JP5831190B2 - Catalyst for simultaneous production of 1,3-butadiene and methacrolein, and method for producing 1,3-butadiene and methacrolein using the same - Google Patents

Description

  The present invention relates to a catalyst for simultaneous production of 1,3-butadiene and methacrolein, a method for producing 1,3-butadiene and methacrolein using the catalyst, and more specifically, n-butene and iso-butene. 1. Production of 1,3-butadiene, which is industrially useful as a raw material for synthetic rubber, and methacrylic acid, methyl methacrylate (MMA), and methacrolein, which is industrially useful as a raw material for MMA resin, at the same time with high production efficiency Is a catalyst for simultaneous production of 1,3-butadiene and methacrolein, and a method for producing 1,3-butadiene and methacrolein using the same.

  As a method for producing 1,3-butadiene and methacrolein by contacting a C4 hydrocarbon containing n-butene and iso-butene with molecular oxygen and an oxidation reaction catalyst, there are methods using several oxidation reaction catalysts. Are known.

  For example, in addition to Mo, Bi, Ni, Co and Fe, a composite composed of at least one element selected from P, As and B and at least one element selected from K, Rb and Cs An oxidation reaction catalyst that is an oxide (see, for example, Patent Document 1), Mo, Bi, Fe, Co, Ni, Ce, Be, and at least one element selected from P, As, B, and K, Rb, Cs , Tl, an oxidation reaction catalyst that is a composite oxide in which at least one element selected from Tl is added (see, for example, Patent Document 2), Mo, Bi, Co, Fe, Sb, Li, Na, K, Cs, Tl. An oxidation reaction catalyst (see, for example, Patent Documents 3 and 4) that is a composite oxide to which at least one element selected from the above is added has been proposed.

Japanese Patent Publication No. 49-004441 (for example, see page 1) Japanese Patent Laid-Open No. 52-11506 (see, for example, page 1) Japanese Patent Laid-Open No. 50-130709 (for example, see page 1) JP-A-58-074622 (for example, see page 1)

  For general industrial catalysts, if the activity is low, a process for collecting and recycling unreacted raw materials is required. If the selectivity is low, the raw materials are wasted. If the productivity is low, the reaction is required to obtain the required production volume. If the scale of the vessel is large or the catalyst life is short, the frequency of catalyst replacement will increase and problems such as inability to produce stably will result, resulting in high activity, selectivity, and productivity (space-time yield: STY) And it is calculated | required to have a long catalyst lifetime.

  However, although the oxidation reaction catalyst proposed in Patent Document 1 has high activity and selectivity, it is necessary to increase the scale of the reactor because of the low productivity of 1,3-butadiene. The catalyst life is unknown, and the oxidation reaction catalyst proposed in Patent Document 2 has a very high activity, although the productivity of 1,3-butadiene is higher than necessary. Since it is low, it has a problem that it is necessary to collect and recycle the raw material. The oxidation reaction catalysts proposed in Patent Documents 3 and 4 have a long catalyst life of 2000 hours. However, there is a problem that it is necessary to increase the scale of the reactor because the activity is low and the raw material needs to be recovered and recycled, and the productivity of 1,3-butadiene is low. It was.

  As described above, in any of the proposals, since the activity as a catalyst and / or the productivity of 1,3-butadiene is low, it is necessary to recover and recycle the raw materials or to increase the scale of the reactor. 1,3-butadiene cannot be efficiently produced, is not satisfactory in industrial productivity, and has high activity as a catalyst. The advent of a catalyst that can produce 1,3-butadiene efficiently and has a long life, particularly a catalyst that can simultaneously produce 1,3-butadiene and methacrolein is desired. It was.

  Therefore, as a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a composite oxide composed of a specific metal element is obtained by converting 1,3-butadiene and methacrolein from n-butene, iso-butene and molecular oxygen. At the same time, it was found that the catalyst can be produced simultaneously with 1,3-butadiene and methacrolein having high selectivity and long life, and the present invention has been completed.

That is, the present invention is, in general formula _{Mo 12 Co b Fe c Bi d} Ce e Tl f Sb g O j ( where, b = 3~15, c = 0.4~5 , d = 0.01~3, e = 0.01-2, f = 0.01-2, g = 0.01-3, j = 40-79, c / b = 0.3-1.2) The present invention relates to a catalyst for simultaneous production of 1,3-butanediene and methacrolein, which is a composite oxide, and a method for simultaneous production of 1,3-butanediene and methacrolein using the same.

1,3 butadiene and methacrolein coproduction catalyst of the present invention is made of a multi-element-based composite oxide represented by the general formula _{Mo 12 Co b Fe c Bi d} Ce e Tl f Sb g O j, In particular, since it contains Ce and Tl as a multi-element composite oxide, it becomes a catalyst that makes it possible to produce 1,3-butadiene and methacrolein with high activity and high selectivity.

  B to g are composition ratios of Mo to metal elements (Mo, Co, Fe, Bi, Ce, Tl, Sb) constituting the multi-element composite oxide (Mo reference; 12), and j is It is the composition ratio (Mo reference | standard; 12) of oxygen which comprises a multi-element system complex oxide. Here, b to g are b = 3 to 15, c = 0.4 to 6, d = 0.01 to 3, e = 0.01 to 2, f = 0.01 to 2, g = 0, respectively. 0.01 to 3 and j = 40 to 79, and a multi-element composite oxide outside these ranges cannot be a catalyst having high activity, high selectivity, high productivity, and long life. Further, in the catalyst for simultaneous production of 1,3-butanediene and methacrolein of the present invention, since it is a catalyst exhibiting particularly high activity and high selectivity, b = 4 to 10, c = 1 to 5, d = 0. 0.1-2, e = 0.05-1, f = 0.05-1, g = 0.01-2, and j = 40-79 are preferred.

  Further, the catalyst for simultaneous production of 1,3-butanediene and methacrolein of the present invention has a composition ratio of Fe and Co in the multi-element composite oxide at c / b = 0.3 to 1.2. A multi-element composite oxide outside this range cannot be a catalyst having high activity, high selectivity, high productivity, and long life. Moreover, in the catalyst for simultaneous production of 1,3-butanediene and methacrolein of the present invention, a catalyst having particularly high activity and high selectivity is present. preferable.

  In the catalyst for simultaneous production of 1,3-butanediene and methacrolein according to the present invention, the composition ratio of cobalt, iron, and bismuth is d / (b + c) because it is a catalyst having particularly high activity, high selectivity, and high efficiency. × 1.5) = preferably composed of a multi-element complex oxide in a relationship of 0.01 to 1, particularly preferably composed of a multi-element complex oxide in a relationship of 0.02 to 0.5. .

  Further, in the catalyst for simultaneous production of 1,3-butanediene and methacrolein of the present invention, since it becomes a catalyst exhibiting higher activity and higher selectivity, further from vanadium, niobium, lanthanum, samarium, potassium, rubidium and cesium. It is preferably composed of a multi-element composite oxide containing an oxide of one or more elements selected from the group consisting of the elements, and the composition ratio at that time is preferably 0.01 to 2 with Mo as the reference 12.

  The catalyst for simultaneous production of 1,3-butanediene and methacrolein of the present invention can be used as it is as long as it is composed of a multi-element composite oxide represented by the above general formula. Since it is excellent in handling property as a catalyst and sustainability of activity, it is preferable that it is supported on an inert carrier, or diluted with an inert carrier. Examples of the inert carrier include silica, Examples of the inert carrier include alumina, silica alumina, and silicon carbide. Among them, silica is particularly preferable because of excellent moldability when used as a catalyst. Moreover, there is no restriction | limiting in particular in the addition amount at the time of using an inert support | carrier, Among them, 1-50 wt. %, Particularly 5-30 wt. % Is preferred.

  As a method for producing a catalyst for simultaneous production of 1,3-butanediene and methacrolein of the present invention, a multi-element composite oxidation containing molybdenum, cobalt, iron, bismuth, cerium, thallium and antimony represented by the general formula as metal elements Any method can be used as long as the product can be produced, for example, nitrates, ammonium salts, organic acid salts, halides, hydroxides and other salts of metal elements, oxides, or These salts can be produced in combination, and each can be used in combination, and can also be produced by evaporation to dryness.

  As a more detailed production method, for example, after dissolving hexammonium hexamolybdate tetrahydrate in heated distilled water, thallium nitrate, cobalt nitrate hexahydrate, iron nitrate (III) 9 An aqueous solution in which hydrate is dissolved, an aqueous nitric acid solution in which bismuth nitrate hexahydrate is dissolved, an aqueous solution in which cerium nitrate hexahydrate is dissolved, and antimony oxide are sequentially added with stirring, and finally Hyflo, a type of silica, is added. A method of adding a supercell, heating and concentrating with stirring to form a slurry, and drying, heat-treating and firing the slurry can be mentioned.

  Concentration time at the time of heating concentration is arbitrary, and among them, since a highly active catalyst for simultaneous production of 1,3-butanediene and methacrolein is obtained, it is preferably 1 to 24 hours, and further 2 It is preferably ~ 12 hours. Further, examples of the drying method for performing drying include spray drying, drying in a thermostatic bath, an annular furnace, a muffle furnace, and the like. The drying temperature is preferably 90 to 150 ° C, particularly 100 to 120 ° C. Preferably there is.

  The solid heat treatment after drying decomposes the salt and the like, and in that case, the heat treatment can also be performed in an air stream. For example, the heat treatment method includes a muffle furnace, a ring furnace, a rotary kiln. The heat treatment temperature at that time is not particularly limited, and among them, a catalyst for simultaneous production of 1,3-butanediene and methacrolein having high activity and high selectivity can be obtained. Therefore, it is preferable that it is 200-400 degreeC, and it is especially preferable that it is 250-350 degreeC. Also, the heat treatment time is not particularly limited, and a catalyst for simultaneous production of 1,3-butanediene and methacrolein having particularly high activity and high selectivity is obtained. Preferably it is 6 hours. Furthermore, the firing after the heat treatment can be performed in an air stream, and for example, firing can be performed using a muffle furnace, a ring furnace, a rotary kiln, or the like. The firing temperature at that time is preferably 400 to 600 ° C., particularly 450 to 550 ° C., because a catalyst for simultaneous production of 1,3-butanediene and methacrolein having particularly high activity and high selectivity is obtained. Is preferred.

  The shape of the catalyst for simultaneous production of 1,3-butanediene and methacrolein of the present invention is not limited, and may be any shape, for example, spherical, elliptical, cylindrical, cylindrical, honeycomb, powder In particular, it has a spherical shape, a cylindrical shape, a cylindrical shape, a honeycomb shape, and a granular shape because it is a highly efficient catalyst for producing 1,3-butadiene. It is preferable. In addition, examples of the molding method at that time include tableting molding, extrusion molding, and a method in which the slurry is heat-treated after drying, pulverized and sieved. In molding, if necessary, molding aids such as silica, silica sol, alumina, alumina sol, graphite, and cellulose may be mixed.

  The catalyst for simultaneous production of 1,3-butanediene and methacrolein according to the present invention acts as a catalyst for reacting n-butene, iso-butene and molecular oxygen, thereby simultaneously producing 1,3-butadiene and methacrolein. In this case, the catalytic action exhibits high activity, high selectivity, high productivity, and a long catalyst life. As n-butene, 1-butene and 2-butene are known. Examples of the n-butene include 1-butene, 2-butene, and a mixture of 1-butene and 2-butene. it can. 1,3-butadiene is produced from n-butene as a raw material, and methacrolein is produced from iso-butene as a raw material.

  In this case, the n-butene and iso-butene may be a mixture of n-butene and iso-butene or a C4 hydrocarbon containing n-butene and iso-butene. As the C4 hydrocarbon, for example, Examples thereof include an S-C4 fraction obtained by removing butadiene from a C4 fraction produced by cracking of naphtha, and an SS-C4 fraction obtained by further removing a part of iso-butene from a spent C4 fraction. Further, the ratio of n-butene and iso-butene is arbitrary, and among them, in particular, since it is a production method for efficiently obtaining 1,3-butadiene, the iso-butene / n-butene ratio (capacity ratio) is 0. 0.1 to 1.5, and in the case of C4 hydrocarbon, the composition ratio is 50 to 93% by volume of n-butene, 7 to 50% by volume of iso-butene, n-butane and iso- The sum of butane is preferably 0 to 30% by volume, and is preferably a C4 hydrocarbon having an iso-butene / n-butene ratio (volume ratio) of 0.1 to 1.5.

  Further, the molecular oxygen source is not particularly limited, and examples thereof include pure oxygen and air.

  And, since the simultaneous production method of 1,3-butanediene and methacrolein is excellent in its reaction efficiency, it is preferable to carry out the reaction by a gas phase method. Examples include fluidized beds. Further, the mixed gas concentration of n-butene and iso-butene (gas concentration of C4 hydrocarbon) in the raw material gas in the reaction field at the time of production by the gas phase method may be outside the explosion range, and efficiency among them 1 to 20% by volume is preferable, and 3 to 15% by volume is particularly preferable. And the concentration of molecular oxygen in the raw material gas may be outside the explosion range, and among them, it becomes an efficient method for producing 1,3-butadiene and methacrolein. It is preferable to be 3 to 20% by volume. Furthermore, if necessary, the raw material gas may be diluted by adding an inert gas such as nitrogen, water vapor or carbon dioxide.

In addition, there is no limitation on the gas hourly space velocity (GHSV) of the raw material gas when the simultaneous production method of 1,3-butanediene and methacrolein is performed by a gas phase method, and among them, particularly efficient 1,3-butadiene and since methacrolein manufacturing becomes possible, preferably a gas hourly space velocity 100～10000H ^-1, it is particularly preferably 200~5000h ^-1. There is no restriction | limiting also in the reaction pressure in that case, 0.05-1.0 Mpa is preferable especially since it becomes possible to manufacture efficiently 1,3-butadiene and methacrolein, and 0.1-0. 5 MPa is preferred. In addition, there is no restriction on the reaction temperature, and among them, efficient production of 1,3-butadiene and methacrolein is possible. It is preferable that it is 300-450 degreeC.

  By reacting n-butene and iso-butene with molecular oxygen, 1,3-butadiene and methacrolein can be produced simultaneously with high activity and high selectivity, and have a long lifetime. A catalyst for simultaneous production of rain is provided.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

  The reaction evaluation method for simultaneous production of 1,3-butadiene and methacrolein carried out in the examples is shown below.

(Quantification of reaction products)
Gas chromatograph (manufactured by Shimadzu Corporation, (trade name) GC-14A), capillary column (manufactured by GL Sciences, (trade name) TC-FFAP), capillary column (manufactured by GL Sciences, (trade name) Al ₂ O ₃ / KCl), a flame ionization detector (FID), and packed column (GL Science, (trade name) MS-5A), packed column (GL Science, (trade name) Porapak Q) The reaction product (1,3-butadiene, methacrolein, by-product) was quantified using a thermal conductivity detector (TCD).

(N-butene conversion)
The amount was calculated from the following formula (1) from the amount of 1,3-butadiene produced, the amount of by-products derived from n-butene, and the amount of unreacted n-butene.

（１，３−ブタジエン選択率）
１，３−ブタジエン生成量、ｎ−ブテン由来副生成物量から下記式（２）より算出した。

(1,3-butadiene selectivity)
It calculated from the following formula (2) from the amount of 1,3-butadiene and the amount of by-products derived from n-butene.

（１，３−ブタジエン収率）
１，３−ブタジエン生成量、ｎ−ブテン由来副生成物量、未反応ｎ−ブテン量から下記式（３）より算出した。

(1,3-butadiene yield)
The amount was calculated from the following formula (3) from the amount of 1,3-butadiene produced, the amount of by-products derived from n-butene, and the amount of unreacted n-butene.

（１，３−ブタジエンの空時収率（ＳＴＹ））
１−ブテン供給量、１，３−ブタジエン収率、触媒量から下記式（４）より算出した。

(Space-time yield of 1,3-butadiene (STY))
It calculated from the following formula (4) from 1-butene supply amount, 1,3-butadiene yield, and catalyst amount.

（ｉｓｏ−ブテン転化率）
メタクロレイン生成量、ｉｓｏ−ブテン由来副生成物量、未反応ｉｓｏ−ブテン量から下記式（５）より算出した。

(Iso-butene conversion)
It calculated from the following formula (5) from the amount of methacrolein production, the amount of by-products derived from iso-butene, and the amount of unreacted iso-butene.

（メタクロレイン選択率）
メタクロレイン生成量、ｉｓｏ−ブテン由来副生成物量から下記式（６）より算出した。

(Metachlorein selectivity)
It calculated from the following formula (6) from the amount of methacrolein production and the amount of by-product derived from iso-butene.

（メタクロレイン収率）
メタクロレイン生成量、ｉｓｏ−ブテン由来副生成物量、未反応ｉｓｏ−ブテン量から下記式（７）より算出した。

(Methacrolein yield)
The amount was calculated from the following formula (7) from the amount of methacrolein produced, the amount of by-product derived from iso-butene, and the amount of unreacted iso-butene.

実施例１
蒸留水４８ｍｌに七モリブデン酸六アンモニウム四水和物（和光純薬製）３３．９ｇを加え、８５℃に加熱し撹拌、溶解した。次に４８ｍｌの蒸留水に硝酸タリウム（和光純薬製）２．５ｇ、硝酸コバルト六水和物（和光純薬製）２５．４ｇ、硝酸鉄九水和物（和光純薬製）２３．３ｇを加え、８５℃に加熱して溶解した後、七モリブデン酸六アンモニウム水溶液に添加した。次に、蒸留水８ｍｌに比重１．３８の硝酸（和光純薬製）１ｍｌを加え、硝酸ビスマス六水和物（和光純薬製）７．７ｇを添加し溶解した溶液を準備しておき添加した。更に、蒸留水８ｍｌに硝酸セリウム六水和物（和光純薬製）０．７ｇを添加し溶解させた溶液も準備し、添加した。

Example 1
33.9 g of hexaammonium heptamolybdate tetrahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 48 ml of distilled water, heated to 85 ° C., stirred and dissolved. Next, in 48 ml of distilled water, 2.5 g of thallium nitrate (manufactured by Wako Pure Chemical), 25.4 g of cobalt nitrate hexahydrate (manufactured by Wako Pure Chemical), 23.3 g of iron nitrate nonahydrate (manufactured by Wako Pure Chemical) Was added and dissolved in an aqueous solution of hexaammonium heptamolybdate. Next, 1 ml of nitric acid with a specific gravity of 1.38 (manufactured by Wako Pure Chemical Industries) is added to 8 ml of distilled water, and 7.7 g of bismuth nitrate hexahydrate (manufactured by Wako Pure Chemical Industries) is added to prepare a dissolved solution. did. Furthermore, a solution in which 0.7 g of cerium nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added and dissolved in 8 ml of distilled water was also prepared and added.

  Then, 2.1 g of antimony trioxide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.6 g of Hyflo Supercell (manufactured by Wako Pure Chemical Industries), which is a kind of silica, were added and stirred at 85 ° C. for 5 hours to obtain a slurry.

  The obtained slurry was dried at 110 ° C. for 18 hours and then pulverized, and 0.6 g of graphite (manufactured by Wako Pure Chemical Industries, Ltd.) was added to form a cylindrical shape having a diameter of 3 mm × length of 3 mm.

  The resulting molded product was calcined at 300 ° C. for 2 hours and at 500 ° C. for 5 hours while aeration with air of 200 ml / min to obtain a catalyst for simultaneous production of 1,3-butanediene and methacrolein.

The resulting catalyst for simultaneous production of 1,3-butanediene and methacrolein was Mo ₁₂ Co _5.4 Fe _3.6 Bi _1.0 Ce _0.1 Tl _0.6 Sb _0.9 O _50.1 (c / b = 0.67, d / (b + c × 1.5) = 0.09), and the SiO ₂ is 10 wt. %.

  To the obtained catalyst for simultaneous production of 1,3-butanediene and methacrolein, 10 ml of a cylindrical magnetic Raschig ring having a diameter of 3 mm × length of 3 mm was added as a diluent and filled into a stainless steel reaction tube.

  As n-butene, 1-butene 31.2 ml / min, iso-butene 5.3 ml / min (iso-butene / n-butene (volume ratio) = 0.17), molecular oxygen 46 ml / min, nitrogen 253 ml / Min and 144 ml / min of water vapor were passed through the reaction tube and the reaction was carried out at a reaction temperature of 380 ° C. to simultaneously produce 1,3-butanediene and methacrolein. The results are shown in Table 1.

Comparative Example 1
Instead of 25.4 g of cobalt nitrate hexahydrate, 23.3 g of iron nitrate nonahydrate, and 4.6 g of Hyflo Supercell, 42.3 g of cobalt nitrate hexahydrate, 7.8 g of iron nitrate nonahydrate, A catalyst was prepared in the same manner as in Example 1 except that 4.8 g of Hyflo Supercell was used.

The obtained catalyst was Mo ₁₂ Co ₉ Fe _1.2 Bi _1.0 Ce _0.1 Tl _0.6 Sb _0.9 O _50.1 (c / b = 0.13, d / (b + c × 1. 5) = 0.09) and is made of a multi-element-based composite oxide, 10 wt of SiO _2. %.

  The obtained catalyst was used in the same manner as in Example 1, and 1,3-butanediene and methacrolein were simultaneously produced. The results are shown in Table 1.

  Since the obtained catalyst had a low c / d of 0.13, it was inferior in n-butene conversion and 1,3-butadiene yield.

Comparative Example 2
Instead of 25.4 g of cobalt nitrate hexahydrate, 23.3 g of iron nitrate nonahydrate, and 4.6 g of Hyflo Supercell, 16.9 g of cobalt nitrate hexahydrate, 31.0 g of iron nitrate nonahydrate, A catalyst was prepared in the same manner as in Example 1 except that 4.6 g of Hyflo Supercell was used.

The obtained catalyst was Mo ₁₂ Co _3.6 Fe _4.8 Bi _1.0 Ce _0.1 Tl _0.6 Sb _0.9 O _50.1 (c / b = 1.3, d / (b + c × 1.5) = 0.09) and is composed of a multi-element composite oxide, and SiO ₂ is 10 wt. %.

  The obtained catalyst was used in the same manner as in Example 1, and 1,3-butanediene and methacrolein were simultaneously produced. The results are shown in Table 1.

  Since the obtained catalyst had a high c / d of 1.3, it was inferior to the n-butene conversion, 1,3-butadiene yield, and methacrolein yield.

Example 2
2.5 g of thallium nitrate, 25.4 g of cobalt nitrate hexahydrate, 23.3 g of iron nitrate nonahydrate, 7.7 g of bismuth nitrate hexahydrate, 0.7 g of cerium nitrate hexahydrate, antimony trioxide 2 .1 g, instead of Hyflo Supercell 4.6 g, thallium nitrate 1.3 g, cobalt nitrate hexahydrate 26.7 g, iron nitrate nonahydrate 24.5 g, bismuth nitrate hexahydrate 4.1 g, nitric acid A catalyst for simultaneous production of 1,3-butanediene and methacrolein was obtained in the same manner as in Example 1 except that 0.4 g of cerium hexahydrate, 1.1 g of antimony trioxide, and 4.3 g of Hyflo supercell were used. .

The resulting catalyst for simultaneous production of 1,3-butanediene and methacrolein was Mo ₁₂ Co _5.7 Fe _3.8 Bi _0.5 Ce _0.1 Tl _0.3 Sb _0.5 O _49.1 (c / b = 0.67 and d / (b + c × 1.5) = 0.04), and the SiO ₂ is 10 wt. %.

  The obtained catalyst was used in the same manner as in Example 1, and 1,3-butanediene and methacrolein were simultaneously produced. The results are shown in Table 1. Even after 1000 hours of production, the catalyst was confirmed to be a long-life catalyst having high activity and high selectivity.

Comparative Example 3
2.5 g of thallium nitrate, 25.4 g of cobalt nitrate hexahydrate, 23.3 g of iron nitrate nonahydrate, 7.7 g of bismuth nitrate hexahydrate, 0.7 g of cerium nitrate hexahydrate, antimony trioxide 2 .1 g, instead of Hyflo Supercell 4.6 g, thallium nitrate 1.3 g, cobalt nitrate hexahydrate 44.6 g, iron nitrate nonahydrate 8.1 g, bismuth nitrate hexahydrate 4.1 g, nitric acid A catalyst was prepared in the same manner as in Example 1 except that 0.4 g of cerium hexahydrate, 1.1 g of antimony trioxide, and 4.4 g of Hyflo supercell were used.

The obtained catalyst was Mo ₁₂ Co _9.5 Fe _1.3 Bi _0.5 Ce _0.1 Tl _0.3 Sb _0.5 O _49.4 (c / b = 0.14, d / (b + c × 1.5) = 0.04) and is made of a multi-element-based composite oxide, 10 wt of SiO _2. %.

  The obtained catalyst was used in the same manner as in Example 1, and 1,3-butanediene and methacrolein were simultaneously produced. The results are shown in Table 1.

  Since the obtained catalyst had a high c / d of 1.4, the yield of 1,3-butadiene was inferior.

  The catalyst for simultaneous production of 1,3-butadiene and methacrolein of the present invention is a raw material for synthetic rubber having high activity, high selectivity and high efficiency by reacting n-butene and iso-butene with molecular oxygen. Industrially useful 1,3-butadiene and methacrylic acid, methyl methacrylate (MMA) and industrially useful methacrolein as a raw material for MMA resin can be produced simultaneously, and its industrial applicability is extremely high It is.

Claims (8)

In general formula _{Mo 12 Co b Fe c Bi d} Ce e Tl f Sb g O j ( where, b = 3~15, c = 0.4~5 , d = 0.01~3, e = 0.01~ 2, f = 0.01-2, g = 0.01-3, j = 40-79, and c / b = 0.3-1.2). A catalyst for simultaneous production of 1,3-butanediene and methacrolein. The simultaneous production of 1,3-butanediene and methacrolein according to claim 1, wherein elemental contents of cobalt, iron and bismuth are in a relationship of d / (b + c x 1.5) = 0.01-1. Catalyst. In general formula _{Mo 12 Co b Fe c Bi d} Ce e Tl f Sb g O j ( where, b = 3~15, c = 0.4~5 , d = 0.01~3, e = 0.01~ 2, f = 0.01-2, g = 0.01-3, j = 40-79, and c / b = 0.3-1.2). A catalyst for simultaneous production of 1,3-butanediene and methacrolein, which is supported on at least one inert carrier selected from the group consisting of alumina, silica alumina and silicon carbide . In general formula _{Mo 12 Co b Fe c Bi d} Ce e Tl f Sb g O j ( where, b = 3~15, c = 0.4~5 , d = 0.01~3, e = 0.01~ 2, f = 0.01-2, g = 0.01-3, j = 40-79, and c / b = 0.3-1.2). A catalyst for simultaneous production of 1,3-butanediene and methacrolein, which is diluted with at least one inert carrier selected from the group consisting of alumina, silica alumina, and silicon carbide . 5. 1,3-butanediene and methacrolein according to any one of claims 1 to 4, wherein n-butene, iso-butene and molecular oxygen are reacted in the presence of the catalyst for simultaneous production of 1,3-butanediene and methacrolein. A method for simultaneously producing butadiene and methacrolein. 6. The method for simultaneously producing 1,3-butadiene and methacrolein according to claim 5, wherein the reaction is carried out as a C4 hydrocarbon containing n-butene and iso-butene. The method for simultaneously producing 1,3-butadiene and methacrolein according to claim 6, wherein the iso-butene concentration in the C4 hydrocarbon is 7 to 50% by volume. It reacts in the range of iso-butene / n-butene ratio (volume ratio) = 0.1-1.5, The 1,3-butadiene and methacrolein of any one of Claims 5-7 characterized by the above-mentioned. Simultaneous manufacturing method.