JPH11267526A - Method and apparatus for producing highly active catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a high-quality active catalyst by forming a metal layer with a controlled crystal structure on a catalyst carrier, which can easily produce a highly active catalyst having a long length. . SOLUTION: A raw material source 2 charged in an evaporating part 1 is heated to an evaporating temperature to evaporate, and the vapor of the raw material source 2 in the evaporating part 1 is conveyed by an inert gas 5 to form a reaction tube as a raw material gas 14. The raw material gas 1 is supplied to the catalyst support 30 heated to the decomposition temperature of the raw material gas provided in the reaction tube 22 and brought into contact with the raw material gas 1.
When the metal in 4 is supported on the catalyst carrier 30, the reaction tube 2
At least one of the heater 31 and the catalyst carrier 30 which surrounds the outer periphery of the reaction tube 22 with a required width outside the tube 2 is moved relative to the other in the axial direction of the reaction tube 22.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method and an apparatus for producing a highly active catalyst.

[0002]

2. Description of the Related Art Conventionally, when treating exhaust gas or the like, harmful components in the exhaust gas have been detoxified by a decomposition reaction and a reduction reaction using a catalyst.

[0003] As a catalyst used for such an exhaust gas treatment or the like, various forms such as a honeycomb shape or a pellet shape mainly composed of titanium oxide, alumina, silica and the like have been used.

On the other hand, in recent years, a catalyst mainly comprising the above-mentioned titanium oxide, alumina, silica or the like has been used as a catalyst carrier, and iron (Fe), copper (Cu), nickel (N
By supporting a metal such as i) and the like, it is becoming more and more effective to increase the activity of the catalyst.

[0005] As a method for producing a highly active catalyst by supporting a metal on such a catalyst carrier, CVD (Chemi) is used.
CAL (AtomicLayer Epitax) that is deposited at the atomic level, which is one of the methods of cal vapor deposition (CVD) or CVD.
It is conceivable to use y) or the like.

[0006] CVD, which has not been industrially implemented yet but is considered as a method for producing a highly active catalyst at a laboratory level, will be described. An apparatus for producing a highly active catalyst as shown in FIG. it can.

In FIG. 1, reference numeral 1 denotes an evaporator for heating a raw material source 2 to an evaporating temperature. The evaporator 1 includes a CV such as a metal chloride, metal alkoxide, metal carbonyl, or metal acetate.
D, a raw material source 2 generally used is accommodated, and a raw material heater 3 for heating the raw material source 2 to an evaporation temperature is provided outside the evaporating section 1. Various heaters such as a high-frequency heater and an electric heater can be used as the raw material heater 3. As the raw material source 2, for example, a material that exhibits a liquid state at room temperature or about 100 ° C. is used.

In FIG. 3, two evaporating units 1 are provided, and the evaporating unit 1 may accommodate another raw material source 2 or the same raw material source 2. . Further, three or more evaporating units 1 may be provided to accommodate different raw material sources 2.

Each of the evaporating sections 1 includes an inert gas supply device 4
An inert gas supply main pipe 6 for supplying an inert gas 5 such as argon gas, helium gas, nitrogen gas, etc.
8 and connected in parallel, and each branch pipe 7, 8
A flow controller 9, which can individually adjust the flow rate of the inert gas 5 supplied from the inert gas supply device 4,
10 are provided. Each outlet of the evaporator 1 is connected to a mixing pipe 11. Further, the respective evaporating sections 1 may be provided independently without being provided in parallel.

Further, a flow controller 13 is connected to the inert gas supply main pipe 6 via a branch pipe 12, and the inert gas 5 from the flow controller 13 is introduced into the mixing pipe 11. The concentration adjusting device 15 is configured to generate the source gas 14 having a predetermined concentration by mixing.

In the figure, 16, 17, and 18 are the branch pipes 7,
Opening / closing valves provided at 8, 12 respectively indicate opening / closing valves provided at outlets of the evaporating section 1 and the flow controller 13 respectively.

In FIG. 1, reference numeral 22 denotes a reaction tube connected to the mixing tube 11, and a carrier support 2 provided inside the reaction tube 22.
On 3, a catalyst carrier 24 mainly composed of titanium oxide, alumina, silica, or the like is held. The reaction tube 22 is configured so that the raw material gas 14 from the mixing tube 11 is introduced from one end side and is led out from the outlet tube 25 on the other end side. In the figure, reference numeral 26 denotes an exhaust pump connected to the outlet pipe 25.

The reaction tube 22 is located outside the reaction tube 22.
Is provided so as to entirely heat the catalyst carrier 24 held inside the reaction tube 22 by surrounding the outer periphery of the reaction tube 22. The heater 27 is fixed to a fixing table 28. Has become.

In order to produce a highly active catalyst using the conventional highly active catalyst producing apparatus shown in FIG. 3, a catalyst support 24 is held on a carrier support 23 inside a reaction tube 22 and the evaporating section 1 The raw material source 2 which is a metal compound to be supported on the catalyst carrier 24 is charged.

The heater 27 is operated to heat the catalyst carrier 24 inside the reaction tube 22 to the decomposition temperature of the raw material gas 14, while opening the on-off valves 16, 17, 18, 19, 20, 21 and controlling the flow rate. The inert gas 5 is supplied to the reaction tube 22 by opening the 9, 10, 13 and operating the suction device 26, and the inside of the reaction tube 22 is replaced with the inert gas 5.

Subsequently, the raw material heater 3 of the evaporating section 1 is operated to heat the raw material source 2 to a temperature at which the raw material source 2 evaporates, and the openings of the flow rate controllers 9 and 10 are adjusted to thereby control the evaporating section 1.
The concentration of the source gas 14 is adjusted by adjusting the flow rate of the inert gas 5 to be supplied to the apparatus and adjusting the opening of the flow rate adjuster 13 of the concentration adjusting device 15.

The raw material gas 14 whose concentration has been adjusted and supplied to the reaction tube 22 is decomposed by coming into contact with the catalyst carrier 24 heated by the heater 27 up to the decomposition temperature of the raw material gas 14 to be decomposed. The metal inside is the catalyst support 24
It is carried on. After performing this operation for a predetermined time, the heating of the catalyst source 24 by the source heater 2 and the heater 27 by the source heater 3 is stopped, and the supply of the inert gas 5 is stopped. A highly active catalyst having a metal supported thereon is taken out.

[0018]

However, as described above, even if an attempt is made to obtain a highly active catalyst by supporting a metal on the catalyst carrier 24 using CVD, the conventional apparatus as shown in FIG. However, it was difficult to produce a large, high-activity catalyst having a long length, and it could not be used industrially.

In order to obtain a large and highly active catalyst having a long length in the conventional apparatus, it is necessary to heat the catalyst carrier 24 as uniformly as possible by a heater 27 provided at a position far away. Requires that the capacity of the reaction tube 22 be increased, which causes a problem that the entire apparatus becomes extremely large.

Further, in the conventional apparatus, since the entire catalyst carrier 24 is heated by the heater 27 fixed to the outside of the reaction tube 22, it is impossible to heat the entire catalyst carrier 24 to a uniform temperature. It is very difficult, so that the temperature of the catalyst carrier 24 varies and the metal adheres intensively to the portion where the temperature is likely to adhere to the metal, which makes it difficult to control the crystal structure, and There are problems such as a decrease in activation and a decrease in selectivity during a catalytic reaction.

The present invention has been made to solve such a conventional problem. A long active catalyst having a long length can be easily produced, and a metal layer having a controlled crystal structure is formed on a catalyst carrier. It is an object of the present invention to provide a method and an apparatus for producing a catalyst that can be formed to produce a high-quality, high-activity catalyst.

[0022]

According to the first aspect of the present invention,
The raw material source charged in the evaporating section is heated to the evaporating temperature to evaporate, and the vapor of the raw material source in the evaporating section is supplied to the reaction tube as a raw material gas by transporting the vapor with an inert gas,
When the metal in the raw material gas is supported on the catalyst carrier by bringing the raw material gas into contact with the catalyst carrier that is provided inside the reaction tube and heated to the decomposition temperature of the raw material gas, the reaction is performed outside the reaction tube. A method for producing a highly active catalyst, characterized in that at least one of the heater and the catalyst carrier, which surrounds the outer periphery of a tube with a required width, is relatively moved in the axial direction of the reaction tube with respect to the other. It is.

According to a second aspect of the present invention, there is provided an evaporating section for charging a raw material source and heating it to an evaporating temperature, an inert gas supply apparatus for supplying an inert gas to the evaporating section, and an inert gas supply apparatus. A flow controller for controlling the flow rate of the inert gas supplied to the evaporator; and a concentration controller for the raw material gas mixed at the outlet of the evaporator by controlling the flow rate of the inert gas branched from the inert gas supply device. And a reaction tube provided with a catalyst carrier therein and adapted to introduce a source gas whose concentration is adjusted from one end side and to lead out from the other end side, and arranged so as to surround the outer periphery of the reaction tube with a required width. And a heater moving device for moving the heater in the axial direction of the reaction tube.

According to a third aspect of the present invention, there is provided an evaporating section for charging a raw material source and heating to an evaporating temperature, an inert gas supply device for supplying an inert gas to the evaporating section, and an inert gas supply device. A flow controller for controlling the flow rate of the inert gas supplied to the evaporator; and a concentration controller for the raw material gas mixed at the outlet of the evaporator by controlling the flow rate of the inert gas branched from the inert gas supply device. And a reaction tube that holds the catalyst carrier via a transfer support member therein and introduces a source gas whose concentration has been adjusted from one end and discharges the reaction gas from the other end. A high activity catalyst manufacturing apparatus, comprising: a heater arranged so as to surround a required width, and a carrier moving device that moves the moving support member in the axial direction of the reaction tube. is there.

According to the above-mentioned means, at least one of the heater provided outside the reaction tube and the catalyst carrier held inside the reaction tube is disposed in the axial direction of the reaction tube with respect to the other. Since it is made to move relatively, even if the catalyst support of a long length without increasing the size of the equipment,
A metal layer having a controlled crystal structure can be efficiently formed on the catalyst carrier by performing uniform heating, so that a highly active catalyst having a long length and uniform activity can be efficiently produced.

[0026]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below with reference to the drawings.

FIG. 1 shows an example of an apparatus for carrying out the method of the present invention. In FIG. 1, the same components as those in FIG. 3 are denoted by the same reference numerals, and detailed description is omitted. .

As shown in FIG. 1, inside the reaction tube 22,
A catalyst support 30 having a long length in the axial direction of the reaction tube 22 is provided via a support support 29.

Outside the reaction tube 22, there is provided a heater 31 for performing high-frequency heating or the like in which the outer periphery of the reaction tube 22 has a required width and is annularly surrounded.

Further, the heater 31 is supported on a movable table 33 movable along a guide rail 32 provided in parallel with the axial direction of the reaction tube 22. The ball screw 34 is screwed and extended in the axial direction of the reaction tube 22, and is moved by a heater moving device 36 including a motor 35 that drives the rotation of the ball screw 34.

The operation of the apparatus shown in FIG. 1 will be described below.

In order to produce a highly active catalyst using the apparatus shown in FIG. 1, a long catalyst carrier 30 is held on a carrier support base 29 inside the reaction tube 22 and the above-described evaporation is performed in the same manner as described with reference to the apparatus shown in FIG. A raw material source 2 which is a compound of a metal to be supported on the catalyst carrier 30 is charged into the part 1.

The heater 3 is driven by the heater moving device 36.
1 is moved to a position where the heater 31 heats one end (left side) of the catalyst carrier 30 inside the reaction tube 22.

The heater 31 is operated to heat one end of the catalyst carrier 30 inside the reaction tube 22 to the decomposition temperature of the raw material gas 14 as shown by hatching in FIG.
The inert gas 5 is supplied to the reaction tube 22 by opening the flow rate controllers 9, 10, and 13 and opening the flow controllers 9, 10 and 13 and operating the suction device 26.
Is replaced with an inert gas 5.

Subsequently, the raw material heater 3 of the evaporating section 1 is operated to heat the raw material source 2 to a temperature at which the raw material source 2 evaporates, and the openings of the flow rate controllers 9 and 10 are adjusted to thereby control the evaporating section 1.
The concentration of the source gas 14 is adjusted by adjusting the flow rate of the inert gas 5 to be supplied to the apparatus and adjusting the opening of the flow rate adjuster 13 of the concentration adjusting device 15.

The raw material gas 14 whose concentration has been adjusted and supplied to the reaction tube 22 contacts one end (left end) of the catalyst carrier 30 which is heated by the heater 31 to the decomposition temperature of the raw material gas 14. , And the metal in the raw material gas 14 is supported on one end side of the catalyst carrier 30.

Subsequently, the heater moving device 36 is driven so that the heating of the catalyst carrier 30 by the heater 31 is directed from one end (left end) to the other end (right end) as indicated by an arrow. The heater 31 is moved at a constant speed.

As a result, even if the catalyst carrier 30 has a long length, it is possible to efficiently form a metal layer having a controlled crystal structure on the catalyst carrier 30 by performing uniform heating.
Therefore, a highly active catalyst having a long length and uniform activity can be efficiently produced.

FIG. 2 shows another example of an apparatus for carrying out the method of the present invention.
A heater 37 having a required width and surrounding the outer periphery of the heater in an annular shape is fixed on a fixed base 38.

A catalyst support 30 having a long length in the axial direction of the reaction tube 22 is provided inside the reaction tube 22 via a movement support member 39 such as a roller. Is provided.

In order to produce a highly active catalyst using the apparatus shown in FIG. 2, the carrier support device 39 is operated by driving the carrier moving device 40 to move the catalyst carrier 30, and the heater 37 is moved.
With this, the other end (right end) of the catalyst carrier 30 is adjusted to a position where it is heated.

The heater 37 is operated to heat one end of the catalyst carrier 30 inside the reaction tube 22 to the decomposition temperature of the raw material gas 14, while opening and closing valves 16, 17, 18, 19, 20, 2.
Open 1 and open the flow controllers 9, 10, 13
The inert gas 5 is supplied to the reaction tube 22 by operating the suction device 26, and the inside of the reaction tube 22 is replaced with the inert gas 5.

Subsequently, the raw material heater 3 of the evaporating section 1 is operated to heat the raw material source 2 to a temperature at which the raw material source 2 evaporates, and the openings of the flow controllers 9 and 10 are adjusted to adjust the opening degree of the evaporating section 1.
The concentration of the source gas 14 is adjusted by adjusting the flow rate of the inert gas 5 to be supplied to the apparatus and adjusting the opening of the flow rate adjuster 13 of the concentration adjusting device 15.

The raw material gas 14 whose concentration has been adjusted and supplied to the reaction tube 22 comes into contact with the other end (right end) of the catalyst carrier 30 which is heated by the heater 37 to the decomposition temperature of the raw material gas 14. As a result, the metal in the raw material gas 14 is supported on the other end of the catalyst carrier 30.

Subsequently, by driving the carrier moving device 40 to operate the moving support member 39 such as a roller, the heating of the catalyst carrier 30 by the heater 37 is performed as shown by the arrow in the drawing. The catalyst carrier 30 is moved at a constant speed from the right end to the one end (left end).

Thus, even if the catalyst carrier 30 has a long length, the metal layer having a constant thickness can be efficiently formed on the catalyst carrier 30 by performing uniform heating. A highly active catalyst having a high activity can be efficiently produced.

A case where a metal is supported on a catalyst carrier 30 mainly composed of titanium oxide by the apparatus shown in FIGS. 1 and 2 to actually produce a highly active catalyst will be described.
When CuCl3 is used for the raw material source 2, an argon gas is used as the inert gas 5, and the raw material source 2 is evaporated by heating the raw material source 2 at about 500 to 700 [deg.] C. by the raw material heater 3. By heating the catalyst support 30 in the reaction tube 22 to about 550 ° C. to 1000 ° C., the raw material gas 14 was decomposed and the metal was effectively supported on the catalyst support 30 to produce a highly active catalyst. .

When Ni (CO) ₄ is used for the raw material source 2 when an active catalyst is actually produced by supporting a metal on a catalyst carrier 30 mainly composed of titanium oxide, an inert gas The raw material source 2 is heated at about 43 ° C. by the raw material heater 3 to evaporate it by using an argon gas as 5, and the catalyst carrier 30 in the reaction tube 22 is heated to about 182 ° C. to 200 ° C. By heating, the raw material gas was decomposed, and the metal was effectively supported on the catalyst carrier 30 to produce a highly active catalyst.

The present invention is not limited only to the above-described embodiment, and various configurations of the heater moving device and the carrier moving device can be selected, and various changes can be made without departing from the gist of the present invention. Can of course be added.

[0050]

According to the present invention, at least one of the heater provided outside the reaction tube and the catalyst carrier held inside the reaction tube is moved relative to the other in the axial direction of the reaction tube. Therefore, even if the catalyst support has a long length without increasing the size of the equipment, it is possible to efficiently form a metal layer having a controlled crystal structure on the catalyst support by performing uniform heating. Accordingly, an excellent effect that a highly active catalyst having a long length and a uniform activity can be efficiently produced can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic system diagram showing an example of a highly active catalyst production apparatus according to the present invention.

FIG. 2 is a schematic system diagram showing another example of the high activity catalyst production apparatus according to the present invention.

FIG. 3 is a schematic system diagram showing an example of a conventional high activity catalyst production apparatus.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Evaporation part 2 Raw material source 4 Inert gas supply device 5 Inert gas 9,10,13 Flow controller 14 Raw material gas 15 Concentration controller 22 Reaction tube 30 Catalyst carrier 31 Heater 36 Heater moving device 37 Heater 39 Move Support member 40 carrier moving device

Claims (3)

[Claims] 1. A raw material source charged in an evaporating section is heated to an evaporating temperature to evaporate the raw material source, and the vapor of the raw material source in the evaporating section is supplied to a reaction tube as a raw material gas by being conveyed by an inert gas. When the metal in the raw material gas is supported on the catalyst carrier by bringing the raw material gas into contact with the catalyst carrier which is provided inside the tube and heated to the decomposition temperature of the raw material gas, the reaction tube is provided outside the reaction tube. A method for producing a highly active catalyst, characterized in that at least one of a heater and a catalyst carrier surrounding the outer periphery of a predetermined width is moved relative to the other in the axial direction of the reaction tube. 2. An evaporating section for charging a raw material source and heating to an evaporating temperature, an inert gas supply device for supplying an inert gas to the evaporating section, and an inert gas supply device for supplying the inert gas from the inert gas supplying device to the evaporating section. A flow rate controller for controlling the flow rate of the active gas, a flow rate controller for controlling the flow rate of the inert gas branched from the inert gas supply device and mixing the raw material gas at the outlet of the evaporator, and a catalyst carrier therein. A reaction tube which is provided with a source gas whose concentration is adjusted from one end side and is led out from the other end side; a heater arranged so as to surround an outer periphery of the reaction tube with a required width; And a heater moving device for moving a heater in the axial direction of the reaction tube. 3. An evaporating section for charging a raw material source and heating to an evaporating temperature, an inert gas supply device for supplying an inert gas to the evaporating section, and an inert gas supply device for supplying the inert gas from the inert gas supplying device to the evaporating section. A flow controller for controlling the flow rate of the active gas, a flow rate controller for controlling the flow rate of the inert gas branched from the inert gas supply device and a concentration control device for the raw material gas mixed at the outlet of the evaporating section, A reaction tube holding the catalyst carrier via the support member and introducing a source gas whose concentration has been adjusted from one end side and drawing it out from the other end side, and surrounding the reaction tube with a required width. And a carrier moving device for moving the moving support member in the axial direction of the reaction tube.