JPH10114689A - Production of metacrolein, methacrilic acid and 1,3-butadiene - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain ethacrolein, methacrylic acid and 1,3-butadiene efficiently, in high selectivity and in high yield by catalytically oxidizing a spent 4C fraction with molecular oxygen in a vapor phase in the presence of a specific catalyst. SOLUTION: A spent 4C fraction is catalytically oxidized with molecular oxygen in a vapor phase in the presence of a compound of the formula (A is Ni or Co; X is Mg, Zn, Mn, Cr, Sn, or Pd; Y is P, B, S or Se; Z is Na, K, rubidium, thallium or cesium; when (a) 12, 0.001<=b<=2.0, 0.1<=c<=5, 0.1<=d<=5, 0.01<=e<=5, 1<=f<=12, 0<=g<=10, 0<=h<=5, 0.01<=i<=2, 0<=j<=20 and (k) is the number of oxygen atoms required for satisfying the valence of each component) to give methacrolein, methacrylic acid and 1,3-butadiene.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a process for producing methacrolein, methacrylic acid and 1,3-butadiene by subjecting a spent C4 fraction to gas phase catalytic oxidation with molecular oxygen in the presence of a catalyst.

[0002]

2. Description of the Related Art As a method of industrially producing methacrolein and methacrylic acid, a method of catalytically oxidizing isobutylene, tertiary butanol or methyl tert-butyl ether in the gas phase with molecular oxygen is generally known. . As for 1,3-butadiene, a method based on dehydrogenation of butane or butylene is known.

In all of these reactions, isobutylene and 1-butene in a spent C4 fraction produced by naphtha cracking are generally separated and used as a raw material. Have been. Therefore, if the spent C4 fraction can be used as it is as a raw material for the reaction, the process is simplified.

A method for producing methacrolein, methacrylic acid and 1,3-butadiene using a spent C4 fraction as a raw material is described in a molybdenum-bismuth catalyst (JP-B-47-42, JP-B-56-10288). ), Molybdenum-tellurium catalysts (JP-B-46-339)
No. 31, JP-B-46-43524, JP-B-5
It has been proposed to use a catalyst which is generally improved from the industrial point of view due to the problem that, if the reaction rate of the raw material is increased, the selectivity of the target product is generally lowered. Was desired.

[0005]

SUMMARY OF THE INVENTION The present invention provides a novel catalyst for catalytically oxidizing a spent C4 fraction with molecular oxygen to obtain methacrolein, methacrylic acid and 1,3 in high yield.
An object of the present invention is to provide a process for producing butadiene with high conversion and high selectivity.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a Spent C4
Fractions gas-phase catalytic oxidation with molecular oxygen, methacrolein, in producing methacrylic acid and 1,3-butadiene of the general formula _{Mo a W b Bi c Fe d} Sb e A f X g Y h Z _i Si _j
O _k (wherein, Mo, W, Bi, Fe, Sb, Si and O represent molybdenum, tonten, bismuth, iron, antimony, silicon and oxygen, respectively, and A is at least one selected from the group consisting of nickel and cobalt. One element, X is at least one element selected from the group consisting of magnesium, zinc, manganese, chromium, tin and lead, and Y is at least one element selected from the group consisting of phosphorus, boron, sulfur and selenium And Z represents at least one element selected from the group consisting of sodium, potassium, rubidium, cesium and thallium, provided that a, b, c,
d, e, f, g, h, i, j and k represent the atomic ratio of each element, and when a = 12, 0.001 ≦ b ≦ 2, 0.1 ≦
c ≦ 5, 0.1 ≦ d ≦ 5, 0.01 ≦ e ≦ 5, 1 ≦ f ≦
12, 0 ≦ g ≦ 10, 0 ≦ h ≦ 5, 0.01 ≦ i ≦ 2,
0 ≦ j ≦ 20, and k is the number of oxygen atoms required to satisfy the valence of each component. ) The catalyst indicated or, a general formula _{Mo a Te b Fe c Pb d} Sb e Si f D g E h Z i O
_j (wherein, Mo, Te, Fe, Pb, Sb, Si and O represent molybdenum, tellurium, iron, lead, antimony, silicon and oxygen, respectively, and D represents nickel, cobalt, magnesium, manganese, chromium and zinc. At least one element selected from the group consisting of: E is at least one element selected from the group consisting of phosphorus, cerium, tungsten, lanthanum, silver and tin; Z is sodium, potassium;
It shows at least one element selected from the group consisting of rubidium, cesium and thallium. Where a, b,
c, d, e, f, g, h, i and j represent the atomic ratio of each element, and when a = 12, 0.1 ≦ b ≦ 8 and 0.1 ≦ c ≦
8, 1 ≦ d ≦ 12, 0.1 ≦ e ≦ 10, 1 ≦ f ≦ 30,
0 ≦ g ≦ 12, 0 ≦ h ≦ 8, 0.01 ≦ i ≦ 2,
j is the number of oxygen atoms required to satisfy the valence of each component. The method for producing methacrolein, methacrylic acid and 1,3-butadiene is characterized by using a catalyst represented by the formula

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The spent C4 fraction used as a reaction raw material in the present invention generally refers to spent BB produced by naphtha cracking, and contains about 4 parts of isobutylene.
2 to 52% by volume, about 22 to 30% by volume of 1-butene, and normal butane, isobutane, trans-2
-Butene, cis-2-butene, 1,3-butadiene and the like.

The raw materials of the elements constituting the catalyst of the present invention which are used in the gas phase catalytic oxidation of the spent C4 fraction with molecular oxygen include oxides, sulfates, nitrates, carbonates, and hydroxides. , Ammonium salt or a mixture thereof can be used. For example, raw materials of molybdenum, iron, bismuth and tellurium include ammonium molybdate, molybdic acid, molybdenum oxide, iron ammonium citrate, ferric ammonium oxalate, iron nitrate, iron sulfate, bismuth acetate, bismuth carbonate, bismuth nitrate , Bismuth oxide, bismuth sulfate, telluric acid, tellurium oxide and the like.

The catalyst can be prepared from the above-mentioned raw materials by a known method such as an evaporation to dryness method, a precipitation method, and an oxide mixing method. It is also preferable to use a carrier in preparing the catalyst. As the carrier, for example, silica, alumina, silica-alumina and the like can be used.

In the present invention, when the spent C4 fraction is subjected to gas phase catalytic oxidation with molecular oxygen using the above-mentioned catalyst to produce methacrolein, methacrylic acid and 1,3-butadiene, the spent C4 fraction is used in combination with the spent C4 fraction. The molar ratio of oxygen is preferably in the range of 1: 0.5 to 3. The molecular oxygen used for the oxidation may be pure oxygen gas, but the use of air is industrially advantageous.

The reaction pressure is from normal pressure to several atmospheres. The reaction temperature is preferably in the range of 250 to 450 ° C. The reaction can be carried out in a fixed bed or a fluidized bed.

[0012]

The present invention will be described below with reference to examples and comparative examples. “Parts” in the description means parts by weight. The analysis was performed by gas chromatography. The reaction rate and the selectivity of methacrolein, methacrylic acid and 1,3-butadiene to be formed are defined as follows based on isobutylene and 1-butene contained in the spent C4 fraction.

[0013]

(Equation 1)

[0014]

(Equation 2)

[0015]

(Equation 3)

[0016]

(Equation 4)

[0017]

(Equation 5)

Example 1 50 parts of 60% by weight nitric acid was added to 500 parts of pure water to make it uniform, and then 57.3 parts of bismuth nitrate was added and dissolved. After dissolving 23.0 parts of cesium nitrate, 30.8 parts of ammonium paratungstate was added and heated and stirred to evaporate most of the water. The obtained cake-like substance is
After drying at 400 ° C., the mixture was baked at 400 ° C. for 3 hours and pulverized in a mortar to obtain a composite oxide powder (composite oxide A).

Separately, 500 parts of ammonium molybdate, 7.3 parts of boric acid and cesium nitrate in 1000 parts of pure water.
2 parts were added and heated and stirred (Solution A). Separately, pure water 8
After adding 50 parts of 60% by weight nitric acid to 50 parts and making it uniform,
34.3 parts of bismuth nitrate was added and dissolved. 286.0 parts of ferric nitrate, 343.2 parts of nickel nitrate, 68.7 parts of cobalt nitrate, 60.5 parts of magnesium nitrate and 70.2 parts of zinc nitrate were sequentially added and dissolved (solution B).

After the mixed oxides A and B were added to the liquid A to form a slurry, 51.6 parts of antimony trioxide was added and heated and stirred to evaporate most of the water. The obtained cake-like substance was dried at 120 ° C., baked at 500 ° C. for 10 hours, press-molded, and then crushed to fractionate 10 to 20 mesh portions.

The composition of the catalyst thus obtained was as shown in the following formula. In the formula, the atomic ratio x of oxygen is a value that is naturally determined by the valence of another atom, and hence the description of oxygen is omitted. Mo ₁₂ W _0.5 Bi _0.8 Fe ₃ Ni ₅ Co ₁ Mg ₁ Zn ₁
B _0.5 Sb _1.5 Cs _0.7 O _x

The catalyst is filled in a stainless steel reaction tube,
Isobutylene 47.6%, 1-butene 29.5%, propylene 0.2%, isobutane 1.1%, normal butane 5.0%, trans-2-butene 8.3%, cis-2-
Butene 7.9%, 1,3-butadiene 0.3% and C5
Spent C4 fraction gas composed of 0.1% (volume%) of fraction or more 5% gas, 12% oxygen, 10% steam and 73% nitrogen
(Volume%) of the raw material mixed gas was passed through the catalyst layer at a contact time of 3.6 seconds, and the reaction was carried out at 340 ° C. As a result, the conversion of isobutylene was 97.2%, and the conversion of 1-butene was 9%.
3.0%, methacrolein selectivity 84.2%, methacrylic acid selectivity 3.2%, 1,3-butadiene selectivity 95.2%.

Example 2 500 parts of ammonium molybdate in 1000 parts of pure water
18.5 parts of ammonium paratungstate, 2.4 parts of potassium nitrate and 32.2 parts of cesium nitrate were added and heated and stirred (Solution A). Separately, 250 parts of 60% by weight nitric acid was added to 1500 parts of pure water to make the mixture uniform, and then bismuth nitrate was added.
6 parts were added and dissolved. 238.4 parts of ferric nitrate,
205.9 parts of nickel nitrate, 274.7 parts of cobalt nitrate and 39.1 parts of lead nitrate were sequentially added and dissolved (solution B).

Solution B was added to Solution A to form a slurry, and then 44.7 parts of antimony trioxide and stannous oxide 3
1.8 parts were added and heated and stirred to evaporate most of the water. After drying the obtained cake-like substance at 120 ° C., baking it at 500 ° C. for 10 hours, press-molding,
It was crushed and a 10-20 mesh portion was collected.

The composition of the catalyst thus obtained was as shown in the following formula. Mo ₁₂ W _0.3 Bi _0.8 Fe _2.5 Ni ₃ Co ₄ Pb _0.5 S
b _1.3 Sn ₁ K _0.1 Cs _0.7

Using this catalyst, a reaction was carried out under the same conditions as in Example 1. As a result, the conversion of isobutylene was 95.6.
%, Conversion of 1-butene 92.7%, selectivity of methacrolein 82.3%, selectivity of methacrylic acid 4.8%,
The selectivity for 1,3-butadiene was 94.7%.

Example 3 500 parts of ammonium molybdate in 1000 parts of pure water
18.5 parts of ammonium paratungstate, 6.3 parts of thallium nitrate and 9.2 parts of cesium nitrate were added and heated and stirred (Solution A). Separately, 60 parts by weight of nitric acid 2
After adding 50 parts to make uniform, bismuth nitrate 114.5
Was added and dissolved. 286.0 parts of ferric nitrate, 412.1 parts of cobalt nitrate, 30.3 parts of magnesium nitrate and 105.3 parts of zinc nitrate were sequentially added and dissolved therein (B
liquid).

Solution B was added to Solution A to form a slurry, and then 34.4 parts of antimony trioxide, 2.4 parts of chromium oxide, and 472.6 parts of 30% by weight silica sol were added, and the mixture was heated and stirred. Was evaporated. The obtained cake-like substance was dried at 120 ° C., baked at 500 ° C. for 6 hours, press-molded, crushed and fractionated into 10 to 20 mesh portions.

The composition of the catalyst thus obtained was as shown in the following formula. Mo ₁₂ W _0.3 Bi ₁ Fe ₃ Co ₆ Mg _0.5 Zn _1.5 Cr
_0.1 Sb ₁ Tl _0.1 Cs _0.2 Si ₁₀

Using this catalyst, a reaction was carried out under the same conditions as in Example 1. As a result, the reaction rate of isobutylene was 95.8.
%, Reaction rate of 1-butene 94.5%, selectivity of methacrolein 85.0%, selectivity of methacrylic acid 2.9%,
The selectivity for 1,3-butadiene was 92.7%.

Example 4 500 parts of ammonium molybdate in 1000 parts of pure water
32.2 parts of cesium nitrate and 30.8 parts of ammonium paratungstate were added and heated and stirred (Solution A). Separately, 250 parts of 60% by weight nitric acid was added to 1500 parts of pure water to make the mixture uniform, and 103.0 parts of bismuth nitrate was added and dissolved. 257.4 parts of ferric nitrate and 68.6 of nickel nitrate
Parts, 343.3 parts of cobalt nitrate, magnesium nitrate 6
0.5 part and 24.3 parts of selenous acid were sequentially added and dissolved (solution B).

The solution B was added to the solution A to form a slurry, and then 51.6 parts of antimony trioxide and 37.8 parts of a 30% by weight silica sol were added and heated with stirring to evaporate most of the water. The obtained cake-like substance was dried at 120 ° C., baked at 500 ° C. for 10 hours, press-molded, and then crushed to fractionate 10 to 20 mesh portions. The composition of the catalyst thus obtained was as shown in the following formula. Mo ₁₂ W _0.5 Bi _0.9 Fe _2.7 Ni ₁ Co ₅ Mg ₁ Se
_0.8 Sb _1.5 Cs _{0. 7} Si _0.8

Using this catalyst, a reaction was carried out under the same conditions as in Example 1. As a result, the conversion of isobutylene was 96.1.
%, Conversion of 1-butene 93.8%, selectivity of methacrolein 83.4%, selectivity of methacrylic acid 3.6%,
The selectivity for 1,3-butadiene was 95.2%.

Example 5 500 parts of ammonium molybdate was added to and dissolved in 2000 parts of pure water, and 257.4 parts of ferric nitrate was added to 3 parts of pure water.
The solution dissolved in 00 parts was added. The resulting slurry was heated and stirred at 95 ° C. for 1 hour under reflux. A solution obtained by adding 30.8 parts of ammonium paratungstate and 1.4 parts of 85% by weight phosphoric acid to 100 parts of pure water was added to the slurry after the heat treatment, followed by stirring (Solution A). Separately, 250 parts of 60% by weight nitric acid was added to 850 parts of pure water to make the mixture uniform, and 114.5 parts of bismuth nitrate was added and dissolved. Nickel nitrate 4
80.4 parts, cobalt nitrate 68.7 parts, manganese nitrate 3
3.9 parts and rubidium nitrate (17.4 parts) were sequentially added and dissolved (solution B).

The solution B was added to the solution A to form a slurry, 68.8 parts of antimony trioxide was added, and the mixture was heated and stirred to evaporate most of the water. The cake-like substance obtained was 12
After drying at 0 ° C., it was baked at 500 ° C. for 10 hours, press-molded, and then crushed to fractionate 10 to 20 mesh portions. The composition of the catalyst thus obtained was as shown in the following formula. Mo ₁₂ W _0.5 Bi ₁ Fe _2.7 Ni ₇ Mn _0.5 Co ₁ P
_0.05 Sb ₂ Rb _0.5

Using this catalyst, a reaction was carried out under the same conditions as in Example 1. As a result, the conversion of isobutylene was 94.7.
%, Reaction rate of 1-butene 92.9%, selectivity of methacrolein 84.8%, selectivity of methacrylic acid 3.9%,
The selectivity for 1,3-butadiene was 93.8%.

Example 6 A solution prepared by adding 500 parts of ammonium molybdate to 1000 parts of pure water and dissolving the same, and dissolving 209.8 parts of ferric nitrate and 52.5 parts of ferrous sulfate in 300 parts of pure water. Was added. A solution obtained by adding 6.2 parts of ammonium paratungstate to 100 parts of pure water was added to the resulting slurry and stirred (Solution A). Separately, 250 parts of 60% by weight nitric acid was added to 850 parts of pure water to make the mixture uniform, and 114.5 parts of bismuth nitrate was added and dissolved. To this, 274.5 parts of nickel nitrate, 206.0 parts of cobalt nitrate, 9.4 parts of chromium nitrate, 7.8 parts of lead nitrate and 12.6 parts of thallous nitrate were sequentially added and dissolved (solution B).

A slurry was prepared by adding 850.7 parts of a 20% silica sol and a B solution to the A solution, and then 34.4 parts of antimony trioxide was added and heated and stirred to evaporate most of the water. After drying the obtained cake-like substance at 120 ° C., baking it at 500 ° C. for 10 hours, press-molding,
It was crushed and a 10-20 mesh portion was collected. The composition of the catalyst thus obtained was as shown in the following formula. Mo ₁₂ W _0.1 Bi ₁ Fe ₃ Cr _0.1 Ni ₄ Co ₃ Pb
_0.1 S _0.8 Sb ₁ Tl _0.2 Si ₁₂

Using this catalyst, a reaction was carried out under the same conditions as in Example 1. As a result, the reaction rate of isobutylene was 93.7.
%, Reaction rate of 1-butene 93.6%, selectivity of methacrolein 87.0%, selectivity of methacrylic acid 3.1%,
The selectivity for 1,3-butadiene was 93.2%.

Example 7 500 parts of ammonium molybdate and 9.2 parts of cesium nitrate were added to 1000 parts of pure water and dissolved by heating. To this, 190.7 parts of ferric nitrate, 625.3 parts of lead nitrate and telluric acid were added. A solution prepared by dissolving 162.6 parts in 3000 parts of pure water was added. 172.0 parts of antimony trioxide and 709.0 parts of a 30% by weight silica sol were added to the resulting slurry, followed by heating and stirring to evaporate most of the water.

The obtained cake was dried at 120 ° C. The obtained dried material was press-molded, crushed, fractionated into 10 to 20 mesh portions, and fired at 500 ° C. for 3 hours. The composition of the catalyst thus obtained was as shown in the following formula. Mo ₁₂ Te ₃ Fe ₂ Pb ₈ Sb ₅ Cs _0.2 Si ₁₅

This catalyst was filled in a stainless steel reaction tube,
Isobutylene 47.6%, 1-butene 29.5%, propylene 0.2%, isobutane 1.1%, normal butane 5.0%, trans-2-butene 8.3%, cis-2-
Butene 7.9%, 1,3-butadiene 0.3% and C5
Spent C4 fraction gas composed of 0.1% (volume%) of fraction or more 5% gas, 12% oxygen, 10% steam and 73% nitrogen
(Volume%) of the raw material mixed gas was passed through the catalyst layer at a contact time of 3.6 seconds, and the reaction was carried out at 360 ° C.

As a result, the conversion of isobutylene was 95.3.
%, 1-butene conversion 14.2%, methacrolein selectivity 83.5%, methacrylic acid selectivity 2.2%,
The selectivity for 1,3-butadiene was 98.5%.

Example 8 Using the catalyst of Example 7, a reaction was carried out under the same conditions as in Example 7 except that the reaction temperature was 340 ° C. As a result, the conversion of isobutylene was 90.5%, and the conversion of 1-butene was 1
The selectivity for methacrolein was 8.5%, the selectivity for methacrylic acid was 1.8%, and the selectivity for 1,3-butadiene was 94.8%.

Example 9 Using the catalyst of Example 7, the reaction was carried out under the same conditions as in Example 7 except that the reaction temperature was 370 ° C. As a result, the conversion of isobutylene was 97.4% and the conversion of 1-butene was 1
4.3%, methacrolein selectivity 85.6%, methacrylic acid selectivity 2.3%, 1,3-butadiene selectivity 98.6%.

Example 10 500 parts of ammonium molybdate, 4.6 parts of cesium nitrate and 2.4 parts of potassium nitrate were added to 1000 parts of pure water and dissolved by heating. To this, 190.7 parts of ferric nitrate and 312 parts of lead nitrate were added. 0.7 part, 274.5 parts of nickel nitrate and 162.6 parts of telluric acid dissolved in 3000 parts of pure water were added. 172.0 parts of antimony trioxide and 472.7 parts of 30% by weight silica sol were added to the resulting slurry, and the mixture was heated and stirred to evaporate most of the water.

The obtained cake was dried at 120 ° C. The obtained dried material was press-molded, crushed, fractionated into 10 to 20 mesh portions, and fired at 500 ° C. for 3 hours. The composition of the catalyst thus obtained was as shown in the following formula. Mo ₁₂ Te ₃ Fe ₂ Pb ₄ Ni ₄ Sb ₅ Cs _0.1 K _0.1
Si ₁₀

Using this catalyst, a reaction was carried out under the same conditions as in Example 7. As a result, the reaction rate of isobutylene was 94.8.
%, 1-butene conversion 16.8%, methacrolein selectivity 84.1%, methacrylic acid selectivity 1.6%,
The selectivity for 1,3-butadiene exceeded 100%.

Example 11 500 parts of ammonium molybdate in 1000 parts of pure water
3.1 parts of ammonium paratungstate, 4.6 parts of cesium nitrate and 2.0 parts of sodium nitrate were added and dissolved by heating, and 286.0 parts of ferric nitrate and 312.
7 parts, 274.7 parts of cobalt nitrate and 162.
A solution obtained by dissolving 6 parts in 3000 parts of pure water was added. 103.2 parts of antimony trioxide and 236.3 parts of a 30% by weight silica sol were added to the resulting slurry, followed by heating and stirring,
Most of the water was evaporated.

The obtained cake was dried at 120 ° C. The obtained dried material was press-molded, crushed, fractionated into 10 to 20 mesh portions, and fired at 500 ° C. for 3 hours. The composition of the catalyst thus obtained was as shown in the following formula. Mo ₁₂ Te ₃ Fe ₃ Pb ₄ Co ₄ Sb ₃ Cs _0.1 Na
_0.1 W _0.05 Si ₅

Using this catalyst, a reaction was carried out under the same conditions as in Example 7. As a result, the reaction rate of isobutylene was 96.4.
%, The selectivity of 1-butene was 16.4%, the selectivity of methacrolein was 83.8%, the selectivity of methacrylic acid was 1.3%, and the selectivity of 1,3-butadiene exceeded 100%.

Example 12 500 parts of ammonium molybdate and 7.0 parts of rubidium nitrate were added to 1000 parts of pure water and dissolved by heating, and 286.0 parts of ferric nitrate, 312.7 parts of lead nitrate, and A solution prepared by dissolving 121.0 parts of magnesium, 140.4 parts of zinc nitrate, 10.2 parts of lanthanum nitrate, and 108.4 parts of telluric acid in 3000 parts of pure water was added. 103.2 parts of antimony trioxide, 4.1 parts of ceric oxide and 472.7 parts of 30% by weight silica sol were added to the resulting slurry, and the mixture was heated and stirred to evaporate most of the water.

The obtained cake was dried at 120 ° C. After the obtained dried substance was press-molded, it was crushed and fractionated into 10 to 20 mesh portions, which were baked at 500 ° C. for 3 hours. The composition of the catalyst thus obtained was as shown in the following formula. Mo ₁₂ Te ₂ Fe ₃ Pb ₄ Mg ₂ Zn ₂ Sb ₃ Rb _0.2
Ce _0.1 La _0.1 Si ₁₀

Using this catalyst, a reaction was carried out under the same conditions as in Example 7. As a result, the conversion of isobutylene was 95.0.
%, 1-butene conversion 20.2%, methacrolein selectivity 84.2%, methacrylic acid selectivity 1.5%,
The selectivity for 1,3-butadiene was 99.5%.

Example 13 500 parts of ammonium molybdate and 12.6 parts of thallium nitrate were added to 1000 parts of pure water and dissolved by heating. 228.8 parts of ferric nitrate, 390.8 parts of lead nitrate, and manganese nitrate were added. 67.7 parts, chromium oxide 23.6 parts, silver nitrate 2.
A solution of 0 part and 162.6 parts of telluric acid dissolved in 3000 parts of pure water was added. After adding 103.2 parts of antimony trioxide and 236.3 parts of a 30% by weight silica sol to the resulting slurry, the mixture was heated and stirred to evaporate most of the water.

The obtained cake was dried at 120 ° C. After the obtained dried substance was press-molded, it was crushed and fractionated into 10 to 20 mesh portions, which were baked at 500 ° C. for 3 hours. The composition of the catalyst thus obtained was as shown in the following formula. Mo ₁₂ Te ₃ Fe _2.4 Pb ₅ Mn ₁ Cr ₁ Tl _0.2 Sb
₃ Ag _0.05 Si ₅

Using this catalyst, a reaction was carried out under the same conditions as in Example 7. As a result, the conversion of isobutylene was 95.1.
%, The reaction rate of 1-butene was 11.8%, the selectivity of methacrolein was 84.3%, and the selectivity of methacrylic acid was 1.7%, and the selectivity of 1,3-butadiene exceeded 100%.

Example 14 500 parts of ammonium molybdate was added to 1000 parts of pure water.
14.2 parts of 50% cesium hydroxide was added and dissolved by heating.
To this was added a solution in which 381.4 parts of ferric nitrate, 625.3 parts of lead nitrate and 162.6 parts of telluric acid were dissolved in 3000 parts of pure water. Antimony trioxide 17 was added to the resulting slurry.
After adding 2.0 parts, 15.9 parts of stannous oxide and 709.0 parts of a 30% by weight silica sol, the mixture was heated and stirred to evaporate most of the water.

The obtained cake was dried at 120 ° C. After the obtained dried substance was press-molded, it was crushed and fractionated into 10 to 20 mesh portions, which were baked at 500 ° C. for 3 hours. The composition of the catalyst thus obtained was as shown in the following formula. Mo ₁₂ Te ₃ Fe ₄ Pb ₈ Sb ₅ Cs _0.2 Sn _0.5 Si
_Fifteen

Using this catalyst, a reaction was carried out under the same conditions as in Example 7. As a result, the reaction rate of isobutylene was 94.9.
%, 1-butene conversion rate 15.0%, methacrolein selectivity 84.0%, methacrylic acid selectivity 2.0%, and 1,3-butadiene selectivity exceeded 100%.

Comparative Example 1 A catalyst having the composition shown in the following formula was obtained in the same manner as in Example 1 except that ammonium paratungstate was not used in the preparation of the composite oxide A of Example 1. Mo ₁₂ Bi _0.8 Fe ₃ Ni ₅ Co ₁ Mg ₁ Zn ₁ B _0.5
Sb _1.5 Cs _0.7

Using this catalyst, a reaction was carried out under the same conditions as in Example 1. As a result, the conversion of isobutylene was 92.2.
%, 1-butene conversion 90.1%, methacrolein selectivity 83.0%, methacrylic acid selectivity 4.0%,
The selectivity for 1,3-butadiene was 95.3%.

Comparative Example 2 A catalyst represented by the following formula was obtained in the same manner as in Example 7 except that telluric acid was not used. Mo ₁₂ Fe ₂ Pb ₈ Sb ₅ Cs _0.2 Si ₁₅

Using this catalyst, a reaction was carried out under the same conditions as in Example 7. As a result, the conversion of isobutylene was 89.8.
%, 1-butene conversion 14.0%, methacrolein selectivity 81.5%, methacrylic acid selectivity 3.0%,
The selectivity for 1,3-butadiene was 97.2%.

Comparative Example 3 A catalyst represented by the following formula was obtained in the same manner as in Example 7 except that no silica sol was used. Mo ₁₂ Te ₃ Fe ₂ Pb ₈ Sb ₅ Cs _0.2

Using this catalyst, a reaction was carried out under the same conditions as in Example 7. As a result, the conversion of isobutylene was 60.3.
%, 1-butene conversion 12.1%, methacrolein selectivity 85.7%, methacrylic acid selectivity 0.8%,
The selectivity of 1,3-butadiene was 98.0%.

According to the present invention, methacrolein, methacrylic acid and 1,1 are prepared from inexpensive spent C4 fraction.
3-Butadiene can be obtained with high conversion and high selectivity.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 57/05 C07C 57/05 // C07B 61/00 300 C07B 61/00 300

Claims (2)

[Claims] 1. A gas-phase catalytic oxidation using a spent C4 molecular oxygen fraction, methacrolein, in producing methacrylic acid and 1,3-butadiene of the general formula _{Mo a W b Bi c Fe d} Sb e A _f X _g Y _h Z _i Si _j
O _k (wherein, Mo, W, Bi, Fe, Sb, Si and O represent molybdenum, tonten, bismuth, iron, antimony, silicon and oxygen, respectively, and A is at least one selected from the group consisting of nickel and cobalt. One element, X is at least one element selected from the group consisting of magnesium, zinc, manganese, chromium, tin and lead, and Y is at least one element selected from the group consisting of phosphorus, boron, sulfur and selenium And Z represents at least one element selected from the group consisting of sodium, potassium, rubidium, cesium and thallium, provided that a, b, c,
d, e, f, g, h, i, j and k represent the atomic ratio of each element, and when a = 12, 0.001 ≦ b ≦ 2, 0.1 ≦
c ≦ 5, 0.1 ≦ d ≦ 5, 0.01 ≦ e ≦ 5, 1 ≦ f ≦
12, 0 ≦ g ≦ 10, 0 ≦ h ≦ 5, 0.01 ≦ i ≦ 2,
0 ≦ j ≦ 20, and k is the number of oxygen atoms required to satisfy the valence of each component. A method for producing methacrolein, methacrylic acid and 1,3-butadiene, characterized by using the catalyst represented by the formula (1). 2. A gas phase catalytic oxidation with a spent C4 fraction with molecular oxygen, methacrolein, in producing methacrylic acid and 1,3-butadiene of the general formula _{Mo a Te b Fe c Pb d} Sb e _{Si f D g E h Z i} O
_j (wherein, Mo, Te, Fe, Pb, Sb, Si and O represent molybdenum, tellurium, iron, lead, antimony, silicon and oxygen, respectively, and D represents nickel, cobalt, magnesium, manganese, chromium and zinc. At least one element selected from the group consisting of: E is at least one element selected from the group consisting of phosphorus, cerium, tungsten, lanthanum, silver and tin; Z is sodium, potassium;
It shows at least one element selected from the group consisting of rubidium, cesium and thallium. Where a, b,
c, d, e, f, g, h, i and j represent the atomic ratio of each element, and when a = 12, 0.1 ≦ b ≦ 8 and 0.1 ≦ c ≦
8, 1 ≦ d ≦ 12, 0.1 ≦ e ≦ 10, 1 ≦ f ≦ 30,
0 ≦ g ≦ 12, 0 ≦ h ≦ 8, 0.01 ≦ i ≦ 2,
j is the number of oxygen atoms required to satisfy the valence of each component. A method for producing methacrolein, methacrylic acid and 1,3-butadiene, characterized by using the catalyst represented by the formula (1).