JP2003245556A - Catalyst for reacting hydrocarbon and reaction method using this - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst capable of manufacturing an oxygen-containing product having a high added value as an industrial material and olefins from alkanes as raw materials, and a manufacturing method. <P>SOLUTION: The catalyst is obtained by bonding a tellurium compound and an antimony compound to a molybdenum - cobalt composite oxide and a molybdenum - nickel composite oxide. In the method for manufacturing an oxygen-containing compound such as acrolein and acrylic acid and the method for dehydrating the alkanes, the alkanes are subjected to a partial oxidation reaction using this catalyst. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention is used for partial oxidation of hydrocarbons and dehydration of saturated hydrocarbons, and particularly for production of oxygen-containing compounds such as methacrylic acid, acrolein and methacrolein by partial oxidation of alkanes. The present invention relates to a hydrocarbon reaction catalyst and a reaction method using the same.

[0002]

2. Description of the Related Art Conventionally, olefins have been widely used as industrial raw materials, but since alkanes are significantly less reactive than olefins, they are used as fuels. Was the center. By using alkanes as industrial raw materials, the cost of industrial raw materials can be reduced, the demand and supply of industrial raw materials can be easily adjusted, and advantages such as saving fossil resources can be obtained. The development of a process that uses as a basic raw material is under study. In particular, conventionally, oxygen-containing compounds such as acrylic acid, methacrylic acid, acrolein, and methacrolein have been produced from olefins as raw materials. However, the raw materials for oxygen-containing compounds are actively converted from olefins to alkanes. Is being considered.

Conventionally, the partial oxidation reaction of alkanes is more difficult as the carbon number of alkanes is smaller. For example, the partial oxidation reaction of propane for producing acrylic acid has a yield of acrylic acid of 10%. It was a difficult reaction called the limit. In recent years, a catalyst capable of producing acrylic acid with a yield of about 50% has been proposed (JP-A-10-5).
No. 7813), when this catalyst is used, a side reaction which produces acetic acid, carbon monoxide, and carbon dioxide is likely to occur, and there is a problem in selectivity for industrial implementation. Further, a catalyst having improved selectivity has been proposed by paying attention to the above points (Japanese Patent Application Laid-Open No. 10-120617), but it has not yet reached the industrially required selectivity. Therefore, a catalyst with high selectivity and high activity, which is suitable for industrial implementation,
Still required today. Further, this catalyst is also required to be easily prepared and excellent in reproducibility and stability.

Further, the selective partial oxidation of alkanes requires much larger activation energy than the oxidation of olefins, and almost no reaction is possible with conventional olefin oxidation catalysts. Further, alkanes are activated at a high temperature of 500 ° C. or higher, but complete oxidation of the product is extremely likely to occur, resulting in a low selectivity of olefins. Therefore, in order to selectively convert alkanes into useful partial oxidation products, a catalyst that can activate alkanes at a relatively low temperature of about 300 to 450 ° C., which is easy to prepare and has extremely high stability. It was necessary to develop a catalyst. It is desirable that this catalyst works at low steam concentration and high propane concentration. Further, industrially, if a catalyst that can handle both propane and propylene can be developed, it is possible to secure the operation stability by diversifying the raw materials.

By the way, among molybdates, cobalt salts and nickel salts are compounds showing high oxidative dehydrogenation activity for alkanes, but their partial oxidation selectivity is low, and cracking and complete oxidation tend to be strong. . On the other hand, it is known that transition metal elements such as tellurium and antimony are blended with a partial oxidation catalyst of propylene (bismuth-molybdenum composite oxide) and the like and have the ability to assist the allyl oxidation of olefins. An element such as antimony alone has a poor ability to activate alkanes regardless of the type of compound such as metal, metal oxide, or heteropoly acid, and industrially satisfactory results have not been obtained.

[0006]

An object of the present invention is to provide a catalyst capable of producing an oxygen-containing chemical product or olefin having a high added value as an industrial raw material using alkanes as a raw material.

[0007]

As a result of intensive studies on the above problems, the present inventors have found that a catalyst in which a tellurium compound or an antimony compound is bonded to a molybdenum-cobalt composite oxide or a molybdenum-nickel composite oxide is used. It has been found that the object of the present invention is met. That is, Anderson type heteropolyacids having a planar structure, oxo acids such as telluric acid, and oxides such as tellurium oxide and antimony oxide are particularly effective as precursors of transition metal compounds such as tellurium compounds and antimony compounds. As a carrier, it was found that molybdenum-cobalt composite oxide or molybdenum-nickel composite oxide is effective. When a catalyst supported on such a molybdenum-cobalt composite oxide or a molybdenum-nickel composite oxide is used, the alkanes are selectively partially oxidized to be converted into various oxygen-containing compounds or saturated hydrocarbons. It has been found that it can be used for dehydrogenation reaction and various oxygen-containing compounds such as acetaldehyde, acrolein and acrylic acid can be obtained from alkanes and olefins. The present invention has been completed based on such findings.

That is, the present invention provides the following hydrocarbon reaction catalyst and a reaction method using the same. 1. A catalyst for a hydrocarbon reaction, comprising at least one selected from a tellurium compound and an antimony compound bound to a molybdenum-cobalt composite oxide and / or a molybdenum-nickel composite oxide. 2. The catalyst for hydrocarbon reaction according to 1 above, wherein the tellurium compound is at least one compound selected from Anderson heteropoly acid or telluric acid, an organic salt thereof and tellurium oxide. 3. The catalyst for hydrocarbon reaction according to 1 or 2 above, wherein the antimony compound is at least one compound selected from antimony oxide, antimony organic acid salt, antimony inorganic acid salt and antimonylammonium complex salt. 4. A method for reacting a hydrocarbon, which comprises reacting a hydrocarbon using the catalyst according to any one of 1 to 3 above. 5. 5. The hydrocarbon reaction method according to the above 4, wherein the reaction of the hydrocarbon is a partial oxidation reaction of the hydrocarbon. 6. 6. The method for reacting a hydrocarbon as described in 5 above, wherein the hydrocarbon is an alkane and / or an olefin. 7. 7. The method for reacting a hydrocarbon according to 6 above, wherein the hydrocarbon is propane and / or propylene, and the reaction product is acetaldehyde, acrolein, and one or more oxygen-containing compounds selected from acrylic acid. 8. 5. The hydrocarbon reaction method according to the above 4, wherein the reaction of hydrocarbon is a dehydrogenation reaction of saturated hydrocarbon in the absence of oxygen.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The hydrocarbon reaction catalyst of the present invention comprises:
A tellurium compound or an antimony compound is bonded to a composite oxide containing molybdenum-cobalt or molybdenum-nickel as a main element. The tellurium compound used for the catalyst includes Anderson type heteropoly acid or telluric acid and its organic salt and tellurium oxide. Anderson-type heteropolyacid has a central atom of Fe, Co, Ni, R
It is a transition metal atom such as h, Pt, Te, or Al and has a structure in which the poly atom is Mo or W. Specifically, H ₆ TeMo ₆ O ₂₄ , H ₉ CoMo ₆ O _24, etc. Is mentioned. In addition, these acids are partially or completely ammonium ion, alkali metal, alkaline earth metal,
A salt substituted with a cation such as a transition metal or various amines can also be used. The salt of the heteropoly acid may be a hydrate. In the present invention, the one in which the central atom is Te is used, and (NH ₄ ) ₆ TeMo ₆ O ₂₄ , (N
_{H 4) 6 TeMo 6 O 24} · 7H 2 O are particularly preferred. Further, the counter cation (NH ₄ group) may be exchanged with a proton or an organic base cation such as tetrabutylammonium or cetyltrimethylammonium. Regarding the oxo acid telluric acid (H ₆ TeO ₆ ),
Use a salt obtained by partially or completely substituting an acid with a cation such as ammonium ion, alkali metal, alkaline earth metal, transition metal, or various amines, for example, ammonium tellurate [(NH ₄ ) ₆ TeO ₆ ]. You can also The salt may be a hydrate.

Among the antimony compounds, antimony oxides include diantimony trioxide, diantimony tetroxide,
Examples of the antimony organic acid salt include antimony acetate, antimony tartrate, and the like, antimony inorganic acid salts such as antimony sulfate, and antimonylammonium complex salts such as antimonylammonium oxalate [(NH ₄ ). ₃ [Sb (C ₂ O ₄ ) ₃ ]], antimonylammonium tartrate [(NH ₄ ) ₂ Sb ₂ (C ₄
H ₂ O ₆ ) ₂ ] and the like.

A molybdenum-cobalt composite oxide or a molybdenum-nickel composite oxide is used as a carrier for supporting the above-mentioned heteropolyacids or oxoacids. Examples of such complex metal oxides include stoichiometric compounds (CoMoO ₄ , NiMoO ₄ ) and various Co / Mo.
Ratio, Ni / Mo ratio compound, mixture or supported catalyst can be mentioned, and those having a composition with a slight excess of Mo (for example, Co _0.92 MoO _3.92 , Ni _0.92 MoO _3.92 ) are preferable. Further, as auxiliary components, V, Nb, Sb, P, Bi,
Ta, Cu, Cr, Fe, Co or Pt, Pd, R
A noble metal such as e and an alkali metal such as Na, K, Cs, or a heteropolyacid such as 12 molybdonic acid may be added.

Heteropoly acids and salts thereof are molybdenum-containing
The supporting on the cobalt composite oxide or the molybdenum-nickel composite oxide can be carried out by an ordinary impregnation method. Alternatively, the catalyst can be prepared by ion exchange or sputtering. The catalyst of the present invention may be a composite oxide obtained by subjecting these to raw materials and subjected to operations such as heat treatment and hydrothermal synthesis, and a catalyst in which silica, alumina or the like is dispersed and supported on the catalyst itself of the present invention as an active site. Is also included. By using such a catalyst, it is possible to obtain a desired oxygen-containing compound or olefin with high selectivity, which is stable even at high temperature. From the viewpoint of optimizing the interaction with the carrier, the supported amount of the heteropolyacid or its salt on the molybdenum-cobalt composite oxide or the molybdenum-nickel composite oxide is preferably 0.5 to 30% by weight. , 5 to 20% by weight is particularly preferable.

By using the catalyst of the present invention, it is possible to carry out a partial oxidation reaction of saturated hydrocarbons, dehydrogenation and partial oxidation of alkanes and other substrates in the absence of oxygen, and production of oxygen-containing chemical products. Further, although it can be used for partial oxidation of olefin or oxidation of mixed raw material of alkane / olefin, it is particularly preferably used for partial oxidation of propane or propylene, and an oxygen-containing compound can be produced. Here, the oxygen-containing compound means, for example, acetic acid, acetaldehyde, acrolein, acrylic acid when propane is used as a substrate, and acetic acid, acrylic acid, acetaldehyde, methacrylic acid, methacrolein (butane is used when butane is used as a substrate). Especially when the substrate is isobutane)
Etc.

The catalyst of the present invention usually functions in the coexistence of oxygen molecules and alkane molecules, but the alkanes are reacted with the catalyst under the condition that oxygen is absent or an extremely low concentration of oxygen is present. After that, the catalyst can be brought into contact with a gas containing oxygen at an arbitrary concentration to perform non-aerobic oxidation in which the catalyst is regenerated. Further, in this reaction, formation of an oxygen-containing compound by partial cleavage of carbon-carbon bond may proceed as a side reaction. Further, not only oxygen but also a substrate such as ammonia can coexist to promote a reaction such as ammoxidation.

Various oxygen-containing compounds and olefins can be produced from alkanes using the catalyst of the present invention under various conditions, but the reaction temperature is from 200 ° C to 60 ° C.
0 ° C., preferably about 300 ° C. to 500 ° C. is desirable.
The reaction is usually carried out under atmospheric pressure, but may be under slight pressure or under reduced pressure. Further, as a diluting gas for adjusting the space velocity and the oxygen partial pressure, nitrogen, argon, helium,
An inert gas such as carbon dioxide or water vapor can be used. As the reaction system, either a fixed bed or a fluidized bed can be adopted.

Among molybdates, cobalt salts and nickel salts are compounds showing high oxidative dehydrogenation activity for alkanes, but their partial oxidation selectivity is low and they tend to be strongly cracked or completely oxidized. On the other hand, tellurium is mixed with a partial oxidation catalyst of propylene (Bi-Mo composite oxide) and the like, and is known to have an auxiliary ability for allylic oxidation of olefins, but alone, metal tellurium and its oxide, Tellurium
Regardless of the type of compound such as heteropoly acid, the activation ability of alkane is poor. The inventor believes that by supporting a tellurium compound very thinly on a molybdate having a high ability to activate alkanes, the shortcomings of the two are compensated for, and the alkane intermediate activated by the molybdate is replaced by a tellurium compound. Attempts were made to prepare a catalyst for the partial oxidation. The problem here is the distance between the active sites of nickel molybdate and tellurium, and in order to facilitate the transfer of the intermediate, the two are as close as possible, ideally they are integrated as a compound. Is desirable. To this end, we have developed a tellurium compound that uniformly adsorbs on the surface of nickel molybdate, which is a carrier, and forms an ideal active site. Since it is different, we thought it necessary to examine the composition and preparation method.

As a result of extensive studies based on the above policy, the present invention shows that telluromolybdic acid, which is an Anderson type heteropolyacid having a planar structure, is effective as a precursor of tellurium compounds, and that the carrier has a stoichiometric ratio. A little more M
It has been found that Mo-Ni composite oxide having an excessive composition is effective, and addition of a small amount of vanadium or the like is preferable. These catalysts function with various raw material compositions, contact times and reaction temperatures, and are capable of producing acrylic acid from propane even under high propane concentration and low steam concentration conditions. Also,
It has been confirmed that the oxidation to acrolein and acrylic acid selectively proceeds even when propylene is used as a raw material on such a telluromolybdic acid / nickel molybdate catalyst, which makes it industrially applicable to a propane / propylene mixed raw material. I know that I can handle it.

In many cases, the activity of the composite oxide catalyst containing tellurium tends to decrease over time due to volatilization, but this has not been particularly confirmed in the catalyst of the present invention. Further, the composite oxide catalyst in which tellurium is replaced by antimony can maintain stable activity even under non-aerobic conditions such as a fluidized bed. As a method for preparing the antimony / nickel molybdate catalyst, an oxide kneading method can be used, whereby a large amount of the catalyst can be prepared rapidly. It has been confirmed that this catalyst system can improve the reactivity by adding a small amount of 12 molybdophosphoric acid and adjusting the solution reaction time.

[0019]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 (Catalyst composition: 6 wt% (NH_Four)₆TeMo₆O_{twenty four}
・ 7H₂O / Ni_0.92MoO_3.92) (Catalyst preparation) Nickel nitrate hexahydrate [Ni (NO₃)₂・ 6H₂O]
Add 40.000g to a 500ml beaker and add distilled water
275 g was added and heated to 80 ° C. with stirring to dissolve (A-
1). Ammonium paramolybdate tetrahydrate [(NH_Four)₆M
o₇O_{twenty four}・ 4H₂O] 26.494 g in a 100 ml beaker
, Add 43 g of distilled water, heat to 80 ° C and stir to dissolve
I understood (B-1). Ammonium hydrogen carbonate [NH_FourHCO₃] 7.5
Place 4g in a 100ml beaker and add 55.6g of distilled water.
The solution was stirred and dissolved (C-1). Stir the solution (A-1) at 80 ℃.
Solution (B-1) was added dropwise with stirring, and then the pH of this solution
Solution (C-1) is slowly added dropwise until the value reaches 5, then 80
It was evaporated to dryness with stirring at ° C. At this time, add (C-1) solution as appropriate.
The pH was maintained at 5 by dropping. Place the solid in an alumina crucible.
Put it in the oven and dry it in an oven at 120 ° C for 24 hours, then agate mortar
Crushed with Ni_0.92MoO_3.92-Containing catalyst carrier precursor (D-1)
Got Ammonium paramolybdate 80.156g
In a 500 ml SPC eggplant flask and add distilled water 162
g was added, and the solution was immersed in an ultrasonic cleaner to dissolve it (E-1). Tell
Acid [H₆TeO₆] Put 17.376g into a 100ml beaker
81 g of distilled water was added and stirred to dissolve (F-1). (E-1) liquid
The solution (F-1) was added dropwise with stirring to obtain the homogeneous solution.
The solution was depressurized at 30 ° C using a rotary evaporator.
And concentrated until crystals were precipitated. Suction filtration of the concentrate
After washing the residue with a small amount of cold water, insert it in filter paper and
Dried overnight in a loft, ammonium telluromolybdate
White crystals of [(NH _Four)₆Mo₆TeO_{twenty four} ・ 7H₂O] 69.5 g was obtained
(G-1). The elemental analysis results of this substance are Te: 9.5wt%, Mo: 43.
5wt%, Ni: 6.1wt%, H₂O: It was 9.7 wt%. Carrier precursor (D
-1) 5.00 g and carrier (G-1) 0.2272 g to 200
Transfer to a 1 ml SPC flask and add 50 g of distilled water at room temperature.
Then, it was put on an ultrasonic cleaner to obtain a green suspension. Rotary
-Evaporated to dryness at 37 ° C by an evaporator. Obtained
Put the solids into an alumina crucible and use a muffle furnace.
Firing was performed at 500 ° C. for 2 hours under air circulation. Firing
Immediately after, remove the crucible from the muffle furnace, cool it, and
After crushing in an agate mortar, it is molded into 16-36 mesh to make a catalyst
It was (Reaction method) 1 g of catalyst was charged into a reaction tube, and 50 ml of nitrogen was added.
The temperature is raised to 300 ° C while circulating / min.
Is propane 6 ml / min, oxygen 4 ml / min, nitrogen 20 ml
/ Min, and steam mixed gas of 20 ml / min
The reaction temperature to 350 ° C and turn on 1 hour later.
Analyze the reactants with a line gas chromatograph
It was After that, the temperature is raised to 380 ° C and then temporarily to 450 ° C.
The reaction product at each temperature is increased stepwise by 10 ° C.
Was analyzed. The results are shown in Table 1.

Example 2 (Catalyst composition: 9 wt% (NH ₄ ) ₆ TeMo ₆ O ₂₄
7H ₂ O / Ni _0.92 MoO _3.92 ) Carrier precursor (D-1) 5.0 prepared in the same manner as in Example 1
A catalyst was prepared from 00 g and 0.3520 g of the supported material (G-1) by the same operation as in Example 1. Using this catalyst, the same reaction as in Example 1 was performed and the same analysis was performed. The results are shown in Table 1.

Example 3 (Catalyst composition: 9 wt% (NH ₄ ) ₆ TeMo ₆ O ₂₄
7H ₂ O / Ni _0.38 MoO _3.38 ) Example 1 except that the solution (C-1) was not completely evaporated to dryness after dropping the solution (C-1) in Example 1, and suction filtration was performed at the stage of concentrating the liquid amount to about 100 ml. The same operation was performed. The paste obtained by suction filtration was washed 3 times with 50 ml of cold water and then air dried overnight. Next, the obtained solid substance was put into an alumina crucible, dried in an oven adjusted to 120 ° C. for 24 hours, and pulverized in an agate mortar to obtain a catalyst carrier precursor (D-4). Supported material (G-1) prepared in the same manner as in Example 1.
A catalyst was prepared from 1915 g and 3.000 g of the carrier precursor (D-4) by the same operation as in Example 1. Using this catalyst, the same reaction as in Example 1 was performed and the same analysis was performed. The results are shown in Table 1. In addition, as a result of analyzing this catalyst, N
The i / Mo molar ratio is 0.38 and the surface area is 17.0 m ² /
g, the pore volume was 3.9 ml / g.

Comparative Example 1 (Catalyst composition: Ni _0.92 Mo
O _3.92 ) [(NH ₄ ) ₆ TeMo ₆ O _{24 was} added to the carrier precursor (D-1) in Example 1.
A catalyst was prepared in the same manner as in Example 1 except that [7H ₂ O] (G-1) was not impregnated and supported. Using this catalyst, the same reaction as in Example 1 was performed and the same analysis was performed. The results are shown in Table 1.

Example 4 (Catalyst composition: 6 wt% (NH ₄ ) ₆ TeMo ₆ O ₂₄
7H ₂ O / Ni _0.92 MoO _3.92 ) 1 g of the catalyst obtained in Example 1 was charged into a reaction tube and nitrogen was added to 50
While circulating ml / min, raise the temperature to 300 ° C
From propane 1 ml / min, oxygen 4 ml / min, nitrogen 25
The temperature was raised to 420 ° C. while flowing a mixed gas of ml / min and steam of 20 ml / min, and after 2 hours, the reaction product was analyzed by an online gas chromatograph. After that, the propane flow rate was changed to 2 ml / min and the nitrogen flow rate was changed to 24 ml / min, the reaction was performed for 2 hours, and then the reaction product was analyzed. Similarly, the reaction product was analyzed under the conditions that the propane flow rate was 4 ml / min, the nitrogen flow rate was 22 ml / min, and the propane flow rate was 9.7 ml / min and the nitrogen flow rate was 16.3 ml / min. The results are shown in Table 2.

Example 5 (Catalyst composition: 9 wt% (NH ₄ ) ₆ TeMo ₆ O ₂₄
7H ₂ O / Ni _0.38 MoO _3.38 ) The reaction was performed in the same manner as in Example 4 except that the catalyst obtained in Example 3 was used, and the same analysis was performed. The results are shown in Table 2.

Comparative Example 2 (Catalyst composition: Ni _0.92 Mo
O _3.92 ) The reaction was performed in the same manner as in Example 4 except that the catalyst obtained in Comparative Example 1 was used, and the same analysis was performed. The results are shown in Table 2.

Example 6 (Catalyst composition: 6 wt% (NH ₄ ) ₆ TeMo ₆ O ₂₄
7H ₂ O / Ni _0.92 MoO _3.92 ) 1 g of the catalyst obtained in Example 1 was charged into a reaction tube and nitrogen was added to 50
While circulating ml / min, raise the temperature to 300 ° C
From propane 6 ml / min, oxygen 4 ml / min, nitrogen 40
While flowing a mixed gas of ml / min, raise the temperature to 420 ° C,
After 2 hours, the reaction product was analyzed by online gas chromatography. After that, the steam flow rate was changed to 5 ml / min and the nitrogen flow rate was changed to 35 ml / min, the reaction was performed for 2 hours, and then the reaction product was analyzed. Similarly, steam flow rate 10 ml / min, nitrogen flow rate 30 ml / min, steam flow rate 30 ml / min, nitrogen flow rate 1
The reaction was analyzed by changing the conditions to 0 ml / min. The results are shown in Table 2.

Example 7 (Catalyst composition: 9 wt% (NH ₄ ) ₆ TeMo ₆ O ₂₄
7H ₂ O / Ni _0.38 MoO _3.38 ) The reaction was performed in the same manner as in Example 6 except that the catalyst obtained in Example 3 was used, and the same analysis was performed. The results are shown in Table 2.

Comparative Example 3 (Catalyst composition: Ni _0.92 Mo
O _3.92 ) The reaction was performed in the same manner as in Example 6 except that the catalyst obtained in Comparative Example 1 was used, and the same analysis was performed. The results are shown in Table 2.

Example 8 (Catalyst composition: 6 wt% (NH ₄ ) ₆ TeMo ₆ O ₂₄
- using the resulting catalyst _{7H 2 O / Ni 0.92 MoO 3.92} ) Example 1 was reacted in the following manner. That is, 1 g of catalyst was charged in a reaction tube and 50
While circulating ml / min, raise the temperature to 300 ° C
Is heated to 420 ° C while flowing a mixed gas of 6 ml / min of propane, 9.5 ml / min of oxygen, 14.5 ml / min of nitrogen, and 20 ml / min of steam, and after 2 hours, analyze the reaction products by online gas chromatography. did. Then, the oxygen flow rate was changed to 8 ml / min and the nitrogen flow rate was changed to 16 ml / min, the reaction was performed for 2 hours, and then the reaction product was analyzed. Similarly, oxygen flow rate 6 ml / min, nitrogen flow rate 18 ml / min, and oxygen flow rate 3
The reaction product was analyzed under the conditions of ml / min and nitrogen flow rate of 21 ml / min. The results are shown in Table 2.

Example 9 (Catalyst composition: 9 wt% (NH ₄ ) ₆ TeMo ₆ O ₂₄
7H ₂ O / Ni _0.38 MoO _3.38 ) The reaction was performed and analyzed in the same manner as in Example 8 except that the catalyst obtained in Example 3 was used. The results are shown in Table 2.

Comparative Example 4 (Catalyst composition: Ni _0.92 Mo
O _3.92 ) The reaction was performed in the same manner as in Example 8 except that the catalyst obtained in Comparative Example 1 was used, and the same analysis was performed. The results are shown in Table 2.

Example 10 (Catalyst composition: 6 wt% (NH ₄ ) ₆ TeMo ₆ O
_{24 · 7H 2 O / Ni 0.92} MoO 3.92) was heated catalyst 0.5g obtained in Example 1 to 300 ° C. while flowing nitrogen 50ml / min was filled into a reaction tube, 30
From 0 ° C, propane 20ml / min, oxygen 13.3ml /
Min, nitrogen 66.7 ml / min and steam 66.7 ml / min while flowing a mixed gas, the temperature was raised to 420 ° C., and after 2 hours, the reaction product was analyzed by an online gas chromatograph.
Then, the flow rate of propane is 10 m without changing the partial pressure of the mixed gas.
1 / min, oxygen 6.7 ml / min, nitrogen 33.3 ml / min,
After changing the steam to 33.3 ml / min and performing the reaction for 2 hours, the reaction product was analyzed. Similarly, propane 6 ml / min, oxygen 4 ml / min, nitrogen 20 ml / min, steam 20 ml / min
Min, propane 4 ml / min, oxygen 2.7 ml / min, nitrogen 13.3 ml / min, steam 13.3 ml / min, and the reaction products were analyzed. The results are shown in Table 3.

Example 11 (Catalyst composition: 6 wt% (NH ₄ ) ₆ TeMo ₆ O
_{24 · 7H 2 O / Ni 0.92} MoO 3.92) filled with a catalyst 2g obtained in Example 1 in a reaction tube of nitrogen 50
While circulating ml / min, raise the temperature to 300 ° C
Propane 8 ml / min, oxygen 5.3 ml / min, nitrogen 26.7 ml / min, steam 26.7 ml / min while flowing to 420 ° C., and after 2 hours online gas chromatograph Was analyzed. afterwards,
After changing the flow rate to 6 ml / min of propane, 4 ml / min of oxygen, 20 ml / min of nitrogen, and 20 ml / min of steam without changing the partial pressure of the mixed gas, the reaction was conducted for 2 hours, and then the reaction product was analyzed. Similarly, propane 4 ml / min, oxygen 2.7 ml / min, nitrogen 1
3.3 ml / min, steam 13.3 ml / min, and propane 3 ml / min, oxygen 2 ml / min, nitrogen 10 ml / min,
The reaction product was analyzed under the changed conditions of steam of 10 ml / min.
The results are shown in Table 3.

Example 12 (Catalyst composition: 9 wt% (NH ₄ ) ₆ TeMo ₆ O
Except for using the catalyst obtained in _{24 · 7H 2 O / Ni 0.38} MoO 3.38) Example 3 performs the same reaction as Example 10, were analyzed in the same manner. The results are shown in Table 3.

Example 13 (Catalyst composition: 9 wt% (NH ₄ ) ₆ TeMo ₆ O
Except for using the catalyst obtained in _{24 · 7H 2 O / Ni 0.38} MoO 3.38) Example 3 performs the same reaction as Example 11, were analyzed in the same manner. The results are shown in Table 3.

Comparative Example 5 (Catalyst composition: Ni _0.92 Mo
O _3.92 ) The reaction was performed in the same manner as in Example 10 except that the catalyst obtained in Comparative Example 1 was used, and the same analysis was performed. The results are shown in Table 3.

Comparative Example 6 (Catalyst composition: Ni _0.92 Mo
O _3.92 ) The catalyst obtained in Comparative Example 1 (catalyst composition: Ni _0.92 MoO
_The reaction was carried out in the same manner as in Example 11 except that _3.92 ) was used, and the same analysis was performed. The results are shown in Table 3.

Example 14 (Catalyst composition: 6 wt% (NH ₄ ) ₆ Mo ₆ TeO
The _{24 · 7H 2 O / V 0.017} Ni 0.92 MoO 3.96) ( Catalyst Preparation) Nickel nitrate 39.87g beaker of 1L, distilled water 274g were added and dissolved by heating with stirring to 80 ° C. on a hot plate stirrer ( A-20).
26.41 g of ammonium paramolybdate and 0.29 g of ammonium vanadate [NH ₄ VO ₃ ] were placed in a 100 ml beaker, 75 g of water was added, and the mixture was heated and stirred at 60 ° C. on a hot plate stirrer to be dissolved (B-20). Example 1
An ammonium hydrogen carbonate solution (C-1) was prepared in the same manner as in.
After stirring solution (A-20) and adding solution (B-20), (C-
1) The liquid was slowly dropped to adjust the pH to 5, and the mixture was evaporated to dryness with stirring at a liquid temperature of 80 ° C. At this time, pH (5) was maintained by appropriately adding the liquid (C-1). Thereafter, the catalyst carrier precursor containing V _0.017 Ni _0.92 MoO _3.96 was dried and pulverized in the same manner as in Example 1 (D-2
I got 0). 5.000 g of the carrier precursor (D-20) and the carrier [(NH ₄ ) ₆ Mo ₆ TeO ₂₄ · 7H ₂ ] (G-1) 0.2 prepared in Example 1.
1 g was placed in a 200 ml SPC flask, 50 g of distilled water was added at room temperature, and the mixture was ultrasonically washed to give a green suspension. Thereafter, in the same manner as in Example 1, a catalyst was obtained by evaporating to dryness with a rotary evaporator, calcining, pulverizing and molding. (Reaction method) 1 g of catalyst was charged into a reaction tube, and 50 ml of nitrogen was added.
The temperature rises to 300 ° C while circulating / min, and from 300 ° C propane 6 ml / min, oxygen 4 ml / min, nitrogen 20 ml.
/ Min and steam 20 ml / min while flowing a mixed gas, the reaction temperature is raised stepwise to 399 ° C and 420 ° C every 3 hours, and the reaction product is analyzed by an online gas chromatograph at each reaction temperature. It was The results are shown in Table 4.

Example 15 (Catalyst composition: 9 wt% (NH ₄ ) ₆ Mo ₆ TeO
_{24 · 7H 2 O / V 0.017} Ni 0.92 MoO 3.96) support precursor was prepared in the same manner as in Example 14 (D-20)
A catalyst was prepared from 5.000 g and the supported material (G-1) 0.289 g by the same operation as in Example 1, and the reaction temperature was set to 400 ° C. and 421 ° C. using this catalyst. The same reaction was performed and the same analysis was performed. The fourth result
Shown in the table.

Comparative Example 7 (Catalyst composition: 6 wt% (NH ₄ ) ₆ Mo ₆ TeO ₂₄
・ 7H ₂ O / V _0.008 Ni _0.92 MoO _3.94 ) Put 40.028 g of nickel nitrate in a 1 L beaker,
Distilled water (275 g) was added, and the mixture was heated and stirred at 80 ° C. on a hot plate stirrer to dissolve (A-22). 26.51 g of ammonium paramolybdate and 0.13 g of ammonium vanadate [NH ₄ VO ₃ ] are placed in a 100 ml beaker, 75 g of water is added, and the temperature is 60 ° C. on a hot plate stirrer.
It was heated and stirred to dissolve it (B-22). An ammonium hydrogen carbonate solution (C-1) was prepared in the same manner as in Example 1. The solution (A-22) was added dropwise with stirring the solution (B-22), and then the solution (C-1) was slowly added dropwise to adjust the pH to 5, and the solution was evaporated to dryness with stirring at a solution temperature of 80 ° C. At this time, the solution (C-1) was appropriately added dropwise to maintain pH 5. After that, it was dried and pulverized in the same manner as in Example 1 to obtain V _0.008.
A catalyst carrier precursor (D-22) containing Ni _0.92 MoO _3.94 was obtained. 20.50 g of the carrier precursor (D-22) and 0.19 g of the carrier [(NH ₄ ) ₆ Mo ₆ TeO ₂₄ · 7H ₂ O] (G-1) prepared in Example 1 were used.
Into a 0 ml SPC flask, 50 g of distilled water was added at room temperature, and the mixture was ultrasonically washed to give a green suspension. Less than,
As in Example 1, a catalyst was obtained by evaporating to dryness using a rotary evaporator, calcining, pulverizing and molding. Using this catalyst, the same reaction as in Example 14 was carried out except that the reaction temperatures were changed to 399 ° C. and 420 ° C., and the same analysis was carried out. The results are shown in Table 4.

Comparative Example 8 (Catalyst composition: 9 wt% (NH ₄ ) ₆ Mo ₆ TeO ₂₄
7H ₂ O / V _0.008 Ni _0.92 MoO _3.94 ) Carrier precursor (D-22) prepared in the same manner as in Comparative Example 7.
A catalyst was prepared from 000 g and 0.289 g of the supported material (G-1) by the same operation as in Example 1, and the reaction temperature was 399 ° C. and 420 ° C. using this catalyst. Was carried out and analyzed in the same manner. The results are shown in Table 4.

Comparative Example 9 (Catalyst composition: 6 wt% (NH ₄ ) ₆ Mo ₆ TeO ₂₄
・ 7H ₂ O / V _0.08 NiMo _0.92 O _3.96 ) Nickel nitrate 40.85g is put in a 1L beaker, distilled water 280g is added, and it is 8 on a hot plate stirrer.
It was heated to 0 ° C. with stirring to dissolve (A-24). 24.80 g ammonium paramolybdate and ammonium vanadate
Add 1.49 g of [NH ₄ VO ₃ ] to a 200 ml beaker and water 1
00 g was added, and the mixture was heated and stirred at 60 ° C. on a hot plate stirrer to dissolve (B-24). An ammonium hydrogen carbonate solution (C-1) was prepared in the same manner as in Example 1. The liquid (B-24) was added dropwise while stirring the liquid (A-24), and then the liquid (C-1) was slowly added dropwise to adjust the pH to 5, and the mixture was evaporated to dryness while stirring at a liquid temperature of 80 ° C. At this time, the solution (C-1) was appropriately added dropwise to maintain pH 5. After that, it was dried and pulverized in the same manner as in Example 1 to obtain V _0.08 NiMo.
_A catalyst carrier precursor (D-24) containing _0.92 O _3.96 was obtained. 6.00 g of carrier precursor (D-24) and the supported material prepared in Example 1
_{[(NH 4) 6 Mo 6} TeO 24 · 7H 2 O] (G-1) and 0.22 g 200 ml
Into an SPC flask of No. 3, 500 g of distilled water was added at room temperature, and the mixture was ultrasonically washed to give a green suspension. Thereafter, in the same manner as in Example 1, a catalyst was obtained by evaporating to dryness with a rotary evaporator, calcining, pulverizing and molding. Using this catalyst, the same reaction as in Example 14 was carried out except that the reaction temperatures were changed to 399 ° C. and 420 ° C., and the same analysis was carried out. The fourth result
Shown in the table

Comparative Example 10 (Catalyst composition: 9 wt% (NH ₄ ) ₆ Mo ₆ TeO
_{24 · 7H 2 O / V 0.08} NiMo 0.92 O 3.96) support precursor was prepared in the same manner as in Comparative Example 9 (D-24) 5.
A catalyst was prepared from 000 g and 0.321 g of the supported material (G-1) by the same operation as in Example 1, and the reaction temperature was 398 ° C. and 420 ° C. using this catalyst. Was carried out and analyzed in the same manner. The results are shown in Table 4.

Example 16 (Catalyst composition: 0.28 wt% Sb / Ni _0.83
MoO _3.83 , antimony complex impregnation method) 37.46 g of nickel nitrate was placed in a 1 L beaker, 258 g of distilled water was added, and 8 on a hot plate stirrer.
It was heated and stirred at 0 ° C. to be dissolved (A-26). Add 27.29 g of ammonium paramolybdate to a 100 ml beaker, add 44 g of water, and add 6 on a hot plate stirrer.
It was heated and stirred at 0 ° C. to dissolve (B-26). 7.54 g of ammonium hydrogen carbonate was placed in a 100 ml beaker, and 55.6 g of distilled water was added and dissolved by stirring (C-26). The solution (B-26) was added dropwise with stirring the solution (A-26), and then the solution (C-26) was slowly added dropwise to adjust the pH to 5, and the mixture was evaporated to dryness with stirring at a solution temperature of 80 ° C. At this time, the solution (C-26) was appropriately added dropwise to maintain pH 5. Thereafter, as in Example 1, dried and pulverized to _obtain Ni _0.83 Mo.
A catalyst carrier precursor (D-26) containing O _3.83 was obtained. Antimony trioxide [Sb ₂ O ₃ , Patox-U made by Nippon Seiko Co., Ltd.] 10.00
0 g and ammonium hydrogen tartrate (NH ₄ HC ₄ H ₄ O ₆ ) 11.46
Put 6g and 600ml distilled water into a 1L four-necked flask,
It was immersed in an oil bath at 130 ° C. and refluxed for 5 hours with stirring. Antimony oxide gradually dissolved. The solution was cooled to room temperature, filtered, and the filtrate (colorless and transparent) was decompressed using an evaporator and concentrated at 50 ° C. until crystals were precipitated.
The obtained concentrate was suction filtered, washed with a very small amount of cold water, then sandwiched between filter papers and dried, and antimonylammonium tartrate [white crystals, (NH ₄ ) ₂ Sb ₂ (C ₄ H ₂ O ₂ ) ₂ ] was obtained. Obtained (H-26). As a result of elemental analysis of this substance, the Sb content was 3
It was 7.0%. 6.00 g of the carrier precursor (D-26) and 0.035 g of the supported material (H-26) were placed in a 200 ml SPC flask, 50 g of distilled water was added at room temperature, and the mixture was ultrasonicated to give a green suspension. It was evaporated to dryness at 37 ° C. on a rotary evaporator. The solid obtained is put in an alumina crucible and heated in air using a muffle furnace to 50
It was calcined at 0 ° C. for 2 hours. Immediately after firing, remove the crucible from the muffle furnace, cool it, and crush it in an agate mortar.
It was molded into 36 mesh to obtain a catalyst. Using this catalyst, the same reaction as in Example 14 was carried out except that the reaction temperatures were changed to 401 ° C., 420 ° C. and 427 ° C., and the same analysis was carried out. The fourth result
Shown in the table

Example 17 (Catalyst composition: 0.58 wt% Sb / Ni _0.83)
MoO _3.83 , antimony complex impregnation method) Carrier precursor prepared in the same manner as in Example 16 (D-26) 6.
Example 1 except that a catalyst was prepared from 00 g and 0.075 g of the supported material (H-26) by the same operation as in Example 1 and the reaction temperature was 400 ° C. or 420 ° C. using this catalyst.
The same reaction as in 4 was performed and analyzed in the same manner. The results are shown in Table 4.

Example 18 (Catalyst composition: 0.90 wt% Sb / Ni _0.83
MoO _3.83 , antimony complex impregnation method) Carrier precursor prepared in the same manner as in Example 16 (D-26))
A catalyst was prepared from 6.00 g and the supported material (H-260.112 g) by the same operation as in Example 1, and the reaction temperature was set to 400 ° C. and 420 ° C. using this catalyst. The same reaction was performed and analyzed in the same manner, and the results are shown in Table 4.

Comparative Example 11 (Catalyst composition: 0.28 wt% Sb / Ni _0.92
MoO _3.92 , antimony complex impregnation method) Carrier precursor (D-1) 7.0 prepared in the same manner as in Example 1
0 g and the supported material [(NH ₄ ) ₂ Sb prepared in the same manner as in Example 16
_A catalyst was prepared from 0.0435 g of ₂ (C ₄ H ₂ O ₆ ) ₂ ] (H-26) by the same operation as in Example 1, and the reaction temperature was adjusted to 400 ° C. and 421 ° C. using this catalyst. Others are Example 14
The same reaction was performed and the same analysis was performed. The results are shown in Table 4.

Comparative Example 12 (Catalyst composition: 0.52 wt% Sb / Ni _0.92
MoO _3.92 , antimony complex impregnation method) Carrier precursor (D-1) 5.0 prepared in the same manner as in Example 1
0 g and the supported material [(NH ₄ ) ₂ Sb prepared in the same manner as in Example 16
_A catalyst was prepared from 0.0641 g of ₂ (C ₄ H ₂ O ₆ ) ₂ ] (H-26) by the same operation as in Example 1, and the reaction temperature was adjusted to 401 ° C., 419 ° C., 430 ° C. using this catalyst. The same reaction as in Example 14 was carried out except that the temperature was changed to ° C, and the same analysis was performed. The results are shown in Table 4.

Comparative Example 13 (Catalyst composition: 0.90 wt% Sb / Ni _0.92
MoO _3.92 , antimony complex impregnation method) Carrier precursor (D-1) 5.0 prepared in the same manner as in Example 1
0 g and the supported material [(NH ₄ ) ₂ Sb prepared in the same manner as in Example 16
_A catalyst was prepared from 0.994 g of ₂ (C ₄ H ₂ O ₆ ) ₂ ] (H-26) by the same operation as in Example 1, and the reaction temperature was 400 ° C., 419 ° C., 430 ° C. using this catalyst. The same reaction as in Example 14 was carried out except that the temperature was changed to ° C, and the same analysis was performed. The results are shown in Table 4.

Example 19 (Catalyst composition: 0.58 wt% Sb / Ni _0.83 Mo
O _3.83 Antimony oxide complex kneading method) 37.46 g of nickel nitrate and 0.23 of diantimony trioxide
g in a 1 L beaker, 258 g of distilled water was added, and the mixture was heated and stirred at 80 ° C. on a hot plate stirrer (A-3
2). An ammonium paramolybdate solution (B-1) and an ammonium hydrogen carbonate solution (C-1) were prepared in the same manner as in Example 1. By the same operation as in Example 1, the solution (B-1) was added dropwise to the solution (A-32) and then evaporated to dryness while adjusting the pH to 5 using the solution (C-1). Put the solid in an alumina crucible,
After drying in an oven at 0 ° C for 24 hours, put it in an alumina crucible and use a muffle furnace at 500 ° C under air flow.
It was baked for 2 hours. Immediately after firing, take out the crucible from the muffle furnace, cool it, and crush it in an agate mortar.
It was molded into mesh and used as a catalyst. The same reaction as in Example 1 was carried out except that the reaction temperature was changed to 402 ° C. and 421 ° C. using this catalyst, and the same analysis was carried out. The results are shown in Table 5.

Comparative Example 14 (Catalyst composition: 0.58 wt% Sb / Ni _0.83
MoO _3.83 , antimony oxide impregnation method) A carrier precursor prepared by the same operation as in Example 16 (D-2
6) 6.00 g and 2 parts of antimony trioxide 0.032 g
Transfer to a 00ml SPC flask and add 50g of distilled water at room temperature.
Was added and the mixture was applied to an ultrasonic cleaner to give a suspension. Thereafter, a catalyst was prepared by the same operation as in Example 1, and the same reaction as in Example 14 was carried out except that the reaction temperature was changed to 400 ° C., 419 ° C. and 430 ° C. using this catalyst, and the same analysis was conducted. . The results are shown in Table 5.

Example 20 (Catalyst composition: 0.58 wt% Sb / Ni _0.92
MoO _3.92 , scale-up by antimony oxide kneading method) 125.49 g nickel nitrate and diantimony trioxide 0.
Place 672 g in a 2 L separable flask and add distilled water 8
63 g was added, a stirring shaft, a dropping funnel, and a Liebig cooling tube were attached, and the mixture was immersed in an oil bath and heated and stirred at 80 ° C (A-3
Four). 79.42 g of ammonium paramolybdate,
It was put in a 200 ml beaker, 129 g of water was added, and the mixture was heated and stirred at 60 ° C. on a hot plate stirrer to dissolve (B-34). Distilled water (115.6 g) was added to ammonium hydrogen carbonate (15.168 g) and stirred to dissolve at room temperature (C-3
Four). The liquid (B-34) was added dropwise while stirring the liquid (A-34), and then the liquid (C-34) was slowly added dropwise to adjust the pH to 5. The separable flask was pulled up from the oil bath, the lid was removed, and it was transferred onto a hot plate stirrer, heated to 80 ° C. with stirring with a three-one motor, and evaporated to dryness. During this period (C-
34) The pH of the solution was maintained at 5 while dropping the solution. Thereafter, in the same manner as in Example 19, calcination, pulverization and molding were carried out to obtain a catalyst. Using this catalyst, the same reaction as in Example 14 was carried out except that the reaction temperatures were changed to 399 ° C. and 420 ° C., and the same analysis was carried out. The results are shown in Table 5.

Comparative Example 15 (Catalyst composition: 0.58 wt% Sb / Ni _0.92
MoO _3.92 , scale-up by the tartaric acid complex impregnation method) 125.52 g of nickel nitrate was placed in a 2 L separable flask, 863 g of distilled water was added, a stirring shaft, a dropping funnel, and a Liebig cooling pipe were attached and heated to 80 ° C. It was dissolved by stirring (A-35). Add 83.199 g of ammonium paramolybdate to a 200 ml beaker and add water 1
39 g was added, and the mixture was heated and stirred at 60 ° C. on a hot plate stirrer to dissolve (B-35). 25 wt% ammonia water 7
1 ml was diluted with 433 ml of distilled water at room temperature (C-35). Solution (B-35) while stirring solution (A-35)
After dropping the solution, slowly add the solution (C-35) to pH 5
The mixture was adjusted to 80 ° C. and evaporated to dryness at 80 ° C. with stirring. During this period, the solution (C-35) was added dropwise to maintain the pH of the solution at 5. The obtained solid was put into an alumina crucible and dried in an oven at 120 ° C for 24 hours. Crush in an agate mortar, Ni
_A catalyst carrier precursor (D-35) containing _0.92 MoO _3.92 was obtained. 60 g of the carrier precursor (D-35) and 0.768 g of the carrier (H-26) prepared in the same manner as in Example 16 were placed in a 1 L SPC flask, 480 g of distilled water was added at room temperature, and the mixture was placed on an ultrasonic cleaner. It was a green suspension. Thereafter, in the same manner as in Example 1, the catalyst was obtained by evaporation to dryness, drying, calcination, crushing and molding. The same reaction as in Example 14 was carried out except that the reaction temperature was adjusted to 400 ° C. and 420 ° C. using this catalyst, and the same analysis was performed. The results are shown in Table 5.

Comparative Example 16 (Catalyst composition: 0.58 wt% Sb / Ni _0.83
MoO _3.83 , antimony oxide kneading method, nitrogen firing for 2 hours) A catalyst was prepared in the same manner as in Example 19 except that firing was performed in a nitrogen atmosphere instead of air. Using this catalyst, the same reaction as in Example 14 was carried out except that the reaction temperatures were changed to 401 ° C., 419 ° C. and 430 ° C., and the same analysis was carried out. The results are shown in Table 5.

Comparative Example 17 (Catalyst composition: 0.58 wt% Sb / Ni _0.83
MoO _3.83 , antimony oxide kneading method, air calcination for 4 hours) A catalyst was prepared in the same manner as in Example 19 except that the calcination time was 4 hours. Example 14 except that the reaction temperature was set to 398 ° C., 419 ° C., and 433 ° C. using this catalyst.
The same reaction was performed and the same analysis was performed. The results are shown in Table 5.

Comparative Example 18 (Catalyst composition: 0.58 wt% Sb / Ni _0.83
MoO _3.83 , antimony oxide kneading method, air calcination for 6 hours) A catalyst was prepared in the same manner as in Example 19 except that the calcination time was 6 hours. Using this catalyst, the same reaction as in Example 14 was carried out except that the reaction temperatures were set to 398 ° C. and 420 ° C., and the same analysis was carried out. The results are shown in Table 5.

Comparative Example 19 (Catalyst composition: 0.58 wt% Sb / Ni _0.83
MoO _3.83 , (Sb ₂ O ₃ + Sb ₂ O ₄ ) kneading method) Instead of 0.23 g of diantimony trioxide, 0.116 g of diantimony trioxide and diantimony tetroxide [Sb ₂ O ₄ ]
A catalyst was prepared in the same manner as in Example 19, except that 0.121 g was used. With this catalyst, the reaction temperature is 4
The same reaction as in Example 14 was carried out except that the temperature was changed to 00 ° C. and 419 ° C., and the same analysis was carried out. The results are shown in Table 5.

Comparative Example 20 (Catalyst composition: 0.58 wt% Sb / Ni _0.83
MoO _3.83 , (Sb ₂ O ₃ + Sb ₂ O ₅ ) kneading method) Instead of 0.23 g of diantimony trioxide, 0.116 g of diantimony trioxide and antimony pentoxide [Sb ₂ O ₅ ]
A catalyst was prepared in the same manner as in Example 19, except that 0.128 g was used. With this catalyst, the reaction temperature is 4
The same reaction as in Example 14 was carried out except that the temperature was changed to 00 ° C. and 419 ° C., and the same analysis was carried out. The results are shown in Table 5.

Example 21 (Catalyst composition: 0.04% H ₄ PMo ₁₂ O ₄₀ /
0.6% Sb / Ni _0.83 MoO _3.83 ) 9.495 g of diantimony trioxide and 12 molybdophosphoric acid
0.648 g of [H ₄ PMo ₁₂ O ₄₀ · 30H ₂ O] was placed in a 50 ml beaker, 20 ml of distilled water was added, and the mixture was stirred on a hot plate stirrer for 30 minutes at room temperature, then heated to 50 ° C. and evaporated to dryness ( I-41). Carrier precursor prepared as in Example 16
(D-26) 6.00 g and antimony compound (I-41) 0.031
g in a 200 ml SPC flask and 50 g of distilled water
After adding and stirring, the same procedure as in Example 1 was performed to evaporate to dryness using an evaporator, followed by drying, firing and molding to obtain a catalyst. Using this catalyst, the reaction temperature was 401 ° C, 41
The same reaction as in Example 1 was carried out except that the temperature was changed to 9 ° C., and the same analysis was performed. The results are shown in Table 5.

Comparative Example 21 (Catalyst composition: 0.04% H ₄ PMo ₁₂ O ₄₀ /
0.6% Sb / Ni _0.83 MoO _3.83 ) 9.50 g of diantimony trioxide and 11 molybdo 1 vanadolinic acid H ₄ PMo 1 ₁ O ₄₀ · 30 H ₂ O] 0.637 g are put in a 50 ml beaker, 20 ml of distilled water is added, and a hot plate stirrer is added. After stirring at room temperature for 30 minutes above, the temperature was raised to 50 ° C. and evaporated to dryness (I-42). 6.00 g of the carrier precursor (D-26) prepared in the same manner as in Example 16 and the antimony compound (I-42) 0.
031 g was put in a 200 ml SPC flask, 50 g of distilled water was added, and the mixture was stirred, and then evaporated to dryness using an evaporator in the same manner as in Example 1, dried, calcined, and molded to obtain a catalyst. The reaction temperature is 400 with this catalyst.
The same reaction as in Example 1 was carried out except that the temperature was changed to 419 ° C and the same analysis was performed. The results are shown in Table 5.

Comparative Example 22 (Catalyst composition: 0.04% H ₄ PMo ₁₂ O ₄₀ /
Ni _0.83 MoO _3.83 ) Carrier precursor (D-26) 6.00 prepared as in Example 16
g and 12 molybdophosphoric acid H ₃ PMo ₁₂ O ₄₀ · 30H ₂ O] 0.0009
After putting 50 g in a 200 ml SPC flask and adding 50 g of distilled water and stirring, the mixture was evaporated to dryness using an evaporator in the same manner as in Example 1, dried, calcined and molded to obtain a catalyst. Using this catalyst, the reaction temperature was 400 ° C., 419
The same reaction as in Example 1 was carried out except that the temperature was changed to ° C, and the same analysis was performed. The results are shown in Table 5.

Example 22 (Catalyst composition: 0.58 wt% Sb / Ni _0.92
MoO _3.92 , antimony oxide kneading method, thermal history 40 hours) Nickel nitrate 37.46 g and diantimony trioxide 0.23
g was put in a 1 L four-necked flask, 258 g of distilled water was added, a stirring blade, a Dimroth condenser tube and a thermocouple sheath tube were attached, and the mixture was immersed in an oil bath and heated and stirred at 80 ° C. (A-44). As in Example 1, ammonium paramolybdate solution (B-1),
An ammonium hydrogen carbonate solution (C-1) was prepared. (A-44)
After the liquid (B-1) was added dropwise while stirring the liquid, the liquid (C-1) was slowly added dropwise to adjust the pH to 5. Total 40 hours 80
The mixture was heated under reflux at 0 ° C., and pH (5) was maintained during this period by the liquid (C-1). Thereafter, the catalyst was obtained by calcination, pulverization and molding in the same manner as in Example 4. Using this catalyst, the reaction temperature is 400 ° C, 4
The same reaction as in Example 1 was carried out except that the temperature was set to 20 ° C., and the same analysis was carried out. The results are shown in Table 5.

Comparative Example 23 (Catalyst composition: 6 wt% (NH ₄ ) ₆ TeMo ₆ O
_{24 · 7H 2 O / Ni 0.92} MoO 3.92, prepared from the acetate starting material) of nickel acetate tetrahydrate _{[Ni (OCOCH 3) 2 ·} 4H 2 O] 34.23
g was placed in a 1 L beaker, 275 g of distilled water was added, and the mixture was heated and stirred at 80 ° C. on a hot plate stirrer to dissolve (A-45). Ammonium paramolybdate 26.49
Add 3g into a 100ml beaker, add 43g of water,
It was heated and stirred at 60 ° C. on a hot plate stirrer to dissolve (B-45). The liquid (B-46) was added dropwise with stirring the liquid (A-46) to give a white-green slurry having a pH of 5.0, which was evaporated to dryness with stirring at 80 ° C. Thereafter, the catalyst carrier precursor (D-45) containing Ni _0.92 MoO _3.92 was obtained by drying and pulverizing in the same manner as in Example 1. Carrier precursor (D-45) 4.
000 g and the supported material [(NH ₄ ) ₆ TeMo ₆ O prepared in Example 1
0.210 g of ₂₄ · 7H ₂ O] (G-1) was placed in a 200 ml SPC flask, 50 g of distilled water was added at room temperature, and the mixture was ultrasonicated to give a green suspension. Thereafter, in the same manner as in Example 1, a catalyst was obtained by evaporating to dryness with a rotary evaporator, calcining, pulverizing and molding. The same reaction as in Example 14 was carried out except that the reaction temperature was adjusted to 400 ° C. and 420 ° C. using this catalyst, and the same analysis was performed. The results are shown in Table 6.

Comparative Example 24 (Catalyst composition: 6 wt% (NH ₄ ) ₆ TeMo ₆ O
_{24 · 7H 2 O / Ni 0.92} MoO 3.92, prepared from formic acid salt material) nickel formate dihydrate _{[Ni (OCOCH) 2 · 4H} 2 O] 25.417
g was placed in a 1 L beaker, 275 g of distilled water was added, and the mixture was heated and stirred at 80 ° C. on a hot plate stirrer to dissolve. The salt was not completely dissolved and became a white green slurry having a pH of 6.0 (A-46). Ammonium paramolybdate 2
6.493 g was added to a 100 ml beaker and 43 g of water was added.
Was added, and the mixture was heated and stirred at 60 ° C on a hot plate stirrer to dissolve (B-46). Ammonium hydrogen carbonate [NH ₄ HC
15 g of O ₃ ] was dissolved in 100 ml of water (C-46). (A-4
6) Add the liquid (B-46) dropwise while stirring the liquid, and then add the pH.
Liquid (C-46) was added dropwise until the mixture reached 5.0, and the mixture was evaporated to dryness at 80 ° C with stirring. During this period, the pH of the solution was maintained at 5 while dropping the (C-46) solution. Thereafter, the catalyst carrier precursor (D-46) containing Ni _0.92 MoO _3.92 was obtained by drying and pulverizing in the same manner as in Example 1. Carrier precursor (D-46) 6. 000
g, and the supported product [(NH ₄ ) ₆ TeMo ₆ O ₂₄ · 7H ₂ prepared in Example 1
O] (G-1) (0.307 g) was placed in a 200 ml SPC flask, 50 g of distilled water was added at room temperature, and the mixture was subjected to an ultrasonic cleaner to give a green suspension. Thereafter, in the same manner as in Example 1, a catalyst was obtained by evaporating to dryness with a rotary evaporator, calcining, pulverizing and molding. The reaction temperature is 400 with this catalyst.
The same reaction as in Example 14 was carried out except that the temperature was changed to 420 ° C., and the same analysis was performed. The results are shown in Table 6.

Comparative Example 25 (Catalyst composition: 6 wt% (NH ₄ ) ₆ TeMo ₆ O
_{24 · 7H 2 O / Ni 0.92} MoO 3.92, prepared from sulfate material) placed nickel sulfate hexahydrate _{[NiSO 4 · 6H 2 O]} 22.14g beaker 500 ml, distilled water 170g was added,
It was heated and stirred at 80 ° C. on a hot plate stirrer to dissolve (A-47). Ammonium paramolybdate 16.2
249 g was placed in a 100 ml beaker, 26 g of water was added, and the mixture was heated and stirred at 60 ° C. on a hot plate stirrer to dissolve (B-47). Ammonium hydrogen carbonate [NH ₄ HCO ₃ ]
7.5 g was dissolved in 55.6 ml of water (C-47). (A-4
7) Add the solution (B-47) dropwise while stirring the solution, and then add the pH.
The solution (C-47) was added dropwise until it reached 5.0, and the mixture was evaporated to dryness at 80 ° C with stirring. During this period, the pH of the solution was maintained at 5 while dropping the (C-47) solution. Thereafter, the catalyst carrier precursor (D-47) containing Ni _0.92 MoO _3.92 was obtained by drying and pulverizing in the same manner as in Example 1. Carrier precursor (D-47) 6. 000
g, and the supported product [(NH ₄ ) ₆ TeMo ₆ O ₂₄ · 7H ₂ prepared in Example 1
O] (G-1) (0.307 g) was placed in a 200 ml SPC flask, 50 g of distilled water was added at room temperature, and the mixture was subjected to an ultrasonic cleaner to give a green suspension. Thereafter, in the same manner as in Example 1, a catalyst was obtained by evaporating to dryness with a rotary evaporator, calcining, pulverizing and molding. The reaction temperature was adjusted to 401
The same reaction as in Example 14 was carried out except that the temperature was changed to 420 ° C., and the same analysis was performed. The results are shown in Table 6.

Comparative Example 26 (Catalyst composition: 6 wt% (NH ₄ ) ₆ TeMo ₆ O
_{24 · 7H 2 O / Ni 0.92} MoO 3.92, citrate prepared from the raw material) nickel citrate heptahydrate _{[Ni 3 (C 6 H 5} O 7) 2 · 4H 2 O] 48.
Put 494 g in a 1 L beaker, add 360 g of distilled water, heat and stir at 70 ° C. on a hot plate stirrer, and gradually add 80 ml of 28% ammonia water. The salt slowly dissolved into a dark green solution with a pH of 9.1 (A-4
8). Ammonium paramolybdate 41.1808 g
Was added to a 200 ml beaker, 67 g of water was added, and the mixture was heated and stirred at 60 ° C on a hot plate stirrer to dissolve (B-
48). When the (B-48) solution was added dropwise while stirring the (A-48) solution, a dark green uniform solution having a pH of 8.5 was obtained, and the pH changed to a white-green slurry of 7 to 8 while continuing heating and stirring at 70 ° C. did. Thereafter, the mixture was evaporated to dryness at 70 ° C., and a carrier precursor (D-48) containing Ni _0.92 MoO _3.92 was obtained by the same operation as in Example 1. Carrier precursor (D-48) 6. 000 g and the supported material [(NH ₄ ) ₆ TeMo ₆ O ₂₄ · 7H ₂ O] (G-1) 0.24 prepared in Example 1.
4 g was placed in a 200 ml SPC flask, 50 g of distilled water was added at room temperature, and the mixture was ultrasonically washed to give a green suspension. Thereafter, in the same manner as in Example 1, a catalyst was obtained by evaporating to dryness with a rotary evaporator, calcining, pulverizing and molding.
Using this catalyst, the same reaction as in Example 14 was carried out except that the reaction temperatures were changed to 401 ° C. and 420 ° C., and the same analysis was carried out. The results are shown in Table 6.

Comparative Example 27 (Catalyst composition: 6 wt% (NH ₄ ) ₆ TeMo ₆ O
_{24 · 7H 2 O / Ni 0.92} MoO 3.92, putting nickel prepared from chloride material) chloride anhydride [NiCl _2] 26.08g beaker 1L, distilled water 400g was added, heated and stirred to 80 ° C. on a hot plate stirrer And dissolved (A-49). 38.754 g of ammonium paramolybdate, 200
In a beaker of ml, add 65.2 g of water, and heat and stir on a hot plate stirrer at 60 ° C. to dissolve (B-4
9). Ammonium hydrogen carbonate [NH ₄ HCO ₃ ] 15 g of ammonium hydrogen carbonate [NH ₄ HCO ₃ ] was dissolved in 100 ml of water (C-
49). While stirring the (A-49) liquid, the (B-49) liquid was dropped.
Then add (C-49) solution dropwise until the pH reaches 5.0, and add 8 more.
It was evaporated to dryness at 0 ° C. with stirring. During this period, the pH of the solution was maintained at 5 while dropping the (C-49) solution. Thereafter, the catalyst carrier precursor (D-49) containing Ni _0.92 MoO _3.92 was obtained by drying and pulverizing in the same manner as in Example 1. Carrier precursor (D-48)
6． 000 g and the supported material [(NH ₄ ) ₆ TeM prepared in Example 1
_{o 6 O 24 · 7H 2 O} ] (G-1) 0.275g of 200 ml SPC
The mixture was placed in a flask, 60 g of distilled water was added at room temperature, and the mixture was ultrasonically washed to give a green suspension. Then, in the same manner as in Example 1, the mixture was evaporated to dryness by a rotary evaporator and then calcined,
It was crushed and molded into a catalyst. Using this catalyst, the same reaction as in Example 14 was carried out except that the reaction temperatures were changed to 400 ° C. and 419 ° C., and the same analysis was carried out. The results are shown in Table 6.

Comparative Example 28 (Catalyst composition: 6 wt% (NH ₄ ) ₆ TeMo ₆ O
_{24 · 7H 2 O / Ni 0.92} MoO 3.92, prepared from basic nickel carbonate) basic nickel carbonate _{[NiCO 3 · 2Ni (OH)} 2] 13.948
g was put in a 1 L beaker, 275 g of distilled water was added, and the mixture was heated and stirred at 80 ° C. on a hot plate stirrer to obtain a white-green slurry (A-50). Add 26.494 g of ammonium paramolybdate to a 100 ml beaker and add water 4
3.5 g was added, and the mixture was heated and stirred at 60 ° C. on a hot plate stirrer to dissolve (B-50). The liquid (B-50) was added dropwise while stirring the liquid (A-50), and the mixture was heated and stirred at 80 ° C. to evaporate to dryness. After that, Ni _0.92 MoO
_The carrier precursor (D-50) containing _3.92 was obtained.
0) 5,000 g and the supported material [(NH ₄ ) ₆ prepared in Example 1
_{TeMo 6 O 24 · 7H 2 O} ] (G-1) 0.288g of 200 ml S
It was taken in a PC flask, 60 g of distilled water was added at room temperature, and the mixture was ultrasonically washed to give a green suspension. Thereafter, in the same manner as in Example 1, a catalyst was obtained by evaporating to dryness with a rotary evaporator, calcining, pulverizing and molding. The same reaction as in Example 14 was carried out except that the reaction temperature was adjusted to 400 ° C. and 420 ° C. using this catalyst, and the same analysis was performed. The results are shown in Table 6.

Comparative Example 29 (Catalyst composition: 6 wt% (NH_Four)₆TeMo₆O
_{twenty four}・ 7H₂O / Ni_0.92MoO_3.92, 0.7M ammonium as a precipitant
A. Use water) Instead of ammonium bicarbonate solution (A-1),
Same operation as in Example 1 except that ammonia water was used.
Ri Ni_0.92MoO_3.92A carrier precursor (D-51) containing
It was Prepared in Example 1 with 6,000 g of carrier precursor (D-51).
Made carrier [(NH _Four)₆TeMo₆O_{twenty four}・ 7H₂O] (G-1) 0.285
g in a 200 ml SPC flask and distilled water at room temperature
Add 60 g and apply ultrasonic wave to make a green suspension.
It was Thereafter, as in Example 1, a rotary evaporator is used.
After that, it was evaporated to dryness, calcined, pulverized and molded to obtain a catalyst.
Using this catalyst, the reaction temperatures were set to 399 ° C and 418 ° C.
Otherwise, the same reaction as in Example 14 was carried out, and the same analysis was carried out.
It was The results are shown in Table 6.

Comparative Example 30 (Catalyst composition: 6 wt% (NH ₄ ) ₆ TeMo ₆ O
_{24 · 7H 2 O / Ni 0.92} MoO 3.92, N in the same manner as in Example 1 except for using a 3M aqueous ammonia instead of a 3M aqueous ammonia used) ammonium bicarbonate solution precipitant (A-1)
A carrier precursor (D-52) containing i _0.92 MoO _3.92 was prepared. 6,000 g of the carrier precursor (D-52) and 0.266 g of the carrier [(NH ₄ ) ₆ TeMo ₆ O ₂₄ · 7H ₂ O] (G-1) prepared in Example 1 were used.
Transfer to a 00ml SPC flask and add 60g of distilled water at room temperature.
Was added, and the mixture was subjected to an ultrasonic cleaner to give a green suspension. Thereafter, in the same manner as in Example 1, a catalyst was obtained by evaporating to dryness with a rotary evaporator, calcining, pulverizing and molding. The same reaction as in Example 14 was carried out except that the reaction temperatures were changed to 399 ° C. and 419 ° C. using this catalyst, and the same analysis was performed. The results are shown in Table 6.

Comparative Example 31 (Catalyst composition: 6 wt% (NH ₄ ) ₆ TeMo ₆ O
_{24 · 7H 2 O / Ni 0.92} MoO 3.92, N in the same manner as in Example 1 except for using a 6M aqueous ammonia instead of a 6M aqueous ammonia used) ammonium bicarbonate solution precipitant (A-1)
A carrier precursor (D-53) containing i _0.92 MoO _3.92 was prepared. 6,000 g of the carrier precursor (D-53) and 0.265 g of the carrier [(NH ₄ ) ₆ TeMo ₆ O ₂₄ · 7H ₂ O] (G-1) prepared in Example 1 were used.
Transfer to a 00ml SPC flask and add 60g of distilled water at room temperature.
Was added, and the mixture was subjected to an ultrasonic cleaner to give a green suspension. Thereafter, in the same manner as in Example 1, a catalyst was obtained by evaporating to dryness with a rotary evaporator, calcining, pulverizing and molding. The same reaction as in Example 14 was carried out except that the reaction temperature was adjusted to 400 ° C. and 420 ° C. using this catalyst, and the same analysis was performed. The results are shown in Table 6.

Comparative Example 32 (Catalyst composition: 6 wt% (NH_Four)₆TeMo₆O
_{twenty four}・ 7H₂O / Ni_0.92MoO_3.92, At pH 5.5 when preparing the carrier
Preparation) Example 1 except that the pH of the solution was adjusted to 5.5 instead of 5.
By the same operation as Ni _0.92MoO_3.92Carrier precursor containing
(D-54) was prepared. Carrier precursor (D-54) 6.000 g
And the carrier [(NH_Four)₆TeMo₆O_{twenty four}・ 7H₂O]
Transfer 0.247 g of (G-1) to a 200 ml SPC flask.
Then, add 60g of distilled water at room temperature and put on an ultrasonic cleaner.
It was a green suspension. Thereafter, as in Example 1, the rotary
Evaporate to dryness with an evaporator, bake, crush, and mold
As a catalyst. Using this catalyst, the reaction temperature is 400 ° C,
The same reaction as in Example 14 was carried out except that the temperature was 420 ° C.,
The same analysis was conducted. The results are shown in Table 6.

Comparative Example 33 (Catalyst composition: 6 wt% (NH_Four)₆TeMo₆O
_{twenty four}・ 7H₂O / Ni_0.92MoO_3.92, PH 6.0 at the time of carrier preparation
Preparation) Example 1 except that the pH of the solution was adjusted to 6.0 instead of 5.
By the same operation as Ni _0.92MoO_3.92Carrier precursor containing
(D-55) was prepared. Carrier precursor (D-55) 6.000 g
And the carrier [(NH_Four)₆TeMo₆O_{twenty four}・ 7H₂O]
Transfer 0.263 g of (G-1) to a 200 ml SPC flask.
Then, add 60g of distilled water at room temperature and put on an ultrasonic cleaner.
It was a green suspension. Thereafter, as in Example 1, the rotary
Evaporate to dryness with an evaporator, bake, crush, and mold
As a catalyst. Using this catalyst, the reaction temperature is 400 ° C,
The same reaction as in Example 14 was carried out except that the temperature was 420 ° C.,
The same analysis was conducted. The results are shown in Table 6.

Comparative Example 34 (Catalyst composition: 6 wt% (NH_Four)₆TeMo₆O
_{twenty four}・ 7H₂O / Ni_0.92MoO_3.92, Telluro when preparing the carrier precursor
(Coexist with ammonium molybdate) Beaker of 500 ml of nickel nitrate 40.000 g
Add 275 g of distilled water and heat to 80 ° C with stirring to dissolve.
I understood (A-56). Ammonium paramolybdate 26.
494 g and the telluromolybdate prepared in Example 1
Monium [(NH_Four) ₆Mo₆TeO_{twenty four} ・ 7H₂O] (G-1) 7.54 g
Place in a 100 ml beaker and add 55.6 g of distilled water.
It was dissolved by stirring (C-56). Stir the solution (A-56) at 80 ℃.
The solution (B-56) was added dropwise with stirring, and then p of this solution was added.
Solution (C-56) was slowly added dropwise until H became 5, and
It was evaporated to dryness at 80 ° C. with stirring. At this time, appropriately (C-5
6) The solution was added dropwise to maintain pH 5. The resulting solid is
Drying, calcination, crushing and molding were carried out in the same manner as in Example 19 to obtain a catalyst.
It was Using this catalyst, the reaction temperature was set to 400 ° C, 418 ° C
The same reaction as in Example 14 was carried out except that
did. The results are shown in Table 6.

Comparative Example 35 (Catalyst composition: 1.1 wt% HO ₆ / Ni _0.83
MoO _3.83 and coexisting telluric acid at the time of preparing the carrier precursor) 37.46 g of nickel nitrate was placed in a 1 L beaker, 258 g of distilled water was added, and 8 on a hot plate stirrer.
It was heated and stirred at 0 ° C. to be dissolved (A-57). Ammonium paramolybdate (27.29 g) and telluric acid (0.365 g) were placed in a 100 ml beaker, water (75 g) was added, and the mixture was heated and stirred at 60 ° C. on a hot plate stirrer to dissolve (B-
57). 7.54 g of ammonium hydrogen carbonate was placed in a 100 ml beaker, and 55.6 g of distilled water was added and dissolved by stirring (C-57). After liquid (B-57) was added dropwise while stirring liquid (A-57), liquid (C-57) was slowly added dropwise to adjust to pH 5, and the mixture was evaporated to dryness at liquid temperature 80 ° C. with stirring. At this time, the solution (C-57) was appropriately added dropwise to maintain pH 5. The obtained solid was dried, calcined, crushed and molded in the same manner as in Example 19 to obtain a catalyst. Using this catalyst, the reaction temperature is 400 ° C, 41
The same reaction as in Example 14 was carried out except that the temperature was changed to 9 ° C and 437 ° C, and the same analysis was performed. The results are shown in Table 6.

Comparative Example 36 (Catalyst composition: 10.6 wt% [(C ₄ H ₇ )]
₄ N] ₆ TeMo ₅ O ₂₄ / Ni _0.92 MoO _3.92 ) 200 m of ammonium paramolybdate 8.016 g
It was put in a beaker of 1 l, 16.2 g of distilled water was added, and the mixture was heated and stirred at 60 ° C on a hot plate stirrer to dissolve (E-5
8). 1.73 g of telluric acid [H ₆ TeO ₆ ] was placed in a 50 ml beaker, 8 g of distilled water was added, and the mixture was stirred and dissolved (F-58). Tetrabutylammonium bromide (14.64 g) was placed in a 100 ml beaker, 50 g of distilled water was added, and the mixture was stirred at room temperature to dissolve (J-58). The solution (F-58) was added dropwise while the solution (E-58) was stirred, and when the solution (J-58) was further added dropwise, white precipitation occurred. The solid matter (G-58) was collected by filtration and washing with water. As a result of elemental analysis, Te: 5.2 wt%, Mo: 33.0 wt%, Br: 0.1 wt%,
It was C: 33.0 wt%, H: 6.4 wt%, N: 3.3 wt%. Carrier precursor (D-1) 3.000 prepared by the same method as in Example 1
g and 0.356 g of the supported material (G-58) in 200 ml of SP
The mixture was placed in a C flask, 5 g of acetonitrile was added, and the mixture was stirred. Thereafter, in the same manner as in Example 1, a catalyst was obtained by evaporating to dryness with a rotary evaporator, calcining, pulverizing and molding.
Using this catalyst, the same reaction as in Example 14 was carried out except that the reaction temperatures were changed to 399 ° C. and 420 ° C., and the same analysis was carried out.
The results are shown in Table 6.

Comparative Example 37 (Catalyst composition: 1.1 wt% HO ₆ / Ni _0.83
MoO _3.83 ) A carrier precursor prepared by the same method as in Example 16 (D-2
6) 200 ml of 6.000 g and 0.045 g of telluric acid
Into an SPC flask of No. 1, 50 g of distilled water was added and stirred. Thereafter, in the same manner as in Example 1, a catalyst was obtained by evaporating to dryness with a rotary evaporator, calcining, pulverizing and molding.
The same reaction as in Example 14 was carried out except that the reaction temperature was adjusted to 400 ° C. and 420 ° C. using this catalyst, and the same analysis was performed. The results are shown in Table 6.

Comparative Example 38 (Catalyst composition: 1.1 wt% HO ₆ / Ni _0.83
MoO _3.83 ) A carrier precursor prepared by the same method as in Example 16 (D-2
6) 200 ml of 6.000 g and telluric acid 0.068 g
Into an SPC flask of No. 1, 50 g of distilled water was added and stirred. Thereafter, in the same manner as in Example 1, a catalyst was obtained by evaporating to dryness with a rotary evaporator, calcining, pulverizing and molding.
Using this catalyst, the same reaction as in Example 14 was carried out except that the reaction temperatures were changed to 391 ° C. and 420 ° C., and the same analysis was carried out. The results are shown in Table 6.

[0080] Example _{23 (6wt% (NH 4)} 6 TeMo 6 O 24 · 7H 2 O /
Ni _0.92 MoO _3.92 catalytic propylene oxidation) catalyst obtained in Example _{1 [6wt% (NH 4)} 6 TeMo 6 O 24 · 7H 2 O /
Ni _0.92 MoO _3.9 ] and reacted as follows.
That is, 1 g of the catalyst was filled in a reaction tube and the temperature was raised to 250 ° C. while flowing 50 ml / min of nitrogen. From 250 ° C., 2.7 ml / min of propylene, 4 ml / min of oxygen and 23.
The mixture was heated to 299 ° C. while flowing a mixed gas of 3 ml / min and steam of 20 ml / min, and after 1 hour, the reaction product was analyzed by an online gas chromatograph. After that, 325 ℃,
352 ° C, 360 ° C, 370 ° C, 380 ° C, 390 ° C,
The temperature was raised stepwise to 397 ° C. and the reaction product at each reaction temperature was analyzed. The results are shown in Table 7.

[0081] Example _{24 (9wt% (NH 4)} 6 TeMo 6 O 24 · 7H 2 O /
Ni _0.38 MoO _3.38 catalytic propylene oxidation) catalyst obtained in Example _{3 [9wt% (NH 4)} 6 TeMo 6 O 24 · 7H 2 O /
Ni _0.38 MoO _3.38 ], and the reaction temperature is 298 ° C, 324
℃, 351 ℃, 375 ℃, 388 ℃, 400 ℃, 409
The reaction was performed in the same manner as in Example 23 except that the temperature was changed to 419 ° C. The results are shown in Table 7.

Comparative Example 39 (Propylene Oxidation with Ni _0.92 MoO _3.92 Catalyst) Using the catalyst [Ni _0.92 MoO _3.92 ] obtained in Comparative Example 1, the reaction temperature was 296 ° C., 325 ° C., 356 ° C., 370.
C., 380.degree. C., 391.degree. C., 399.degree. C.
It reacted similarly to 23 and analyzed similarly. The results are shown in Table 7.

[0083]

[Table 1]

[0084]

[Table 2]

[0085]

[Table 3]

[0086]

[Table 4]

[0087]

[Table 5]

[0088]

[Table 6]

[0089]

[Table 7]

[0090]

EFFECTS OF THE INVENTION The catalyst of the present invention can activate alkanes and the like at a relatively low temperature of about 300 to 450 ° C. and produces C as a by-product.
Oxygen-containing compounds such as acetaldehyde, acrolein, acrylic acid, and methacrylic acid can be efficiently obtained with a high selectivity, with a small amount of O and CO _2, and can also be applied to a dehydrogenation reaction in the absence of oxygen. Therefore, according to the present invention, an alkane or the like as a raw material can be used to produce an oxygen-containing chemical product or olefin having a high added value as an industrial raw material.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C07C 27/14 C07C 27/14 Z 45/32 45/32 47/07 47/07 47/22 47/22 B 51 / 215 51/215 57/05 57/05 // C07B 61/00 300 C07B 61/00 300 (72) Inventor Noriyuki Oue 1-1-1 Shingumachi, Tokuyama City, Yamaguchi Prefecture Inventor Wataru Ueda Hokkaido Sapporo Kita-ku, Kita 11-jo Nishi 10-chome Hokkaido University F-term (reference) 4G069 AA03 AA08 BB06A BB06B BC26B BC54B BC59A BC59B BC68A BC68B BD01B BD06B BD07B BD10B CB07 CB10 CB17 BA30 BA21 BA21 BA21 BA21 BA14 BA21 BA21 BA14 BA21 BA14 AC14 BA20 BA14 AC14 BA20 BA14 AC14 BS10 4H039 CA21 CA62 CA65 CC10 CC40

Claims (8)

[Claims] 1. A catalyst for hydrocarbon reaction, comprising at least one selected from tellurium compounds and antimony compounds bound to a molybdenum-cobalt composite oxide and / or a molybdenum-nickel composite oxide. 2. The catalyst for hydrocarbon reaction according to claim 1, wherein the tellurium compound is at least one compound selected from Anderson-type heteropoly acid or telluric acid, an organic salt thereof and tellurium oxide. 3. The hydrocarbon reaction according to claim 1, wherein the antimony compound is at least one compound selected from antimony oxide, antimony organic acid salt, antimony inorganic acid salt, and antimonylammonium complex salt. Catalyst. 4. A method for reacting hydrocarbons, which comprises reacting hydrocarbons using the catalyst according to claim 1. 5. The method for reacting a hydrocarbon according to claim 4, wherein the reaction of the hydrocarbon is a partial oxidation reaction of the hydrocarbon. 6. The hydrocarbon reaction method according to claim 5, wherein the hydrocarbon is an alkane and / or an olefin. 7. The method for reacting a hydrocarbon according to claim 6, wherein the hydrocarbon is propane and / or propylene, and the reaction product is acetaldehyde, acrolein, and one or more oxygen-containing compounds selected from acrylic acid. . 8. The method for reacting a hydrocarbon according to claim 4, wherein the reaction of the hydrocarbon is a dehydrogenation reaction of a saturated hydrocarbon in the absence of oxygen.