JPH0971781A - Repair and/or reinforcement of bulkhead of bulkhead heat exchanger - Google Patents

Abstract

PROBLEM TO BE SOLVED: To repair a bulkhead having a crack or the like of a heat exchanger made of inorganic materials (e.g. a coke oven) by making a solid compound deposited inside the bulkhead by introducing a gas containing a metal compound in one side of the bulkhead and a reactive gas in the other side. SOLUTION: In a heat exchanger having a bulkhead composed of an air permeable material (including air permeable due to damage), the bulkhead is repaired or reinforced by practically blocking the permeability by introducing (G1 ) a gas containing a metal or a metal compound in one side of the bulkhead and (G2 ) a gas containing a reactive gas which reacts with G1 to deposit a solid metal compound in the other side and making each of them reach the inside of the bulkhead and the solid metal compound deposited there. Mg, SiH4 , an alkyl metal, AlCl4 , SiCl4 , TiCl4 , or the like and an oxyhalogenated compound or the like exemplify G1 and O2 , H2 , NH3 , a hydrocarbon, etc., exemplify G2 . A solid oxide, nitride and carbide can be deposited depending on the combination of G1 and G2 . This method is particularly effective for the repair of a coke oven with a brick bulkhead.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of repairing and / or strengthening a partition of a partition heat exchanger.

[0002]

2. Description of the Related Art Conventionally, a heating gas is arranged on one side of a partition wall and an object to be heated is arranged on the other side, and heat is transferred from the heating gas to the object to be heated through the partition wall to raise the temperature of the object to be heated. ,
A partition wall type heat exchanger for the purpose of performing treatments such as phase transformation and reaction is known.

For example, "CERAMIC HEAT EXCHANGER CONCE
PTS AND TECHNOLOGY ", NOTES PUBULICATIONS, 1985) discloses various partition type heat exchangers for gas-gas heat exchangers (hereinafter referred to as" Prior Art 1 ").
That is, the prior art 1 is a FINNED PLATE type, TUBU
It is disclosed that there are IN SHELL type, TUBU IN TUBU type and HELICAL type, and examples of the material of the partition wall include cordierite (2MgO.2Al ₂ O ₃ .5SiO ₂ ), magnesia-alumina-silicate and silicon carbide. ing. Such a ceramic partition wall deteriorates after a long period of use and cracks occur. When this grows into a through crack, the gas on the high pressure side passes through the partition wall and leaks to the low pressure side, so that the partition wall cannot be used. However, it does not describe a method for repairing a through crack that has occurred in a partition wall. Therefore, it is presumed that the damaged partition wall is discarded in the heat exchanger.

The coke oven is a furnace for carbonizing carbon to produce coke, and is also a heat exchanger for gas and solid. In this furnace, a carbonization chamber that stores coal and a combustion chamber that generates heating gas are alternately arranged via partition walls. Then, the partition wall is heated by the heating gas, and the heat is transferred to the coal charged in the carbonization chamber through the partition wall to thermally decompose the coal, and the carbonization proceeds. Here, the partition wall is usually
Silica brick is used, but it is disclosed in JP-A-52-9100.
Publication 1 discloses the use of silicon carbide bricks. The partition wall has a thickness of 50 to 150 mm.

The high temperature coke produced by the completion of the carbonization is, after the lids on the extrusion side and the coke side are removed,
It is discharged from the extrusion side to the coke side by the extruder. Next, the next-charged room temperature coal is charged from the upper charging port, and the above-described cycle is repeated. The partition walls are scraped by the coke pushed out, and joints between bricks are broken and cracks are damaged by repeated heating and cooling. If this results in crack damage such that the carbonization chamber and the combustion chamber penetrate, the carbonization gas containing aromatic hydrocarbons leaks from the carbonization chamber to the combustion chamber, making carbon carbonization difficult. Therefore, some methods for repairing the above-mentioned crack damage are known.

As one of them, there is known a method in which refractory powder is pneumatically transported to an empty carbonization chamber to close a through crack portion. Although it is possible to temporarily reduce gas leakage by this method, it does not reach the level of reinforcing the brick,
Moreover, the effect of reducing gas leakage does not last long. This is because the refractory powder deposited on the through cracks shrinks as sintering progresses, so that voids are unavoidably generated, and gas flows from this portion, the sintered pieces scatter, and the cracks expand again. Also,
A problem arises when powder passes through the through cracks during construction and reaches the combustion chamber on the opposite side and deposits there. That is, it is difficult to remove the powder from the combustion chamber, and if it is left unattended, the combustion space becomes narrow and the combustion performance deteriorates. As a method for repairing the furnace wall near the furnace lid, a wet spraying method is known in which a mixture of refractory powder and water is sprayed on the damaged part. This method is only a temporary measure because the refractory does not exhibit strength and is easily peeled off by a slight impact.

A spraying method is also known as a method for repairing the partition wall. The furnace wall is scraped by coke extruded after carbonization, and damaged by thermal spalling, and unevenness is generated on the wall surface on the carbonization chamber side for a long time. For this reason, the pressure applied to the coke extruder increases, and the coke cannot be extruded depending on the situation. In such a case, thermal spraying repair is performed also from the viewpoint of preventing unevenness from becoming excessive. In this method, refractory powder is adhered to a damaged portion of a partition wall in a flame composed of oxygen and fuel gas or in a semi-molten or molten state by burning aluminum or silicon. For example, Japanese Examined Patent Publication No. 62-15508
The publication discloses a flame spray material applied to such a purpose (hereinafter referred to as "prior art 2"). Also,
Japanese Examined Patent Publication No. 3-9185 discloses a specific ratio of SiO ₂ , A.
Disclosed is a high siliceous thermal spray material that is formed from 1 ₂ O ₃ , CaO, Fe ₂ O ₃ and Na ₂ O to form a thermal spray repair body that can withstand long-term use (hereinafter referred to as “Prior Art 3”). That). In construction, such thermal spray material is melted by the flame, collides with the repaired part and rapidly solidifies,
A sprayed body mainly composed of a glass phase is formed. This glass phase undergoes volume contraction when it further transforms into a crystalline phase in the cooling process, and cracks occur. For this reason, the thermal spray repair body is insufficiently bonded to the base material and cannot be used for a long period of time. In particular, when the base material is deteriorated and its strength is lowered, a crack develops from the base material side, and the thermal spraying material comes off. In addition, in order to apply this method, it is necessary to specify the damaged portion in advance. However, the region that can be observed from the outside is limited to the vicinity of the lids on the extrusion side and the coke side, and it is extremely difficult to observe the inside than that. Therefore, this method has a problem that it is difficult to apply the method to the inside of the carbonization chamber.

When the silica bricks constituting the furnace wall are seriously damaged, the damaged bricks are reloaded. Transshipment is done hot to avoid damage due to cooling of the remaining bricks. Japanese Unexamined Patent Publication (Kokai) No. 5-132355 discloses a silica brick for hot repair which is excellent in abrasion resistance as well as heat spalling resistance used for hot transshipment repair of coke oven wall bricks (hereinafter, referred to as "Prior art 4"). However, hot repair work is not only accompanied by high-temperature heavy-duty work, but also the production of coke is stopped for a long period of time, resulting in a large economic loss.

As described above, although there are many problems in the conventional method, among the conventional methods, the thermal spraying method is excellent in workability and economical efficiency, and the abrasion resistance and durability of the applied thermal sprayed body are relatively excellent. However, it is still insufficient, and the life of the thermal spraying body is not determined only by the strength and spalling resistance of the thermal spraying body itself, but the life of the thermal spraying body is about half a year due to the problem of the thermal spraying body dropping out as described above.

[0010]

A partition wall of a partition wall heat exchanger, for example, a partition wall between a carbonization chamber and a combustion chamber of a coke oven (hereinafter referred to as "coke furnace partition wall") penetrates from the carbonization chamber to the combustion chamber. It is desirable to maintain a smooth wall surface with no through cracks. Therefore, it is important to improve the strength and wear resistance of the furnace wall. However, if a through crack occurs in the partition wall, the damaged portion of the partition wall must be replaced or repaired by a thermal spraying method. As described above, replacement of the damaged part requires a long shutdown of the device. In a facility such as a coke oven where cooling of the furnace is practically impossible to protect the partition, there is a problem that the partition must be exchanged hot. Further, in order to replace the partition wall or to spray the damaged wall of the partition wall, it is necessary to specify the damaged portion in advance, but there is also a problem that this must be performed in a hot working environment.

Therefore, an object of the present invention is to solve the above-mentioned problems, and in repairing a partition wall of a partition type heat exchanger, a gas for the partition wall is simply repaired by repairing damage such as cracks and irregularities as in the conventional case. Not only can the flow be blocked and a smooth flat surface can be formed, but at the same time, it can be strengthened into a partition having excellent strength and abrasion resistance, and furthermore, it can be easily performed without specifying the damaged portion. It is to provide a repair and / or strengthening method that can be done.

[0012]

Means for Solving the Problems The inventors of the present application have made the following discoveries as a result of intensive studies to achieve the above-mentioned object. That is, metal from one side of a material having air permeability, such as partition walls having through cracks, partition walls having open pores, and formed bodies filled with inorganic powder (hereinafter referred to as “inorganic powder filled body”). Alternatively, a metal compound-containing gas (referred to as "gas G-1" in this specification) is supplied, and a reactive gas containing a solid metal compound is precipitated when the metal compound-containing gas is reacted with the above metal or metal compound from the other side. By supplying a gas (in this specification, referred to as “gas G-2”), the gas G-1 and the gas G-2 are caused to react with each other to deposit a solid metal compound in the vent and deposit it in the vent. It is possible to prevent gas from substantially passing through the partition wall and the inorganic powder filling body, and it is possible to improve the strength and abrasion resistance of the partition wall and the inorganic powder filling body. Knowing that .

The present invention was made based on the above-mentioned findings, and is as follows. The method for repairing and / or strengthening a partition according to the invention of claim 1 is a heat exchanger having a partition made of a material having air permeability,
A gas (G-1) containing a metal or / and a metal compound is supplied to one side of the partition wall, and a reactive gas that reacts with the metal or the metal compound to precipitate a solid metal compound is contained on the other side of the partition wall. By supplying the gas (G-2) to each of the gas (G-1 and G-2) from the one side and the other side of the partition wall to reach the inside of the partition wall, and then both inside the partition wall. Gas (G-1 and G-2
And) are caused to react with each other to produce a solid metal compound, and the solid metal compound thus produced is deposited inside the partition walls.

Repair and / or repair of the partition wall of the invention according to claim 2
Alternatively, the strengthening method is characterized in that, in the method of the invention described in claim 1, the heat exchanger has a through damage portion in the partition wall.

Repair and / or repair of the partition wall of the invention according to claim 3
Alternatively, the strengthening method is characterized in that, in the method of the invention described in claim 1 or 2, the metal compound is a metal halide.

Repair and / or repair of the partition wall of the invention according to claim 4
Alternatively, the strengthening method is the method of the present invention according to claim 1 or 2, wherein the metal is magnesium and the reactive gas is one or more gases selected from the group consisting of oxygen, carbon monoxide and water. It has a special feature.

Repair and / or repair of the partition wall of the invention according to claim 5
Alternatively, the strengthening method is characterized in that in the method of the invention according to claim 4, magnesium is magnesium vapor generated by reacting magnesium oxide and aluminum at a temperature within a range of 850 to 1700 ° C. Is.

Repair and / or repair of the partition wall of the invention according to claim 6
Alternatively, the strengthening method is the method of the invention according to claim 1 or 2, wherein the partition wall heat exchanger is a coke oven having a carbonization chamber and a combustion chamber, and one side of the partition wall is a carbonization chamber,
The other side of the partition wall is a combustion chamber, the gas (G-1) containing a metal compound is a silicon compound-containing gas, and the gas (G-2) containing a reactive gas is generated in the combustion chamber. Combustion gas, and both of these gases (G
-1 and G-2) is performed by changing the pressure difference between the carbonization chamber and the combustion chamber positively and negatively a plurality of times, and the solid metal compound deposited inside the partition wall is silicon dioxide. It is characterized by being

Repair and / or repair of the partition wall of the invention according to claim 7
Alternatively, the method for strengthening is a gas (G-1) containing a metal or / and a metal compound on one side in addition to the method for repairing and / or strengthening the partition wall of the invention according to claim 2.
It is characterized in that the damaged portion is preliminarily repaired before the supply of.

Repair and / or repair of the partition wall of the invention according to claim 8
Alternatively, the strengthening method is the method of the invention according to claim 7, wherein a gas containing a metal or / and a metal compound is produced by causing positive and negative repeated fluctuations in the pressure difference between one side and the other side of the partition wall. It is characterized in that the reaction between (G-1) and a gas (G-2) containing a reactive gas that reacts with a metal or a metal compound to precipitate a solid metal compound is carried out.

Repair and / or repair of the partition wall of the invention according to claim 9
Alternatively, the strengthening method is characterized in that, in the method according to claim 6 or 7, the metal compound is a metal halide.

According to a tenth aspect of the invention, there is provided a method for repairing and / or strengthening a partition wall according to the sixth or seventh aspect of the invention, wherein the metal is magnesium and the reactive gas is oxygen, carbon monoxide and water. It is characterized in that it is one or more gases selected from the group consisting of

According to the eleventh aspect of the present invention, in the method for repairing and / or strengthening the partition wall, the method of the tenth aspect of the invention is that magnesium reacts with magnesium oxide and aluminum at a temperature within a range of 850 to 1700 ° C. It is characterized in that it is magnesium vapor generated by the operation.

According to a twelfth aspect of the present invention, in the method of repairing and / or strengthening a partition wall, the pressure difference is -200 to +200 mmAq in the method of the sixth or eighth aspect.
Is within the range.

According to a thirteenth aspect of the present invention, there is provided a method for repairing and / or strengthening a partition wall according to the sixth or eighth aspect, wherein the silicon compound-containing gas contains 0.1 vol.% Or more of silicon tetrachloride. Gas and combustion gas is 1 vo
It is characterized by being a gas containing l.% or more of water.

According to a fourteenth aspect of the present invention, there is provided a method for repairing and / or strengthening a partition wall, wherein in a heat exchanger having a partition wall made of a gas permeable material, a gas permeable flat plate is provided on the partition wall of the heated chamber. Is placed close to or partly in contact with the wall surface of the plate, the space formed between the wall surface and the flat plate is filled with inorganic powder, and then the heated chamber contains a metal or / and a metal compound. Gas (G-
1) while a gas (G-2) containing a reactive gas that reacts with the metal or / and the metal compound to precipitate a solid metal compound is supplied to the heating chamber. The gas (G-1 and G-2) is allowed to reach between the inorganic powder particles and the inside of the partition wall to react between the respective gases (between G-1 and G-2), and thus, It is characterized in that the solid metal compound is generated between the inorganic powder particles and inside the partition walls.

The method of repairing and / or strengthening the partition wall according to the fifteenth aspect of the present invention is characterized in that, in the method of the fourteenth aspect of the invention, the heat exchanger has a damaged portion in the partition wall. is there.

According to a sixteenth aspect of the present invention, in the method for repairing and / or strengthening a partition wall according to the fourteenth or fifteenth aspect of the invention, the partition wall heat exchanger is a coke oven having a carbonization chamber and a combustion chamber. , One side of the partition wall is a carbonization chamber, the other side of the partition wall is a combustion chamber, the gas containing a metal compound (G-1) is a silicon compound containing gas, and a gas containing a reactive gas ( G-2) is a combustion gas generated in the combustion chamber, and the reaction between the respective gases (between G-1 and G-2) has a plurality of positive and negative pressure differences between the carbonization chamber and the combustion chamber. It is characterized in that silicon dioxide is a solid metal compound that is deposited by varying the number of times and is deposited inside the partition walls.

The method of repairing and / or strengthening a partition wall according to the seventeenth aspect of the present invention is the method of the present invention according to the fifteenth aspect, further comprising a metal or / and the metal compound on one side of the partition wall. This is characterized in that the damaged portion of the partition wall is preliminarily repaired before the supply of the gas (G-1) to be used.

The method of repairing and / or strengthening a partition wall according to the invention of claim 18 is the method of claim 17 wherein the gas (G-1) containing a metal or / and a metal compound, and the metal or metal. A gas containing a reactive gas that reacts with a compound to precipitate a solid metal compound (G-
The reaction with 2) is characterized in that it is performed by changing the pressure difference between one side of the partition wall and the other side of the partition wall positively and negatively a plurality of times.

The method of repairing and / or strengthening the partition wall according to the invention of claim 19 is the method of claim 16 or 18, wherein the pressure difference is -200 to +200 mmA.
It is characterized by being within the range of q.

According to a twentieth aspect of the invention, the partition wall repairing and / or strengthening method is the method of the sixteenth or eighteenth aspect, wherein the silicon compound-containing gas is 0.1 vol.
% Is a gas containing silicon tetrachloride or more, and the combustion gas is
It is characterized by being a gas containing 1 vol.% Or more of water.

There is no particular limitation on the structure of the partition wall which separates the heating gas and the object to be heated in the partition wall type heat exchanger to which the above-mentioned repair and / or strengthening method of the present invention is applied. As the form of the partition wall, for example, a plate, a tube or the like can be applied. The material of the partition is not limited, and a known material can be applied. For example, silica, mullite, cordierite (2
MgO ・ 2Al ₂ O ₃ .5SiO ₂ ) and oxides such as magnesia, alumina, silicate, etc., carbides such as silicon carbide, nitrides such as silicon nitride, and composite materials such as silicon nitride bonded silicon carbide, etc. Strong materials are desirable. For example, as the furnace wall material between the carbonization chamber and the combustion chamber of the coke furnace, the most commonly used silica brick mainly composed of tridymite crystals is used, and the thickness of the furnace wall is 50 to
It is about 150 mm.

It is essential that the material forming the partition walls of the heat exchanger has pores in order to ensure thermal shock resistance. When the material is manufactured by a known powder sintering method, the pores are mainly open pores having air permeability. Here, having air permeability means that a gas containing a metal or / and a metal compound can pass, but an inorganic powder cannot. Further, it is essential that the material forming the flat plate used in the repairing method of the present invention also has the same air permeability as the partition wall. In this invention,
This is because it is essential that the various gases used enter the interior of both sides of the partition wall and the flat plate and come into contact therewith to cause a precipitation reaction of the solid metal compound.

In order for the partition wall and the flat plate to have air permeability, it is sufficient that the material forming the partition wall and the flat plate have open pores. Refractory bricks used for partition walls of coke ovens have open pores. For example, the open porosity of silica bricks is 15-40 vol.%.
It is. In the present invention, the open porosity is preferably 5 vol.% Or more. When the open porosity is 5 vol.% Or less, it is difficult to deposit a sufficient amount of the metal compound inside the pores for a desired purpose. On the other hand, the desirable upper limit value of the open porosity is not particularly limited as long as it is within the range of ordinary refractory materials, since it causes no problem.

The gas containing a metal and / or a metal compound will be described below. Since the metal or / and metal compound-containing gas (G-1) needs to pass through the gas permeable material, it should be a gas containing a gaseous metal or a gaseous metal compound. As a metal,
A metal having a high vapor pressure such as Mg is desirable, and as the metal compound, a hydride such as SiH ₄ or Al (CH ₃ ) ₃ or A is used.
_{l (C 2 H 5) 3} , Si (CH 3) 4 and Si (C ₂ H ₅₎
Alkyl metals such as ₄ , AlCl ₃ , SiCl ₄ , TiC
halides such as l ₄ and ZrCl ₄ , Si ₂ OCl
Oxyhalides such as ₆ and ZrOCl ₂ , SiH
Hydrohalides such as ₂ Cl ₂ and Al (C ₃
H ₇ O) ₃ , Si (CH ₃ O) ₄ , and Si (C ₂ H ₅
Examples thereof include alkoxides such as O) ₄ . The metal or metal compound may be used alone, or may be diluted with a gas that does not react with the metal or / and the metal compound. As the diluent gas, for example, N ₂ and Ar
Is used as appropriate.

The gas (G-2) containing the reactive gas is
It should contain a gas which reacts with the metals or / and metal compounds mentioned above to precipitate solids of the metal compounds. As a reactive gas, O ₂ , H ₂ O, CO ₂ , N ₂ , NH ₃ , N ₂
Examples of O and various hydrocarbons (eg, alkanes such as CH ₄ , C ₂ H ₅ and C ₃ H ₇ , alkenes such as C ₂ H ₄ and C ₃ H ₆ , and alkynes such as C ₂ H ₂ ) be able to.

If, for example, O ₂ is selected as the reactive gas, the following reaction occurs depending on the combination with various metals or metal compounds: Al ₂ Cl ₆ + 3 / 2O ₂ → Al ₂ O ₃ + 3Cl ₂ SiH ₄ + O ₂ → SiO ₂ + 2H ₂ MgCl ₂ + 1 / 2O ₂ → MgO + Cl ₂ SiCl ₄ + O ₂ → SiO ₂ + 2Cl ₂ TiCl ₄ + O ₂ → TiO ₂ + 2Cl ₂ ZrCl ₄ + O ₂ → ZrO ₂ + 2Cl ₂ Al (CH ₃ ) ₃ + 15 / 2O ₂ → 1/2 Al ₂ O ₃ +3
The solid oxide can be deposited by CO ₂ +9/2 H ₂ Mg + 1 / 2O ₂ → MgO ₂ .

When H ₂ O, for example, is selected as the reactive gas, the following reaction occurs depending on the combination with various metals or metal compounds: MgCl ₂ + H ₂ O → MgO + 2HCl SiCl ₄ + 2H ₂ O → SiO ₂ + 4HCl TiCl ₄ + 2H ₂ O → TiO ₂ + 4HCl ZrCl ₄ + 2H ₂ O → ZrO ₂ + 4HCl Al ₂ Cl ₆ + 3H ₂ O → Al ₂ O ₃ + 6HCl Al (C ₂ H ₅ ) ₃ + 3 / 2H ₂ O → 1 / 2Al ₂ O ₃ +
3C ₂ H ₆ Si (CH ₃ O) ₄ + 2H ₂ O → SiO ₂ + 4CH ₃ OH Si (C ₂ H ₅ O) ₄ + 2H ₂ O → SiO ₂ + 4C ₂ H ₅
A solid oxide can be precipitated by OH Mg + H ₂ O → MgO + H ₂ .

If, for example, CO ₂ is selected as the reactive gas, a solid oxide is deposited by the following reaction depending on the combination with various metals or metal compounds: SiH ₄ + 2CO ₂ → SiO ₂ + 2CO + 2H ₂ Mg + CO ₂ → MgO + CO. be able to.

If, for example, CO ₂ and H ₂ are selected as the reactive gas, for example, the following reaction: MgCl ₂ + CO ₂ + H ₂ → MgO + CO + 2HCl Al ₂ Cl ₆ + 3CO ₂ + 3H ₂ → Al ₂ O ₃ + 3CO
A solid oxide of Al ₂ O ₃ can be precipitated by + 6HCl.

As the reactive gas, for example, N ₂ and H
_{When 2} is selected, the nitride AlN can be deposited by, for example, the following reaction: Al ₂ Cl ₆ + N ₂ + 3H ₂ → 2AlN + 6HCl.

If, for example, NH ₃ is selected as the reactive gas, the following reaction occurs: SiH ₄ + 4 / 3NH ₃ → 1 / 3Si ₃ N ₄ + 4H ₂ 3SiH ₂ Cl ₂ + 10NH ₃ → Si ₃ N ₄ + 6NH ₄
Cl + 6H ₂ SiCl ₄ + 16 / 3NH ₃ → 1 / 3Si ₃ N ₄ + 4N
H ₄ Cl TiCl ₄ + 4 / 3NH ₃ → TiN + 4HCl + ／
N ₂ ZrCl ₄ + 4 / 3NH ₃ → ZrN + 4HCl + ／
N ₂ can precipitate a nitride.

If, for example, CH ₄ is selected as the reactive gas, the carbide can be deposited by the following reaction: SiH ₄ + CH ₄ → SiC + 4H ₂ TiCl ₄ + CH ₄ → TiC + 4HCl TiI ₄ + CH ₄ → TiC + 4HI.

If, for example, C ₂ H ₂ and H ₂ are selected as the reactive gas, for example, the following reaction: TiI ₄ + 1 / 2C ₂ H ₂ + 3 / 2H ₂ → TiC + 4H
With I 2, carbide TiC can be precipitated.

When, for example, CH ₄ and H ₂ are selected as the reactive gas, for example, the following reaction: CrCl ₃ + 2 / 3CH ₄ + 1 / 3H ₂ → 1 / 3Cr ₃
The carbide Cr ₃ C ₂ can be precipitated with C ₂ + 3HCl.

As the metal oxide contained in the gas G-1, a plurality of metal oxides may be mixed and used. Further, as the reactive gas contained in the gas G-2, a plurality of reactive gases may be mixed and used. In this case, a precipitate composed of a plurality of components can be obtained.

The appropriate reaction temperature between the metal compound-containing gas G-1 and the reactive gas-containing gas G-2 differs depending on the combination of the metal compound and the reactive gas. For example, for a combination of an alkyl metal with O ₂ and H ₂ O, a temperature in the range of 300-800 ° C is desirable. This is because the reaction rate is too slow below 300 ° C, while
This is because when the temperature exceeds ℃, the alkyl metal is thermally decomposed in the preheating stage and the stage of transfer to the reaction site, which makes it difficult to carry out the intended reaction.

For combinations of alkoxides and H ₂ O, temperatures in the range of 200-700 ° C are desirable. In this case, if the temperature is less than 200 ° C., the reaction rate is too slow,
This is because if the temperature exceeds 0 ° C, the alkoxide is thermally decomposed at the preheating stage, making it difficult to carry out the intended reaction.

Further, a halide, an oxyhalide and / or a hydrohalide, and O ₂ , H ₂ O,
In combination with N ₂ , NH ₃ , N ₂ O and / or various hydrocarbons, a temperature of 600 ° C. or higher is desirable. This is because the reaction rate is too slow below 600 ° C.

A combination of Mg vapor and one or more gases selected from the group consisting of O ₂ , H ₂ O and CO ₂ preferably has a temperature of 700 ° C. or higher. This is 700 ℃
If the amount is less than the above, a part of the Mg vapor is likely to be condensed at the stage of transfer to the reaction site, so that Mg is not effectively used in the intended reaction.

The Mg vapor may be generated by heating molten magnesium. In this case, the heating temperature is 700 ~
It is desirable that the temperature is within the range of 1200 ° C. This is because below 700 ° C., the reaction rate is too slow, while on the other hand, 1200
This is because if the temperature exceeds ° C, the generated Mg vapor is violently generated, and it becomes difficult to control the flow rate and pressure of the metal compound-containing gas. The starting magnesium may be ingot or powder. If magnesium is powder, Mg
A single powder or a mixed powder such as Mg-CaO and Mg-Al may be used. However, since the Mg powder easily ignites, the mixed powder is more preferable.

Mg vapor may generate MgO and Al by the following reaction: 3MgO + 2Al → 3Mg + Al ₂ O ₃ . However, the reaction temperature is 850 to
The temperature is preferably within the range of 1700 ° C. This has a reaction temperature of 8
This is because if the temperature is less than 50 ° C., the reaction rate is too slow.
When the temperature exceeds 1700 ° C., the generated Mg vapor is violently generated, which makes it difficult to control the flow rate and pressure of the metal compound-containing gas.

The concentration of the metal or metal compound in the metal or metal compound-containing gas G-1 is preferably 0.1 vol.% Or more. This is because the reaction rate is too slow when the concentration of the metal or the metal compound is less than 0.1 vol.%. If the concentration of the reactive gas in the gas G-2 containing the reactive gas is less than 1 vol.%, The reaction rate is too slow, so it is desirable to set the concentration to 1 vol.% Or more.

As the gas G-2 containing the reactive gas,
When two or more gases selected from the group consisting of N ₂ , CO ₂ , H ₂ O and O ₂ are contained, pure gases may be mixed, or various combustion gases may be applied. Good. Examples of various combustion gases include gases obtained by burning natural gas, liquefied petroleum gas, kerosene, heavy oil, coal, coke oven gas, blast furnace gas and converter gas with air and / or oxygen. . Moreover, you may use the exhaust gas of various heating furnaces as needed. When CH ₄ is used as the reactive gas, natural gas and / or coke oven gas may be heated before use.

The pressure of each of the metal or metal compound-containing gas G-1 and the reactive gas-containing gas G-2 is preferably as high as possible within the service capacity of the heat exchanger.
This is because the higher the pressure of each gas is, the faster the reaction between both gases proceeds. Incidentally, when the pressure of each gas is low, the reaction product is deposited on the solid, whereas when the pressure is high, the reaction product particles are deposited in the gas phase of each gas, It then becomes an aggregate and accumulates on the solid. Therefore, even if it is a relatively large void like the penetration damage that has occurred in the partition walls, or even a small void like the open pores in the refractory material having air permeability between the particles of the inorganic powder molded body, According to this method, the solid metal compound becomes a deposit and accumulates in the voids, and repairs and strengthens.

A gas G-1 containing a metal or a metal compound is supplied from one side across the partition wall, a gas G-2 containing a reactive gas is supplied from the other side, and both are supplied at the penetrating damage portion of the partition wall. The above gas is contacted and reacted. In this case, it is important to allow both gases to reach the entire area of the penetrating damage, and the means for this may be the flow of both gases or the diffusion of both gases. Here, since the diffusion rate of the metal and the metal compound is smaller than that of the reactive gas, the pressure of the metal or metal compound-containing gas G-1 is higher than the pressure of the gas G-2 containing the reactive gas. Forced convection may be caused by doing. Further, by periodically reversing the magnitude relationship of the gas pressures on both sides of the partition wall, the pressure gradient in the length direction of the penetration damage portion of the partition wall is periodically reversed, and both gases are alternately applied to the penetration damage portion. Movement may be facilitated.

When the solid metal compound is deposited and the penetrating damaged portion is closed, both gases cannot contact each other, so that the reaction automatically ends. However, since it takes time to completely close the penetration damage portion in this manner, the degree of closure may be limited to a practical range. That is,
It may be occluded to the extent that gas cannot substantially pass therethrough. Such a determination of blockage to the extent that the gas cannot substantially pass is performed by, for example, setting a predetermined lower limit value to the consumption rate of the metal or metal compound-containing gas, and reaching this lower limit value. Good. In addition, as another determination method example, a gas containing a metal or a metal compound is
Since the time until the gas pressure reaches the lower limit value, that is, the time when the gas reaches the lower limit value, which is intermittently supplied to the pierced damaged portion, becomes significantly longer, the pressure decrease rate. The time when is less than or equal to a predetermined value may be regarded as the time of substantial blockage.

Next, the pressure difference between one side of the partition wall to which the gas G-1 of the partition wall heat exchanger is supplied and the other side of the partition wall to which the gas G-2 is supplied fluctuates positively and negatively. Why it is desirable to return it, and gas G-1 and gas G-2
The desirable form of is described. For example, a coke oven is used as the partition wall heat exchanger, and a silicon compound-containing gas is used as the gas G-1. By repeating positive and negative fluctuations in the pressure difference between the carbonization chamber and the combustion chamber, the inflow velocity of the silicon compound-containing gas and the combustion gas into the pores in the partition wall of the coke oven is increased, and the pressure difference is reversed. Sometimes
Part of the gas on the receding side remains in the open pores of the partition wall of the coke, and at the same time, the gas on the advancing side flows into the open pores, improving the contact efficiency of both gases and opening the silicon dioxide. Precipitation in the pores is promoted. By repeating the above-mentioned process, the repair work efficiency is further improved, and further, silicon dioxide can be uniformly deposited between the damaged parts of the entire partition wall, the open pores, and the particles of the inorganic powder filled body. Silicon dioxide may be amorphous or crystalline. Since the coefficient of thermal expansion is small in each case, the thermal shock resistance does not deteriorate even if the porosity decreases due to precipitation.

Here, it is desirable that the pressure difference between the carbonization chamber and the combustion chamber fluctuates positively and negatively within a range of -200 to +200 mmAq. The pressure in the combustion chamber is usually in the range of -20 to +20 mmAq with respect to atmospheric pressure. When the pressure in the carbonization chamber becomes lower than the pressure in the combustion chamber, and the pressure difference exceeds -200 mmAq (when the absolute value becomes large), invasion of air from the outside of the coke oven into the carbonization chamber cannot be avoided, Therefore, a part of the gas containing the silicon compound is consumed by reacting with air in the carbonization chamber, and is not used for repairing the penetrating damage portion of the partition wall and the flat plate. On the other hand, contrary to the above, if the pressure in the carbonization chamber becomes larger than the pressure in the combustion chamber and the pressure difference exceeds +200 mmAq, the gas containing the silicon compound cannot escape from the coke oven. Therefore, not only the gas containing the silicon compound is not effectively used, but also the working environment is impaired.

Examples of the silicon compound include hydrides such as SiH ₄ , alkyl metals such as Si (CH ₃ ) ₄ and Si (C ₂ H ₅ ) ₄ , halides such as SiCl ₄ and oxyhalogen such as Si ₂ OCl _6. Compounds, hydrohalides such as SiH ₂ Cl ₂ and alkoxides such as Si (CH ₃ O) ₄ and Si (C ₂ H ₅ O) ₄ . These may be used alone, or two or more kinds of silicides selected from the group consisting of these may be used. Moreover, you may dilute and use it with the gas which does not react with these metal compounds. Examples of this diluent gas include N ₂ and Ar.

Among the silicon compounds, SiCl ₄
Is a thermally stable substance, and is not particularly thermally decomposed within the entire range of the partition wall temperature of 900 to 1450 ° C. during the normal operation of the coke oven.
As a combustion gas component which reacts with SiCl ₄ , H ₂ O is used.
Is most desirable. Since the reaction rate with SiCl ₄ is extremely high in the above temperature range, SiCl ₄ will not be emitted unreacted unless the amount of H ₂ O supplied falls below the stoichiometric value. Further, it is desirable that the concentration of SiCl ₄ in the gas containing the silicon compound be within the range of 0.1 to 100 vol.%. This is because if it is less than 0.1 vol.%, The reaction rate is too slow to be practical.

The combustion gas may be generated in the combustion chamber by a known method. As a method, if coke oven gas and / or blast furnace gas is burned with air, H ₂ O = 1
A gas containing ˜25 vol.% And CO ₂ = 5-30 vol.% Is obtained. At this time, a gas containing O ₂ can be prepared by burning with excess air. Enriched with O ₂ ,
Furthermore, if steam is blown in, H
It is also possible to increase the ₂ O, CO ₂ and O ₂ concentrations. It is desirable that the concentration of H ₂ O, CO ₂ and / or O _{2 in} the combustion gas be within the range of 1 to 100 vol.%.
This is because if it is less than 1 vol.%, The reaction rate is too slow to be practical.

In addition, the inventors of the present invention also supply a refractory powder as a carrier gas to the evacuated carbonization chamber in the coke oven (air transport) to fill the penetrating damaged portion of the partition wall with the silicon compound. It was found that the penetration damage part can be closed in a short time by supplying the gas containing the gas to the carbonization chamber.

FIGS. 1, 2 and 3 show a method of repairing a penetrating damaged portion of a partition wall according to the present invention, in which inorganic powder is air-transported and filled in the penetrating damaged portion, and SiO 2 is filled between particles of the filled inorganic powder. FIG. 3 is a diagram for explaining the principle of a repairing method by depositing ₂ and is a schematic vertical cross-sectional view of a penetrating damage portion of a partition wall. As shown in FIG. 1, it is assumed that the penetrating damage portion 2 exists in the partition wall 1 between the carbonization chamber and the combustion chamber. First, FIG.
As shown in FIG.
Is air-flowed to cause at least a part of the refractory powder 3 to enter the penetrating damage portion 2 having a size into which the refractory powder 3 can enter to form a filling layer 3 ′ of the refractory powder 3. Then, as shown in FIG. 3, a gas 4 containing a silicon compound is supplied from the carbonization chamber side P, and the pressure difference between the carbonization chamber and the combustion chamber measured at the top of the coke oven is kept at about 0 mmAq. Or in the vicinity of 0 mmAq, the gap between the refractory powders 3 in the penetration damage portion 2 and the minute penetration damage portion (not shown) in which the refractory powder 3 could not enter. On the deposited SiO ₂
To form a deposited layer 3 ″. In this manner, the substantial blockage of the penetrating damage portion generated in the partition wall is completed.

The refractory powder used in the method of repairing the partition having a through damage portion is a fine powder having a maximum particle size of 0.2 mm or less, and has a characteristic of sintering the powder at a temperature in the range of 900 to 1450 ° C. It is desirable to have. For example, a material containing 80 wt.% Or more of SiO ₂ and / or Al ₂ O ₃ can be applied. Such a powder enters a penetrating damaged portion having an opening of 1 mm or more with relative ease and forms a packed layer of the powder. Then, the pores of such a packed bed are blocked by the subsequent deposition of SiO _{2 which} is deposited by the reaction between the gas containing the silicon compound and the combustion gas. The method described above is particularly effective for repairing penetration damage having an opening of 1 mm or more.

The present inventors have also found the following items. In a coke oven having a partition wall made of a material having air permeability, a gas permeable flat plate is arranged in the carbonization chamber in close proximity to the partition wall surface, and the flat plate-shaped space formed by the flat plate and the partition wall surface is made of inorganic material. After the powder is supplied to prepare the inorganic powder filling body, the carbonization chamber is occupied by the silicon compound-containing gas, and then the combustion gas is generated in the combustion chamber to change the pressure difference between the carbonization chamber and the combustion chamber to positive or negative. By repeating, the inorganic powder particles are precipitated between the particles, silicon dioxide is firmly bonded to the inorganic powder particles, and at the same time, silicon dioxide is also similarly precipitated inside the pores of the partition wall to strengthen the partition wall. I found out that

The air-permeable flat plate is required to have heat resistance at the partition wall temperature of a normal coke oven and corrosion resistance to HCl. The flat plate has two functions, one is a function as a form for forming a space to be filled with the inorganic powder,
The other one is a function of supplying the silicon compound-containing gas as uniformly as possible inside the flat inorganic powder filler having a large area. Therefore, this breathable flat plate requires characteristics that allow the passage of gas but not the supplied inorganic powder. As such a material, for example, molded products or woven fabrics of glass wool, rock wool, alumina fiber, zirconia fiber and carbon fiber, gypsum board, and calcium silicate board are suitable.

Ceramics are suitable as the inorganic powder to be filled, but a metal may be added to the ceramics. The components of ceramics include SiO ₂ and Al ₂ O.
Oxides such as ₃ , ZrO ₂ and MgO, complex oxides containing oxides selected from these oxides, carbides such as SiC, nitrides such as Si ₃ N ₄ , and oxynitrides such as SiAlON. Is suitable. These may be synthetic or natural minerals. Examples include silica sand, natural mullite and chamotte. Fused quartz is desirable because it has a low coefficient of thermal expansion. Further, SiC is also preferable because it has good heat conduction and excellent wear resistance. As the additive metal,
Si and Al are desirable. This is because stable SiO ₂ and Al ₂ O ₃ are obtained by oxidation. Even if the inorganic powder is filled in the narrow space between the air-permeable flat plate and the partition wall, the inorganic powder must be filled so as not to generate an unfilled portion. It is desirable to fill fine irregularities and cracks. Therefore, it is desirable that the inorganic powder be transported by air. There are no restrictions on the transportation medium, but for example, air and nitrogen are applied.

According to the present invention which does not use a flat plate, the strength of the partition wall of the coke oven of the new brick is improved, the gas flow is blocked at the through crack damage portion generated in the partition wall, and the strength of the partition wall of the working coke oven is improved. Can be achieved. On the other hand, according to the above-mentioned repair method using the air-permeable flat plate, in addition to this, the effect of smoothing unevenness due to abrasion or the like generated on the surface of the working coke oven on the carbonization chamber side is exerted. .

[0071]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described with reference to the drawings, corresponding to the main claims.

The first embodiment will be described. The first embodiment repairs and / or strengthens the partition wall by depositing a metal compound generated by the reaction between the gas G-1 and the gas G-2 inside the partition wall of the heat exchanger. It is an embodiment of the invention according to Item 1 or 2. However, the case where the partition wall is not damaged corresponds to claim 1, and the case where it is damaged corresponds to claim 2.

FIG. 4 is a schematic vertical sectional view of a partition type heat exchanger showing a first embodiment, and an embodiment of the repairing method of the invention according to claims 1 and 2 will be described with reference to this drawing. 10
Is a partition wall, 11 is a heating chamber, 12 is a heated chamber, 35 is a lid, 3
Reference numerals 6 and 37 denote gas inlets, and this figure shows a part of a heat exchanger in which heating chambers and heated chambers are alternately connected with a partition wall in between. In the first embodiment, the gas (G-1) 47 containing a metal compound is supplied from the gas inlet 37 to the heated chamber 12 on one side of the partition wall 10 having air permeability of the heat exchanger. On the other hand, the heating chamber 11 on the other side of the partition wall 10
In addition, a gas (G-2) 48 containing a reactive gas that reacts with the metal compound to precipitate the metal compound is added to the gas inlet 3
Supply from 6. A fuel gas (not shown) is supplied from the gas inlet 36 to the heating chamber 11 and burned in the heating chamber 11 to be changed into a combustion gas as a gas (G-2) 48 containing a reactive gas. Good.

Since the partition wall 10 has air permeability of a predetermined open porosity, both gases (G-1 and G-2) enter the partition wall 10 from both sides of the partition wall 10 and both gases (G-1 and G-2). −
2) contact in the open pores of the partition wall 10 and react with each other to precipitate the solid metal compound 50 in the open pores. The solid metal compound 50 deposited in the open pores of the partition wall 10 is inside the partition wall and contributes to improving the strength of the partition wall. In the above-described embodiment, both gases (G-1 and G-2) are allowed to flow into the open pores of the partition wall 10 by changing the pressure difference between the pressure inside the heated chamber 12 and the pressure inside the heating chamber 11 between positive and negative. The entry is facilitated and the reaction between both gases is promoted.

The second embodiment will be described. The second embodiment is a solid deposited by a reaction between the gas G-1 and the gas G-2 after forming a flat plate-like filler of an inorganic powder adhered to the surface of the partition wall of the heat exchanger on the heated chamber side. Oxide repairs and strengthens not only the partition walls but also the above-mentioned inorganic powder filling body at the same time, which is an embodiment of the invention of claims 14 and 15. However, the case where the partition wall is not damaged corresponds to claim 14, and the case where it is damaged corresponds to claim 15.

FIGS. 5 and 6 are schematic longitudinal sectional views of a partition type heat exchanger showing a second embodiment, and an embodiment of the repairing method of the invention according to claims 14 and 15 will be described with reference to the drawings. To do. Reference numeral 10 is a partition wall, 11a is a part of a heating chamber, 12 is a heated chamber, 35 is a lid, 37 is a gas inlet, 41 is a through crack damage, 42 is a flat plate, 44 is an inorganic powder, 45 is a space, and 46 is a partition wall. This is a concavo-convex pattern on the surface of the heated chamber 12, and this figure shows a part of a heat exchanger in which heating chambers and heated chambers are alternately arranged with a partition wall in between.

In the second embodiment, as shown in FIGS. 5 and 6, the wall surface of the partition wall 10 of the heated chamber 12 of the heat exchanger having the partition wall 10 having air permeability is brought close to or partially in contact with the wall surface. And place a flat plate 42 having air permeability (Fig. 5 (a)
Space 4 formed between the wall surface and the flat plate 42.
5 is filled with the inorganic powder 44 (see FIG. 5B), and then the heated chamber 12 is filled with a gas containing a metal compound (G-
1) 47 is supplied, while a gas (G-2) 48 containing a reactive gas that reacts with the metal compound to precipitate the solid metal compound 50 is supplied to the heating chamber 11. Since the partition wall 10 and the flat plate 43 have air permeability of a predetermined open porosity, both gases (G-1 and G-2) are inside the partition wall 10 and the space 4.
The gas (G-1 and G-2) entered into the layer of the inorganic powder 44 filled in No. 5 contacted with each other in the open pores of the partition wall 10 and between the particles of the inorganic powder 44, and reacted to deposit. The solid metal compound 50 is deposited at each place (see FIG. 6A). The metal compound deposited in the open pores of the partition wall 10 is inside the partition wall and contributes to improving the strength of the partition wall, and the metal compound deposited between the particles of the inorganic powder 44 is the inorganic powder 4
The inorganic powder layer 51 which is firmly bonded inside the four layers is formed and bonded to the partition wall surface.

In this embodiment, both gases (G-1 and G-2) are separated from the partition wall 1 by varying the positive / negative differential pressure between the pressure in the heated chamber 12 and the pressure in the heating chamber 11.
It becomes easy to enter the open pores of 0 and between the particles of the inorganic powder 44, and the reaction between both gases is promoted. Partition 1
The inorganic powder 44 was filled inside the through crack damage 41 that had occurred at 0, and the solid metal compound 50, which is a reaction product of both gases that entered between the powder particles, was precipitated, and a strong inorganic powder layer 51 was formed. The penetrating crack damage 41 formed is repaired by blockage. Similarly, the unevenness 46 generated on the partition wall surface is also restored to a smooth wall surface by forming the strong inorganic powder layer 51 (see FIG. 6B).

The third embodiment will be described. In the third embodiment, when the partition wall of the heat exchanger is damaged on the heated chamber side, the partition wall in the first embodiment is damaged after the damaged portion is preliminarily repaired. In order to repair and strengthen the partition in the case, it is an embodiment of the invention as set forth in claim 7. Preliminary repair method, if there is a through crack in the partition wall, the method of pre-filling this part by gas transportation with inorganic powder, and if the partition wall is peeled or worn. There are a method of spraying an inorganic powder to this portion while hot, and a method of spraying a thermal spray material.

FIG. 7 is a schematic vertical sectional view of a partition type heat exchanger showing a third embodiment. 10 is a partition wall, 11 is a heating chamber, 12 is a heated chamber, 49 is a damaged part, 50 is a solid metal compound, and 53 is a thermal spraying material. In the figure, the heating chamber and the heated chamber alternate with each other. The part of the heat exchanger which is connected to is shown. As shown in the figure, the partition wall 10 having air permeability is damaged on the heated chamber 12 side. The sprayed material 53 covers the damaged part 49 by spraying the repairing spray material onto the damaged part 49. Next, the gas (G-1) 47 containing the metal compound is supplied to the heated chamber 12 from the gas inlet 37. On the other hand, a gas (G-2) 48 containing a reactive gas that reacts with the metal compound to precipitate a solid metal compound is supplied to the heating chamber 11 from the gas inlet 36. Partition wall 10
Has a predetermined open porosity, so both gases (G-
1 and G-2) not only enter into the open pores inside the partition wall 10 from both sides of the partition wall 10, but also between the material particles that form the joint between the damaged portion 49 and the thermal spray body 53 that have been preliminarily repaired. The solid metal compound 50 is deposited and reacts inside the open pores and between the material particles in the joint portion to deposit the solid metal compound 50. Thus, the septum 10 is repaired and strengthened.

In this embodiment, both gases (G-1 and G-2) are generated by opening the open pores of the partition wall 10 by varying the positive / negative differential pressure between the pressure inside the heated chamber 12 and the pressure inside the heating chamber 11. It becomes easy to enter the inside, and the reaction between both gases is promoted to improve the work efficiency.

The fourth embodiment will be described. In the fourth embodiment, when damage occurs on the heated chamber side of the partition wall of the heat exchanger, after repairing the damaged portion, the partition wall is repaired and strengthened according to the second embodiment. Is something
It is an embodiment of claim 16.

In this embodiment, when damage occurs on the heated chamber side of the partition wall of the heat exchanger, a predetermined preparatory repair is applied to the damaged portion to repair the repaired body, for example, by spraying repair. After forming the sprayed body, a flat plate having air permeability is arranged in parallel with the wall surface of the partition wall of the heat exchanger in close proximity or in partial contact with the wall surface on the heated chamber side, and then,
The inorganic powder is gas-transported in the space between the wall surface and the flat plate to form the inorganic powder filling body. Then, the gas G-
1, while supplying gas G-2 to the heating chamber. In this way, the solid metal compound is deposited inside the partition walls, inside the thermal spraying body, between the material particles at the joint between the damaged portion and the thermal spraying body, and between the particles inside the inorganic powder filling body. Thus, the septum is repaired and strengthened.

[0084]

The present invention will be described in more detail with reference to the following examples. (Example 1) As an example of the first embodiment, a case where the partition wall heat exchanger is a coke oven will be described with reference to FIG. The coke oven is composed of a coke oven group in which a carbonization chamber as the heated chamber 12 and a combustion chamber as the heating chamber 11 are alternately connected. Silica bricks having an open porosity of 20 vol.% Are used for the partition walls 10 between the carbonization chamber and the combustion chamber, and the silica stone bricks are connected to each other with a joint material. The carbonization chamber has a coal charging lid as the upper heating material charging lid 35,
The two furnace lids forming the front and rear side surfaces can open to the outside air. Two flame passages are arranged in the combustion chamber, and fuel gas 49 and air are supplied to one flame passage to burn and rise, and enter the other flame passage.
The combustion gas as the gas (G-2) 48 containing the reactive gas exchanges heat with air to recover heat, and then is released to the atmosphere. The gas containing the metal compound (G
-1) An inlet 37 for the SiCl ₄ containing gas as 47, an exhaust port and a pressure outlet 38 are installed, while a pressure outlet 39 is installed at the inspection port at the upper part of the combustion chamber, and the carbonization chamber and the combustion chamber are connected. The differential pressure can be detected by the differential pressure detector 40 that detects the pressure difference between the chamber and the chamber. The coke oven gas is burned in the flame passage to generate combustion gas containing H ₂ O = 15 to 25 vol.%, And the flame outlet temperature is 900 to
Adjust to a predetermined temperature of 1450 ° C. On the other hand, the coke is discharged from the carbonization chamber into an empty kiln, the furnace lid is attached, the gas diffusion valve connected to the carbonization chamber is opened, the air is replaced with nitrogen gas, and then the diffusion valve is closed.

Next, SiCl ₄ = 10 vol.% And N ₂
= 90vol.% Gas is supplied to the carbonization chamber. When the pressure difference between the carbonization chamber and the combustion chamber reaches +50 mmAq with the differential pressure detector, the supply is stopped. The SiCl ₄ -containing gas penetrates into the open pores of the silica bricks and the joints constituting the furnace wall, and also in the joint breaks if there are joint breaks, and the differential pressure gradually decreases. When it reaches +5 mmAq, the supply of the SiCl ₄ -containing gas is stopped. Then, immediately using the exhaust fan, the SiCl ₄ gas is exhausted from the exhaust port. Exhaust is stopped immediately when the differential pressure decreases and changes from positive to negative and reaches -50 mmAq. When the differential pressure becomes negative, the combustion gas permeates into the furnace from the combustion chamber toward the carbonization chamber. The H ₂ O in the combustion gas remains in the furnace wall
React with l ₄ to precipitate SiO ₂ . Precipitated SiO ₂
Acts as a binder to improve the strength of silica bricks and joint materials. Immediately after reaching -50 mmAq and stopping the exhaustion, the SiCl ₄ -containing gas is supplied again and the above cycle is repeated. Then, after a lapse of a predetermined time, for example, after repeating the above cycle for 7 hours, the operation is ended.

(Example 2) As an example of the second embodiment, in the case where the partition wall type heat exchanger is a coke oven,
A description will be given with reference to FIGS. 5 and 6. The structure and function of the coke oven are the same as described in Example 1,
The open porosity of the partition wall 10 between the carbonization chamber and the combustion chamber is 20 vo
Although silica stone bricks of l.% are used and the silica stone bricks are connected by joint material, the partition wall surface on the carbonization chamber side is worn and uneven, and there are through cracks 41 in the partition walls. It is characteristic. The carbonization chamber can be opened to the atmosphere by means of an upper coal charging lid and two furnace lids. The coal charging lid is provided with an inlet 37 for the gas containing SiCl ₄ , an outlet and a pressure outlet. The coke oven gas is burned in the flame passage to generate a combustion gas containing H ₂ O = 15 to 25 vol.%, And the flame outlet temperature is adjusted to a predetermined temperature of 900 to 1450 ° C.

On the other hand, the thickness of the air-permeable flat plate 42 is 20
A mm-mm calcium silicate plate is fixed to a steel support, the height is a coal charging level, the depth is a size corresponding to the depth of the carbonization chamber, and the distribution plate 43 fixed to the upper end of the form. Assemble a structure consisting of and. Then, the coke is discharged from the carbonization chamber to form an empty kiln, and then the structure is placed in the carbonization chamber. After attaching the furnace lid, the diffusion tube of the carbonization chamber is opened, and the fused silica particles passing through the sieve mesh of 325 mesh as the inorganic powder 44 are air-transported by using the gas inlet containing SiCl ₄ to carbonize the carbonization chamber. Supply to. The supply is stopped as soon as the fused silica particles are filled to the top of the mold. The fused silica particles spread to the space 45 formed by the mold and the partition wall 10 and the through crack 41 portion by pneumatic transportation.

Next, the air in the carbonization chamber is replaced with nitrogen gas, and the diffusion valve is closed. And SiCl ₄ = 10 vol.%
And N ₂ = 90 vol.% Gas is fed to the carbonization chamber. The pressure difference between the carbonization chamber and the combustion chamber is + 50mm with the differential pressure detector.
When it becomes Aq, the supply is stopped. The SiCl ₄ -containing gas permeates the fused silica packed layer, the open pores of the silica bricks and the joints forming the furnace wall, and the joint breakage, if any, and the differential pressure gradually decreases. When it reaches +5 mmAq, the supply of the SiCl ₄ -containing gas is stopped. And
Immediately use the exhaust fan to exhaust the SiCl ₄ gas from the exhaust port. Exhaust is stopped immediately when the differential pressure decreases and changes from positive to negative and reaches -50 mmAq.
When the differential pressure becomes negative, the combustion gas permeates into the furnace from the combustion chamber toward the carbonization chamber. Then, H ₂ O in the combustion gas as the gas (G-2) 48 containing the reactive gas is
The fused silica-filled layer as the inorganic powder layer 51 reacts with the SiCl ₄ remaining in the furnace wall to deposit SiO ₂ as the metal compound 50. The deposited SiO ₂ acts as a binder, imparts a strong shape-retaining property to the fused silica filling layer, and improves the strength of the silica brick and the joint material. Immediately after reaching -50 mmAq and stopping the exhaustion, the SiCl ₄ -containing gas is supplied again and the above cycle is repeated. Then, after a lapse of a predetermined time, for example, after repeating the cycle for 7 hours, the carbonization chamber is replaced with nitrogen and the operation is completed. The furnace lid is then opened and the extruder is used to push the construct out of the furnace from the carbonization chamber. In this way, the partition wall surface of the carbonization chamber is restored to a smooth wall surface, the through cracks are repaired, and the strength of the silica bricks and joints constituting the original partition wall is improved.

(Example 3) As an example of the third embodiment, in the case where the partition wall heat exchanger is a coke oven,
This will be described with reference to FIG. The structure and function of the coke oven are the same as those described in Example 1, and the open porosity of the partition wall 10 between the carbonization chamber as the heated chamber 12 and the combustion chamber as the heating chamber 11 is 20 vol.%. The silica stone bricks are used, and the silica stone bricks are connected by joint material,
Cracks and irregularities are generated on the surface of the partition wall on the carbonization chamber side due to heat spalling and abrasion during coke discharge. An inlet 37 for a SiCl ₄ -containing gas, a gas exhaust port 37 ′, and a pressure outlet 38 are provided on the coal charging lid as the heated material charging lid 35. The coke oven gas is burned on the flame path to generate combustion gas as the gas G-2 (48). The combustion gas contains H ₂ O = 15 to 25 vol.%, While adjusting the flame outlet temperature to a predetermined temperature of 900 to 1450 ° C. After removing the coke from the carbonization chamber to make an empty kiln, the furnace lid is removed. Next, the furnace wall damaged part 49
Use a horizontal bar to scrape off the deposits. Then, a thermal spray nozzle is inserted close to the damaged portion 49, and a thermal spray material of silica (94 wt.% SiO ₂ , 3 wt.% Al ₂ O ₃ ) containing Si and Al is sprayed. This operation is repeated for the plurality of damaged portions 49, and the thermal spraying body 53 is applied to the furnace wall base material.

After attaching the furnace lid, a diffusion valve (not shown) for gas diffusion connected to the carbonization chamber was opened to send N ₂ gas, and air was expelled into the atmosphere to convert the inside of the carbonization chamber into N ₂ gas. Replace and close the strip valve. Next, a gas consisting of 10 vol.% SiCl ₄ and 90 vol.% N ₂ is supplied from the gas inlet 37 to the carbonization chamber. When the differential pressure detector 40 supplies the SiCl ₄ containing gas until the pressure difference between the carbonization chamber and the combustion chamber becomes +50 mmAq, the supply is stopped. The SiCl ₄ -containing gas permeates the silica brick of the base material forming the furnace wall, and also the open pores of the joints, the open pores of the thermal spray material, and the joint breaks when there are joint breaks, and the differential pressure is removed. Filling drops. Differential pressure is +5 mm
When reaching Aq, the supply of the SiCl ₄ -containing gas is stopped.
Next, the exhaust pump 52 immediately exhausts the SiCl ₄ -containing gas. The differential pressure decreases and changes from positive to negative, -50mmA
Evacuate until q is reached, then immediately stop. During this time,
When the differential pressure becomes negative, the combustion gas permeates the base material of the partition wall 10 and the thermal spray material 53 from the combustion chamber toward the carbonization chamber. Then, H ₂ O in the combustion gas reacts with SiCl ₄ remaining in the partition walls 10 to deposit SiO ₂ . Immediately after the evacuation is stopped, the SiCl ₄ -containing gas is supplied again.
The SiCl ₄ -containing gas is supplied and stopped until the differential pressure rises and changes from negative to positive and reaches +50 mmAq. During this time,
When the differential pressure becomes positive, SiC flows from the carbonization chamber to the combustion chamber.
l ₄ permeates into the base material of the partition wall 10 and the thermal spray material 53.
Then, SiCl ₄ is used as the base material of the partition wall 10 and the sprayed material 53.
SiO ₂ is precipitated by reacting with H ₂ O remaining inside. This cycle is repeated.

In this way, the cycle time becomes longer as the amount of SiO ₂ accumulated in the partition wall 10 base material and the thermal spray material 53 increases. For example, the cycle that was 3 min / cycle at the beginning is 40 min / cycle after 7 hours.
Extended to a cycle. It was found that the accumulation of SiO ₂ in SiO ₂ proceeded smoothly and that the open pores were close to the closed state after 7 hours. Therefore, the work was completed in 7 hours. The deposited SiO ₂ acted as a binder to improve the strength and adhesiveness of the base material (silica brick and joint material) and the thermal spray material forming the partition wall 10 and, at the same time, improved the thermal conductivity.

(Example 4) Example 4 is an example on a laboratory scale in which an artificial penetrating crack is closed by a metal compound deposited by the reaction of gas G-1 and gas G-2. Al ₂ C as a metal compound contained in G-1
₁₆ gas was used, and CO ₂ was used as the gas G-2. FIG. 8 is a schematic vertical sectional view showing an apparatus used in Example 4. This device consists of a heat exchanger bulkhead,
This is for simulating a heating chamber and a heated chamber. As shown in the figure, a quartz outer tube 7 is arranged inside the tubular heating body 6, and a quartz inner tube 8 is arranged inside thereof. The heating chamber 11 and the heated chamber 12 of the heat exchanger are formed. Then, at one end of the inner tube 7 made of quartz, a supply port 14 for the metal compound-containing gas 14 'for repairing the through crack is provided.
The partition wall 10 was provided at the other end. On the other hand, the partition wall 10 is made of high alumina brick (Al ₂ O ₃ : 93 wt.%, SiO ₂ : 3 w).
The thickness t of the partition wall 10 was set to 100 mm. A slit-shaped artificial through crack 9 having a gap of 1 mm was provided at a position at a height ½ of the partition wall 10. Sandwiching the partition wall 10,
A differential pressure gauge 15 for measuring a pressure difference between the heated chamber 12 and the heating chamber 11 (a value obtained by subtracting the pressure of the heating chamber from the pressure of the heating chamber) was attached. A vacuum pump 16 for reducing the pressure in the heated chamber 12 to adjust the pressure difference is provided in the heated chamber 1
2 was connected to the one end by piping. A supply port 13 for the reactive gas-containing gas 13 ′ is provided at one end of the quartz outer tube 7,
In addition, a discharge port 13 ″ for this gas is provided at the other end.

In this example, the pressure difference between the heating chamber and the heated chamber was maintained at 0 mmAq, and the reactive gas containing gas 1
While supplying CO ₂ gas from the supply port 13 of 3 ′ and H ₂ gas from the supply port 14 of the metal compound-containing gas 14 ′, power is supplied to the tubular heating furnace 5 while maintaining the pressure difference at 0 mmAq. The temperature inside the furnace was raised to 900 ° C. Next, H ₂ from the supply port 14 for the metal compound-containing gas 14 ′ is set to 3
Al ₂ Cl ₆ : 10 vol.% And H ₂ : 9 preheated to 50 ° C.
The gas mixture was switched to 0 vol.%. The above Al ₂
As Cl ₆ , powder AlCl ₃ generated by heating and vaporizing AlCl ₃ was used.

Then, Al ₂ O ₃ was deposited in the artificial through crack 9 by the following steps (1) to (3). (1) The metal compound-containing gas 14 'is supplied until the pressure difference reaches 10 mmAq, and then stopped. (2) When the pressure difference decreases to 1 mmAq, the vacuum pump 16 for adjusting the pressure difference sucks the inside of the heated chamber 12 to -10 mm.
When reaching Aq, the vacuum pump 16 is stopped. (3) After stopping the vacuum pump 16, leave it as it is for 5 minutes,
Return to step (1).

When the above procedure was repeated for 7 hours, 36 minutes were finally required for the transition from the step (1) to the step (2), and the state where it could be regarded as substantial occlusion was reached. . Then, after the operation of the apparatus was stopped and the system was allowed to cool, the state of the partition wall was examined, and it was found that the state of appearance was completely blocked.

(Example 5) Example 5 is another example on a laboratory scale in which an artificial penetrating crack is closed by a metal compound deposited by the reaction of gas G-1 and gas G-2. , Mg gas was used as the metal contained in the gas G-1, and air was used as the gas G-2. FIG. 9 is a schematic vertical sectional view showing an apparatus used in Example 5. As shown in the figure, inside the tubular heating element 6,
A quartz outer tube 7 is arranged, a quartz inner tube 8 is arranged inside thereof, and a heating chamber 11 and a heated chamber 12 of the heat exchanger are formed. A supply port 14 for the metal compound-containing gas 14 ′ is provided at one end of the quartz inner tube 7, and a partition wall 10 is provided at the other end. Then, a supply port 14 for the metal compound-containing gas 14 'for repairing the through cracks was provided at one end of the inner tube 7 made of quartz, and a partition wall 10 was provided at the other end. On the other hand, the partition wall 10 was made of silica brick and had a thickness t of 100 mm. A slit-shaped artificial through crack 9 having a gap of 1 mm was provided at a position at a height ½ of the partition wall 10. A differential pressure gauge 15 for measuring the pressure difference (value obtained by subtracting the pressure of the heating chamber from the pressure of the heating chamber) between the heating chamber 12 and the heating chamber 11 with the partition wall 10 interposed therebetween was attached. A vacuum pump 16 for reducing the pressure in the heated chamber 12 to adjust the pressure difference was connected to the one end of the heated chamber 12 by a pipe. Quartz outer tube 7
At one end, the supply port 13 for the reactive gas-containing gas 13 '
Is provided at the other end.

Metal magnesium powder 1 was placed on the inner tube 8 made of quartz.
8 (purity: 99.9 wt.%, Particle size: 14 mesh passed): 100 g was placed in an alumina boat 17. Then, set the pressure difference between the heating chamber and the heated chamber to 0 m.
Supply port 1 for the reactive gas-containing gas 13 ', keeping it at mAq
3 from the air, the supply port 14 of the metal compound-containing gas 14 '
While the Ar gas was being supplied to the tubular heating furnace 5 while maintaining the pressure difference at 0 mmAq, power was supplied to the tubular heating furnace 5 to raise the furnace temperature to 800 ° C. Next, metal compound-containing gas 1
The Ar gas from the 4 ′ supply port 14 was switched to the magnesium gas preheated to 800 ° C. obtained by melting the metal magnesium and then evaporating it as described above.

Then, MgO was deposited in the artificial through crack 9 by the following steps (1) to (3). (1) Ar gas is supplied until the pressure difference reaches 50 mmAq, and then stopped. (2) When the pressure difference decreases to 1 mmAq, the vacuum pump 16 for adjusting the pressure difference sucks the inside of the heated chamber 12 to -10 mm.
When reaching Aq, the vacuum pump 16 is stopped. (3) After stopping the vacuum pump 16, leave it as it is for 5 minutes,
Return to step (1).

When the above procedure was repeated for 3 hours, finally, it took 42 minutes to shift from the step (1) to the step (2), and it became possible to regard it as a substantial blockage. . Then, after the operation of the apparatus was stopped and the system was allowed to cool, the state of the partition wall was examined, and it was found that the state of appearance was completely blocked.

Example 6 In Example 6, artificial penetrating cracks were provided in the partition wall of a small coke oven, and SiO ₂ precipitated by the reaction between SiCl ₄ gas and the combustion gas of the coke oven gas.
This is an example in which the artificial through crack is closed by using Mg gas as the metal contained in the gas G-1 and air as the gas G-2. FIG.
FIG. 8 is a schematic vertical sectional view showing a small coke oven used in Example 6. As shown in the figure, there are provided a carbonization chamber 20 having a furnace width of 430 mm and a depth of 1400 mm, and a combustion chamber 21 sandwiching both sides of the carbonization chamber 20 via partition walls 22a and 22b. The carbonization chamber 20, SiCl ₄ evaporator 24 for generating a vapor of SiCl ₄ is equipped through a pipe, while the one end of each combustion chamber 21, coke oven gas 2
8 and a pipe 34 for supplying the combustion air 29 are provided respectively, and a flue 31 for exhausting combustion exhaust gas is provided at the other end, which leads to a chimney (not shown). Further, a differential pressure gauge 26 for measuring the pressure difference between the carbonization chamber 20 and the combustion chamber 21 is
1 is provided.

Each partition wall 22a, 22b has a thickness of 100 m.
As shown in FIG. 10, a silica stone brick 23 having a slit-like artificial through crack 23 ′ with a gap of 1 mm and a width of 100 mm is formed in a part of one partition wall 22a as shown in FIG.
Are arranged. SiCl ₄ vapor generated in SiCl ₄ evaporator 24, the N ₂ gas 25 and carrier gas, is fed to the carbonization chamber 20 through line 34.

Using the above apparatus, the coke oven gas 28 and the combustion air 29 are supplied to the combustion chamber 21 and burned in the combustion chamber 21, and the combustion exhaust gas temperature at the combustion chamber outlet 30 is set to 1
It was kept at 050 ° C. The flue gas was discharged from the chimney through the flue 31. Then, N ₂ gas 25 is added to the carbonization chamber 20.
And the atmosphere in the carbonization chamber 20 is replaced with N ₂ gas 25, and then Si from the SiCl ₄ evaporator 24 is replaced with N ₂ gas.
Cl ₄ gas was fed to switch to a mixed gas of SiCl ₄ gas and N ₂ gas. The mixed gas composition is SiCl ₄ :
10 vol.% And N ₂ : 90 vol.%.

Then, SiO ₂ was deposited in the artificial through crack 23 'by the following steps (1) to (3). (1) SiCl until the pressure difference reaches 10 mmAq
_The gas containing ₄ is supplied to the carbonization chamber 20 and then stopped. (2) When the pressure difference decreases to 1 mmAq, the inside of the carbonization chamber 20 is sucked by the differential pressure adjusting vacuum pump 27 to -10 mmAq.
When q is reached, the vacuum pump 27 is stopped. (3) After stopping the vacuum pump 27, leave it as it is for 5 minutes,
Return to step (1).

When the above procedure was repeated for 7 hours, it finally took 27 minutes to shift from the step (1) to the step (2), and the state where it could be regarded as substantial occlusion was reached. . Then, after the operation of the apparatus was stopped and the system was allowed to cool, the state of the partition wall was examined, and it was found that the state of appearance was completely blocked.

(Embodiment 7) In Embodiment 7, an air flow transport pipe (not shown) is attached to a coal charging hole lid (not shown) above the carbonization chamber 20 of the apparatus shown in FIG. 10 used in Embodiment 6. 10) is used, except that the refractory powder is supplied to the inside of the artificial through crack in the carbonization chamber by the air flow oil feeding pipe,
Precipitated SiO ₂ was deposited between the refractory powder particles.

Therefore, the seventh embodiment will be described with reference to FIG. 10 which illustrates the sixth embodiment. The coke oven gas 28 and the combustion air 29 are supplied to the combustion chamber 21 and burned in the combustion chamber 21, and the combustion exhaust gas temperature at the combustion chamber outlet 30 is set to 10
Hold at 50 ° C. The flue gas was discharged from the chimney through the flue 31. First, a refractory powder (SiO ₂ : 77 w) is introduced into the carbonization chamber 20 through an air flow transport pipe (not shown) attached to a coal charging hole lid (not shown) above the carbonization chamber 20.
t.%, Al ₂ O ₃ : 17 wt.%, particle size: 200 mesh) are supplied by pneumatic transportation, and the inside of the carbonization chamber 20 and the combustion chamber 21 are supplied.
When the pressure difference between the inside and the inside reached 70 mmAq, the supply of the refractory powder was stopped.

Next, the N ₂ gas 25 is supplied to the carbonization chamber 20, while the carbonization chamber 2 is supplied by the differential pressure adjusting vacuum pump 27.
By exhausting the inside of 0, the atmosphere in the carbonization chamber 20 becomes N
After it was replaced with ₂ gas, SiCl ₄ evaporator with N ₂ gas 24
By air the SiCl ₄ gas from, SiCl ₄ gas and N
Switched to mixed gas with ₂ gases. The mixed gas composition is S
_{iCl 4:. 10vol%, N} 2: a 90vol%..

Then, SiO ₂ was deposited in the artificial through crack 23 'by the following steps (1) to (3). (1) SiCl until the pressure difference reaches 10 mmAq
_The gas containing ₄ is supplied to the carbonization chamber 20 and then stopped. (2) When the pressure difference decreases to 1 mmAq, the inside of the carbonization chamber 20 is sucked by the differential pressure adjusting vacuum pump 27 to -10 mmAq.
When q is reached, the vacuum pump 27 is stopped. (3) After stopping the vacuum pump 27, leave it as it is for 5 minutes,
Return to step (1).

When the above procedure was repeated for 3 hours, finally, it took 44 minutes to shift from the step (1) to the step (2), and it became possible to regard it as a substantial blockage. . Then, after the operation of the apparatus was stopped and the system was allowed to cool, the state of the partition wall was examined, and it was found that the state of appearance was completely blocked.

As described above, SiCl is contained in the carbonization chamber 20.
₍₄₎ Before the gas is fed, the through cracks are filled with refractory powder in advance, so that SiO
_The time required for the deposition of ₂ can be greatly shortened.

(Embodiment 8) FIG. 11 is a schematic vertical sectional view showing an apparatus used in Embodiment 8. This apparatus is a small coke oven, and the SiCl ₄ evaporator 24 is removed from the apparatus (FIG. 10) used in the above-mentioned sixth embodiment, while N ₂ gas 2 which is a carrier gas of SiCl ₄ gas is removed.
Pipe 3 for supplying Ar gas 33 to the carbonization chamber 20 instead of 5
4 is the same as that of FIG. 10 except that a gas oil feeding pipe (not shown) is attached to the coal charging hole lid (not shown) in the upper part of the carbonization chamber 20. Hereinafter, description will be given with reference to FIG.

Coke oven gas 28 and combustion air 29 were supplied to the combustion chamber 21, burned in the combustion chamber 21, and the temperature of the exhaust gas at the combustion chamber outlet 30 was maintained at 1050 ° C. The flue gas was discharged from the chimney through the flue 31. First, the extrusion side furnace lid (not shown) of the carbonization chamber 20 is opened, and the mixed powder 32 (MgO: 70 wt.%, Al: 30 wt.%) Of MgO and Al placed in the alumina crucible 32 '.
Immediately after placing 500 g of Ar in the carbonization chamber 20, immediately
The gas 33 was supplied to the carbonization chamber 20, and the inside of the carbonization chamber 20 was evacuated by the vacuum pump 27 for adjusting the differential pressure, whereby the atmosphere inside the carbonization chamber 20 was replaced with Ar gas 33.

Next, MgO was deposited in the artificial through crack 23 'by the following steps (1) to (3). (1) Ar gas 33 is supplied to the carbonization chamber 20 until the pressure difference reaches 10 mmAq, and then stopped. (2) When the pressure difference decreases to 1 mmAq, the inside of the carbonization chamber 20 is sucked by the differential pressure adjusting vacuum pump 27 to -10 mmAq.
When q is reached, the vacuum pump 27 is stopped. (3) After stopping the vacuum pump 27, leave it as it is for 5 minutes,
Return to step (1).

When the above procedure was repeated for 6 hours, it took finally 31 minutes to shift from the step (1) to the step (2), and the state where it could be regarded as substantial occlusion was reached. . Then, after the operation of the apparatus was stopped and the system was allowed to cool, the state of the partition wall was examined, and it was found that the state of appearance was completely blocked.

[0115]

Since the present invention is configured as described above, when a flat plate is not used, it is possible to improve the strength and wear resistance of a partition wall in a new state at the beginning of operation of the heat exchanger, It is possible to block the gas flow in the damaged portion generated on the furnace wall after the operation. Further, according to the present invention using a flat plate, in addition to the effects described above, it is possible to further smoothly restore the unevenness caused by the abrasion of the heated object after the operation. Further, according to the present invention, in repairing the partition wall, it is not necessary to identify the damaged portion existing in the high heat portion, and further, the high heat work as in the past is not required, and the damaged portion can be repaired safely and easily. It is possible to provide a method for repairing and / or strengthening the partition wall of the partition wall heat exchanger, which brings about an extremely useful effect industrially.

[Brief description of drawings]

FIG. 1 is a schematic vertical cross-sectional view of a penetrating damage portion of a partition wall for explaining a first stage of the principle of the repairing method of the present invention.

FIG. 2 is a schematic vertical sectional view of a penetrating damaged portion of a partition wall for explaining a second stage of the principle of the repair method of the present invention.

FIG. 3 is a schematic vertical cross-sectional view of a penetrating damaged portion of a partition wall for explaining a third stage of the principle of the repair method of the present invention.

FIG. 4 is a schematic vertical sectional view of a partition wall heat exchanger showing the first embodiment.

FIG. 5 is a schematic vertical cross-sectional view of a partition-type heat exchanger showing the first half of the second embodiment.

FIG. 6 is a schematic vertical cross-sectional view of a partition-type heat exchanger showing the latter half of the second embodiment.

FIG. 7 is a schematic vertical cross-sectional view of a partition wall type heat exchanger showing a third embodiment.

FIG. 8 is a schematic vertical sectional view showing an apparatus used in Example 4.

FIG. 9 is a schematic vertical sectional view showing an apparatus used in Example 5.

FIG. 10 is a schematic vertical sectional view showing an apparatus used in Example 6.

FIG. 11 is a schematic vertical sectional view showing an apparatus used in Example 8.

[Explanation of symbols]

1 Partition 2 Penetration Damaged Part 3 Refractory Powder 3'Filled Layer 3 "Precipitated Layer 4 Silicon Compound-Containing Gas 5 Tubular Heating Furnace 6 Tubular Heating Body 7 Quartz Outer Tube 8 Quartz Inner Tube 9 Artificial Through Crack 10 Partition Wall 11 Heating Chamber 11a Part of heating chamber 12 Heated chamber 13 Supply port 13 'Reactive gas-containing gas 13 "Discharge port 14 Supply port 14' Metal compound-containing gas 15 Differential pressure gauge 16 Vacuum pump 17 Alumina boat 18 Metal magnesium powder 19 Small size Coke oven 20 Carbonization chamber 21 Combustion chamber 22a, 22b Partition wall 23 Silica brick 23 'Artificial through crack 24 SiCl ₄ evaporator 25 N ₂ gas 26 Differential pressure gauge 27 Vacuum pump 28 Coke oven gas 29 Combustion air 30 Combustion chamber outlet 31 Smoke Road 32 Mixed powder of MgO and Al 32 'Alumina crucible 33 Ar gas 34 Piping 35 Heated material charging lid 36 Gas inlet 37 Gas inlet 37 'Gas exhaust port 38 Pressure outlet 39 Pressure outlet 40 Differential pressure detector 41 Through crack damage 42 Flat plate 43 Distribution plate 44 Inorganic powder 45 Space 46 Roughness 47 Gas containing metal compound (G- 1) 48 Gas Containing Reactive Gas (G-2) 49 Damaged Part 50 Solid Metal Compound 51 Inorganic Powder Layer 52 Exhaust Pump 53 Thermal Spraying Body P Carbonization Chamber Side t Partition Thickness

Claims (20)

[Claims] 1. A heat exchanger having a partition wall made of a material having air permeability, wherein a gas (G-1) containing a metal or / and a metal compound is supplied to one side of the partition wall to form the partition wall. By supplying a gas (G-2) containing a reactive gas that reacts with the metal or the metal compound to precipitate a solid metal compound to the other side of the gas (G-1 and G- 2) to reach the inside of the partition wall from each of the one side and the other side of the partition wall, and then the both gas (G
-1 and G-2) to produce the solid metal compound, and the solid metal compound thus produced is deposited inside the partition wall. Repair and / or strengthening method. 2. The method for repairing and / or strengthening a partition of a partition heat exchanger according to claim 1, wherein the heat exchanger has a damaged part in the partition. 3. The method for repairing and / or strengthening a partition of a partition heat exchanger according to claim 1, wherein the metal compound is a metal halide. 4. The partition wall type heat exchange according to claim 1, wherein the metal is magnesium, and the reactive gas is at least one gas selected from the group consisting of oxygen, carbon monoxide, and water. Method for repairing and / or strengthening the bulkhead of the vessel. 5. The repair of the partition wall of the partition heat exchanger according to claim 4, wherein the magnesium is magnesium vapor generated by reacting magnesium oxide and aluminum at a temperature within a range of 850 to 1700 ° C. And / or strengthening methods. 6. The partition wall heat exchanger is a coke oven having a carbonization chamber and a combustion chamber, the one side of the partition wall is the carbonization chamber, and the other side of the partition wall is the combustion chamber. Chamber, the gas (G-1) containing the metal or / and the metal compound is a silicon compound-containing gas, and the gas (G-2) containing the reactive gas is generated in the combustion chamber. Combustion gas, and the reaction of both the gases (G-1 and G-2) is performed by changing the pressure difference between the carbonization chamber and the combustion chamber positively and negatively a plurality of times, and The method for repairing and / or strengthening a partition of a partition heat exchanger according to claim 1 or 2, wherein the solid metal compound deposited inside the partition is silicon dioxide. 7. A method for repairing and / or strengthening a partition wall according to claim 2, further comprising a gas (G-1) containing the metal or / and the metal compound on the one side. A method for repairing and / or strengthening a partition wall of a partition heat exchanger, characterized in that the damaged portion is subjected to preliminary repair before being supplied. 8. A gas (G-1) containing the metal or / and a metal compound and a reactive gas which reacts with the metal or the metal compound to precipitate a solid metal compound (G-2). The repair and / or strengthening method according to claim 7, wherein the reaction with (1) is performed by changing the pressure difference between one side of the partition wall and the other side of the partition wall positively and negatively a plurality of times. 9. The method for repairing and / or strengthening a partition of a partition heat exchanger according to claim 6, wherein the metal compound is a metal halide. 10. The gas (G-1) is a gas containing a metal, the metal is magnesium, and the reactive gas is one selected from the group consisting of oxygen, carbon monoxide and water. The method for repairing and / or strengthening the partition walls of the partition heat exchanger according to claim 6 or 7, which is the above gas. 11. The partition wall repair of a partition wall heat exchanger according to claim 10, wherein the magnesium is magnesium vapor generated by reacting magnesium oxide and aluminum at a temperature within a range of 850 to 1700 ° C. And / or strengthening methods. 12. The pressure difference is −200 to +200.
The method for repairing and / or strengthening the partition walls of the partition heat exchanger according to claim 6 or 8, which is within a range of mmAq. 13. The silicon compound-containing gas is 0.1
Repair and / or repair of the partition walls of the partition heat exchanger according to claim 6 or 8, wherein the partition wall heat exchanger is a gas containing vol.% or more of silicon tetrachloride, and the combustion gas is a gas containing 1 vol.% or more of water.
Or how to strengthen. 14. A breathable flat plate is arranged in close proximity or partly in contact with the wall surface of the partition wall of the heated chamber of the heat exchanger having the partition wall made of a breathable material, The space formed between the wall surface and the flat plate is filled with an inorganic powder, and then a gas (G-1) containing a metal or / and a metal compound is supplied to the heated chamber, while the heating chamber is supplied. By supplying a gas (G-2) containing a reactive gas that reacts with the metal or / and the metal compound to precipitate a solid metal compound, whereby the respective gas (G-1 and G-2) To reach between the inorganic powder particles and the inside of the partition wall, and between the respective gas (G
-1 and G-2) to produce the solid metal compound between the inorganic powder particles and inside the partition wall in this way. Repair and / or strengthening method. 15. The method for repairing and / or strengthening a partition of a partition heat exchanger according to claim 14, wherein the heat exchanger has a damaged part in the partition. 16. The partition wall heat exchanger is a coke oven having a carbonization chamber and a combustion chamber, the heated chamber is the carbonization chamber, the heating chamber is the combustion chamber, and the metal compound is The gas containing (G-1) is a silicon compound-containing gas, the gas containing the reactive gas (G-2) is a combustion gas generated in the combustion chamber, (Between G-1 and G-2)
16. The solid metal compound deposited by fluctuating the pressure difference between the carbonization chamber and the combustion chamber a plurality of times in positive and negative directions, and the solid metal compound deposited inside the partition wall is silicon dioxide. A method for repairing and / or strengthening a partition wall of a partition heat exchanger. 17. In addition to the method for repairing and / or strengthening a partition wall according to claim 15, a gas (G-1) containing the metal or / and the metal compound is further provided on the one side. A method for repairing and / or strengthening a partition wall of a partition heat exchanger, characterized in that the damaged portion is subjected to preliminary repair before being supplied. 18. A gas (G-1) containing the metal or / and a metal compound and a reactive gas (G-2) which reacts with the metal or the metal compound to precipitate a solid metal compound. The repair and / or strengthening method according to claim 17, wherein the reaction with (1) is performed by changing the pressure difference between one side of the partition wall and the other side of the partition wall positively and negatively a plurality of times. 19. The pressure difference is -200 to +200.
The method for repairing and / or strengthening the partition walls of the partition wall heat exchanger according to claim 16 or 18, which is within the range of mmAq. 20. The silicon compound-containing gas is 0.1
The repair and / or the partition of the partition type heat exchanger according to claim 16 or 18, which is a gas containing vol.% or more of silicon tetrachloride, and the combustion gas is a gas containing 1 vol.% or more of water. How to strengthen.