JPH06182201A - High temperature stable catalyst, preparation method thereof and chemical reaction method using the catalyst - Google Patents

Abstract

(57) [Summary] [Object] To provide a catalyst having a high specific surface area at high temperature and a method of using the same. [Structure] A catalytically active component is supported on a rare earth element β-alumina carrier containing at least one of lanthanum, neodymium and praseodymium (excluding lanthanum alone), and a chemical reaction is carried out. [Effect] High catalytic activity can be obtained at a high temperature of around 1000 ° C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst stable at high temperature, a method for preparing the same and a catalytic reaction process using the catalyst.
The catalyst used in the present invention is used in a wide temperature range, and can be stable and maintain high activity particularly at a temperature of 800 ° C. or higher.

[0002]

BACKGROUND OF THE INVENTION There are various methods for carrying out a reaction at a high temperature using a catalyst, such as oxidative removal of organic solvent, odor treatment, automobile exhaust gas purification, high temperature steam reforming and high temperature denitration. Also recently
There is a movement to apply catalytic combustion technology to large-capacity boilers, gas turbines, gas turbines for aircraft, and so on.

In these methods, the reaction temperature is about 60.
0 ° C or higher, depending on conditions 1400 to 1500 ° C
Reach up to. Therefore, even in such a high temperature range, there is a demand for a catalyst having a small decrease in catalytic activity and high thermal stability.

Conventionally, the catalysts used as high temperature catalysts are those having alumina, silica, silica-alumina or the like as a carrier and carrying these noble metals or base metal components, or zirconia, aluminum titanate, cordierite, nitriding. It has been used that a ceramic material such as silicon is used as a carrier, the surface of which is coated with activated alumina or the like, and a precious metal component is supported on the carrier.

However, when the temperature of these catalysts exceeds 800 ° C., the crystal structure of the carrier usually changes (for example, phase transition from γ type to α type in the case of alumina) and the specific surface area decreases with crystal growth. Accordingly, there is a drawback that the active sites are reduced due to the aggregation of the active ingredient, and the catalytic activity is lost. The catalyst using the above-mentioned ceramic material has a high heat resistance of the ceramic itself, but has a drawback that the catalytically active component is not effectively used because the heat resistance of the coating material is low.

Heretofore, the following patents have been known as patents relating to a catalyst using a carrier composed of alumina and a rare earth.

(1) US Pat. No. 3,993,572 "Catalyst component consisting of rare earth and platinum group" (2) US Pat. No. 3,966,391 "Combustion method using high temperature stable catalyst" (3) US Patent 3,956,188 "Composition and preparation method of high temperature stable catalyst" “(4) US Patent 3,899,444“ Exhaust Gas Treatment Catalyst ”(5) US Patent 3,867,312“ Exhaust Gas Treatment Catalyst ”(6) US Patent 3,714,071“ Low Density Alumina Particles with High Strength at High Temperature ”(7) US Patent 4,056,489“ High temperature stable catalyst composition and its preparation method "(8) US Pat. No. 4,021,185" Composition and preparation method of high temperature stable catalyst "(9) US patent 4,220,559" High temperature stable catalyst "(10) US patent 4,061,594" Stable at high temperature Alumina-based carrier "As another prior art, US Patents 3,978,004, 3,956,18
6, 3,931,050, 3,898,183, 3,894,4140, 3,883,445
, 3,880,775, 3,867,309, 3,819,536, 4,374,819,
4,369,130, 4,318,894, 4,233,180, 4,206,087, 4
There are 177,163,4,153,580,4,170,573, 4,054,642.

Among these, US Pat. Nos. 3,966,391, 4,170,
573, 4,061,594 are believed to be relevant to the present invention.

US Pat. No. 3,966,391 describes La (NO ₂ ) ₃ , C
Alumina powder was added to a solution containing rO ₃ and Sr (NO ₂ ) ₃ to support these components by an impregnation method, and after drying at 110 ° C.,
Baking at 1200 ℃ for 2 hours. This catalyst is used for burning carbonized oil.

In US Pat. No. 4,170,573, La (NO ₂ ) ₃ is impregnated in alumina powder, dried at 160 ° C. for 16 hours, and then
After firing at 50 ° C. for 1 hour, it is impregnated with a Ce (NO ₂ ) ₃ solution and dried at 160 ° C. for 16 hours. After that, it was impregnated with a PtCl ₄ solution and baked at 427 to 649 ° C. to obtain Pt-La-Ce-.
Al ₂ O ₃ catalyst is obtained.

In US Pat. No. 4,061,594, alumina autoclaved at 600 ° C. is calcined at 500 ° C. to obtain La
(NO _{2) 3} was impregnated with, creating a _{La 3 O 3 -Al 3 O 3} ,
This is impregnated with platinum group and baked at 1000 to 1200 ° C.

On the other hand, the Journal of Solid State Chemistr
y) 19 , 193-204 (1976), lantern · β
-While conducting research on crystals of alumina, there is no description of catalysts for the crystals.

[0013]

An object of the present invention is to provide a catalyst having high heat resistance and a catalytic reaction process using the same.

[0014]

SUMMARY OF THE INVENTION Alumina such as γ- or η-has a high specific surface area and is widely used as a carrier or a coating agent at present. Due to the transition and the growth of crystal particles, a sintered body is formed, and the specific surface area is significantly reduced. Along with this, particles of the noble metal, base metal and the like which are catalytically active components are aggregated, and the catalytic activity is reduced. The inventors of the present invention have conducted extensive studies in order to improve such thermal instability of alumina and prevent aggregation of catalytically active components. As a result, lanthanum β-alumina (La ₂ O ₃ · 11-14Al ₂ O ₃ ), praseodymium β-alumina (Pr ₂ O ₃ · 11-14Al ₂ O ₃ ),
Neodymium β-alumina (Nd ₂ O ₃ · 11-14Al ₂
O ₃ ), (hereinafter the carrier is referred to as L-β-alumina)
It was found that a catalyst in which a carrier carries a catalytically active component, such as a noble metal or a base metal, is very effective.

The present invention is a heat-resistant catalyst in which an active component is supported on a carrier composed of a composite oxide of aluminum and lanthanum.

The composite oxide of aluminum and lanthanum is composed of a mixture of lanthanum β-alumina and its precursor, and the precursor can be transformed into lanthanum β-alumina when heated at 1000 ° C. for 2 hours. Further, the composite oxide may be essentially composed of a precursor of lanthanum β-alumina.

The high temperature stable catalyst according to the present invention is a complex oxide containing aluminum and at least one rare earth element selected from lanthanum, neodymium and praseodymium, and a catalytically active component supported on the complex oxide. The specific surface area is at least 10 m ² / g or more, and chromium, strontium, and cerium are 1% by weight or less, and L-
It consists of a mixture of β-alumina and a precursor capable of converting to L-β-alumina when heated at 1000 ° C. within 10 hours or essentially a precursor of L-β-alumina. The details of the present invention will be described below. In the present invention, L-β-alumina is La ₂ O ₃ .11-14 Al ₂ O ₃ , P as described above.
_{r 2 O 3 · 11-14Al 2 O} 3, Nd 2 O 3 · 11~14A
It is a composite oxide represented by the chemical formula of l ₂ O ₃ . These complex oxides are obtained by heat-treating a mixture of Al, La, Nd, and Pr hydroxides and oxides at a temperature of 800 ° C. or higher. Even if the catalyst in which the catalytically active component is supported on this carrier is used at a temperature of 1000 ° C. or higher, the catalytically active component does not easily agglomerate due to heat and can maintain high activity. This is because the interaction between the composite oxide of aluminum and lanthanum, neodymium, or praseodymium and the catalytically active component is strong.

The composite oxide comprises a mixture of L-β-alumina and its precursor or a precursor thereof. The composite oxide has excellent heat resistance and a high specific surface area. From the X-ray diffraction and the electron microscopic observation, it was found that this composite oxide suppressed the phase transition of alumina and was unlikely to cause crystal growth. Further, the specific surface area of the phase body of the present invention obtained from the amount of adsorbed nitrogen is extremely small even at high temperature. When palladium or platinum is loaded on the above carrier as an active ingredient, the dispersion state (crystal particle diameter) of these active ingredients is examined from an electron microscope and the amount of chemisorption of CO, and the particle diameter is small even when fired at 1200 ° C. It turns out that it is highly dispersed.

The composite oxide of Al and La, Nb or Pr may be coated on a ceramic compact, or powders of both may be mixed to form a carrier. For example, heat-resistant oxides of α-alumina, titania, zirconia, magnesia, cordierite, mullite, aluminum titanate and the like and the above composite oxides can be mixed and used. It can also be used as a mixture with a non-oxide heat resistant material such as silicon nitride or silicon carbide. A molded product made of the above heat-resistant material can be coated with the complex oxide of the present invention for use. In this case, it is desirable that the composite oxide consisting of Al and La or Nb or Pr accounts for at least 50% or more of the total carrier.

The present inventors have clarified the following facts (hereinafter, to simplify the description, only La will be described).

(1) La has a similar effect on the stabilization of the alumina carrier when heated at a high temperature, but Ce has no effect on the stabilization even with the same rare earth. Further Cr, Z
When r, Sr, Ca, Na, etc. are added to alumina, 1
When baked at 200 ° C. or higher, it promotes crystal growth. When this phenomenon occurs, the specific surface area of the carrier is significantly reduced.

(2) At least 10 m ^{2 of} this composite oxide
State of L-β-alumina having a specific surface area of / g and having an amorphous form or a crystalline state close to this, or a precursor of L-β-alumina which can be transformed into L-β-alumina when heated at 1400 ° C. for 2 hours. Exists in. The chemical forms of alumina in the complex oxide are α-, γ-, θ-, η-, κ-,
Other than χ-, ρ-, and δ-, the specific surface area is preferably 2
It has 0 to 100 m ² / g.

(3) The content of L-β-alumina in the composite oxide is 15 to 95% by weight. The molar ratio of La ₂ O ₃ to Al ₂ O ₃ in the starting material (before firing) (La
₂ O ₃ / Al ₂ O ₃ ) is 1/99 and the content of L-β-alumina is 15% by weight. La ₂ O ₃ / Al ₂ O ₃ = 20/8
When it is 0 (molar ratio), the content of L-β-Al ₂ O ₃ is 95% by weight. Similarly, when La ₂ O ₃ / Al ₂ O ₃ = 10/90, 90 wt% of L-β-alumina and La ₂ O ₃ / Al _{2 are} contained.
When O ₃ = 5/95, 64% by weight, La ₂ O ₃ / Al ₂ O ₃ =
It is 27% by weight at 2/98.

The main component in the complex oxide is a mixture or precursor of L-β-alumina and its precursor, and contains at least 50% by weight.

In powder X-ray diffraction, L-β-alumina has a Bragg angle 2θ of 1 when Cu-Kα rays are used.
8.9 ° (7), 20.1 ° (9), 32.3 ° (5), 34.0
° (2), 36.2 ° (1), 39.4 ° (8), 40.9 ° (1
0), 42.8 ° (4), 45.1 ° (6), 58.0 ° (1
1), 67.4 ° (3) (the numbers in parentheses indicate the order of relative intensities). In the case of the complex oxide calcined at 1200 ° C., as shown in FIGS.
8.9 °, 20.1 °, 32.3 °, 34.0 °, 36.2
It has peaks at °, 42.8 °, 45.1 °, 58.0 °, and 67.4 °. This means that the composite oxide is L-β
-Indicates that it contains alumina. Figure 3b,
The X-ray diffractogram shown in FIG. 3c has a weaker peak and a broader peak than those in FIGS. 3a and 3b. Therefore, this composite oxide is L-β-alumina and α-, γ-, θ-, η. -,
It can be seen that the precursor includes an L-β-alumina precursor having a morphology other than κ-, δ-, χ-, and ρ-, and the precursor is amorphous. In FIGS. 3b and 3c, peaks indicated by black circles are 32.3 °, 36.2 °, 42.8 °, 45.1 °, 6
It is 7.4 degrees.

(4) α-, γ-, θ-, δ-, η-, κ
An alumina carrier having a morphology such as −, χ−, ρ− was impregnated with a solution of lanthanum, praseodymium, and neodymium salt, and 1
When calcined at 000 to 1200 ° C. for 2 hours, the amount of L-β-alumina is not sufficiently generated.

According to the present invention, the catalyst which is stable at high temperature has a carrier composed of a complex oxide. The high temperature stable catalyst of the present invention can have a honeycomb structure. The high temperature stable catalyst of the present invention can also be composed of a carrier carrying a catalytically active component and a support for supporting the carrier. In this case, the support can be selected from a metal plate, a wire mesh, and a spongy metal. It is also possible to coat the surface of a carrier with a complex oxide having an active ingredient supported thereon.

A preferred method for preparing the high temperature stable catalyst of the present invention is to filter and separate a coprecipitate obtained by adding an alkali to a mixed solution of an aluminum salt and a lanthanum, praseodymium or neodymium salt, and after molding, , 100
Bake at a temperature of 0 ° C. or higher. By this firing, Al, La, N
A complex oxide with at least one of b and Pr rare earth elements is formed. That is, a complex oxide having a specific surface area of at least 10 m ² / g or more is obtained, and the complex oxide is α
−, Γ−, θ−, η−, κ−, χ−, ρ−, δ− have an alumina structure other than L-β-alumina when heated at 1000 ° C. or higher for 2 hours or less. Or a mixture of this precursor with L-β-alumina.

Further, in the catalyst carrier according to the present invention, aluminum and fine powder of lanthanum, neodymium or praseodymium oxide or salt are uniformly mixed by a dry or wet method, and calcined at 800 ° C. or higher, preferably 1000 ° C. or higher. ,
A precursor of L-β-alumina or L-β-alumina can be prepared.

When the firing temperature is 800 ° C. or lower, L-β
-Alumina precursor formation not observed.

The carrier of the present invention is prepared by the following method.

(A) Starting materials for the composite oxide, that is, Al and L
The homogeneous mixture of a, Nb and Pr salts is fired at a temperature of 800 ° C. or lower, for example. Then, fire at a temperature of 900 ° C. or higher,
Heating above 1000 ° C. within 10 hours forms a mixture of L-β-alumina and its precursor.

(B) The starting material of the composite oxide is 800
Baking at a temperature of ℃ or less. Next, the precursor of the complex oxide is impregnated with a solution containing the active ingredient, or a carrier containing the complex oxide and the active ingredient is coated on the carrier. This is baked at 900 to 1500 ° C. for a certain period of time to form a precursor of L-β-alumina and a mixture thereof.

The firing temperature for forming the composite oxide of Al and La is 900 ° C. or higher, preferably 1000 ° C. or higher. If the calcination temperature is 900 ° C. or lower, the desired complex oxide is not formed.

The crystal of the composite oxide of the present invention has a structure close to an amorphous form or close to L-β-alumina. This structure is determined by the baking temperature and baking time. As the temperature increases, the proportion of L-β-alumina in the composite oxide increases.

When the precursor of the composite oxide is heated at 1500 ° C. for 1 hour or more, crystal growth of the composite oxide becomes remarkable,
The specific surface area will decrease. Even when heated at 900 ° C., heating for 100 hours or more is sufficient to obtain the desired composite oxide. The firing conditions should be selected from a practical point of view. Desirable firing conditions are 1000 ° C. for at least 1 hour to 1400 ° C. for 0.5 hours or less.
The pressure at the time of firing is not so important. The most preferable firing condition is 1100 ° C. for 10 hours to 130.
The pressure is 100 Kg / cm ² or less at 0 ° C. for 0.5 to 2 hours.

The powder of the complex oxide is used in various shapes, for example, spherical shape, cylindrical shape, cylindrical shape, ring shape, honeycomb shape and the like. In addition, powders containing complex oxides are used in various shapes such as metal plates, wire nets, spongy metals, or inorganic heat-resistant substrates such as mullite, cordierite, α-alumina, zirconia, aluminum titanate, silicon carbide, silicon. It can be used by coating it on a nitride. In this case, the coating amount of the composite oxide is at least 5% by weight, preferably 5 to 30% by weight, based on the whole carrier. The composite oxide of aluminum and lanthanum can be prepared by the usual precipitation method, deposition method, kneading method, impregnation method, or the like. Among these methods, the coprecipitation method is most suitable because it can form a dense composite oxide.
Furthermore, the coprecipitation method is the most effective method for producing L-β-alumina and its precursor.

The composite oxide can be obtained by a coprecipitation method or by calcining a uniform mixture of alumina or alumina sol and lanthanum oxide or lanthanum hydroxide, or by impregnating alumina with an aqueous solution of lanthanum and heating. It is desirable to add an alkali to a mixed solution of aluminum and lanthanum to prepare a uniform co-precipitate. According to this method, a target composite oxide of aluminum and lanthanum can be obtained even at a relatively low temperature.

In the present invention, as a starting material of aluminum, nitrates, sulfates, chlorides, organic salts such as alkoxides, hydroxides and oxides are used. The starting materials for lanthanum, neodymium and praseodymium are:
Water-soluble salts such as nitrates, chlorides and bromates, hydroxides and oxides are used. Alternatively, mixed rare earth containing lanthanum, neodymium, praseodymium and not containing cerium may be used.

The catalytically active component is supported on the carrier by a metal or a metal oxide. In this case, the active ingredient is loaded on the carrier by a conventional method such as an impregnation method or a kneading method.
Starting materials for the active ingredient include inorganic salts and complex salts.

The catalyst of the present invention is used for combustion reaction of fuels such as hydrogen, carbon monoxide, hydrocarbons and alcohols, removal of offensive odors, denitration reaction, automobile exhaust gas treatment and the like. When the catalyst of the present invention is used for the reaction of a gas containing at least one of hydrogen, carbon monoxide, alcohols and hydrocarbons as a combustion component, the catalyst active component is Group VIII of the periodic table, manganese, chromium, Zirconium, rare earth, tin, zinc, copper,
It is desirable to use magnesium, barium, strontium, and calcium. Fuels used in such combustion reaction include methane, ethane, propane, butane, kerosene, diesel oil, light oil, liquefied natural gas, petroleum gas and the like. Although the reaction temperature varies depending on the type of gas, a wide range of room temperature to 1500 ° C. can usually be applied. When carrying out the combustion reaction, the gas is brought into contact with the catalyst in the presence of a gas containing oxygen. When the fuel is methane, the reaction temperature is particularly preferably 400 to 1500 ° C., and the platinum group element is preferable as the active component.

When the catalyst of the present invention is used for purifying exhaust gas of an internal combustion engine such as automobile exhaust gas, it is used as a catalytically active component as a group VIII of the periodic table, manganese, chromium, zirconium, rare earth elements, tin, zinc and copper. , Magnesium, barium, strontium, and calcium, containing at least one or more, and exhaust gas and oxygen in the presence of a catalyst 1
Contact at a temperature of 50 to 1500 ° C. Group VIII elements are particularly desirable as active ingredients. In this case, carbon monoxide,
Hydrocarbons are oxidized and nitrogen oxides are converted to harmless nitrogen and water.

When the catalyst of the present invention is used to reduce nitrogen oxides contained in the exhaust gas of a boiler, gas turbine, etc., ammonia is used as a reducing agent for 400 to 15
Perform at 00 ° C. In this case, the active ingredient is
Group VIII, alkaline earth metals, titanium, zirconium, vanadium, rare earths, Group VaVIa of the Periodic Table, manganese,
At least one element selected from zinc, aluminum and tin is desirable. These elements are supported on the carrier in the form of oxides, and the most preferable element is at least one of tungsten, vanadium, titanium, tin, cerium, iron, nickel and cobalt.

When the catalyst of the present invention is used as a methanation catalyst, the active ingredients of Group VIII, zinc, chromium,
Molybdenum, tin, vanadium, and cerium are desirable, and carbon monoxide or carbon dioxide and hydrogen are heated at 250 to 800 ° C.
Contact with. Most desirable is element VIII of the periodic table, nickel.

When the catalyst of the present invention is used in a hydrocarbon dehydrogenation reaction, chromium, zinc, vanadium,
A hydrocarbon is brought into contact with the catalyst in the range of room temperature to 1500 ° C. containing at least one selected from copper, silver, iron, nickel and cobalt. In this case, the active ingredient is copper,
Contain at least one kind of zinc and the temperature is 300-1000 ℃
Is desirable.

Method for Preparing La ₂ O ₃ —Al ₂ O ₃ Carrier A method for preparing La ₂ O ₃ —Al ₂ O ₃ -based carrier is shown in FIG. La (N
Ammonia water is added dropwise to a mixed solution of O ₂ ) ₃ and Al (NO ₂ ) ₃ , and the precipitate is washed with water and dried. After pre-baking at 500 ℃, add 1% by weight of graphite and add 3mm in diameter and 3mm in length.
It is molded into a cylindrical shape. Then, pre-baking is performed at 700 ° C. for 2 hours. For comparison, Al ₂ O ₃ alone or La ₂ O ₃ alone was similarly prepared. 5 mol% of La ₂ O ₃ , A
l ₂ La ₂ the case of O ₃ and containing 95 _{mol% O 3 · Al 2 O 3} (5
/ 95). La ₂ O at 700 ° C firing
_The specific surface area of the ₃ · Al ₂ O ₃ (5/95) carrier is 130 m ²
/ G, the pore volume (measured from the water content) was 0.4 ml / g.

Preparation Method of Pd Catalyst A palladium nitrate solution was supported on the above carrier by an impregnation method. P
The d content is 1% by weight. After supporting Pd, 500
Pre-baking was performed at 30 ° C. for 30 minutes, and then baking was performed at 1200 ° C. for 2 hours.

Experimental apparatus The activity of the catalyst was examined for the oxidation activity of methane using a quartz tube having an inner diameter of 18 mm and a conventional flow system. Methane 0.1
% Air was introduced into the catalyst layer, and the methane reaction rate was measured under isothermal conditions. Further, in order to examine the durability of the catalyst, air containing 3% of methane was preheated to 500 ° C., introduced into the catalyst layer and maintained at about 1150 ° C. (adiabatic temperature is 1200 ° C.
that's all). The catalyst amount is 8 ml and the space velocity is 30,000 h.
^-1 was set. The concentration of methane was measured by gas chromatography. The crystal structure of the support was examined by X-ray diffraction and transmission electron microscopy. The dispersion state of Pd supported on the carrier is CO
The specific surface area was determined by N ₂ adsorption.

The specific surface area of the La ₂ O ₃ -Al ₂ O ₃ -based carrier and the binding
A La ₂ O ₃ .Al ₂ O ₃ -based carrier containing 0,2,5,10,20,50,75,100 mol% of the crystal structure La was prepared.
Baked at 0 ° C. 1000 ° C (curve 11), 1
Firing was performed at 200 ° C. (curve 12) and 1400 ° C. (curve 13) for 2 hours. FIG. 2 shows the measurement results of the specific surface area. It can be seen that the specific surface area shows the maximum value when La is contained in an amount of 2 to 5 mol%. When fired at 1200 ° C, La ₂ O ₃ · Al ₂
O ₃ (2/98) 33m ² / g, (5/95) 37m
It was ² / g. On the other hand, Al ₂ O ₃ alone is 5.6
It was m ² / g. When the La content increases from 10 to 100 mol%, the specific surface area gradually decreases. from this result,
Addition of a small amount of La ₂ O ₃ to Al ₂ O ₃ significantly increases the thermal stability.

The crystal structure of the La ₂ O ₃ -Al ₂ O ₃ -based carrier is represented by X.
It was examined by line diffraction. 3a to 3d show X-ray diffraction patterns of the carrier heated at 1200 ° C. for 2 hours. Al
A peak attributed to α-Al ₂ O ₃ was observed in ₂ O ₃ alone, and lanthanum β-in La ₂ O ₃ .Al ₂ O ₃ (5/95).
Four peaks attributed to Al ₂ O ₃ (La ₂ O ₃ .11Al ₂ O ₃ ) were observed. _{La 2 O 3 -Al 2 O 3} (50/50) in LaAlO ₃ was produced. It can be seen that the peaks attributed to lanthanum β-Al ₂ O ₃ are weak, broad, and crystal growth is slight. Thus, the resulting composite oxide, a precursor of lanthanum β-Al ₂ O ₃ or lanthanum beta-Al ₂
It is considered that the form is close to O ₃ .

When heated at 1000 ° C. for 2 hours, no clear peak was observed in this composite oxide and it showed an amorphous form, which is considered to be a precursor of lanthanum β-alumina. This precursor is converted to lanthanum β-Al ₂ O ₃ when baked at 1400 ° C. for 2 hours. Lanthanum aluminate (LaAlO ₃ ) having a perovskite structure shows a strong peak. In the case of La ₂ O ₃ / Al ₂ O ₃ (10/90), a mixture of lanthanum β-Al ₂ O ₃ and LaAlO ₃ is formed.

In FIG. 4, La baked at 800 to 1400 ° C.
Generating conditions ₂ O ₃ · Al ₂ O ₃ based oxide shows the results of examining the X-ray diffraction. It can be seen that lanthanum β-alumina and its analogues are produced at 2 to 30 mol% La when calcined at 1400 ° C.

LaAlO ₃ easily forms at low temperatures.

When Al ₂ O ₃ alone is burned at 1200 ° C., a very strong peak of α-Al ₂ O ₃ is recognized, but
_{In 2} O ₃ .Al ₂ O ₃ (2/98), a very weak peak attributed to θ-, κ-Al ₂ O ₃ is recognized. These results, by adding a small amount of La ₂ O ₃ to Al ₂ O _3, it can be seen that suppresses the growth of α-Al ₂ O _3.

R. C. Ropp et al. Reported that for lanthanum β-Al ₂ O ₃ , when a mixture of La ₂ O ₃ .Al ₂ O ₃ (8.3 / 91.7) is heated to 1400 ° C. or higher, it is produced via LaAlO _3. (J. Am. Cer. Soc., 63 ,
416 (1980)).

In the present invention, at a low temperature such as 1000 ° C., 2
The formation of lanthanum β-Al ₂ O ₃ is observed even when fired for a long time because of the difference in the preparation method, that is, the coprecipitation method in the present invention, and it is considered that Ropp et al. Was prepared from a mixture of oxides. . In the coprecipitation method, both oxides are sufficiently mixed. The particle size of the La ₂ O ₃ .Al ₂ O ₃ carrier was examined by an electron microscope. As a typical example, it was fired at 1200 ° C.
As a result of examining (A) Al ₂ O ₃ alone and (B) La ₂ O ₃ .Al ₂ O ₃ (5/95), α-Al ₂ O ₃ reached 500 to 1500 Å, whereas La ₂ O ₃ reached 100 for ₃・ Al ₂ O ₃ (5/95)
It was ~ 300Å. La ₂ O ₃ · Al ₂ O ₃ (50/50)
That is, it was about 1000Å for LaAlO ₃ . Schaper
Et al. Reported that La ₂ O ₃ prevents the sintering of γ-Al ₂ O ₃ , but that LaAlO ₃ is produced in the surface layer of the support (H. Schaper. Et. Al, Applied Catalysis,
7 , 211 (1983)). However, in the present invention, the prevention of sintering is due to the formation of lanthanum-β-Al ₂ O ₃ , not the formation of LaAlO ₃ . This difference is
Probably due to the preparation method. That is, Schaper et al. Employs a method of impregnating molded γ-Al ₂ O ₃ with a La (NO ₂ ) O ₃ solution. In the impregnation method, the La ₂ O ₃ concentration becomes high in the surface layer of the carrier, so that LaAlO ₃
Is easily generated.

Activity of Pd-La ₂ O ₃ .Al ₂ O ₃ Catalyst In order to examine the CH ₄ oxidation activity of the Pd catalyst, CH ₄ was adjusted to 0.
The oxidation rate was measured at a temperature of 250 to 700 ° C. using air containing 1%. These measurements were performed under isothermal conditions. FIG. 5 shows the results of examining the activity of catalysts in which Pd is supported on carriers having various La / Al composition ratios. Pd
The catalyst —La ₂ O ₃ .Al ₂ O ₃ (5/95) shows the highest activity (curve 24). Pd-Al ₂ O ₃ catalyst (curve 21) is the lowest activity. Pd-La ₂ O ₃ · Al ₂ O ₃ (2/98)
Is (10/90) (curve 2
It can be seen that it is almost the same as the case of 3). Pd-La
_{2 O 3 · Al 2 O 3} (50/50) is a specific surface area as shown in FIG. 2 activity as shown in regardless curve 22 to the low-potatoes it is seen that relatively high.

In order to examine the dispersion state of Pd supported on the carrier, the Pd surface area was determined by CO adsorption. 250 ° C
After the He treatment was carried out at 200 ° C., the CO adsorption amount was measured at 200 ° C.
FIG. 6 shows the results of determining the surface area of Pd supported on carriers having different La contents. The Pd surface area increases up to 5 to 10 mol% of La and decreases to 0 at 50 mol%. The particle size of the Pd catalyst was observed with an electron microscope. As a result, the particle size of Pd supported on a carrier of Al ₂ O ₃ alone is 1500 to 2000Å, and La ₂ O ₃ · Al ₂ O ₃ (5
The particle size of Pd supported on (/ 95) was 300 to 800Å. As the crystal particles of the carrier grow, Pd particles also agglomerate. The so-called "earthquake effect" is occurring.

Pd supported on lanthanum-β-Al ₂ O ₃
Durability of catalyst To investigate the durability of Pd combustion catalyst, air containing 3 vol% of methane was introduced into the catalyst layer at 500 ° C.
Burned at 0 ° C. _{Pd-La 2 O 3 · Al} 2 O 3 (5/9
5) and two types of Pd-Al ₂ O ₃ catalyst, 100
A continuous test of time was performed. In this case, Pd-Al ₂ O ₃
The catalyst used was calcined at 1000 ° C. This is because firing at 1200 ° C. does not ignite even if the gas temperature is 500 ° C. The durability test is shown in FIG.
Pd-La ₂ O ₃ .Al ₂ O ₃ (5/95) shows a methane reaction rate of 99.5% or more as shown by the curve 32.
As shown by the curve 31, Pd-Al ₂ O ₃ is 99.5%.
To 98% or less.

The catalyst after the durability test was examined by various methods.
The measurement results of BET specific surface area and Pd surface area are shown in Table 1.

[0061]

[Table 1]

In the case of Pd-Al ₂ O ₃ catalyst, these surface areas are remarkably reduced, while Pd-La ₂ O ₃ .Al ₂ O ₃
(5/95) Catalyst is relatively small. The activity of both catalysts after the durability test was 300 to 7 with 0.1% methane.
As a result of examining the reaction rate under the isothermal condition of 00 ° C., Pd-La
₂ O ₃ · Al ₂ O ₃ (5/95)) has a rate constant of 15 to 20
% For Pd-Al ₂ O _{3 while} it was 50% to 8%.
It was 0% lower. Also, from an electron microscope observation, in the Pd-Al ₂ O ₃ catalyst after the durability test, the Pd particle size on the carrier was 3
It reached 000-5000Å.

Examples of the present invention will be specifically described below, but the present invention is not limited to these examples.

[0064]

Examples of the invention

Example 1 375.1 g of aluminum nitrate and 228 g of lanthanum nitrate
Is dissolved in 1 liter of distilled water (La / Al = 5/95). While stirring this solution, 3N ammonia water was added dropwise to adjust the pH.
Neutralize to 7.5. The coprecipitate of aluminum and lanthanum obtained was thoroughly washed with water, dried, and then pulverized to 1000
Calcination was carried out for 5 hours. The obtained powder was made into a columnar shape having a diameter of 3 mm and a length of 3 mm by a press molding machine to obtain a carrier.

On the other hand, in the above-described method, a carrier for comparison was prepared in the same manner except that lanthanum nitrate was not added to obtain a carrier of Comparative Example.

The above two types of carriers were impregnated with 1% by weight of palladium nitrate solution as Pd, dried at 120 ° C. for 5 hours, and then calcined at 1200 ° C. for 3 hours.
A catalyst of Comparative Example 1 was obtained. The methane oxidation activity of this catalyst was investigated. Space velocity 25,000h with the gas of the following composition
^-1 was flown, and a continuous test for 1000 hours was performed.

Gas composition: Methane 3% air residue In this experiment, the reaction gas was preheated to 500 ° C. When the reaction rate of methane reaches 90% or more, the temperature of the catalyst layer becomes about 120.
Since the temperature reaches 0 ° C., the durability of the catalyst at high temperature can be evaluated. The results are shown in Table 2.

[0068]

[Table 2]

It can be seen that the catalyst obtained in Example 1 has excellent high temperature durability. Measurement of the specific surface area after 100 hour test of the catalyst of Example 1 and Comparative Example 1 were respectively 23.5m ² /g,5.6m ² / g. The surface area of Pd in the Example 1 37m ² /g-Pd,13.6m ²
/ G-Pd. Thus, compared to the comparative catalyst,
It can be seen that the catalysts of Examples have good specific surface area and Pd dispersion state and are excellent as heat resistant catalysts.

Example 2 3750 g of aluminum nitrate and 480 g of lanthanum nitrate were dissolved in 10 l of distilled water. Then, 2.5 liters of distilled water was added to 1 kg of 800 ° C. calcined powder obtained in the same manner as in Example 1, and the mixture was ground in a vibration mill until the average particle size of the powder became about 1 μm to prepare a slurry-like immersion liquid. To do. A honeycomb structure made of a commercially available cordierite base material (diameter 90
mm, length 75 mm), and then remove after immersion
Remove excess liquid by blowing compressed air to 120 ℃
After drying at 500 ° C., it was heat treated at 500 ° C. for 1 hour. This operation was repeated, and finally firing was performed at 1000 ° C. for 2 hours. The honeycomb structure thus obtained had a layer of composite oxide of 18.7% by weight, and the specific surface area of this honeycomb carrier was 13.5.
It was m ² / g. Then, the obtained honeycomb structure was immersed in an aqueous solution in which chloroplatinic acid and rhodium chloride were mixed, and 1
After drying at 20 ° C., the product was reduced to 600 ° C. in a hydrogen stream. The catalyst had 1.5% by weight platinum and 0.4% by weight rhodium.

This catalyst was used for oxidation of automobile exhaust gas. It was used as a catalytic converter in an ordinary automobile engine (1800 cc class), and a running test of 10,000 km was performed. As a result, CO mode was 1.0 g / km, HC 0.1 in 10 modes.
It was 9 g / Km. From this result, it is understood that the catalyst using the heat-resistant carrier according to the present invention can be used for treating exhaust gas of an internal combustion engine and maintains stable performance in high temperature reaction.

Example 3 In this example, an example of using the heat-resistant carrier according to the present invention as a catalyst for high temperature denitration reaction will be described.

50 g of powder of the complex oxide before molding prepared by the same method as in Example 1 was sufficiently kneaded with 500 g of metatitanic acid slurry (150 g as TiO ₂ ) by a kneader. After that, it is dried at 150 ℃, crushed to 400
Bake at 4 ° C for 4 hours. The obtained powder is molded into a cylindrical shape having a diameter of 3 mm and a thickness of 3 mm using a press molding machine, and then immersed in an aqueous solution of ammonium tungstate in hydrogen peroxide. Then, it is calcined at 600 ° C. for 2 hours to obtain a catalyst. The catalyst thus obtained contains 5% by weight of tungsten oxide.

The reaction uses a gas having the following composition and a space velocity of 5
It was carried out for 100 hours under the conditions of 000 h ⁻¹ and reaction temperature of 600 ° C.

Reaction gas composition NO ₂ 200 ppm NH ₂ 200 ppm O ₂ 3% H ₂ O 10% N ₂ balance NO ₂ removal rate is 94.8% initially and 9% after 100 hours
It was 4.4%. From the above results, the catalyst using the carrier according to the present invention exhibits excellent performance against high temperature denitration reaction.

Example 4 In this example, an example used as a catalyst for a CO methanation reaction will be described.

The shaped carriers obtained in Example 1 and Comparative Example 1 were impregnated with nickel nitrate, calcined at 500 ° C., further impregnated with ruthenium chloride, and calcined at 1000 ° C. to obtain a finished catalyst.
This catalyst contains 30% of NiO and 3% of Ru. The reaction tube was filled with this catalyst, and CO 5%, H ₂ 17%, N
_The remaining gas was introduced so that SV was 100,000 h ^−1, and a methanation reaction was carried out at a reaction temperature of 350 ° C.
As a result, it was found that the CO methanation yield of the catalyst of this example was about 15 times that of the catalyst of this comparative example. As described above, it is understood that the catalyst of the present invention is very effective not only at high temperatures but also at relatively low temperatures.

Example 5 In this example, a catalyst for dehydrogenating methanol was examined.

The shaped carrier described in Example 1 is impregnated with a solution of copper nitrate and zinc nitrate, dried and calcined at 1000.degree. The contents of Cu and Zn are 20% by weight and 10%, respectively.
% By weight. The catalyst was charged into a reaction tube, the temperature was raised to 800 ° C., methanol was introduced, and a dehydrogenation reaction was carried out to produce formalin. The conversion of methanol was 9%.
It was 8% or more, and the selectivity for formalin was about 5 times that of the conventional one.

Example 6 500 g of aluminum nitrate and 30.7 g of neodymium nitrate
Was dissolved in 5 l of distilled water. 3N while stirring this solution
Ammonia water was added dropwise to neutralize to pH 8. The coprecipitate of aluminum and neodymium thus obtained was thoroughly washed with distilled water by decantation and then filtered at 150 ° C.
It was dried all day and night. Grind to 60 mesh or less, 500
After firing for 2 hours at 0 ° C., 0.5% by weight of graphite was added and molded into a cylindrical shape having a diameter of 3 mm and a thickness of 3 mm using a press molding machine. The composition of the carrier (A) is Nd ₂ O ₃ 5 mole%, an Al ₂ O ₃ 95 mol%. This carrier is 1200 ℃
In calcined for 2 hours, B. E. The specific surface area by N ₂ gas adsorption
It was measured by the T. method. The crystal structure of the carrier was examined by powder X-ray diffractometry. The results are shown in Table 3.

Example 7 Carriers (B), (C), prepared in the same manner as in Example 6 except that the proportions of aluminum nitrate and neodymium nitrate were changed.
(D) was obtained. The obtained carriers have the following compositions, respectively. (B): Nd ₂ O ₃ 2 mol%, Al ₂ O ₃ 98 mol%,
(C): Nd ₂ O ₃ 10 mol%, Al ₂ O ₃ 90 mol%,
(D): Nd ₂ O ₃ 20 mol%, Al ₂ O ₃ 80 mol%. The specific surface area and product morphology of these carriers were measured by the same method as in Example 6. The results are shown in Table 3.

[0082]

[Table 3]

Example 8 500 g of aluminum nitrate and 30% praseodymium nitrate.
Prepared in the same manner as in Example 6 using 5 g as a raw material, and adding P
A carrier (E) consisting of 5 mol% of r ₂ O _{3 and} 95 mol% of Al ₂ O ₃ was obtained. Further, carriers (F), (G) and (H) were obtained by changing the ratio of aluminum nitrate and praseodymium nitrate. The obtained carriers have the following compositions, respectively. (F): Pr ₂ O ₃
2 mol%, Al ₂ O ₃ 95 mol%, (G): Pr ₂ O ₃ 10 mol%, Al ₂ O ₃ 90 mol%, (H): Pr ₂ O ₃ 20 mol%, Al ₂ O ₃ 80 mol% %. Table 4 shows the results of examining the specific surface area of these carriers and the morphology of the products.

[0084]

[Table 4]

Example 9 500 g of aluminum nitrate and 18.6 g of neodymium nitrate
And 18.5 g of praseodymium nitrate as raw materials and Nd ₂ O ₃ 3 mol%, Pr ₂ O ₃ 3 mol%, by the same method as in Example 6.
A carrier (I) containing 94% by mole of Al ₂ O ₃ was prepared. The specific surface area of this carrier was 23.0 m ² / g. In addition, when the crystal structure was examined, it was confirmed that it was mainly composed of neodymium-β alumina and praseodymium-β alumina. As can be seen from these results, the carriers containing these β-alumina have a high specific surface area even at high temperatures.

Example 10 500 g of alumina sol (alumina content rate of 9.8%) and 12.3 g of neodymium carbonate were kneaded in a raikai machine for 2 hours and then dried at 150 ° C. for one day. After crushing to 60 mesh or less and firing at 500 ° C. for 2 hours, 0.5% by weight of graphite was added and molded into a cylindrical shape having a diameter of 3 mm and a thickness of 3 mm using a press molding machine. The composition of this carrier is Nd ₂ O _{3
They are} 4 mol% and Al ₂ O ₃ 96 mol%. 10 this carrier
00 was calcined ° C. or 1200 ° C. for 2 hours, it was measured the specific surface area, respectively 96.5m ² /g,21.6m ² /
It was g.

P using the carrier prepared in Examples 6 to 10
When the durability test of the d catalyst was performed, it was 800 to 1400 ° C.
Showed excellent performance.

As described above, it is understood that the catalyst of the present invention has a large specific surface area even at high temperatures and can be applied not only to low temperatures but also to chemical reactions at high temperatures.

Example 11 The carrier according to the present invention shown in Example 1 is impregnated with a mixed solution of ammonium molybdate and nickel nitrate, dried and calcined at 500 ° C. for 5 hours. The composition of this catalyst is MoO ₃ 1
5 wt% and NiO 5 wt%. 40 ml of this catalyst was filled in a reaction tube having an inner diameter of 15 mm, and hydrogen was passed through at a flow rate of about 1 l / min for reduction at 450 ° C. for 5 hours. 40 after reduction
Under conditions of 0 ° C. and 10 atm, H ₂ was supplied onto the catalyst at a flow rate of 300 ml / min, and a synthetic raw material obtained by adding 100 wt ppm of thiophene as S to n-hexane at a flow rate of 100 ml / h. When the sulfur temperature in n-hexane after the reaction was measured by gas chromatography, it was 0.1% by weight or less as S even after 100 hours.

Example 12 The chloroplatinic acid solution is impregnated into the carrier according to the present invention shown in Example 1, dried and then calcined at 900 ° C. for 2 hours. P of this catalyst
The t content is 1% by weight. 5 cc of this catalyst is filled in a reaction tube, and a gas containing 100 ppm of each of three components of methyl ethyl ketone, toluene and formalin as representatives of malodorous components is introduced into the catalyst layer together with air. At a reaction temperature of 500 ° C., the organic matter at the outlet of the catalyst layer was measured and found to be 0.4 ppm of methyl ethyl ketone, 0.3 ppm of toluene and 0.8 ppm of formalin, and this catalyst is very effective in removing malodorous components. I understood.

Example 13 1 g of a catalyst obtained by kneading and drying fine powder and β-stannic acid slurry into the carrier according to the present invention shown in Example 1 and calcining at 500 ° C. for 3 hours was added to 20 g of heavy oil, and this was automatized. The mixture was filled in a crepe and reacted for 30 minutes while flowing H ₂ at 100 Kg / cm ² 400 ° C. After completion of the reaction, the product was separated into each fraction by distillation under reduced pressure. The results are shown in the table below. It can be seen that this catalyst exhibits excellent performance in lightening heavy oil.

[0092] Example 14 The carrier according to the present invention shown in Example 1 was impregnated with a solution of copper chloride and calcined at 500 ° C. for 2 hours. The composition of this catalyst is Cu
₂ O is 20% by weight. Oxidation reaction of propylene was performed using this catalyst. C as reaction gas in 20 ml of catalyst
_A gas having a composition of ₃ H ₄ 25%, O ₂ 10% and N ₂ residue was introduced at a temperature of 450 ° C., and the produced gas was analyzed. As a result, the conversion of C ₃ H ₄ was 98% and the selectivity for acrolein was 88%. Thus, it can be seen that the oxidation rate of this catalyst is very high.

Example 15 The carrier according to the present invention shown in Example 1 was impregnated with a mixed solution of cobalt nitrate and ferric nitrate and calcined at 800 ° C. for 5 hours. The composition of this catalyst is 12% by weight of CoO and 8% by weight of Fe ₂ O ₃ . 40 ml of CO and 60% of H ₂ are added to 40 ml of this catalyst.
When a gas consisting of the above was reacted under the conditions of 300 ° C. and 50 Kg / cm ² , the conversion rate of [CO + H ₂ ] was 88%.
Moreover, when the selectivity was examined from the analysis of the products, C _{1 to} C ₅
Up to 48%, gasoline fraction 21%, oxygen-containing compounds 12%, heavy oil 29%. From the above results, it is found that the present catalyst is suitable for synthesizing an organic compound from CO and H ₂ .

Example 16 The carrier according to the present invention shown in Example 1 was impregnated with a mixed solution of copper nitrate and zinc nitrate and calcined at 500 ° C. for 2 hours. A mixed gas consisting of 75% hydrogen and 25% carbon monoxide was introduced into this catalyst at a temperature of 300 ° C. and a pressure of 100 Kg / cm ² , and when the produced gas was analyzed, the conversion rate of [CO + H ₂ ] was 90%.
Thus, the selectivity of methanol was 92%. From the above, it can be seen that the present catalyst is suitable for synthesizing methanol from CO and H ₂ .

Example 17 The carrier according to the present invention shown in Example 1 is impregnated with a nickel nitrate solution and calcined at 500 ° C. for 2 hours. The composition of this catalyst is 15% by weight of NiO. When an isomerization reaction of normal butane was carried out using this catalyst at a temperature of 100 ° C., the yield to isobutane was 69%. Thus, it can be seen that the present catalyst is effective for the isomerization reaction.

Example 18 The carrier according to the present invention shown in Example 1 was impregnated with a mixed solution of iron chloride, potassium chloride and copper chloride, dried and calcined at 700 ° C. for 2 hours. The composition of this catalyst is 20 wt% of Fe ₃ O ₄ ,
K ₂ O 2% and CuO 2%. 75% H ₂ and 25% H ₂ were added to this catalyst at a temperature of 550 ° C. and a pressure of 250 ° C. Kg / cm ^2.
When brought into contact with each other under the conditions of, the conversion of [H ₂ + N ₂ ] was 95%. This experiment shows that the catalyst of the present invention is effective for ammonia synthesis by hydrogenation of N ₂ .

[0097]

As described above in detail, the catalyst of the present invention is stable in a wide temperature range and has a very large specific surface area at high temperature. Therefore, it can be used for various chemical reactions,
It has a high catalytic activity.

[Brief description of drawings]

FIG. 1 is a process drawing showing a method for preparing a La ₂ O ₃ —Al ₂ O ₃ -based carrier according to an example of the present invention.

FIG. 2 is a characteristic diagram showing the relationship between the composition and the specific surface area of a La ₂ O ₃ —Al ₂ O ₃ -based carrier.

3A to 3D are X-ray diffraction patterns showing the crystal structure of a La ₂ O ₃ -Al ₂ O ₃ -based carrier.

FIG. 4 is a characteristic diagram showing the relationship between the composition of a La ₂ O ₃ —Al ₂ O ₃ -based carrier and the firing temperature.

FIG. 5: CH ₄ using a Pd-La ₂ O ₃ .Al ₂ O ₃ catalyst
FIG. ₄ is a characteristic diagram showing the relationship between the reaction temperature and the CH ₄ conversion rate in the oxidation reaction.

FIG. 6 is a characteristic diagram showing the relationship between the composition of the carrier and the amount of Pd adsorbed in the Pd-La ₂ O ₃ · Al ₂ O ₃ catalyst.

FIG. 7 is a characteristic diagram showing the relationship between combustion time and CH ₄ conversion rate in methane combustion using a Pd-La ₂ O ₃ .Al ₂ O ₃ catalyst.

[Explanation of symbols]

11, 12, 13 ... La ₂ O ₃ .Al ₂ O ₃ based carrier, 22,
_{23,24,25 ... Pd-La 2 O 3} · Al 2 O 3 catalyst,
_{32 ... Pd-La 2 O 3} · Al 2 O 3 catalyst.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location B01D 53/36 102 D 9042-4D B01J 21/14 M 8017-4G 23/14 M 8017-4G 23 / 30 A 8017-4G 23/56 301 M 8017-4G A 8017-4G 23/76 X 8017-4G Z 8017-4G M 8017-4G 23/78 M 8017-4G 23/80 X 8017-4G Z 8017- 4G 23/88 M 8017-4G 23/89 X 8017-4G 32/00 C01B 3/26 3/40 C01C 1/04 EF C07C 1/04 9280-4H 5/27 7/163 9280-4H 9/04 9280-4H 9/12 9280-4H 9/15 9280-4H 29/154 8930-4H 31/02 8930-4H 31/04 8930-4H 45/35 7457-4H 47/052 7457-4H 47/22 F 7457 -4H C10G 1/06 D 2115-4H 2/00 2115-4H 11/02 6958-4H 45/04 A 2115-4H 45/06 A 2115-4H 45/08 A 2115-4H 45/60 2115-4H 47/12 2115-4H C10L 3/10 F01N 3/28 301 C F23C 11/00 306 7367-3K F23R 3/40 E 7604-3G // C07B 61/00 300 (72) Inventor Shinpei Matsuda, 3-1-1, Saiwaicho, Hitachi, Ibaraki Prefecture, Hitachi Research Laboratory, Hitachi Ltd.

Claims (23)

[Claims] 1. A carrier and a periodic table, VIII, carried on the carrier.
Group, manganese, chromium, zirconium, rare earth elements, tin, zinc, copper, magnesium, barium, strontium, vanadium, tungsten, molybdenum, titanium,
Gallium, indium, lead, bismuth, antimony,
And a catalytically active component comprising at least one of silver and calcium, at least a part of the carrier being lanthanum,
A complex oxide of at least one rare earth element selected from neodymium and praseodymium (excluding lanthanum alone) and aluminum, wherein the complex oxide is at least 1
A precursor having a specific surface area of 0 m ² / g and capable of being transformed into the rare earth element β-alumina substantially when heated with the rare earth element β-alumina at 1000 ° C. or more within 2 hours. A reduction reaction catalyst stable at high temperature, characterized by comprising a mixture with. 2. The composite oxide according to claim 1, wherein the complex oxide is at least one selected from lanthanum, neodymium and praseodymium (excluding lanthanum alone).
1 to 20 mol% as an oxide, the balance being alumina, which is a stable catalyst at high temperature. 3. The composite oxide according to claim 1, wherein the composite oxide is at least one selected from lanthanum, neodymium and praseodymium (excluding lanthanum alone).
Is a stable catalyst at high temperature, characterized by having 3 to 10 mol% as an oxide and the balance being alumina. 4. The high temperature stable catalyst according to claim 1, wherein the complex oxide has a specific surface area of 20 to 100 m ² / g. 5. A high temperature stable catalyst according to claim 1, wherein the carrier has a honeycomb structure. 6. A catalyst stable at high temperature according to claim 1, characterized in that the carrier comprises a portion carrying a catalytically active component and a support of the carrier. 7. A catalyst stable at high temperature according to claim 6, wherein the support is selected from a metal plate, a metal net and a spongy metal. 8. A catalyst stable at high temperature according to claim 1, wherein the surface of the carrier is coated with a complex oxide carrying an active ingredient. 9. A carrier and a periodic table VIII carried on the carrier.
Group, manganese, chromium, zirconium, rare earth elements, tin, zinc, copper, magnesium, barium, strontium, vanadium, tungsten, molybdenum, titanium,
Gallium, indium, lead, bismuth, antimony,
And a catalytically active component comprising at least one of silver and calcium, at least a part of the carrier being lanthanum,
A composite oxide of at least one rare earth element selected from neodymium and praseodymium (excluding lanthanum alone) and aluminum, and the composite oxide is at least 1
It has a specific surface area of 0 m ² / g, a content of chromium, strontium, and cerium of 1 wt% or less, and 1 to 20 mol% of at least one selected from lanthanum, neodymium, and praseodymium as an oxide. However, the balance is alumina, and the reduction reaction catalyst stable at high temperature is characterized in that it is substantially composed of a mixture of the rare earth element β-alumina and a precursor thereof. 10. A carrier and a periodic table VI supported on the carrier.
Group II, manganese, chromium, zirconium, rare earth elements,
A catalytically active component comprising at least one of tin, zinc, copper, magnesium, barium, strontium, vanadium, tungsten, molybdenum, titanium, gallium, indium, lead, bismuth, antimony, silver, calcium, and at least the carrier. A part is a composite oxide of at least one rare earth element selected from lanthanum, neodymium, and praseodymium (excluding lanthanum alone) and aluminum, and the composite oxide has a specific surface area of at least 10 m ² / g. , For alumina α
-, Γ-, θ-, η-, κ-, χ-, ρ-, δ-forms, and the amount of chromium, strontium, and cerium is 1 wt% or less, the rare earth element β -Alumina and a mixture of these precursors that can be transformed into the rare earth element β-alumina by heating at 1000 ° C for 2 hours, and have 1 to 20 mol% of at least one of lanthanum, neodymium and praseodymium as an oxide. ,
A reduction reaction catalyst that is stable at high temperatures, characterized in that the balance is alumina. 11. A carrier and a periodic table VI supported on the carrier.
Group II, manganese, chromium, zirconium, rare earth elements,
A catalytically active component comprising at least one of tin, zinc, copper, magnesium, barium, strontium, vanadium, tungsten, molybdenum, titanium, gallium, indium, lead, bismuth, antimony, silver, calcium, and at least the carrier. A part is a composite oxide of aluminum and at least one rare earth element selected from lanthanum, neodymium and praseodymium (excluding lanthanum alone), and the composite oxide has a specific surface area of at least 10 m ² / g. , A mixture of chromium, strontium, and cerium in an amount of 1% by weight or less, and substantially the rare earth element β-alumina and a precursor which can be transformed into the rare earth element β-alumina by heating at 1000 ° C. for 2 hours or less. Consisting of and consisting of lanthanum, neodymium,
1-2 as at least one praseodymium oxide
A reduction reaction catalyst stable at high temperature, characterized by having 0 mol% and the balance being alumina. 12. An alkali is added to a mixed solution of an aluminum salt and a salt of at least one rare earth element selected from lanthanum, neodymium and praseodymium (excluding lanthanum alone) to precipitate a coprecipitate of the mixture. Process,
A step of separating the coprecipitate, a step of molding the separated coprecipitate into various shapes, and a composite oxide of aluminum and the rare earth element, the composite oxide being at least 10 m ²
/ G or more and the rare earth element β-alumina and the rare earth element β by heating at 1000 ° C. for 2 hours or less.
-Calcining the shaped body at a temperature of 1000 ° C or higher so as to be a precursor that can be converted to alumina or a mixture of substantially the precursor, and
From at least one of Group VIII, manganese, chromium, zirconium, rare earth elements, tin, zinc, copper, magnesium, barium, strontium, vanadium, tungsten, molybdenum, titanium, gallium, indium, lead, bismuth, antimony, silver, calcium And a step of supporting a catalytically active component consisting of 13. A carrier and a catalytically active component carried on the carrier, wherein at least a part of the carrier comprises lanthanum,
A complex oxide of at least one rare earth element selected from neodymium and praseodymium (excluding lanthanum alone) and aluminum, wherein the complex oxide is at least 1
A precursor having a specific surface area of 0 m ² / g and capable of being converted into the rare earth element β-alumina when heated substantially above the rare earth element β-alumina at 1000 ° C. within 2 hours. As a catalytically active component, Group VIII of the periodic table, manganese, rare earth elements, chromium, vanadium, tin, zirconium, magnesium,
A catalytic chemical reaction method comprising contacting exhaust gas of an internal combustion engine with a catalyst carrying at least one of calcium and strontium to reduce nitrogen oxides contained in the gas. 14. A carrier and a catalytically active component supported on the carrier, wherein at least a part of the carrier comprises lanthanum,
A complex oxide of at least one rare earth element selected from neodymium and praseodymium (excluding lanthanum alone) and aluminum, wherein the complex oxide is at least 1
A precursor having a specific surface area of 0 m ² / g and capable of being converted into the rare earth element β-alumina when heated substantially above the rare earth element β-alumina at 1000 ° C. within 2 hours. And a catalyst supporting at least one of tungsten, vanadium, titanium, tin, cerium, iron, nickel and cobalt as the catalytically active component, and an exhaust gas containing nitrogen oxides and ammonia at 150 to 1000 ° C. A catalytic chemical reaction method comprising detoxifying nitrogen oxides by bringing them into contact with each other. 15. A carrier and a catalytically active component supported on the carrier and selected from one or more of chromium, zinc, vanadium, iron, nickel, cobalt, copper and silver, and at least a part of the carrier, It is a composite oxide of at least one kind of rare earth element selected from lanthanum, neodymium, and praseodymium (excluding lanthanum alone) and aluminum, and the composite oxide has a specific surface area of at least 10 m ² / g, and The complex oxide is a catalyst which is substantially a mixture of the rare earth element β-alumina and a precursor which can be converted to the rare earth element β-alumina when heated at 1000 ° C. or higher for 2 hours or less, and alcohol of 500 to 1000.
A catalytic chemical reaction method characterized by carrying out a dehydrogenation reaction by contacting at ° C. 16. A catalytic chemical reaction method according to claim 15, wherein methanol is dehydrogenated at 800 to 1000 ° C. 17. A carrier and a catalytically active component supported on the carrier, wherein at least a part of the carrier comprises lanthanum,
A complex oxide of at least one rare earth element selected from neodymium and praseodymium (excluding lanthanum alone) and aluminum, wherein the complex oxide is at least 1
A precursor having a specific surface area of 0 m ² / g and capable of being converted into the rare earth element β-alumina when heated substantially above the rare earth element β-alumina at 1000 ° C. within 2 hours. And a hydrocarbon oil containing a sulfur compound on a catalyst supporting at least one of molybdenum, tungsten, nickel and cobalt as the catalytically active component, and hydrogen at a reaction temperature of 1 to 100 atm and 250 to 500 ° C. A catalytic chemical reaction method comprising contacting to hydrodesulfurize the hydrocarbon oil. 18. A carrier and a catalytically active component supported on the carrier, at least a part of which is lanthanum,
A complex oxide of at least one rare earth element selected from neodymium and praseodymium (excluding lanthanum alone) and aluminum, wherein the complex oxide is at least 1
A precursor having a specific surface area of 0 m ² / g and capable of being converted into the rare earth element β-alumina when heated substantially above the rare earth element β-alumina at 1000 ° C. within 2 hours. And at least one or more of Group VIII, titanium, zirconium, vanadium, molybdenum, tungsten, manganese, copper, zinc, gallium, indium, tin, lead, bismuth and antimony as the catalytically active component. In the presence of a catalyst supporting C, heavy oil, asphalt or coal and hydrogen are brought into contact with each other at a temperature of 350 to 800 ° C. and a pressure of 1 to 500 Kg / cm ² to obtain a light oil, a catalytic chemical reaction method. . 19. A carrier and a catalytically active component supported on the carrier, wherein at least a part of the carrier comprises lanthanum,
A complex oxide of at least one rare earth element selected from neodymium and praseodymium (excluding lanthanum alone) and aluminum, wherein the complex oxide is at least 1
A precursor having a specific surface area of 0 m ² / g and capable of being converted into the rare earth element β-alumina when heated substantially above the rare earth element β-alumina at 1000 ° C. within 2 hours. And a catalytically active component of Group VIII of the periodic table, manganese, zinc, copper, rare earth elements, tungsten, titanium, molybdenum, tin,
A catalyst that carries at least one of lead, bismuth, and vanadium is contacted with a gas containing carbon monoxide and hydrogen at a temperature of 1000 ° C. or less and a pressure of 1 to 200 Kg / cm ² to synthesize a hydrocarbon. Catalytic chemical reaction method. 20. In claim 19, as the catalytically active component, Group VIII of the Periodic Table, manganese, molybdenum, chromium, zirconium, rare earth elements, tin, zinc, copper, silver, magnesium, barium, 60 for a catalyst supporting at least one of strontium and calcium
A catalytic chemical reaction method characterized in that a mixed gas of carbon monoxide and hydrogen is contacted at a temperature of 0 ° C. or lower and a pressure of 1 to 200 kg / cm ² to synthesize an alcohol. 21. A carrier and a catalytically active component supported on the carrier, wherein at least a part of the carrier comprises lanthanum,
A complex oxide of at least one rare earth element selected from neodymium and praseodymium (excluding lanthanum alone) and aluminum, wherein the complex oxide is at least 1
A precursor having a specific surface area of 0 m ² / g and capable of being converted into the rare earth element β-alumina when heated substantially above the rare earth element β-alumina at 1000 ° C. within 2 hours. And a molybdenum, tungsten, and
Zirconium, silicon, boron, chromium, zinc, copper,
700 ° C for contact supporting at least one of tin and titanium
A catalytic chemical reaction method comprising contacting hydrocarbons at the following temperatures to isomerize the hydrocarbons. 22. A carrier and a catalytically active component supported on the carrier, wherein at least a part of the carrier comprises lanthanum,
A complex oxide of at least one rare earth element selected from neodymium and praseodymium (excluding lanthanum alone) and aluminum, wherein the complex oxide is at least 1
A precursor having a specific surface area of 0 m ² / g and capable of being converted to the rare earth element β-alumina substantially when heated with the rare earth element β-alumina at 1000 ° C. or more within 2 hours. Of the periodic table of Group VIII, tungsten, molybdenum,
A catalyst that carries at least one of zinc, copper, rare earth elements, lead, bismuth, boron, silicon, titanium, and vanadium is contacted with hydrocarbons at a temperature of 1000 ° C or lower to crack heavy petroleum oil. And a catalytic chemical reaction method. 23. A carrier and a catalytically active component supported on the carrier, wherein at least a part of the carrier is lanthanum,
A complex oxide of at least one rare earth element selected from neodymium and praseodymium (excluding lanthanum alone) and aluminum, wherein the complex oxide is at least 1
A precursor having a specific surface area of 0 m ² / g and capable of being converted to the rare earth element β-alumina substantially when heated with the rare earth element β-alumina at 1000 ° C. or more within 2 hours. An organic compound and / or nitrogen on a catalyst comprising at least one of Group VIII of the Periodic Table, copper, chromium, zinc, vanadium, tungsten, tin, potassium, and a rare earth element as the catalytically active component. And hydrogen at a temperature of 800 ° C or less and a pressure of 500 Kg / cm ²
In the following, a catalytic chemical reaction method is characterized in that they are brought into contact with each other to carry out a hydrogenation reaction.