JPH10175885A - Production of ethylene - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain ethylene in a high selectively and in a high yield without using an expensive element and without adding a halogen, etc., to the reaction system, by bringing ethane into contact with a molecular oxygen-containing gas in the presence of a catalyst containing a specific composite metal oxide at a high temperature. SOLUTION: This method for producing ethylene comprises bringing ethane into contact with a molecular oxygen-containing gas at a temperature of 250-500 deg.C in the presence of a catalyst containing a composite metal oxide containing Mo, V and Sb as essential components and having a powder X-ray diffraction mainly having a characteristic pattern of the table. The composite metal oxide is obtained by adding a Mo-containing compound and a compound containing an element such as Ti or Zr to an aqueous solution containing a V-containing component and a Sb-containing component, drying the aqueous solution and subsequently calcining the obtained catalyst precursor.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing ethylene. More specifically, the present invention relates to a method for producing ethylene from ethane by an oxidative dehydrogenation reaction. Ethylene is industrially important as a key raw material for various petrochemical and polymer products.

[0002]

2. Description of the Related Art Low-temperature oxidative dehydrogenation for producing ethylene from ethane is described in "The Oxidative Dehydrogenation".
of Ethane over Catalysts Containing Mixed Oxide
s ofMolybdenum and Vanadium "(Journal of Catalys
is, 52, 116-132 (1978)). This article discloses mixed oxide catalysts containing Mo and V as well as other transition metal oxides (Ti, Cr, Mn, Fe, Co, Ni, Nb, Ta and Ce). The catalyst is active at temperatures as low as 200 ° C. for the oxidative dehydrogenation of ethane to ethylene.

US Pat. No. 4,250,346 and German Patent DE2
No. 644107 and Japanese Patent Application No. 51-116705 and the specification of the patent application filed in a divisional application disclose the oxidative dehydrogenation of ethane to ethylene at a temperature of 450 ° C. or less, in which case the catalyst has the elemental composition Is:

[0004]

## STR1 ## MoaXbYc (where X = Cr, Mn, Nb, Ta, Ti, V and / or W Y = Bi, Ce, Co, Cu, Fe, K, Mg, Ni, P, Pb, Sb, Si, Sn, Tl and / or
Or U a = 1 b = 0-2 c = 0-2)

Consisting of the elements Mo, X and Y represented by
It is a calcined composition. The numerical values of a, b and c in the formula represent the relative molar ratios of the elements Mo, X and Y present in the catalyst composition, respectively. The elements Mo, X and Y are present together with oxygen in the catalyst composition.

[0006] The specifications of the above patent applications disclose a variety of compositions. However, both ethane conversion and ethylene yield have not been satisfactory. For example, Examples 57 and 5 of JP-A-52-42806 are one of the examples showing the highest ethylene yield among these.
_No. 8, the Mo ₁₆ V ₈ Nb ₂ U ₁ catalyst had an ethane conversion of 53% and an ethylene yield of 34% at 400 ° C., and the Mo ₁₆ V ₄ W _1.6 Mn ₄ catalyst had an ethane conversion of 58% at 400 ° C. 34%
Is shown.

Japanese Patent Publication No. 3-5 related to US Pat. No. 4,524,236
No. 4927 discloses the oxidative dehydrogenation of ethane to ethylene at temperatures below 450 ° C., wherein
The catalyst has the following elemental composition:

[0008]

## STR2 ## MoaVbNbcSbdXe (where X = Li, Na, K, Rb, Be, Mg, Ca, Sr, Ba, Ta, Cr, Fe, Co,
Ni, Ce, La, Zn, Cd, Hg, Al, Tl, Pb, As, Bi, U, W
Including one. a = 0.5-0.9, b = 0.1-0.4, c = 0.001-0.2, d = 0.001-0.1, e = 0.001-1.0)

A calcined composition comprising the elements Mo, V, Nb, Sb and X represented by the formula: A, b, c, d in the formula
And the numerical values of e represent the relative molar ratios of the elements Mo, V, Nb, Sb and X present in the catalyst composition, respectively. The elements Mo, V, Nb, Sb and X are present together with oxygen in the catalyst composition.

The above patent also discloses a variety of compositions. However, both ethane conversion and ethylene yield have not been satisfactory. For example, one of the examples showing the highest ethylene yield is described in U.S. Pat.
Is a sixth embodiment of _{No., Mo 1 V 0 .43 Nb 0.11} Sb 0.07 Bi 0.03 ethane conversion of 71% at 400 ° C. in the catalyst, ethylene yield 5
1.1% is shown.

JP-A-64-85945 discloses the production of acetic acid from ethane, ethylene and oxygen, wherein the catalyst has the elemental composition of the following formula:

[0012]

(A) MoxVyZz (where Z = none, or Nb, Sb, Li, Sc, Na, Be, Mg, Ca, S
r, Ba, Ti, Zr, Hf, Y, Ta, Cr, Fe, Co, Ni, Ce, La, Zn, Cd, Hg, Al, T
one or more of l, Pb, As, Bi, Te, U, and W x = 0.5-0.9 y = 0.1-0.4 z = 0.01-1 The numerical values of x, y and z are respectively in the catalyst composition. Represents the relative molar ratio of the elements Mo, V and Z present in Element Mo,
V and Z are present with oxygen in the catalyst composition. A) a calcination composition comprising the elements Mo, X and Y represented by

[0013]

(B) at least one catalyst selected from the group consisting of (x) an ethylene hydration catalyst or (xx) an ethylene oxidation catalyst,
The catalyst mixture contained.

The examples in the above patent specification disclose only MoVNbSbCa or MoVNb mixed oxide as the catalyst (A) composition. It also discloses an oxidation reaction of ethane alone, but the conversion of ethane is low and the selectivity of generated ethylene is not sufficiently high. For example, in Example 7, the raw material gas of 87% of ethane, 6.5% of oxygen, and 6.5% of nitrogen was used.
When oxidized on a combined catalyst of Mo _0.7 V _0.25 Nb _0.02 Sb _0.01 Ca _0.01 Ox and powdered molecular sieve LZ-105 (manufactured by UCC), the conversion of ethane was 3 mol% and the selectivity to ethylene was 3 mol%. Was 56 mol%.

The present inventors have disclosed a method for producing ethylene by oxidative dehydrogenation of ethane in JP-A-7-53414. In this case, the catalyst composition contains Mo, V and Te. It is characterized by containing it as an essential component.

[0016]

However, in these patent documents relating to a technique for obtaining ethylene by oxidative dehydrogenation of ethane, Mo or Mo is disclosed.
Although there is a possibility that a composite oxide catalyst containing V and V is effective for the oxidative dehydrogenation reaction, there is no catalyst other than Japanese Patent Application Laid-Open No. Hei 7-53414 that still shows practically usable catalyst performance. That is, the highest yield of ethylene from ethane is substantially at most about 50 mol%.

Further, in Japanese Patent Application Laid-Open No. Hei 7-53414, there is a problem that the catalyst price is relatively high because relatively expensive elements Nb and Te are used.

[0018]

Means for Solving the Problems The present inventors have intensively studied to solve such problems and found that the catalyst composition was Mo,
As a result of various examinations on the powder X-ray diffraction of a catalyst containing V and Sb as essential components and containing substantially no Te as a constituent element, it was found that a catalyst containing a composite metal oxide mainly having a specific characteristic pattern was ethane. In the production of ethylene by the oxidative dehydrogenation of benzene, it is possible to achieve a higher activity and higher selectivity than the conventional method at a relatively low temperature of about 300 to 450 ° C. without the presence of a halide or the like in the reaction system. The present invention has been found that ethylene can be produced.

That is, the gist of the present invention is that when ethane is contacted with a molecular oxygen-containing gas at a high temperature in the presence of a catalyst to produce ethylene, the catalyst contains Mo, V and Sb as essential components. Wherein the powder X-ray diffraction mainly comprises using a catalyst containing a composite metal oxide having a characteristic pattern shown in Table 1 and / or Table 2 below.

[0020]

Table 1 Table 1 ------------------------- Diffraction angle 2θ (゜) Relative peak intensity (%) ------ −−−−−−−−−−−−−−−−−−−−−−−− 22.2 ± 0.4 (100) 28.3 ± 0.4 (400 to 10) 36.2 ± 0.4 (80-3) 45.1 ± 0.4 (50-3) 50.0 ± 0.4 (50-3) -------------------------------------------------------------------------- −−−− (Using Cu-Kα ray) (The number in parentheses indicates the relative peak intensity when the peak at 22.2 ° is defined as 100.)

[0021]

Table 4 Table 2---------------------Diffraction angle 2θ (゜) Relative peak intensity (%) ---- −−−−−−−−−−−−−−−−−−−−−−− 6.7 ± 0.4 (15 to 1) 7.9 ± 0.4 (20 to 1) 9.1 ± 0 0.4 (20-1) 22.2 ± 0.4 (100) 27.3 ± 0.4 (80-8) 35.5 ± 0.4 (15-3) 45.2 ± 0.4 (50 ~ 3) ------------------------------ (using Cu-Kα radiation) (The number in parentheses is the peak of 22.2%). The relative peak strength when the peak is 100 is shown.)

[0022]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The gist of the present invention is to use a solid catalyst containing a composite metal oxide containing Mo, V, and Sb as essential components. As a specific example of the catalyst, for example, the composite metal oxide constituting the catalyst is Mo, V, Sb and X (however, X
Represents Ti, Zr, Nb, Ta, Cr, W, Mn, Fe,
Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, A
g, Zn, Al, In, Sn, Pb, Bi, and Ce).
Is represented by the molar fraction rM in the total metal elements contained,

[0023]

## EQU2 ## 0.25 <rMo <0.98 0.003 <rV <0.5 0.003 <rSb <0.5 0.003 <rX <0.5

A catalyst containing a composite metal oxide having the above relationship may be mentioned. Even if component X is not contained, sufficiently high performance can be obtained. When component X is used, T
i, Zr, Nb, Ta, W, Cr, Mn, Ce and the like are preferable, and a combination of Ti, W, Nb, Zr and Ce is particularly preferable. That is, another feature of the present invention is that high catalytic performance can be achieved by using a relatively inexpensive element such as Sb without using an expensive element such as Te substantially. is there. Furthermore, a combination of inexpensive elements, such as Ti and Sb, is used without using even expensive element Nb.
It is surprising that high catalyst performance can be exhibited even with the combination of.

There are no particular restrictions on the method of preparing these catalysts, but for example, they are prepared as follows. That is, first, a predetermined amount ratio of the Sb-containing compound is added to the aqueous solution containing the V-containing compound to prepare the aqueous solution. (As used herein, the term "aqueous solution" refers to not only the case where the solute is completely dissolved, but also a slurry state in which a part of the solute is present without being dissolved, and a substantially homogeneous but not a solution. , When it is present in a colloidal state or a suspended state of a metal oxide.) Thereafter, a predetermined amount of the aqueous solution of the Mo-containing compound and the aqueous solution or the powdery solid of the component X are converted to a molar amount of the metal element. Add in a quantitative ratio such that the ratio becomes a predetermined ratio,
The mixture is stirred and mixed, and then dried by evaporation to dryness, spray drying, vacuum drying, or the like to obtain a catalyst precursor.

The above-mentioned V-containing compound includes
Ammonium nadate, V_TwoO_Five, VO (OR)_Three(here
And R is an alkyl group having 1 to 10 carbon atoms) or V
OCI_ThreeA union of one or more raw materials selected from among
Can be used. Also, V_TwoO _FiveSolubilization when using
H_TwoO_TwoCan coexist. Sb-containing compound
As Sb_TwoO_Three, Sb_TwoO_Four, Sb_TwoO_Five, SbOC
1, SbCl_ThreeOne or more raw materials selected from
Can be used. In addition, as a Mo-containing compound
Is ammonium paramolybdate, MoO_Three, Mo
O_Two, MoCl_Five, Phosphomolybdic acid, silico molybdenum
Acid, Mo (OR)_Five(Where R is 1 to 10 carbon atoms)
Alkyl group) or molybdenyl acetylacetona
-(MoO_Two(Acac)_Two1)
Combinations of more than one type of raw material can be used. Also metal elements
X raw materials include oxides, hydroxides, halogenated
Substance, carboxylate, alkoxide, acetylacetona
Ammonium halides or carboxylic acids
A ammonium salt or the like can be used. Furthermore, Mori
Hete of mixed coordination of Mo and V such as budvanadolinic acid
Ropoly acids may be used.

In such a method for producing a catalyst precursor, by coexisting trivalent Sb in an aqueous solution containing pentavalent V, at least a part of V is reduced more than pentavalent, while A method for producing a catalyst precursor containing V and Sb in which at least a part of Sb is oxidized to a pentavalent valence is preferred. It is preferable to heat the aqueous solution to 50 to 200 ° C. to accelerate the reaction. Examples of the heating method include heating in an open vessel, reflux conditions provided with a cooling device, and hydrothermal synthesis conditions in a high-pressure vessel.

The catalyst precursor is calcined at a temperature of usually 350 to 750 ° C., preferably 450 to 680 ° C. to obtain a composite metal oxide. Baking time is 1 minute to 3
Although it is an arbitrary time of 0 hours, about 1 minute to 4 hours is particularly practical. The composite metal oxide thus prepared is mainly composed of the powder X shown in Table 1 and / or Table 2.
X-ray diffraction patterns (here, “X-ray powder diffraction patterns shown in Tables 1 and 2” refer to the X-ray powder diffraction patterns shown in Table 1 and the X-ray powder diffraction patterns shown in Table 2 This means that the pattern appears together.) The atmosphere at the time of firing may be air, but it is preferable to perform firing at an oxygen concentration lower than that of air, especially an atmosphere of an inert gas such as nitrogen, argon, or helium. It is preferable to calcinate under or under these circulations or in a vacuum.

The content of each metal element in the composite metal oxide is represented by a mole fraction r in the total content of the metal elements, and rM
o is usually 0.25 to 0.98, preferably 0.5 to 0.5.
7, rV is usually 0.003 to 0.5, preferably 0.1 to 0.3, and rSb is usually 0.003 to 0.5.
5, preferably 0.03 to 0.3, and rX is usually 0.003 to 0.5, preferably 0.01 to 0.3.

Although these composite metal oxides can be used alone as a catalyst, they can also be used together with known carriers such as silica, alumina, aluminosilicate, titania, zirconia, and silicon carbide. In that case, these carrier components can be added at any step during the preparation of the catalyst precursor. Alternatively, calcination may be performed after mixing with the catalyst precursor before the calcination step. Further, the sintered composite metal oxide and the carrier may be kneaded and molded. The catalyst is formed into an appropriate particle size and shape according to the scale and system of the reaction, and is sized.

Further, by physically pulverizing a composite metal oxide or a catalyst containing a composite metal oxide and a carrier with a known dry or wet pulverizer, 400 ° C. which has been considered impossible until now is considered. It is possible to obtain a highly active catalyst capable of converting ethane sufficiently efficiently while maintaining high selectivity at the following temperatures. In these pulverization operations, the average diameter of the primary particles of the composite metal oxide contained in the catalyst was 5 μm.
The effect can be exerted by setting the average particle size to be below, but it is preferable to use the primary particles with an average diameter of 1 μm or less. The pulverized composite metal oxide or the catalyst containing the composite metal oxide and the carrier is molded into an appropriate particle size and shape by a method suitable for the application as it is or after being mixed with a carrier component, and then adjusted. Granulated and, if necessary, calcined again, are ready for use as a catalyst.

The process of the present invention uses the catalyst described above to
This is to produce ethylene by subjecting ethane to a gas phase catalytic oxidation reaction. The system of the reactor is not particularly limited, but a reaction system such as a fixed bed, a fluidized bed and a moving bed can be suitably used. This reaction is usually carried out under atmospheric pressure,
It can also be performed under low pressure or reduced pressure.

The reaction temperature in the process of the present invention is usually 20
It can be carried out at 0 to 550 ° C, and particularly preferably at about 250 to 500 ° C. Further, the gas space in the gas phase reaction rate SV [hr ^-1] is, 10～5000Hr ^-1
Suitable results are obtained in a wide range, preferably in the range of 100 to 2000 hr ^-1 . In addition, as a diluent gas for adjusting the space velocity and the oxygen partial pressure, nitrogen, argon, an inert gas such as helium or carbon dioxide,
A diluent gas such as steam can be used.

When the ethane oxidation reaction is carried out according to the method of the present invention, carbon monoxide, carbon dioxide,
Acetic acid and the like are by-produced, but the amount produced is usually extremely small.
The raw material ethane is not particularly limited in purity,
For example, methane, ethylene, water, carbon monoxide, carbon dioxide, propane, butane and the like may be mixed as impurities. Further, the oxidation reaction in the present invention is carried out by using oxygen present in the supply gas. When oxygen is present in the supply gas, the oxygen may be pure oxygen gas, but since purity is not particularly required, it is generally economical to use an oxygen-containing gas such as air.

The present invention will be described in more detail with reference to more specific reaction conditions. The ratio of oxygen supplied to the reaction is such that the stoichiometric amount required from the chemical reaction equation is 0.5 to ethane.
The molar amount is usually 0.001 to 5 with respect to ethane.
Suitable ethylene selectivity is obtained in a wide range of 0 mole times, and particularly high ethylene selectivity is shown in the case of 0.02 to 4 times mole.

As is known in the art, generally the lower the conversion of ethane, the higher the selectivity of the produced ethylene. Therefore, in order to obtain a high ethylene selectivity, it is preferable to carry out the reaction with the supplied oxygen amount being lower than the stoichiometric amount (0.5 mole times the amount of ethane) required from the chemical reaction formula. Is advantageous. When the reaction is carried out under these conditions and even under the usual oxygen excess to ethane ratio conditions, part of the supplied ethane is present in the product as unreacted ethane. Recovering such unreacted ethane and supplying it again as a raw material is significant both economically and in terms of resource environment.

The method for recovering such unreacted ethane is not particularly limited, but known techniques such as a flash drum, a distillation column, an adsorption separator, and a pressure swing device, or a combination thereof are preferred. It can be used for When such a method is used, air can be used as the oxygen supply source, but in some cases, the use of oxygen-enriched air or pure oxygen may be preferable.

As a specific example, in the product at the outlet of the reactor, most of water and acetic acid are coagulated and removed after cooling. There are various methods for recovering ethane from the remaining ethane, ethylene, CO, CO ₂ , nitrogen and oxygen to obtain ethylene as a product. In one example, these products are pressurized to liquefy ethane, ethylene and CO ₂ ,
Separates from O, nitrogen and oxygen. Thereafter, ethane, ethylene and CO ₂ are separated by distillation under pressure, the ethane fraction is transferred to a raw material tank, and the reaction is performed again.
Further, by way of another example, after removal of the product water and acetic acid, the CO ₂ is removed in a CO ₂ remover, separate the ethane and ethylene by adsorption separator, by distillation separate them thereafter, A method in which the ethane fraction is transferred to a raw material tank and then used again for the reaction. Further, in addition to the above methods, there is also a method of selectively oxidizing CO to convert the total amount to CO ₂ and then performing a separation operation. Which method is preferred is determined by the cost of the raw material, including the oxygen source, and the efficiency of the overall process.

[0039]

EXAMPLES Next, specific embodiments of the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples unless it exceeds the gist thereof. The ethane conversion (%) and the ethylene yield (%) in the gas phase catalytic oxidation reaction of ethane in the following Examples and Comparative Examples are represented by the following equations, respectively.

[0040]

## EQU3 ## Conversion of ethane (%) = (moles of ethane consumed /
Mole number of supplied ethane) × 100 Ethylene yield (%) = (mol number of produced ethylene / mol number of supplied ethane) × 100

Example 1 In 600 ml of warm water, ammonium metavanadate (NH ₄
After dissolving 35.1 g of VO ₃ ), 19.1 g of antimony trioxide (Sb ₂ O ₃ ) powder was added thereto, and the slurry was heated and stirred for 6 hours, and then ammonium paramolybdate ((NH ₄ ) ₆ Mo ₇ ) O _{2 4} · 4H ₂ O) was added an aqueous solution 600ml containing 176.6 g, further titanium oxalate ammonium _{((NH 4) 2 [TiO} (C 2 O 4) 2] · 2
20 ml of an aqueous solution containing 15.6 g of (H ₂ O) was added to obtain a uniform slurry. This slurry was subjected to a heat treatment to remove water, thereby obtaining a catalyst precursor. After treating the catalyst precursor at 380 ° C. in air, the catalyst precursor was treated at 600 ° C. in a nitrogen stream at 2 ° C.
After calcination for a time, a composite metal oxide was obtained.

When the obtained composite metal oxide was subjected to powder X-ray diffraction measurement (using Cu-Kα ray), the diffraction angle was 2θ.
As (゜), 7.1, 8.2, 9.1, 22.2, 2
7.2, 28.2, 35.5, 36.2, 45.1, 5
A major diffraction peak was observed at 0.0. Using the composite metal oxide as a catalyst, 0.5 g was charged into a reactor, and a reaction temperature of 4 g was used.
At 40 ° C. and a space velocity SV of 500 h ⁻¹ , gas was supplied at a molar ratio of ethane: air = 1: 5 to perform a gas phase contact reaction. The results are shown in Table-3.

Example 2 A fired composite metal oxide was obtained in the same manner as in Example 1, except that the amount of antimony trioxide (Sb ₂ O ₃ ) powder was changed to 24.8 g. When the powder X-ray diffraction measurement of the obtained composite metal oxide was performed, the same main diffraction peak as in Example 1 was observed.

A reactor was charged with 0.5 g of the composite metal oxide as a catalyst, and the reaction temperature was 440 ° C. and the space velocity SV was 4
At 60 h ⁻¹ , gas was supplied at a molar ratio of ethane: air = 1: 5 to perform a gas phase contact reaction. The results are shown in Table-3.

Example 3 Except that 29.2 g of antimony trioxide (Sb ₂ O ₃ ) powder was used, titanium ammonium oxalate was not used, and instead, oxalic acid was added 0.27 mol times of Mo. The same operation as in Example 1 was performed to obtain a catalyst precursor. After treating the catalyst precursor at 400 ° C. under air, under a nitrogen stream,
Calcination was performed at 600 ° C. for 2 hours to obtain a composite metal oxide.

The obtained composite metal oxide was subjected to powder X-ray diffraction measurement, and it was confirmed that a compound having the same major diffraction peak as in Example 1 was present. A reactor was charged with 0.5 g of the composite metal oxide as a catalyst, and the reaction temperature was 440.
℃, space velocity SV is 690 h ^-1 , ethane: air =
Gas was supplied at a molar ratio of 1: 5 to perform a gas phase contact reaction. The results are shown in Table-3.

Example 4 A composite metal was prepared in the same manner as in Example 1 except that ammonium metatungstate was added in place of titanium ammonium oxalate so that W became 0.27 mole times of Mo. An oxide fired product was obtained.

The obtained composite metal oxide was subjected to powder X-ray diffraction measurement. As a result, the same main diffraction peak as in Example 1 was observed. Using the composite metal oxide as a catalyst, 0.5 g was charged into a reactor, the reaction temperature was 460 ° C., and the space velocity SV was 5
At 10 h ⁻¹ , gas was supplied at a molar ratio of ethane: air = 1: 5 to perform a gas phase contact reaction. The results are shown in Table-3.

Example 5 In 600 ml of warm water, ammonium metavanadate (NH ₄
After dissolving 35.1 g of VO ₃ ), 29.2 g of antimony trioxide (Sb ₂ O ₃ ) powder was added thereto, and the slurry was heated and stirred for 6 hours, and then ammonium paramolybdate ((NH ₄ ) ₆ Mo ₇ ) O _{2 4} · 4H ₂ O) was added an aqueous solution 600ml containing 176.6 g, to obtain a uniform slurry further the concentration of Nb was added ammonium niobium oxalate solution 22.4g of 2.23 mol / kg. This slurry was subjected to a heat treatment to remove water, thereby obtaining a catalyst precursor. After treating the catalyst precursor in air at 380 ° C., it was calcined at 600 ° C. for 2 hours in a nitrogen stream to obtain a composite metal oxide.

When the obtained composite metal oxide was subjected to powder X-ray diffraction measurement, the same main diffraction peak as in Example 1 was observed. A reactor was charged with 0.5 g of the composite metal oxide as a catalyst, and the reaction temperature was 440 ° C. and the space velocity SV was 1
At 200 h ⁻¹ , gas was supplied at a molar ratio of ethane: air = 1: 5, and a gas phase contact reaction was performed. The results are shown in Table-3.

Example 6 Using the composite metal oxide prepared in Example 5 as a catalyst, 1.0
g into a reactor, the reaction temperature is 420 ° C., and the space velocity is SV.
As 600h ^-1, ethane: air = 1: gas is supplied at a molar ratio of 5 was subjected to gas-phase catalytic reaction. The results are shown in Table-3.

Example 7 Using the composite metal oxide prepared in Example 5 as a catalyst, 0.5
g into a reactor, the reaction temperature is 420 ° C., and the space velocity is SV.
Was set to 690 h ⁻¹ , and a gas was supplied at a molar ratio of ethane: air = 1: 3 to perform a gas phase contact reaction. The results are shown in Table-3.

Example 8 Using the composite metal oxide prepared in Example 5 as a catalyst, 0.5
g in a reactor, a reaction temperature of 430 ° C., and a space velocity SV.
Was set to 1200 h ^-1 , and a gas was supplied at a molar ratio of ethane: air = 1: 20 to perform a gas phase contact reaction. Table-Results
3 is shown.

Example 9 Using the composite metal oxide prepared in Example 5 as a catalyst, 1.0
g in a reactor, the reaction temperature is 340 ° C., and the space velocity is SV.
Was set to 520 h ⁻¹ , and a gas was supplied at a molar ratio of ethane: air = 3: 1 to perform a gas phase contact reaction. The results are shown in Table-3.

Example 10 After adding the Nb component, 10 wt% of SiO ₂ was calculated in terms of dry weight.
% In the same manner as in Example 5, except that silica sol (20 wt% aqueous sol) was added to obtain a catalyst composition containing a composite metal oxide and a carrier. When the obtained catalyst composition was subjected to powder X-ray diffraction measurement, the same main diffraction peak as in Example 1 was observed.

0.7 g of the catalyst composition was charged into a reactor,
Assuming a reaction temperature of 450 ° C. and a space velocity SV of 750 h ⁻¹ ,
Gas was supplied at a molar ratio of ethane: air = 1: 5 to perform a gas phase contact reaction. The results are shown in Table-3.

Example 11 19.1 g of antimony trioxide (Sb ₂ O ₃ ) powder was used, and niobium ammonium oxalate was not used. Instead of niobium oxide sol, the molar ratio of Nb to Mo was 0.05 mol times. A catalyst precursor was obtained by performing the same operation as in Example 5 except that the catalyst precursor was added as described above. 380 ° C under air
And then calcined at 650 ° C. for 5 minutes under a nitrogen stream to obtain a composite metal oxide.

The obtained composite metal oxide was subjected to powder X-ray diffraction measurement. As a result, the same major diffraction peak as in Example 1 was observed. 0.5 g of the composite metal oxide as a catalyst was charged into a reactor, and the reaction temperature was 460 ° C. and the space velocity SV was 6
At 40 h ⁻¹ , gas was supplied at a molar ratio of ethane: air = 1: 5 to perform a gas phase contact reaction. The results are shown in Table-3.

Example 12 23.5 g of antimony trioxide (Sb ₂ O ₃ ) powder, 211.9 g of ammonium paramolybdate were used, and after adding the Nb component, zirconium oxyhydroxide was added to Z.
The same operation as in Example 5 was carried out except that r was added so as to be 0.08 mol times of Mo, to obtain a fired composite metal oxide.

When the obtained composite metal oxide was subjected to powder X-ray diffraction measurement, the same main diffraction peak as in Example 1 was observed. A reactor was charged with 0.5 g of the composite metal oxide as a catalyst at a reaction temperature of 440 ° C., and a space velocity SV of 5 g.
At 20 h ⁻¹ , gas was supplied at a molar ratio of ethane: air = 1: 5 to perform a gas phase contact reaction. The results are shown in Table-3.

Example 13 Except that 22.0 g of antimony trioxide (Sb ₂ O ₃ ) powder was used, and cerium hydroxide was added after the Nb component was added so that Ce became 0.02 mole times of Mo. Was operated in the same manner as in Example 5 to obtain a catalyst precursor. After treating the catalyst precursor in air at 380 ° C.,
Calcination was performed at 0 ° C. for 2 hours to obtain a composite metal oxide.

When the obtained composite metal oxide was subjected to powder X-ray diffraction measurement, the same major diffraction peak as in Example 1 was observed. A reactor was charged with 0.5 g of the composite metal oxide as a catalyst, and the reaction temperature was 450 ° C. and the space velocity SV was 6
At 90 h ⁻¹ , gas was supplied at a molar ratio of ethane: air = 1: 5 to perform a gas phase contact reaction. The results are shown in Table-3.

Example 14 After adding the Ce component, 10 wt% of SiO ₂ was calculated in terms of dry weight.
%, And the same operation as in Example 13 was carried out except that silica sol (20 wt% aqueous sol) was added to obtain a catalyst composition containing the composite metal oxide and the carrier.

The obtained catalyst composition was subjected to powder X-ray diffraction measurement. As a result, the same main diffraction peak as in Example 1 was observed. 0.7 g of the catalyst composition was charged into a reactor, and a gas was supplied at a reaction temperature of 450 ° C. and a space velocity SV of 670 h ^{−1 at} a molar ratio of ethane: air = 1: 5 to perform a gas phase contact reaction. Was. The results are shown in Table-3.

Example 15 10 g of the composite metal oxide catalyst obtained in Example 5 was dispersed in 60 ml of water and charged into a stainless steel pot together with 230 g of spherical zirconia beads having an average particle size of 2 mm. Filled with a stainless steel stirring blade installed in the pot to 23
The mixture was pulverized with stirring at 00 rpm for 2 hours. The content was separated from the beads by filtration, and then dried to obtain a composite metal oxide solid.

When the obtained composite metal oxide catalyst was subjected to powder X-ray diffraction measurement, the same main diffraction peak as in Example 1 was obtained.
Cracks were observed. Using the composite metal oxide as a catalyst, 1.0
g in a reactor, a reaction temperature of 360 ° C., and a space velocity of SV.
Was set to 550 h ⁻¹ , a gas was supplied at a molar ratio of ethane: air = 1: 5, and a gas phase contact reaction was performed. The results are shown in Table-3.

Example 16 22.0 g of antimony trioxide (Sb ₂ O ₃ ) powder was used, 194.2 g of ammonium paramolybdate was used, no titanium ammonium oxalate was used, and oxalic acid was replaced by Mo. 0.1 mol times the amount of zirconium oxyhydroxide, and then 0.05% of Zr was added to Mo.
A catalyst precursor was obtained by performing the same operation as in Example 1 except that oxalic acid was added after the oxalic acid was added in a molar ratio. The catalyst precursor is treated at 380 ° C. in air and then in a stream of nitrogen for 6 hours.
After the treatment at 00 ° C., the mixture was calcined at 550 ° C. for 2 hours to obtain a composite metal oxide.

When the composite metal oxide thus obtained was subjected to powder X-ray diffraction measurement, the same main diffraction peak as in Example 1 was observed. A reactor was charged with 1.0 g of the composite metal oxide as a catalyst, and a gas was supplied at a reaction temperature of 410 ° C. and a space velocity SV of 270 h ^{−1 at} a molar ratio of ethane: air = 1: 5. A catalytic reaction was performed. The results are shown in Table-3.

Example 17 Using the composite metal oxide prepared in Example 16 as a catalyst,
0 g was charged into the reactor, the reaction temperature was 380 ° C., and the space velocity was S.
The gas was supplied at a molar ratio of ethane: air = 1: 2 with V set to 270 h ⁻¹ to perform a gas phase contact reaction. Table 3 shows the results.
Shown in

Example 18 An aqueous solution of tantalum oxalate containing 22.0 g of antimony trioxide (Sb ₂ O ₃ ) powder without using titanium ammonium oxalate and instead containing 0.67 mol / L of tantalum was used. A catalyst precursor was obtained by performing the same operation as in Example 1 except that 8 ml was added. Catalyst precursor under air,
The treatment was carried out at 380 ° C., then at 600 ° C. in a nitrogen stream, and then calcined at 550 ° C. for 2 hours to obtain a composite metal oxide.

When the composite metal oxide thus obtained was subjected to powder X-ray diffraction measurement, the same main diffraction peak as in Example 1 was observed. A reactor was charged with 1.0 g of the composite metal oxide as a catalyst, a gas was supplied at a reaction temperature of 420 ° C., a space velocity SV of 340 h ⁻¹ , and a ethane: air = 1: 5 molar ratio. A catalytic reaction was performed. The results are shown in Table-3.

Example 19 Using the composite metal oxide prepared in Example 18 as a catalyst,
0 g in a reactor, a reaction temperature of 395 ° C., and a space velocity S
The gas was supplied at a molar ratio of ethane: air = 1: 2 with V set to 340 h ⁻¹ to perform a gas phase contact reaction. Table 3 shows the results.
Shown in

[0073] without the use of Example 20 tantalum oxalate solution, instead added 0.18 mol per mol of oxalic acid with respect to Mo, the then chromium nitrate _{(Cr (NO 3) 3 ·} 9H 2 O) Cr Example 1 was added except that was added so as to be 0.05 mol times with respect to Mo.
By performing the same operation as in Step 8, a composite metal oxide was obtained.

When the composite metal oxide thus obtained was subjected to powder X-ray diffraction measurement, the same main diffraction peak as in Example 1 was observed.

A reactor was charged with 1.0 g of the composite metal oxide as a catalyst, the reaction temperature was 440 ° C., and the space velocity SV was 2
At 60 h ⁻¹ , gas was supplied at a molar ratio of ethane: air = 1: 5 to perform a gas phase contact reaction. The results are shown in Table-3.

Example 21 Instead of using a tantalum oxalate aqueous solution, oxalic acid was added in an amount of 0.15 mol times with respect to Mo, and then manganese nitrate (Mn (NO ₃ ) ₂ .6H ₂ O) was added to Mn. Was performed in the same manner as in Example 18, except that was added in an amount of 0.05 mol times with respect to Mo to obtain a composite metal oxide.

When the composite metal oxide thus obtained was subjected to powder X-ray diffraction measurement, the same main diffraction peak as in Example 1 was observed. A reactor was charged with 1.0 g of the composite metal oxide as a catalyst, a gas was supplied at a reaction temperature of 460 ° C., a space velocity SV of 400 h ⁻¹ , and a gaseous ratio of ethane: air = 1: 5. A catalytic reaction was performed. The results are shown in Table-3.

Example 22 A tantalum oxalate aqueous solution was not used, and instead, ammonium iron oxalate (Fe (NH ₄ ) ₃ (C ₂ O ₄ ) ₃ .3H
_A composite metal oxide was obtained by performing the same operation as in Example 18 except that 2O) was added so that Fe was 0.05 mol times the amount of Mo.

When the composite metal oxide thus obtained was subjected to powder X-ray diffraction measurement, the same main diffraction peak as in Example 1 was observed. A reactor was charged with 1.0 g of the composite metal oxide as a catalyst, a gas was supplied at a reaction temperature of 440 ° C., a space velocity SV of 370 h ^{−1 and} a molar ratio of ethane: air = 1: 5. A catalytic reaction was performed. The results are shown in Table-3.

Example 23 Using the composite metal oxide prepared in Example 22 as a catalyst,
0 g in a reactor, a reaction temperature of 400 ° C., a space velocity S
The gas was supplied at a molar ratio of ethane: air = 1: 2 with V set to 370 h ⁻¹ to perform a gas phase contact reaction. Table 3 shows the results.
Shown in

Example 24 Except that the tantalum oxalate aqueous solution was not used, but instead cobalt nitrate (Co (NO ₃ ) ₂ .6H ₂ O) was added so that Co was 0.05 mol times with respect to Mo. Is Example 1
By performing the same operation as in Step 8, a composite metal oxide was obtained.

When the composite metal oxide thus obtained was subjected to powder X-ray diffraction measurement, the same main diffraction peak as in Example 1 was observed. A reactor was charged with 1.0 g of the composite metal oxide as a catalyst, and a gas was supplied at a reaction temperature of 450 ° C. and a space velocity SV of 250 h ^{−1 at} a molar ratio of ethane: air = 1: 5. A catalytic reaction was performed. The results are shown in Table-3.

Example 25 Instead of using an aqueous tantalum oxalate solution, oxalic acid was added in an amount of 0.15 mol times with respect to Mo, and then nickel nitrate (Ni (NO ₃ ) ₂ .6H ₂ O) was added to Ni. Was performed in the same manner as in Example 18, except that was added in an amount of 0.05 mol times with respect to Mo to obtain a composite metal oxide.

When the composite metal oxide thus obtained was subjected to powder X-ray diffraction measurement, the same main diffraction peak as in Example 1 was observed. A reactor was charged with 1.0 g of the composite metal oxide as a catalyst, a gas was supplied at a reaction temperature of 400 ° C. and a space velocity SV of 280 h ^{−1 at} a molar ratio of ethane: air = 1: 5. A catalytic reaction was performed. The results are shown in Table-3.

Example 26 Instead of using an aqueous tantalum oxalate solution, oxalic acid was added in an amount of 0.15 mol times with respect to Mo, and then copper nitrate (Cu (NO ₃ ) ₂ .3H ₂ O) was added to Cu. Example 18 except that was added so as to be 0.05 mole times the Mo.
By performing the same operation as described above, a composite metal oxide was obtained.

When the composite metal oxide thus obtained was subjected to powder X-ray diffraction measurement, the same main diffraction peak as in Example 1 was observed. A reactor was charged with 1.0 g of the composite metal oxide as a catalyst, a gas was supplied at a reaction temperature of 430 ° C., a space velocity SV of 300 h ^{−1 and} a molar ratio of ethane: air = 1: 5. A catalytic reaction was performed. The results are shown in Table-3.

Example 27 Instead of using an aqueous tantalum oxalate solution, oxalic acid was added in an amount of 0.15 mol times with respect to Mo, and then zinc nitrate (Zn (NO ₃ ) ₂ .6H ₂ O) was added to Zn. Example 18 except that was added so as to be 0.05 mole times the Mo.
By performing the same operation as described above, a composite metal oxide was obtained.

When the composite metal oxide thus obtained was subjected to powder X-ray diffraction measurement, the same main diffraction peak as in Example 1 was observed. A reactor was charged with 1.0 g of the composite metal oxide as a catalyst, a gas was supplied at a reaction temperature of 410 ° C. and a space velocity SV of 280 h ^{−1 at} a molar ratio of ethane: air = 1: 5. A catalytic reaction was performed. The results are shown in Table-3.

Example 28 Using the composite metal oxide prepared in Example 27 as a catalyst,
0 g was charged into the reactor, the reaction temperature was 380 ° C., and the space velocity was S.
A gas was supplied at a molar ratio of ethane: air = 1: 2 with V set to 280 h ⁻¹ to perform a gas phase contact reaction. Table 3 shows the results.
Shown in

Example 29 Instead of using an aqueous solution of tantalum oxalate, oxalic acid was added in an amount of 0.19 mol times with respect to Mo, and then aluminum nitrate (Al (NO ₃ ) ₃ .6H ₂ O) was added to Al. Is Mo
A composite metal oxide was obtained by performing the same operation as in Example 18 except that the addition was performed in a molar amount of 0.05 mol.

When the composite metal oxide thus obtained was subjected to powder X-ray diffraction measurement, the same main diffraction peak as in Example 1 was observed. Using the composite oxide as a catalyst:
0 g was charged into the reactor, the reaction temperature was 420 ° C., and the space velocity S
A gas was supplied at a molar ratio of ethane: air = 1: 5 with V set to 260 h ⁻¹ to perform a gas phase contact reaction. Table 3 shows the results.
Shown in

Example 30 Instead of using a tantalum oxalate aqueous solution, oxalic acid was added in an amount of 0.19 mol times with respect to Mo, and then indium nitrate (In (NO ₃ ) ₃ .3H ₂ O) was added to In. Was performed in the same manner as in Example 18, except that was added in an amount of 0.05 mol times with respect to Mo to obtain a composite metal oxide.

When the composite metal oxide thus obtained was subjected to powder X-ray diffraction measurement, the same main diffraction peak as in Example 1 was observed. A reactor was charged with 1.0 g of the composite metal oxide as a catalyst, a gas was supplied at a reaction temperature of 450 ° C. and a space velocity SV of 270 h ^{−1 at} a molar ratio of ethane: air = 1: 5. A catalytic reaction was performed. The results are shown in Table-3.

Example 31 Using the composite metal oxide prepared in Example 30 as a catalyst,
0 g was charged into the reactor, the reaction temperature was 390 ° C., and the space velocity was S.
The gas was supplied at a molar ratio of ethane: air = 1: 2 with V set to 270 h ⁻¹ to perform a gas phase contact reaction. Table 3 shows the results.
Shown in

Example 32 Instead of using an aqueous solution of tantalum oxalate, oxalic acid was added in an amount of 0.1 mol times with respect to Mo, and then an aqueous solution containing 10 wt% of SnO ₂ was added with an amount of Sn of 0 to Mo. .
A composite metal oxide was obtained in the same manner as in Example 18, except that the addition was performed in a molar amount of 05.

When the composite metal oxide thus obtained was subjected to powder X-ray diffraction measurement, the same main diffraction peak as in Example 1 was observed. A reactor was charged with 1.0 g of the composite metal oxide as a catalyst, a gas was supplied at a reaction temperature of 420 ° C. and a space velocity SV of 290 h ^{−1 at} a molar ratio of ethane: air = 1: 5. A catalytic reaction was performed. The results are shown in Table-3.

Example 33 Using the composite metal oxide prepared in Example 32 as a catalyst,
0 g was charged into the reactor, the reaction temperature was 390 ° C., and the space velocity was S.
A gas was supplied at a molar ratio of ethane: air = 1: 2 with V set to 290 h ⁻¹ to perform a gas phase contact reaction. Table 3 shows the results.
Shown in

Example 34 Without using an aqueous solution of tantalum oxalate, oxalic acid was added in an amount of 0.15 mol times with respect to Mo, and then lead nitrate (Pb (NO ₃ ) ₂ ) was added with respect to that of Mo. A composite metal oxide was obtained in the same manner as in Example 18, except that it was added so as to be 0.05 mol times.

When the composite metal oxide thus obtained was subjected to powder X-ray diffraction measurement, the same main diffraction peak as in Example 1 was observed. A reactor was charged with 1.0 g of the composite metal oxide as a catalyst, a gas was supplied at a reaction temperature of 470 ° C., a space velocity SV of 360 h ^{−1 and} a molar ratio of ethane: air = 1: 5. A catalytic reaction was performed. The results are shown in Table-3.

Example 35 22.0 g of antimony trioxide (Sb ₂ O ₃ ) powder was used, and after the Nb component was added, iron ammonium oxalate (Fe
Example 5 except that (NH ₄ ) ₃ (C ₂ O ₄ ) ₃ .3H ₂ O) was added so that Fe was 0.05 mol times with respect to Mo.
By the same operation as described above, a catalyst precursor was obtained. After treating the catalyst precursor in air at 380 ° C, the catalyst precursor was heated at 600 ° C in a nitrogen stream.
After baking at 550 ° C. for 2 hours, a composite metal oxide was obtained.

When the composite metal oxide thus obtained was subjected to powder X-ray diffraction measurement, the same main diffraction peak as in Example 1 was observed. A reactor was charged with 1.0 g of the composite metal oxide as a catalyst, a gas was supplied at a reaction temperature of 470 ° C., a space velocity SV of 500 h ⁻¹ , and a gaseous ratio of ethane: air = 1: 5. A catalytic reaction was performed. The results are shown in Table-3.

Example 36 Except that ammonium iron oxalate was not used and instead cobalt nitrate (Co (NO ₃ ) ₂ .6H ₂ O) was added so that Co was 0.05 mol times as much as Mo. Is Example 3
By performing the same operation as in Step 5, a composite metal oxide was obtained.

The composite metal oxide thus obtained was subjected to powder X-ray diffraction measurement. As a result, the same major diffraction peak as in Example 1 was observed. A reactor was charged with 1.0 g of the composite metal oxide as a catalyst, a gas was supplied at a reaction temperature of 460 ° C., a space velocity SV of 470 h ⁻¹ , and a gas ratio of ethane: air = 1: 5. A catalytic reaction was performed. The results are shown in Table-3.

Example 37 Except that ammonium iron oxalate was not used and nickel nitrate (Ni (NO ₃ ) ₂ .6H ₂ O) was added instead so that Ni became 0.05 mole times of Mo. Is Example 3
By performing the same operation as in Step 5, a composite metal oxide was obtained.

When the composite metal oxide thus obtained was subjected to powder X-ray diffraction measurement, the same main diffraction peak as in Example 1 was observed. A reactor was charged with 1.0 g of the composite metal oxide as a catalyst, a gas was supplied at a reaction temperature of 420 ° C., a space velocity SV of 360 h ^{−1 and} a molar ratio of ethane: air = 1: 5. A catalytic reaction was performed. The results are shown in Table-3.

Example 38 Same as Example 11 except that 17.6 g of antimony trioxide (Sb ₂ O ₃ ) powder was used, and niobium oxide sol was added so that Nb was 0.10 mol times of Mo. By performing the above operation, a catalyst precursor was obtained. Catalyst precursor under air, 38
After treatment at 0 ° C., the mixture was calcined at 600 ° C. for 5 minutes under a nitrogen stream to obtain a composite metal oxide. When the powder X-ray diffraction measurement of the obtained composite metal oxide was performed, the same main diffraction peak as in Example 1 was observed.

10 g of this composite metal oxide was immersed in 100 ml of a 5 wt% oxalic acid aqueous solution heated to 70 ° C. for 6 hours, filtered, washed with water, dried, and further heated to 70 ° C.
It was immersed in t% hydrogen peroxide for 6 hours, filtered, washed with water and dried. The obtained composite metal oxide was subjected to powder X-ray diffraction measurement (using Cu-Kα rays). Unlike the diffraction pattern of Example 1, the set of diffractions shown in Table 1 did not appear. Only the set of diffractions shown in Table 2 appeared. That is,
As diffraction angles 2θ (゜), 6.8, 8.0, 9.1, 2
Major diffraction peaks were observed at 2.3, 27.3, 35.5, 45.3.

Using the composite metal oxide as a catalyst, 0.5 g was charged into a reactor, and a gas was supplied at a reaction temperature of 420 ° C., a space velocity SV of 550 h ⁻¹ and a ethane: air = 1: 5 molar ratio. A gas phase contact reaction was performed. The results are shown in Table-3.

Example 39 10 g of the composite metal oxide washed with oxalic acid, filtered, washed with water and dried in Example 38 was immersed in 100 ml of ethylene glycol heated to 70 ° C. for 6 hours, filtered, washed with water and dried. The obtained composite metal oxide was subjected to powder X-ray diffraction measurement (Cu
However, unlike the diffraction pattern of Example 1, the diffraction set shown in Table 1 did not appear, and only the diffraction set shown in Table 2 appeared. That is, the diffraction angle 2θ
As (゜), 6.8, 8.0, 9.1, 22.3, 2
Main diffraction peaks were observed at 7.3, 35.5, and 45.3.

Using the composite metal oxide as a catalyst, 0.5 g was charged into a reactor, and a gas was supplied at a reaction temperature of 420 ° C., a space velocity SV of 550 h ^{−1 and} a molar ratio of ethane: air = 1: 5. A gas phase contact reaction was performed. The results are shown in Table-3.

Comparative Example 1 31.5 g of niobium oxalate containing 20.6 wt% of Nb in 300 ml of hot water and antimony trioxide (Sb
₂ O ₃ ) 4.5 g of powder were added and stirred at 75 ° C. for 1 hour.
The mixture was heated for 5 minutes to prepare an Nb / Sb-containing aqueous solution.

24.1 g of ammonium metavanadate was added to 300 ml of hot water at 75 ° C., and the aqueous solution containing Nb and Sb prepared above was added and mixed with the aqueous solution heated and stirred for 15 minutes. While stirring the mixed aqueous solution, 7
The mixture was heated at 5 ° C. for 20 minutes to obtain an aqueous solution containing V · Nb · Sb. 117.7 g of ammonium paramolybdate was added to 600 ml of water, heated at 75 ° C. for 15 minutes with stirring, added to the previously prepared aqueous solution containing V · Nb · Sb, and heated and stirred at 75 ° C. for 15 minutes. .

The obtained aqueous solution was subjected to a heat treatment to remove water, and a solid was obtained. The solid was further dried at 120 ° C. for 12 hours, and then molded into a mesh of 16 to 28 to obtain a catalyst precursor. The catalyst precursor was calcined at 350 ° C. for 5 hours in an air stream to obtain a composite metal oxide. When a powder X-ray diffraction measurement of the obtained composite metal oxide was performed, the diffraction angle was 2θ.
As (゜), only one main diffraction peak of 22.2 was observed.

A reactor was charged with 1.0 g of the composite metal oxide as a catalyst, and the reaction temperature was 430 ° C., and the space velocity SV was 4 g.
At 70 h ⁻¹ , a gas was supplied at a molar ratio of ethane: air = 1: 5 to perform a gas phase contact reaction. The results are shown in Table-4.

[0115]

Table 5 Table 3---------------------------Examples Examples Catalyst composition Reaction temperature Space Rate Ethane conversion Ethylene (° C.) (h ^-1 ) Rate (%) Yield (%) ---------------------------------------- −−−−−−− 1 Mo ₁ V _0.3 Sb _0.13 Ti _0.05 On 440 450 89.1 67.0 2 Mo ₁ V _0.3 Sb _0.17 Ti _0.05 On 440 460 88.0 66.6 3 Mo ₁ V _0.3 Sb _0.20 On 440 690 78.8 61.7 4 Mo ₁ V _0.3 Sb _0.13 W _0.05 On 460 510 84.1 62.3 5 Mo ₁ V _0.3 Sb _0.20 Nb _0.05 On 440 1200 87.9 66.6 6 Mo ₁ V _0.3 Sb _0.20 Nb _0.05 On 420 600 91.5 68.0 7 Mo ₁ V _0.3 Sb _0.20 Nb _0.05 On 420 690 76.8 63.38 Mo ₁ V _0.3 Sb _0.20 Nb _0.05 On 430 1200 87.7 65.4 9 Mo ₁ V _0.3 Sb _0.20 Nb _0.05 On 340 520 11.5 11.0 10 Mo ₁ V _0.3 Sb _0.20 Nb _0.05 On * 450 750 90.6 69.5 11 Mo ₁ V _0.3 Sb _0.13 Nb _0.05 On 460 640 85 0.6 64.2 12 Mo ₁ V _0.25 Sb _0.13 Zr _0.08 440 520 89.9 71.1 Nb _0.04 On 13 Mo ₁ V _0.3 Sb _0.15 Nb _0.05 450 690 90.3 70.2 Ce _0.02 On 14 Mo ₁ V _0.3 Sb _0.15 Nb _0.05 450 670 90.7 70.4 Ce _0.02 On * 15 Mo ₁ V _0.3 Sb _0.20 Nb _0.05 On 360 550 83.5 62.1 −−−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−−−−−− (* indicates 10 wt% of SiO ₂ )

[0116]

Table 6 (Continued)---------------------------Examples Examples Catalyst composition Reaction temperature Space velocity Ethane conversion Ethylene (° C) (h ^-1 ) Rate (%) Yield (%) ------------------------------------------ −−−−−−−−−−− 16 Mo ₁ V _0.27 Sb _0.14 Zr _0.05 On 410 270 87.9 71.2 17 Mo ₁ V _0.27 Sb _0.14 Zr _0.05 On 380 270 59.9 54.8 18 Mo ₁ V _0.3 Sb _0.15 Ta _0.05 On 420 340 88.4 68.2 19 Mo ₁ V _0.3 Sb _0.15 Ta _0.05 On 395 340 57.0 51.1 20 Mo ₁ V _0.3 Sb _0.15 Cr _0.05 On 440 260 84.4 59.2 _{21 Mo 1 V 0.3 Sb 0.15 Mn} 0.05 On 460 400 86.8 64.8 22 Mo 1 V 0.3 Sb 0.15 Fe 0.05 On 440 370 89.8 63.1 23 Mo 1 V 0.3 Sb 0.15 Fe 0.05 On 4 _{0 370 59.0 52.7 24 Mo 1 V} 0.3 Sb 0.15 Co 0.05 On 450 250 84.9 58.6 25 Mo 1 V 0.3 Sb 0.15 Ni 0.05 On 400 280 84.1 64.1 26 Mo 1 V 0.3 Sb _0.15 Cu _0.05 On 430 300 81.0 58.2 27 Mo ₁ V _0.3 Sb _0.15 Zn _0.05 On 410 280 89.3 70.7 28 Mo ₁ V _0.3 Sb _0.15 Zn _0.05 On 380 280 60.6 55.4 29 Mo ₁ V _0.3 Sb _0.15 Al _0.05 On 420 260 85.2 63.0 30 Mo ₁ V _0.3 Sb _0.15 In _0.05 On 450 270 82.7 65.6 31 Mo ₁ V _0.3 Sb _0.15 In _0.05 On 390 270 58.1 52 .4 ---------------------------------------------------------------------------

[0117]

Table 7 Table 3 (continued)-----------------------------Examples Examples Catalyst composition Reaction temperature Space velocity Ethane conversion Ethylene (° C) (h ^-1 ) Rate (%) Yield (%) ------------------------------------------ −−−−−−−−−−− 32 Mo ₁ V _0.3 Sb _0.15 Sn _0.05 On 420 290 89.6 66.2 33 Mo ₁ V _0.3 Sb _0.15 Sn _0.05 On 390 290 57.9 51.8 34 Mo ₁ V _0.3 Sb _0.15 Pb _0.05 On 470 360 84.6 62.3 35 Mo ₁ V _0.3 Sb _0.15 Nb _0.05 470 500 84.1 57.5 Fe _0.05 On 36 Mo ₁ V _0.3 Sb _0.15 Nb _0.05 460 470 82.2 52. _{1 Co 0.05 On 37 Mo 1 V} 0.3 Sb 0.15 Nb 0.05 420 360 87.6 63.8 Ni 0.05 On 38 Mo 1 V 0.26 Sb 0.09 Nb 0.12 O n 420 550 86.5 60.8 39 Mo 1 V 0.2 _{8 Sb 0.09 Nb 0.11 O n 420} 550 85.1 61.1 ----------------------------------- −

[0118]

Table 8 Table 4 ----------------------------------------------------------- Comparative Example Catalyst Composition Reaction Temperature Space Rate Ethane conversion Ethylene (° C.) (h ^-1 ) Rate (%) Yield (%) ---------------------------------------- −−−−−−− 1 Mo ₁ V _0.3 Sb _0.040 Nb _0.10 On 430 470 68.5 32.1 −−−−−−−−−−−−−−−−−−−−−−−−−− −−−−−−−−−−−−−

[0119]

According to the present invention, it is possible to produce ethylene from ethane in a high yield at a relatively low temperature without the coexistence of halogen or the like in the reaction system and without using particularly expensive elements. Can be done.

Claims (5)

[Claims] In producing ethylene by contacting ethane with a molecular oxygen-containing gas at a high temperature in the presence of a catalyst, the catalyst contains Mo, V and Sb as essential components, and its powder X-ray. Diffraction is mainly in the following table-
A method for producing ethylene, comprising using a catalyst containing a composite metal oxide having a characteristic pattern shown in Table 1 and / or Table 2. Table 1 Table 1 ----------------------------------------------------------- Diffraction angle 2θ (゜) Relative peak intensity (%) ------ −−−−−−−−−−−−−−−−−−−−−−−− 22.2 ± 0.4 (100) 28.3 ± 0.4 (400 to 10) 36.2 ± 0.4 (80-3) 45.1 ± 0.4 (50-3) 50.0 ± 0.4 (50-3) -------------------------------------------------------------------------- −−−− (Using Cu-Kα ray) (The number in parentheses indicates the relative peak intensity when the peak of 22.2 ° is set to 100.) −−−−−−−−−−−−−−−−−−−−−−−−−− Diffraction angle 2θ (゜) Relative peak intensity (%) −−−−−−−−−−−−− −−−−−−−−−−−−− 6.7 ± 0.4 (15 to 1) 7.9 ± 0.4 (20 to 1) 9.1 ± 0.4 (20-1) 22.2 ± 0.4 (100) 27.3 ± 0.4 (80-8) 35.5 ± 0.4 (15-3) 45.2 ± 0.4 (50 to 3) (using Cu-Kα radiation) (the number in parentheses is 22.2%). The relative peak strength is shown when the peak is set to 100.) 2. The catalyst according to claim 1, wherein the powder X-ray diffraction is mainly represented by the following formula:
The method for producing ethylene according to claim 1, wherein the catalyst is a catalyst containing a composite metal oxide obtained by physically pulverizing a composite metal oxide having the characteristic pattern shown in Table 1 and / or Table 2. 3. A catalyst comprising Mo, V, Sb and X (where X is
Represents Ti, Zr, Nb, Ta, Cr, W, Mn, Fe,
Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, A
g, at least one metal element selected from Zn, Al, In, Sn, Pb, Bi and Ce) as an essential component, and the ratio of the metal element M to the total contained metal elements is represented by a mole fraction r
When represented by M, there is a relationship of 0.25 <rMo <0.980.003 <rV <0.50.003 <rSb <0.50.003 <rX <0.5 The method for producing ethylene according to claim 1 or 2, which is a catalyst containing such a composite metal oxide. 4. A mixed metal oxide is obtained by adding and mixing a compound containing Mo and a compound containing element X to an aqueous solution containing a V-containing component and an Sb-containing component and then drying the aqueous solution. The method for producing ethylene according to claim 3, which is a composite metal oxide prepared through a step of calcining a catalyst precursor. 5. The method according to claim 1, wherein at least a part of the unreacted ethane present in the reaction product is separated from the reaction product, mixed with the starting ethane, and then subjected to the reaction again. For producing ethylene.