[Technology]
Mutual citations and related applications
This application claims the benefit of the priority date of November 2016 in January based on the Korea Patent Application No. 10-2016-01446 Erhu, and all information disclosed in the literature of the Korea patent application are included as part of the specification.
The present invention relates to a process for producing unsaturated aldehyde and unsaturated carboxylic acid.

- that the technical background of the invention;

In general, the shell-and-tube type heat exchanger of Al-and-tube banung group is one form of reactor that is used for the purpose of efficiently removing the heat generated by the reaction. A heat medium so that in this type of reactor thick and a solid catalyst in a plurality of reaction ryubeu layer, supplying a material gas to the banung tube causes a chemical banung for obtaining the desired component, a chemical reaction can take place at the optimal level to half unggi shell It is circulated.

Multi-tubular shell-and-tube half the unggi tends to hot spot (hot spot) occurs in a localized point of the reaction ryubeu, these hot spots are the selectivity decreases for reduced life to the desired target product due to deterioration of the catalyst and causing the same problem. Thus it has been to efficient heat transfer to the inner half unggi plurality of reaction tubes attempt Various methods for reducing the hot spot. However, in the high load banung process, the degree of improvement in accordance with these attempts do not cheungbun, the development of technology that can achieve a high yield and operational stability, while effectively controlling the silver is in the hot spot is still needed.

[Prior Art Document]

[Patent Document]

[Patent Document 1] JP-Republic of Korea Patent Application Publication No. 2006-009 4 87 4 No. (30.08.2006) Patent Document 2: Republic of Korea Patent Application Publication No. 2012-0079617 call (07.13.2012)

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[Content of invention]

[Problems to be solved;

The present invention provides a method for producing unsaturated aldehyde and unsaturated carboxylic acid shown an improved yield and operational stability by effectively controlling the heat banung eu

[Solving means of a problem]

According to the invention,

The catalyst of the layered fixed bed multi-tube heat medium circulation system shell-and-by using a ryubeu banung, the at least one compound selected from propylene, isobutylene, t- butyl alcohol, and methyl -t- butyl ether as a raw material , and by gas phase oxidation by the molecular oxygen or molecular oxygen-containing gas in the method for producing an unsaturated aldehyde and unsaturated carboxylic acid to Daewoong to the raw material;

Of the multi-stage heat medium circulation system shell-and-tube reactor, a cylindrical shell, a plurality of tube sheets, both a plurality of space independent on the inside of the shell, each spatially contiguous to separate the interior of the shell into a plurality of spatial independent It comprises a baffle (baffle), and a plurality of tubes through said plurality of banung ryubeu sheet and a baffle secured to the inside of the shell to separate the zones, and;

The plurality of independent spaces in the interior of the shell, each independently selected from 280 to 400 by the flow of heating medium separate ° becomes the heat transfer for the tube banung done at a temperature of C;

Banung the tubes there are at least four fixed catalyst bed zone a spatially continuous, and wherein the fixed catalyst bed zone is having a high activity to an exit direction from the inlet of the tube banung,

The method of producing an unsaturated aldehyde and unsaturated carboxylic acid is provided.

According to the following, implementation of the invention will be described in detail for producing the unsaturated aldehyde and unsaturated carboxylic acid.

In the meantime, unless expressly stated herein, the terminology is just

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It intended to refer to a specific embodiment and are not intended to limit the present invention. As used herein, the singular forms also include the plural forms a phrase that does not represent a meaning clearly contrary in this way.

As used herein 11 means including "are specific characteristics, regions, integers, steps, operations, elements, and / or and refine the components, other specific characteristics, regions, integers, steps, operations, elements, components and / or the group the presence of or not to exclude the addition.

The continuous study of the inventors a result, the fixed bed multi-tubular shell-end-in ryubeu unsaturated aldehyde Using a banung and manufacturing methods of the unsaturated carboxylic acid, do the heat transfer to the banung ryubeu as independent temperature through the heat medium circulation of the independent multi-stage and, if from an inlet of banung ryubeu to introduce a fixed catalyst bed zone having the highest activity in the outlet direction, and it was confirmed to be capable of ensuring an improved yield and operational stability. I raw material gas when introduced into banung tube due to high concentration of banung to the front end of the banung tube severe heat generation locally, method of producing unsaturated aldehyde and unsaturated carboxylic acid according to the invention, the shell-tube half unggi-and to give an independent activity and temperature control is possible for the fixed catalyst bed zone, may exhibit an improved yield and operational stability.

More specifically, according to one embodiment of the invention,

The catalyst of the layered fixed bed multi-tube heat medium circulation system shell-and-tube by using a banung, the at least one compound selected from propylene, isobutylene, t- butyl alcohol, and methyl -t- butyl ether as a raw material , and by gas phase oxidation by the molecular oxygen or molecular oxygen-containing gas in the method for producing an unsaturated aldehyde and unsaturated carboxylic acid to Daewoong to the raw material;

The shell of the multi-stage heat medium circulation system-and-tube banung group, cylindrical shell, a plurality of ryubeu sheet, both the plurality of space independent on the inside of the shell, each spatially contiguous to separate the interior of the shell into a plurality of spatial independent baffle (baffle) to separate the zones, and a plurality of banung ryubeu fixed inside the shell passing through the plurality of ryubeu sheet and the baffle;

The plurality of independent spaces in the interior of the shell, each independently by the flow of a separate heating medium 280 to 400 ° at a temperature of C with respect to the tube banung

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The transfer is made;

The banung ryubeu there exist at least four fixed catalyst bed zone a spatially continuous, and wherein the fixed catalyst bed zone is having a high activity to an exit direction from the inlet of the tube banung,

The method of producing an unsaturated aldehyde and unsaturated carboxylic acid is provided.

According to one embodiment of the invention, the method for producing the unsaturated aldehyde and unsaturated carboxylic acid,

Cylindrical shell,

Baffle (baffle) separating a plurality of independent spaces in the interior of the shell into two areas, each spatially contiguous, ryubeu plurality of sheets, to separate the interior of the shell into a plurality of separate spaces, and

Ryubeu the plurality of sheets and to pass through the baffles the plurality of reaction tubes fixed to the inside of the shell

It is carried out by using a ryubeu banung-and-shell comprising a.

The interior of the shell is the is separated into a plurality of ryubeu sheet plurality of space independent by, in the plurality of spaces each independently selected from 280 to 400 by the flow of a separate heating medium ° takes place in heat transfer to the banung ryubeu at a temperature of C .

Preferably, the plurality of independent spaces inside the shell, the flow of the heating medium from the independent multi-stage inlet of the banung tube having a high silver is the exit direction of the heat transfer takes place for the banung ryubeu.

In addition, the tube has banung there are at least four fixed catalyst bed zone a spatially continuous, and wherein the fixed catalyst bed zone is the catalyst is layered so as to have a high activity in the exit direction from the inlet of banung ryubeu.

The tube sheet is to separate the inner space of the shell to enable adjustment of banung temperature by independent heating medium. The plurality of independent spaces inside the shell is provided with annular duct and the annular duct connected to the exhaust duct connected to a heat medium supply duct, thereby enabling each of the independent flow of the heating medium.

In each of the independent flow of the heating medium, a heat medium supplied via the annular conduit connected to the supply duct reaction flows along the S-shaped flow path formed by baffles

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Exchanges heat with the tube.

The source gas is supplied through the supply duct connected to the plurality of banung tube, while passing through the plurality of tubes so banung again collected after banung is made is discharged through the outlet duct.

As the heating medium may be used as a molten salt containing a nitrate and / or nitrite.

Hereinafter, a case in which the interior of the shell separated by an independent two spaces typical example. However, it will be presented an example of one implementation of the present invention, this does not intend to hinjeong the scope of, and various modifications are possible within the scope of the invention eu

In ryubeu half unggi, - a typical example, the unsaturated aldehyde and unsaturated carboxylic acid production process is performed shell-and

The plurality of ryubeu sheet and separating the interior of the shell into two separate spaces;

The two spaces are separated by the plurality of ryubeu sheet is divided into two sections, each spatially contiguous by the baffle;

The banung ryubeu there are four fixed catalyst bed zone to Daewoong the zone formed by the baffles may be present.

Specifically, the fixed catalyst bed zone is the first to fourth fixed catalyst bed comprises a band, and the first fixed catalyst bed zone is catalytically active with a fourth failure catalyst zone from the inlet of banung tube having a high activity to the outlet direction in may have a 75 to 85% active.

Preferably, the first fixed catalyst bed zone represents the fourth fixed catalyst bed zone is 75 to 85% of the activity of the catalyst having activity; The second fixed catalyst bed zone represents the fourth fixed catalyst bed zone is 85 to 95% of the activity of the catalyst having activity; The third fixed catalyst bed zone is the fourth band is a measure of a fixed catalyst bed of 95 to 98% of the activity of the catalyst having activity, it may be advantageous to obtain an improved yield and operational stability.

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And, in the shell interior, and by the plurality of sheets from the entrance of ryubeu banung ryubeu separate independent first and second internal space to an exit direction; 11, the low temperature of the first heat medium flowing through the inner space may be adjusted lower than the temperature of the second heat medium flowing through the second interior space.

Preferably, in the first internal space by the flow of the first medium 295 to 350 ° is the heat transfer to the banung ryubeu done at a temperature of C; In the second internal space and the second flow to 300 to 400 by a heating medium ° may be heat transfer to the banum tube made of silver is in the C.

By performing the heat transfer for each banung ryubeu independent silver is through the heat medium circulation of the independent multi-stage, and introducing a fixed catalyst bed zone having the highest activity in the outlet direction from the inlet of the banung tube as described above, the temperature of the hot spot while effectively controlling it is possible to ensure a high operation stability and sueul.

On the other hand, the catalytic activity of the fixed catalyst bed zone can be controlled through adjustment of the size, volume occupied, of the alkali metal type, the content of the alkali metal-free, the firing temperature of the catalyst of the layered catalyst.

The catalyst may be a complex metal oxide represented by the following general formula (1):

Formula 1

MoaBib M cM 2 dm3 e M 4 fM 5 gM 6 hOi

In the formula 1,

And Mo is molybdenum;

And Bi is bismuth,

M 1 is at least one element selected from the group consisting of W, Sb, As, P, Sn, and Pb,

M 2 is one or more elements selected from the group consisting of Fe, Zn, Cr, Mn, Cu, Pd, Ag, and Ru,

M 3 is at least one element selected from the group consisting of Co, Cd, Ta, Pt, and Ni,

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M 4 is at least one element selected from the group consisting of Al, Zr, V, and Ce, M 5 is at least one element selected from the group consisting of Se, Ga, Ti, Ge, Rh, and Au,

M 6 is at least one element selected from the group consisting of Na, K, Li, Rb, Cs, Ca, Mg, Sr, and Ba,

a, b, c, ά, e, i, g, h, and i are atomic ratios of the elements,

when a = 12 days, b is 0.01 to 20, c is from 0 to 20, d is from 0.001 to 15, e is from 0.001 to 20, f is from 0 to 20, g is from 0 to 10, h is 0Ό01 to 10, i is a numerical value determined by the oxidation states of the respective elements.

There is no particular limitation on the raw material compounds used in the formation of the catalyst may be applied by combining the ammonium salt of the metal element, a nitrate, carbonate, chloride, sulfate, hydroxide, organic acid salt, oxide, or a common compound.

Preparation of the catalyst, comprising: preparing a suspension by dissolving or dispersing the starting compound in water; To afford a solid and the suspension is dried; The step of forming the solid into a suitable shape; And it can be carried out in a process comprising the step of calcining the molded solid.

In addition, the catalysts can be used by supporting on an inert carrier. When using the inert carrier, the step of contacting the suspension with an inert carrier impregnated prior to performing the drying step it may be further carried out with.

There is no particular limitation on the shape of the catalyst may be applied snout spherical, columnar (cylindrical), the cylindrical cavity, ring-like, and irregular. The shape of the charge in the fixed catalyst bed zone catalyst layer may be the same or different from the black (for example, the inlet side of the reaction ryubeu catalyst is spherical, the outlet end of the tube is banung pellet catalyst and the like). However, in general, it is desirable to convey the same shape layer.

The size of the catalyst, in the case of columnar that the ratio (L / D) of length (L) and diameter (D) of the catalyst of 0.5 to 1.3, preferably; For columnar rectangular and preferably the outer diameter (D) of the catalyst is from 3 to 10 mm.

The firing may be carried out for 1 to 10 hours at a temperature of 300 to 600 ° C under a gas flow of 0.2 to 2 m / s. The firing may be performed in the activity block gas, an oxidizing atmosphere, or a reducing atmosphere.

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According to one embodiment of the invention, it banung conditions for the gas phase oxidation is, propylene, isobutylene, t- butyl alcohol, and methyl and -t- of the at least one compound selected from ether as a raw material, molecular oxygen or by gas phase oxidation by the molecular oxygen-containing gas it may be applied in the usual conditions in the method for producing an unsaturated aldehyde and unsaturated carboxylic acid to Daewoong to the raw material.

In one embodiment, gas containing space of inert gas (e.g. nitrogen, carbon dioxide, water vapor, etc.) that acts velocity 90 hr-i or more of propylene, 10 to 20% by volume as the dilution agent of molecular oxygen, and 60 to 80% by volume of common a compound, from 250 to 500 ° there is a C temperature and 0.1 to 3 kg / cm 'G pressures, contacting with the catalyst at a space velocity ranges from 300 to 5000 hr STP) for a total flow banung intention can be performed.

In addition, analysis of the banung water and the product can be carried out through gas chromatography.

【Effects of the Invention】

According to the invention, the shell-and-tube half by an independent activity given to the temperature controllable for the unggi fixed catalyst bed zone of the production process of improved yield and operational stability unsaturated aldehyde and unsaturated carboxylic acid shown to be provided .

- specific information for carrying out the invention;

Or less, it presents a preferred embodiment for better understanding of the invention. However, the practice of the following examples are not intended to limit the may make invention to illustrate the invention to these.

Preparation Example 1

While stirring 2,500 ml of distilled water heated to from 70 to 85 ° C by dissolving 1,000 g of ammonium molybdate was prepared solution (1).

To 400 ml distilled water 274 g of bismuth nitrate, ferric nitrate and 228 g of potassium nitrate was added to 4.7 g, was added by 71 g of nitric acid were mixed well to prepare a dissolved solution (2).

By dissolving 1097 g of cobalt nitrate in 200 ml of distilled water to prepare a solution (3).

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The solution (2) The silver and the water solution after heunhap combined common and the solution (3) from 40 to 60 ° while maintaining the common C were combined in the solution (1) was produced as a catalyst suspension.

Drying the catalyst suspension was obtained the solid catalyst, it was ground to particle size of less than 150.

It was mixed for two hours after the pulverized powders was molded in a cylindrical outer diameter of 7.0 mm (D), and 7.7 mm in length (L) of.

Wherein the cylindrical catalyst in the air atmosphere 480T: fired for 5 hours under the NfeBuFe Cos.oKcu is to obtain a composite metal oxide catalyst (catalyst A).

Preparation 2

Adjusting the content of potassium nitrate to 3.76 g and; Molding a catalyst powder to a cylindrical outside diameter (D) and 6.5 mm in length (L) of 6.0 mm, and; This air atmosphere of 470 ° , except that the calcination for 5 hours under C,

In the same manner as in Production Example 1 M ^ B ^ FeuCos.oKo.os is to obtain a composite metal oxide catalyst (catalyst B).

Preparation 3

The content of the nitric acid kalreum and adjusted to 2.82 g; Molding a catalyst powder to a cylindrical outside diameter (D) and 5.5 mm in length (L) of 5.0 mm, and; This air atmosphere of 460 ° , except that the firing for 5 hours under C,

In the same manner as in Preparation Example 1 to obtain an additive of complex metal oxide catalyst (Catalyst C) Mi2BL2FeL2C08.oKo.06.

Preparation 4

Adjusting the content of potassium nitrate to 2.35 g and; Molding a catalyst powder to a cylindrical outside diameter (D) and 4.5 mm in length (L) of 4.0 mm, and; This air atmosphere of 450 ° , except that the calcination for 5 hours under C,

In the same manner as in Production Example 1 M ^ B ^ Fe Cos.oKo.os is to obtain a composite metal oxide catalyst (catalyst ϋ).

Example 1

Cylindrical shell, the three tube to separate the interior of the shell to separate the two spaces sheet, the baffle that separates the separate two spaces in the interior of the shell into two areas, each spatially contiguous (baffle), and the ryubeu sheet through the baffle shell including a plurality of reaction tubes fixed to the inside of the shell (inner diameter 1 inch, length 300 cm, stainless steel) - groups was prepared banung tube-end.

Banung the tube has, as four fixed catalyst bed zone corresponding to the zone formed by the baffle, from the inlet of the reaction tube it was set to the first to fourth fixed catalyst bed zone having the highest activity in the outlet direction.

Specifically, the banung ryubeu is, to which the catalyst A by a length of 700 mm from the inlet fills the first fixed catalyst charge and the band; 700 mm in length by a second fixed catalyst bed zone to which the catalyst B of the layered; Of the length of 1000 mm it is filled with the catalyst C Source 13 fixed catalyst bed zone; And 000 mm in length by a fourth fixed catalyst bed zone to which the catalyst D was packed in the set.

In the first internal space of the inlet side of the banung tube of separate two spaces in the interior of the shell, the first 295 by the flow of the heating medium (a molten nitrate) ° of the banung tube to a temperature in C: the first and second fixed - the transfer of the catalyst band was done.

In the second inner space of the outlet side of the banung tube of separate two spaces in the interior of the shell, the first heat medium independent of the second heat medium (molten nitrate) 300 by the flow of a ° in the banung tube at a temperature of C the heat transfer to the third and fourth fixed catalyst band was done. '

Reaction ryubeu, the reaction pressure of 1-3 atm under a space velocity of 120 hr 1 of propylene, 16% by volume of oxygen, 10 vol. 0 / 0 of water vapor, and 65 heunhap gas containing nitrogen in a volume% is was supplied, 300 ° C and passed under a contact time of 2 seconds.

Example 2

To the reaction ryubeu, to which the catalyst A as the 700 mm length from the inlet fills the first fixed catalyst bed zone; 700 mm in length by a second fixed catalyst bed zone to which the catalyst B filled in; The length of the 800 mm is filled with the catalyst C that i 3 fixed catalyst charge and the band; And the length of 800 mm, except that the catalyst D of the fourth fixed catalyst bed zone is set to filling,

The gas phase oxidation reaction in the same manner as Example 1 was carried out.

Comparative Example 1

The banung ryubeu on, to which the catalyst A as the 700 mm length from the inlet fills the first fixed catalyst bed zone; A 700 mm by the length of the catalyst B filled with a second fixed catalyst charge and the band; The length of 1600 mm as the catalyst D-filled third fixed catalyst bed was set band;

The crab except that the so that the heat transfer to the third fixed catalyst bed zone carried by the first and second flow of the second heat medium in heat transfer to the second fixing zone comprises a catalyst layer, by the flow of the first medium,

The Example 1 was performed with a gas phase oxidation in the same manner banung di-: '

Comparative Example ί

The first fixed in the reaction tube, the length of 700 mm from the inlet to the catalyst A packed catalyst zone; The length of 2300 mm as the catalyst D-filled second fixed catalyst bed was set band;

The heat transfer to the length of 700 mm of the first first fixed catalyst bed zone and the body 2 fixed catalyst bed zone by the flow of the heat medium is made, by the flow of the second medium 2 : for the rest of the fixed catalyst bed zone except that the heat transfer to occur, and

The gas phase oxidation banung as Example 1 was carried out.

Test Example

Examples and Comparative were measured the temperature of hot spots in the gas phase oxidation banung according to an embodiment, the selectivity (%) of the propylene conversion rate (%), acrylic acid and the arc in accordance with the equation for lane following, and yield (% ) it was calculated.

Equation 1

Conversion of propylene (%) = [(number of moles of the banung propylene) / (mole number of supplied propylene * 100

Equation (2)

Acrylic acid selectivity (%) = [(number of moles of the generated acid and the arc lane) / (mol number of reacted propylene) to (AA), and the lane arc (ACR) 100 *

[Equation 3]

Acrylic acid (AA) and the yield of the arc lane (ACR) (%) = [(number of moles of the generated acid and the arc lane) / (mol number of supplied propylene)] x 100

[Table 1]

Table 1 With reference to, the embodiment of the production method of the unsaturated aldehyde and unsaturated carboxylic acid according to the high selectivity for, as well as a hot spot silver is markedly lower the desired product as compared to the manufacturing method of the non-u For the D was found to represent the yield.

[Claims]
[Claim 1]
All of the catalyst-filled fixed bed shell-and-tube type multi-stage heating medium circulating system shell-and-using ryubeu reactor, the at least one compound selected from propylene, isobutylene, t- butyl alcohol, and methyl -t- butyl ether as a raw material , and by gas phase oxidation by the molecular oxygen or molecular oxygen-containing gas in the method for producing an unsaturated aldehyde and unsaturated carboxylic acid to Daewoong to the raw material;

The shell of the multi-stage heat medium circulation system - the end-tube banung group, cylindrical shell, a plurality of ryubeu sheet, both the plurality of space independent on the inside of the shell, each spatially contiguous to separate the interior of the shell into a plurality of spatial independent baffle (baffle) to separate the zones, and a plurality of banung ryubeu fixed to the interior of the shell through a plurality of tube sheets and the baffle;

In the plurality of spatial independence on the inside of the shell becomes the heat transfer for the banung ryubeu done at a temperature of 280 to 400 ° C each independently by the flow of a separate heating medium;

The reaction tube has a spatially continuous in at least four fixed catalyst bed zone, present, and washing-machine fixed catalyst charge and the band having a high activity in the exit direction from the inlet flow banung beukkoe,

The method of unsaturated aldehyde and unsaturated carboxylic acid.

[Claim 2]

According to claim 1,

The plurality of independent spaces inside the shell, by the flow of an independent multi-stage heating medium from an inlet of the reaction tubes with a high temperature in the outlet direction is formed on the heat transfer tube banung,

The method of unsaturated aldehyde and unsaturated carboxylic acid.

[Claim 3]

According to claim 1,

It said plurality of tube sheets and separating the interior of the shell into two separate spaces;

The two spaces are separated by a plurality of tube sheet is divided into two sections, each spatially contiguous by the baffle;

The banung ryubeu that has four fixed catalyst bed zone corresponding to the zone defined by said baffle is present,

The method of unsaturated aldehyde and unsaturated carboxylic acid.

[Claim 4]

4. The method of claim 3,

The fixed catalyst bed zone is, and from the inlet of banung ryubeu includes first to fourth fixed catalyst bed zone having the highest activity in the outlet direction,

The first fixed catalyst bed zone is indicative of the fourth fixed catalyst bed zone is 75 to 85% of the activity of the catalyst having activity,

The method of unsaturated aldehyde and unsaturated carboxylic acid.

- claims. 5;

4. The method of claim 3,

The interior of the shell, and from the inlet of the tube banung by the plurality of the tube sheet is divided into separate first and second internal space to the outlet direction,

The temperature of the first heat medium flowing through the first internal space is controlled to be lower than the temperature of the second heat medium flowing through the second internal space,

The method of unsaturated aldehyde and unsaturated carboxylic acid.

[6.]

6. The method of claim 5,

In the first internal space by the flow of the first medium 295 to 350 ° is the heat transfer for the reaction tube made of a temperature of C,

The second inner space in the temperature of the first to the flow of the heating medium 2 300 00 ° C comprising a heat transfer for the reaction ryubeu,

The method of unsaturated aldehyde and unsaturated carboxylic acid.

[7.]

According to claim 1,

The catalyst is the following method of producing a composite metal oxide, an unsaturated aldehyde and unsaturated carboxylic acid represented by the general formula (1):

Formula 1

Bib

In the formula 1,

And Mo is molybdenum;

And Βί is bismuth,

Μ 1 is at least one element selected from the group consisting of W, Sb, As, P, Sn, and Pb,

M 2 is Fe, Zn,: is at least one element selected from the group consisting of r, Mn, Cu, Pd, Ag, and Ru,

M 3 is at least one element selected from the group consisting of Co, Cd, Ta, Ft, and Ni,

M 4 is . Αί, Ζϊ, V, and one or casing selected from the group consisting of Ce ' is an element of, M 5 is at least one element selected from the group consisting of Se, Ga / Ti, Ge, Rh, and Au,.

M 6 is at least one element selected from the group consisting of Na, K, Li, Rb, Cs, Ca, Mg, Sr, and Ba,

a, b, c, d, e, f, g, h, and i is the atomic ratio of each element;

when a = 12 days, b is coming from 01 to 20, (: 0 to 20, d is from 0.001 to 15, e is from 0.001 to 20, f is from 0 to 20, g is from 0 to 10, h is from 0.001 to 10, i is a numerical value determined by the oxidation states of the respective elements.