KR20070116724A - Process for preparing unsaturated aldehyde and unsaturated carboxylic acid - Google Patents

Abstract

A method for preparing an unsaturated aldehyde and an unsaturated carboxylic acid is provided to inhibit the excessive heat generation at hot spot, thereby reducing the temperature at hot spot effectively and increasing the yield of acrolein and acrylic acid from propylene or methacrolein and methacrylic acid from isobutylene or t-butanol. A method for preparing an unsaturated aldehyde and an unsaturated carboxylic acid comprises the steps of supplying a compound selected from propylene, isobutylene and t-butyl alcohol and an oxygen molecule to a reactor tube filled with a mixture oxide catalyst; and carrying out the catalytic oxidation of the compound and the oxygen molecule in gas phase, wherein the reactor tube is filled with a plurality of mixture oxide catalysts in such a pattern that the catalytic activity increases from the gas inlet to the outlet. The mixture oxide catalysts comprise molybdenum, bismuth and iron, show different catalytic activities, and are heated in the presence of a reducing compound.

Description

Process for preparing unsaturated aldehyde and unsaturated carboxylic acid {PROCESS FOR PREPARING UNSATURATED ALDEHYDE AND UNSATURATED CARBOXYLIC ACID}

FIELD OF THE INVENTION

The present invention relates to a process for producing unsaturated aldehydes and unsaturated carboxylic acids by catalytically oxidizing a compound selected from the group consisting of propylene, isobutylene and tert.-butyl alcohol in the gas phase using oxygen molecules.

Prior art in the field

It is well known in the art to produce unsaturated aldehydes and unsaturated carboxylic acids by catalytic oxidation of propylene, isobutylene and / or tert.-butyl alcohol in the gas phase in the presence of molybdenum-bismuth-iron mixed oxide catalysts.

This oxidation reaction is typically carried out by feeding the raw gas into a reactor tube filled with a catalyst. Commercially, oxidation reactions are often carried out using multitubular reactors. Since the oxidation reaction is very exothermic, a localized high-temperature zone, commonly called a hot spot, tends to form near the inlet through which the source gas is introduced. Since the oxidation reaction proceeds excessively at the hot spots, the yield of the desired product often decreases. In addition, since a large heat load is applied to the catalyst, the catalyst can be damaged, and the life of the catalyst can be shortened. This problem is especially aggravated when increasing the concentration of the raw compound in the raw material gas or increasing the space velocity of the raw material gas in order to enhance productivity per unit catalyst amount.

Therefore, in order to obtain the desired product in high yield through the above oxidation reaction and to allow the commercial production equipment to operate for a longer time while suppressing the damage of the catalyst, excessive heat of the exothermic reaction at the hot spot is suppressed to lower the temperature of the hot spot. It is very important.

Several proposals have been made to suppress the exothermic reaction heat at the hot spot. For example, JP-A-47-10614 discloses a method comprising diluting a catalyst present in a portion of a reactor where hot spots can be easily formed with a material that is inert to the reaction, and GB 1529384 A discloses a source gas. A method of using a reactor filled with an inlet filled with a supported catalyst and an outlet filled with a conventional shaped catalyst is disclosed. In JP-A-06-192144, the amount of active component supported by the catalyst from the source gas inlet to the outlet is disclosed. To increase, a method of filling the reactor with a supported catalyst having an active component loading gradient of the catalyst is disclosed.

EP 0 450 596 A discloses a method of filling the reactor with a plurality of catalysts with different occupied volumes such that the occupied volume is reduced from the source gas inlet to the outlet. U. S. Patent No. 5,276, 178 discloses a plurality of mixed oxides in which the catalyst activity is controlled by varying the type and / or content of an element selected from the group consisting of alkali metals and thallium constituting the catalyst and varying the calcination temperature during catalyst preparation. A method is disclosed that involves charging a reactor with a catalyst to increase the catalytic activity of the catalyst from the source gas inlet to the outlet.

However, none of the above methods can satisfactorily suppress the exothermic heat of reaction at the hot spot, and the yield, catalyst life and operation of the process may not necessarily be sufficient for commercial production.

Summary of the Invention

An object of the present invention is to catalytically oxidize a compound selected from the group consisting of propylene, isobutylene and tert.-butyl alcohol using oxygen molecules in the gas phase while sufficiently suppressing the exothermic heat of reaction at the hot spot during the oxidation reaction. A process for preparing unsaturated aldehydes and unsaturated carboxylic acids is to increase the yield of the product, to reduce the heat load on the catalyst, to provide a process which is easy to work and advantageous in commercial production.

In order to achieve the above object, the present invention is to supply a compound and oxygen molecules selected from the group consisting of propylene, isobutylene and tert.-butyl alcohol in a reactor tube filled with a mixed oxide catalyst, and the reactor tube A process for preparing unsaturated aldehydes and unsaturated carboxylic acids comprising performing a catalytic oxidation reaction between the compound and oxygen molecules in a gaseous phase, wherein the reactor tube is heated in the presence of a reducing compound Provided are a plurality of mixed oxide catalysts, each different and comprising molybdenum, bismuth, and iron, wherein the catalyst activity of the catalyst is filled so that the catalytic activity of the reactor tube increases from the source gas inlet to the outlet. .

Furthermore, the present invention provides a method for preparing a compound comprising: supplying a compound and oxygen molecules selected from the group consisting of propylene, isobutylene and tert.-butyl alcohol to a reactor tube filled with a mixed oxide catalyst, and the compound and oxygen molecules in the reactor tube A process for preparing unsaturated aldehydes and unsaturated carboxylic acids comprising carrying out a catalytic oxidation reaction of the liver in a gas phase, wherein the reactor tube is heated in the presence of a reducing compound, a mixed oxide catalyst comprising molybdenum, bismuth and iron Unsaturated aldehyde and unsaturated, filled with at least one and mixed oxide catalyst comprising molybdenum, bismuth and iron, which are not heated in the presence of a reducing compound, such that the catalytic activity of the catalyst increases from the source gas inlet to the outlet of the reactor tube Manufacturing method of carboxylic acid The.

According to the present invention, during the production of the unsaturated aldehyde and the unsaturated carboxylic acid, the heat of exothermic reaction at the hot spot can be completely suppressed, and the temperature at the hot spot can be reduced very well, so that the desired product can be produced in high yield. Moreover, the heat load on the catalyst at the hot spot can be reduced.

Detailed description of the preferred embodiment

Catalysts used in the production of unsaturated aldehydes and unsaturated carboxylic acids include mixed oxides containing molybdenum, bismuth and iron as essential elements. The mixed oxide may contain one or more elements in addition to molybdenum (Mo), bismuth (Bi) and iron (Fe). Preferred examples of other elements include nickel, cobalt, potassium, rubidium, cesium, thallium and the like.

Preferred examples of mixed oxides used in the present invention can be represented by the following general formula (1):

Mo _a Bi _b Fe _c A _d B _e D _f D _g O _x (1)

(Wherein A is an element selected from the group consisting of nickel and cobalt, B is an element selected from the group consisting of manganese, zinc, calcium, magnesium, tin and lead, C is phosphorus, boron, arsenic, tellurium, An element selected from the group consisting of tungsten, antimony, silicon, aluminum, titanium, zirconium and cerium, and D is an element selected from the group consisting of potassium, rubidium, cesium and thallium, when a = 12, b, c, d, e, f and g each satisfy 0 <b ≦ 10, 0 <c ≦ 10, 1 ≦ d ≦ 10, 0 ≦ e ≦ 10, 0 ≦ f ≦ 1, and 0 <g ≦ 2, and x Is a value defined as the oxidation state of elements other than oxygen).

Among the catalysts, preferably, those having the following composition (excluding oxygen) are used:

Mo ₁₂ Bi _0.1-5 Fe _0.5-5 Co _5-10 Cs _0.01-1

Mo ₁₂ Bi _0.1-5 Fe _0.5-5 Co _5-10 Sb _0.1-5 Si _0.1-5 K _0.01-1

Mo ₁₂ Bi _0.1-5 Fe _0.5-5 Ni _5-10 Sb _0.1-5 Tl _0.01-1 .

As raw materials for the preparation of the catalyst, compounds of elements contained in the catalyst such as oxides, nitrates, sulfates, carbonates, hydroxides, oxo acids and aluminum salts, halides and the like can be used in an amount sufficient to satisfy the above atomic ratio. Specific examples of the molybdenum compound include molybdenum trioxide, molybdate, ammonium paramolybdate and the like. Specific examples of the bismuth compound include bismuth oxide, bismuth nitrate, bismuth sulfate and the like. Specific examples of the iron compound include iron (III) nitrate, iron (III) sulfate, iron (III) chloride and the like.

A catalyst comprising a mixed oxide is usually prepared by mixing the raw materials of the catalyst in water to obtain an aqueous solution or an aqueous slurry, drying the solution or slurry, and then calcining the dried material in an atmosphere containing oxygen molecules. (See JP-A-59-46132, JP-A-60-163830, JP-A-2000-288396, etc.). Here, it can be dried using a conventional drying apparatus such as a kneader, a box type dryer, a drum type through-flow dryer, a spray dryer, a flash dryer and the like.

The concentration of oxygen molecules used in the calcination method is usually 1 to 30% by volume, preferably 10 to 25% by volume. As the oxygen molecule, air or pure oxygen can be used. Oxygen molecules may optionally be diluted with nitrogen, carbon dioxide, water, helium, argon, and the like.

The calcination temperature is usually 300 to 600 ° C, preferably 400 to 550 ° C. The calcination time is usually 5 minutes to 40 hours, preferably 1 to 20 hours.

The catalyst is usually shaped into the desired form. Preferably, the catalyst is shaped into rings, pellets, spheres and the like through tableting, injection molding and the like. It can be shaped before or after calcination in the atmosphere containing oxygen molecules or after the reduction treatment of the catalyst described below. When shaping the catalyst, inorganic fibers which are substantially inert to the oxidation reaction in which the catalyst is used can be added to the catalyst to improve the mechanical strength of the catalyst (see eg JP-A-09-52053).

The activity of the catalyst can be adjusted by heating the catalyst in the presence of the reducing compound (hereinafter such heating of the catalyst in the presence of the reducing compound may be referred to simply as " reduction treatment ").

Examples of reducing compounds include hydrogen, ammonia, carbon monoxide, hydrocarbons, alcohols, aldehydes, amines and the like. These may optionally be used as a mixture of two or more of them. Preferably, each hydrocarbon, alcohol, aldehyde and amine has 1 to about 6 carbon atoms. Specific examples of the hydrocarbon include saturated aliphatic hydrocarbons such as methane, ecan, propane, n-butane, isobutane, and the like; Unsaturated aliphatic hydrocarbons such as ethylene, propylene, α-butylene, β-butylene, isobutylene and the like; Benzene and the like. Specific examples of the alcohol include saturated aliphatic alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec.-butanol, tert.-butanol, and the like; Unsaturated aliphatic alcohols such as allyl alcohol, crotyl alcohol, metallyl alcohol and the like; And phenols. Specific examples of the aldehyde include saturated aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butylaldehyde, isobutylaldehyde and the like; And unsaturated aliphatic aldehydes such as acrolein, crotonaldehyde, methacrolein and the like. Specific examples of the amine include saturated aliphatic amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, and the like; Unsaturated aliphatic amines such as allylamine, diallylamine and the like; And aniline.

The catalyst is reduced by heating the catalyst in a gas containing the reducing compound. The concentration of the reducing compound in the gas is usually from 0.1 to 50% by volume, preferably from 1 to 30% by volume. The reducing compound is diluted with nitrogen, carbon dioxide, water, helium, argon and the like to obtain the above concentration. Oxygen molecules may be present in an amount such that the reduction effect of the catalyst is not impaired. Preferably, no oxygen molecules are present.

The reduction temperature is usually 200 to 600 ° C, preferably 250 to 550 ° C. The reduction time is usually 5 minutes to 20 hours, preferably 30 minutes to 10 hours. Preferably, the catalyst is charged into a tubular vessel or box vessel, and the gas is reduced by allowing a gas containing a reducing compound to flow through the vessel. In this case, the gas discharged from the container can be recycled to the container, if necessary.

In general, the weight of the catalyst decreases after the reduction treatment. The weight loss percentage of the catalyst is calculated according to the following formula:

Weight loss (%) = [(CW _b -CW _a ) / CW _b ] × 100

(Wherein, CW _b is the weight of the catalyst before the reduction treatment, CW _a is the weight of the catalyst after the reduction treatment).

Loss of weight of the catalyst can result in the loss of lattice oxygen atoms in the catalyst, and the loss of lattice oxygen atoms can change the catalytic activity. The degree of reduction of the catalyst can be adjusted by selecting a reduction time and / or a reduction temperature. On the other hand, the weight loss of the catalyst tends to increase as the reduction of the catalyst proceeds. On the other hand, as the reduction of the catalyst proceeds, the catalyst activity increases for a while, reaches a maximum, and then gradually decreases. Thus, the catalyst activity does not necessarily increase as the weight loss of the catalyst increases. In general, catalysts with a weight loss of 0.01 to 6% have higher catalytic activity than unreduced catalysts. Therefore, it is preferable to use a catalyst having a weight loss of 0.01 to 6% as one of the catalysts filled in the reactor tube. A catalyst with a weight loss of more than 6% can be used by itself, but it is preferred to calcinate again in an oxygen molecule-containing gas and then reduce to adjust its catalytic activity.

In the source treatment process, the decomposing substance derived from the reducing compound itself and / or the reducing compound may remain in the catalyst after the reducing treatment, depending on the kind of reducing compound, heat treatment conditions, and the like. In such a case, the weight of the residue is measured and subtracted from the total weight of the catalyst to calculate the pure catalyst weight. Since the residue can typically be carbon, the total carbon (TC) can be measured to determine the weight of the residue.

In the method of the present invention, a plurality of catalysts having different catalytic activities obtained through the reduction treatment are filled in a reactor tube such that the catalytic activity of the catalyst increases from the source gas inlet to the outlet of the reactor. Optionally, the reduced treated catalyst (s) and unreduced catalyst are charged to the reactor tube such that the catalytic activity of the catalyst increases from the source gas inlet to the outlet of the reactor. A catalytic oxidation reaction in the gas phase between the starting compound and the oxygen molecules is then carried out in the reactor tube. The catalyst can be charged from the inlet or outlet of the reactor tube.

When a plurality of catalysts having controlled catalytic activity are filled in a reactor tube in a specific order, and then the reactor tube is used for carrying out the catalytic oxidation reaction, the exothermic heat of reaction at the hot spot is effectively suppressed, thus increasing the desired product. Can be obtained in total yield.

In the process of the invention, as the type of catalyst increases, the temperature distribution in the reactor tube can be more effectively controlled. However, when the type of catalyst increases, the process of preparing the catalyst and filling the catalyst becomes complicated. Therefore, it is desirable to fill two reactor catalysts in a reactor tube.

The shape of the catalyst filling the reactor may be the same or different. Any of the conventional methods of suppressing exothermic reaction heat at hot spots can be combined with the present invention.

In the process of the present invention, a gaseous catalytic oxidation reaction is carried out by feeding oxygen molecules and a raw material compound selected from the group consisting of propylene, isobutylene and tert.-butyl alcohol. In commercial production, a fixed bed multi-tubular reactor is used comprising the reactor tubes described above.

As the oxygen molecule, air is usually used. Apart from the raw compound and the oxygen molecules, the raw gas may optionally contain other gaseous substances such as nitrogen, carbon dioxide, carbon monoxide, steam and the like.

The reaction temperature is usually 250 to 400 ° C. Decompression may be used, but the reaction pressure is typically from atmospheric pressure to 500 kPa. The molar ratio of oxygen molecules to raw compound is generally from 1: 1 to 3: 1. The space velocity of the feed gas is typically 500 to 5,000 / hour at standard temperature and pressure (STP).

According to the present invention, excessive heat of exothermic reaction at the hot spot can be sufficiently suppressed, so that the temperature at the hot spot can be effectively lowered. Thus, it is possible to produce acrolein and acrylic acid from propylene or methacrolein and methacrylic acid from isobutylene or tert.-butanol in high yields.

Example

The invention will be illustrated by the following examples, which do not in any way limit the scope of the invention. Unless otherwise indicated, the volume and space velocity of the gas are from STP. In the following examples, the conversion rate (%) and total yield (%) are defined as follows:

% Conversion = 100 x [(moles of isobutylene fed)-(moles of unreacted isobutylene)] / (moles of isobutylene fed);

Total yield (%) = 100 × [total moles of methacrolein and methacrylic acid] / (moles of isobutylene fed).

Comparative Example 1

(a) preparation of catalyst

Ammonium molybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O] (13,241 g) was dissolved in warm water (15,000 g). This solution is referred to as "solution A". Separately, iron (III) nitrate [Fe (NO ₃ ) ₃ .9H ₂ O] (6,060 g), cobalt nitrate [Co (NO ₃ ) ₃ .6H ₂ O] (13,096 g) and cesium nitrate [CsNO ₃ ] ( 585 g) was dissolved in warm water (6,000 g), followed by dissolving bismuth nitrate [Bi (NO ₃ ) ₃ .5H ₂ O] (2,910 g). This solution is referred to as "solution B". Solution B was poured into Solution A with stirring to obtain a slurry. The slurry was then dried in a flash dryer to yield a dry matter. 6 parts by weight of silica-alumina fiber (manufactured by RFC 400-SL, manufactured by SAINT-GOBAIN ™) was added to 100 parts by weight of the dried product, and the mixture was molded into rings having an outer diameter of 6.3 mm, an inner diameter of 2.5 mm and a length of 6 mm, respectively. And calcined at 516 ° C. under an air stream for 6 hours to afford catalyst A. This catalyst contained 0.96 bismuth atoms, 2.4 iron atoms, 7.2 cobalt atoms and 0.48 cesium atoms per 12 molybdenum atoms.

(b) oxidation

Catalyst A (13 ml) prepared in the previous step (a) was charged to a glass reactor tube with an internal diameter of 18 mm. Then, through a reactor tube filled with catalyst A, a mixed gas of isobutylene, oxygen, nitrogen and steam (molar ratio of 1: 2.2: 6.7: 2.1) was supplied at a space velocity of 750 / hour to give a reaction temperature of 360 ° C ( Isobutylene was oxidized at the temperature of the heat source for heating the reactor tube. The conversion of isobutylene and the total yield of methacrolein and methacrylic acid are shown in Table 1.

Comparative Example 2

Catalyst A (50 g) prepared in step (a) of Comparative Example 1 was charged to a glass tube, and a mixed gas of hydrogen and nitrogen (volume ratio of 20:80) was supplied to the glass tube at a flow rate of 200 ml / min, Catalyst A was reduced at 400 ° C. for 3 hours. The supply of hydrogen was then stopped and the glass tube containing catalyst A was cooled to room temperature under a stream of nitrogen. This gave Catalyst B as a reduced catalyst. The weight loss of the catalyst generated by the reduction treatment was 3.52%.

The oxidation reaction was carried out in the same manner as in step (b) of Comparative Example 1, except that Catalyst B was used instead of Catalyst A and the reaction temperature was changed from 360 ° C. to 320 ° C. The results are shown in Table 1.

Comparative Example 3

Comparative example except that a mixed gas of hydrogen and nitrogen (volume ratio of 10:90) was used in the reduction treatment, the reduction temperature was changed from 400 ° C to 250 ° C, and the reaction time was changed from 3 hours to 1 hour. Catalyst C, a reduced catalyst, was prepared in the same manner as in Example 2. The weight loss of the catalyst produced by the reduction treatment was 0.04%.

The oxidation reaction was carried out in the same manner as in step (b) of Comparative Example 1, except that Catalyst C was used instead of Catalyst A. The results are shown in Table 1.

Example 1

Catalyst A prepared in step (a) of Comparative Example 1 (6.5 ml; 50% by volume of total catalyst) was charged to the feed gas inlet zone of a glass reactor tube with an internal diameter of 18 mm, and Catalyst B prepared in Comparative Example 2 (6.5 ml; 50 vol% of total catalyst) was charged to the outlet zone of the reactor tube. Into the reactor tube, a mixed gas of isobutylene, oxygen, nitrogen, and steam (volume ratio of 1: 2.2: 6.7: 2.1) was supplied at a space velocity of 750 / hour to perform an oxidation reaction at 330 ° C. The conversion of isobutylene and the total yield of methacrolein and methacrylic acid are shown in Table 1.

Example 2

The oxidation reaction was carried out in the same manner as in Example 1, except that Catalyst C (6.5 ml; 50 vol% of the total catalyst) prepared in Comparative Example 3 was used instead of Catalyst A. The results are shown in Table 1.

Catalyst inlet / outlet Reaction temperature (℃) ΔT (℃) % Conversion Total yield (%) Comparative Example 1 Monolayer of Catalyst A 360 70 99.0 76.6 Comparative Example 2 Monolayer of Catalyst B 320 66 99.3 77.6 Comparative Example 3 Monolayer of Catalyst C 360 73 99.3 76.9 Example 1 Catalyst A / Catalyst B 330 63 99.4 78.8 Example 2 Catalyst C / Catalyst B 330 64 99.3 79.0

In Examples 1 and 2 and Comparative Examples 1 to 3, the reaction results were adjusted by adjusting the reaction temperature (temperature of the heat source for heating the reactor tube) so that the conversion of isobutylene reached about 99%. In Table 1, ΔT represents the difference between the temperature at the hot spot and the reaction temperature (ΔT = former-latter).

In Comparative Examples 1 and 3, in which Catalyst A and Catalyst C were used alone, respectively, the reaction temperature had to be increased in order to achieve about 99% conversion, and the total yield was low. Also, in Comparative Examples 1 and 3, ΔT was large, and thus the heat load on the catalyst was high. In Comparative Example 2 using Catalyst B alone, the reaction temperature and ΔT could be lowered, but the total yield was slightly lower.

In contrast, when the catalyst tubes were filled with catalysts A and B or catalysts C and B such that the catalytic activity of the catalyst increased from the inlet to the outlet of the reactor tube, ΔT was smaller than in the comparative example using a single catalyst, respectively. That is, the heat generation at the hot spot could be effectively suppressed, and the total yield was higher.

According to the present invention, excessive heat generation at the hot spot can be suppressed, so that the temperature at the hot spot can be effectively lowered. Thus, it is possible to produce acrolein and acrylic acid from propylene or methacrolein and methacrylic acid from isobutylene or tert.-butanol in high yields.

Claims (6)

Supplying a compound selected from the group consisting of propylene, isobutylene and tert.-butyl alcohol and oxygen molecules to a reactor tube filled with a mixed oxide catalyst, and catalytic oxidation reaction between the compound and oxygen molecules in the reactor tube A process for preparing unsaturated aldehydes and unsaturated carboxylic acids comprising performing in a gas phase, wherein the reactor tubes are heated in the presence of a reducing compound, each having a plurality of different catalytic activities, each comprising molybdenum, bismuth and iron. A process for producing unsaturated aldehydes and unsaturated carboxylic acids with mixed oxide catalysts, wherein the catalytic activity of the catalyst is increased from the source gas inlet to the outlet of the reactor tube. Supplying a compound selected from the group consisting of propylene, isobutylene and tert.-butyl alcohol and oxygen molecules to a reactor tube filled with a mixed oxide catalyst, and catalytic oxidation reaction between the compound and oxygen molecules in the reactor tube A process for preparing unsaturated aldehydes and unsaturated carboxylic acids comprising performing in a gas phase, wherein at least one mixed oxide catalyst comprising molybdenum, bismuth, and iron, wherein the reactor tube is heated in the presence of a reducing compound, and the reducing compound Process for the preparation of unsaturated aldehydes and unsaturated carboxylic acids with at least one mixed oxide catalyst comprising molybdenum, bismuth and iron, which are not heated in the presence of, so that the catalytic activity of the catalyst increases from the source gas inlet to the outlet of the reactor tube . The compound according to claim 1 or 2, wherein the reducing compound is selected from the group consisting of hydrogen, ammonia, carbon monoxide, hydrocarbons of 1 to 6 carbon atoms, alcohols of 1 to 6 carbon atoms, aldehydes of 1 to 6 carbon atoms and amines of 1 to 6 carbon atoms. At least one compound selected. The process according to claim 1 or 2, wherein the weight loss of the catalyst generated by heat treatment in the presence of a reducing compound is 0.01 to 6%. The process of claim 1 or 2, wherein the reactor tube is filled with two catalysts. The method according to claim 1 or 2, wherein the mixed oxide is a compound represented by the following general formula (1): Mo _a Bi _b Fe _c A _d B _e D _f D _g O _x (1) (Wherein A is an element selected from the group consisting of nickel and cobalt, B is an element selected from the group consisting of manganese, zinc, calcium, magnesium, tin and lead, C is phosphorus, boron, arsenic, tellurium, An element selected from the group consisting of tungsten, antimony, silicon, aluminum, titanium, zirconium and cerium, and D is an element selected from the group consisting of potassium, rubidium, cesium and thallium, when a = 12, b, c, d, e, f and g each satisfy 0 <b ≦ 10, 0 <c ≦ 10, 1 ≦ d ≦ 10, 0 ≦ e ≦ 10, 0 ≦ f ≦ 1, and 0 <g ≦ 2, and x Is a value defined as the oxidation state of the elements other than oxygen).