts of pure water,
57.2 parts of bismuth nitrate was dissolved. To this were sequentially added 238.4 parts of ferric nitrate, 274.7 parts of cobalt nitrate, 240.2 parts of nickel nitrate, and 1200 parts of pure water, and stirred well until completely dissolved (solution B). After adding Solution B to Solution A to form a slurry, 15.9 parts of tin oxide, 9.4 parts of titanium dioxide, and 34.4 parts of antimony dioxide were added and stirred with heating.

The obtained slurry material was dried at 130°C, and then pre-baked at 300°C for 2 hours in an air atmosphere.

After pulverizing this pre-fired product, 3 parts of starch and 2 parts of graphite were added and mixed to 100 parts of the pre-fired product,
After adding pure water, it was extruded into a rod shape.

The molded body was fired at 500° C. for 2 hours in a gas atmosphere consisting of 5% oxygen and 95% nitrogen (volume %), and then for 2 hours at room temperature in an air atmosphere.

The composition of the catalyst thus produced is expressed by the following formula.

MO+Jlo, Fex, acOJla, 5Rbo4
sb+Tla, 5sno, s This catalyst was packed into a stainless steel reaction tube, and a raw material mixed gas of 5% isobutylene, 12% oxygen, 10% steam, and 73% nitrogen (volume %) was applied to the catalyst layer for a contact time of 3.6 seconds. The mixture was allowed to pass through and reacted at 365°C. As a result, the reaction rate of inbutylene was 92.3%.
, the selectivity for tacrolein was 87.1%, and the selectivity for methacrylic acid was 5.5%.

Comparative Example 14 A catalyst having the same composition as in Example 13 was produced in the same manner as in Example 13, except that starch was not added to the pre-calcined product. When a reaction was carried out using this catalyst under the same reaction conditions as in Example 13, the reaction rate for isobutylene was 91.3%, the selectivity for methacrolein was 86.8%, and the selectivity for methacrylic acid was 5.3%. Ta.

Example 14 A catalyst was produced according to Example 2. After drying the resulting slurry at 130°C, 5% oxygen and 95% nitrogen
The pre-stage firing was carried out at 300° C. for 2 hours under a gas atmosphere consisting of % (volume %).

After pulverizing this pre-fired product, 1.5 parts of polymethyl methacrylate and 2 parts of graphite were added and mixed to 100 parts of the pre-fired product, and pure water was added to make a slurry.
It was dried, crushed and formed into pellets. The molded body was post-baked at 500° C. for 3 hours in an air atmosphere. The composition of the catalyst thus produced is expressed by the following formula.

M(1+Jlo, +1Feo, 9CO3,yNao
, 1512 Using this catalyst, a raw material mixed gas of 5% propylene, 12% oxygen, 10% water vapor and 73% nitrogen (volume %) was passed through the catalyst layer for a contact time of 3.6 seconds, and 31
The reaction was carried out at 0°C. As a result, the reaction rate of propylene was 98
．． The selectivity for acrolein was 89.4%, and the selectivity for acrylic acid was 5.0%.

Comparative Example 15 A catalyst having the same composition as in Example 14 was produced in the same manner as in Example 14, except that polymethyl methacrylate was not added to the pre-calcined product. When a reaction was carried out using this catalyst under the same reaction conditions as in Example 14, the reaction rate of propylene was 98.0%, the selectivity of acrolein was 89.0%, and the selectivity of acrylic acid was 48%.

Example 15 A catalyst was produced according to Example 4. The obtained slurry-like material was dried at 130° C., and then pre-calcined at 300° C. for 2 hours in a gas atmosphere consisting of 10% oxygen and 90% nitrogen (volume %).

After pulverizing this pre-fired product, 3 parts of methylcellulose and 2 parts of graphite were added and mixed to 100 parts of the pre-fired product, pure water was added to make a slurry, and the slurry was dried and pulverized.
It was formed into a ring shape.

The molded body was post-baked at 500° C. for 3 hours in an air atmosphere. The composition of the catalyst thus produced is expressed by the following formula.

Mo+ zBl+4Fer, zcOsKo, l51
2110. When the reaction was carried out under the same reaction conditions as in Example 14 using the following catalyst, the conversion rate of propylene was 98.
The selectivity for acrolein was 88.3%, and the selectivity for acrylic acid was 6.3%.

Comparative Example 16 A catalyst having the same composition as in Example 15 was produced in the same manner as in Example 15, except that methylcellulose was not added to the pre-calcined product. When a reaction was carried out using this catalyst under the same reaction conditions as in Example 14, the conversion rate of propylene was 98.3.
%, acrolein selectivity was 87.5%, and acrylic acid selectivity was 6.2%.

Claims (1)

[Scope of Claims] 1. After drying a mixed solution or aqueous slurry containing a molybdenum compound and a bismuth compound as components, pre-baking is carried out, and the obtained pre-baked product is molded or supported on a carrier, and the obtained molded body is obtained. Alternatively, in a production method for obtaining a multi-component unsaturated aldehyde and unsaturated acid synthesis catalyst containing molybdenum and bismuth by post-calcining the support, in at least one of the pre-calcination and post-calcination, molecular 250 to 600 in a gas atmosphere containing 0 to 30% by volume of oxygen.
℃ for 1 to 10 hours, and 0.5 to 10 parts by weight of starch, polymethyl methacrylate, ammonium nitrate, and/or methyl cellulose are added and mixed to 100 parts by weight of the pre-baked product, and then molded or formed into a carrier. A method for producing a catalyst for the synthesis of unsaturated aldehydes and unsaturated acids, characterized in that the catalyst is supported on an unsaturated aldehyde and an unsaturated acid. 2. The composition of the catalyst is the general formula, MoaBibFecAdXeYfZgOh (where A is nickel and/or cobalt, X is sodium, potassium, rubidium, cesium and/or thallium, Y is magnesium, zinc, manganese, lead and/or tin, Z is phosphorus, boron, antimony, silicon, sulfur, titanium, tellurium and/or
or tungsten, a, b, c, d, e, f, g
and h represent the atomic ratio of each element, and when a=12, b
=0.01~3, c=0.5~4, d=1~12, e=
0.01-2, f=0-10, g=0-10, h
2. The method according to claim 1, wherein: is the number of oxygen atoms necessary to satisfy the valence of each component. 3. After drying the mixed solution or aqueous slurry containing a molybdenum compound and a bismuth compound as components, perform pre-baking, and add starch, polymethyl methacrylate, ammonium nitrate and/or methyl cellulose to 100 parts by weight of the obtained pre-baked product. After adding and mixing 0.5 to 10 parts by weight, it is molded or supported on a carrier, and the obtained molded body or carrier is later fired, and in at least one of the first firing and the second firing, molecular oxygen is added. 0-30% by volume
General formula MoaBibFecAdXeYfZgOh (where A is nickel and/or cobalt, X is sodium, potassium, rubidium, cesium and/or or thallium, Y is magnesium, zinc, manganese, lead and/or tin, Z is phosphorus, boron, antimony, silicon, sulfur, titanium, tellurium and/or
or tungsten, a, b, c, d, e, f, g
and h represent the atomic ratio of each element, and when a=12, b=
0.01-3, c=0.5-4, d=1-12, e=0
．． 01 to 2, f = 0 to 10, g = 0 to 10, and h is the number of oxygen atoms necessary to satisfy the valence of each component). A method for synthesizing unsaturated aldehydes and unsaturated acids, characterized by gas phase catalytic oxidation of tertiary butanol with molecular oxygen.