JP2003082355A - Coke oven and its operation method - Google Patents

Abstract

(57) [Problem] To provide a coke oven capable of effectively recovering the sensible heat of a carbonization product gas that has been discarded without being recovered, and a method of operating the coke oven. SOLUTION: The carbonization chamber 2, a riser pipe 7, and an air collecting main pipe 8 are provided, and further the dry distillation production gas 6 is reformed into a reformed gas having higher energy than the dry distillation production gas 6. Using a coke oven 10 equipped with a gas reformer 12, the dry distillation product gas 6 flowing above the coal disposed inside the coking chamber 2 is reformed into a reformed gas. Collect via tube 8.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coke oven and a method for operating the coke oven, and more particularly to a coke oven and an operation method for the coke oven that can effectively recover the sensible heat of the gas produced by dry distillation.

[0002]

2. Description of the Related Art FIG. 3 is an explanatory view schematically showing the structure of a horizontal chamber furnace type coke 1 for producing coke which is a raw material for blast furnace, in the furnace length direction. As shown in the figure, in the horizontal chamber coke oven 1, a carbonization chamber 2 for carbonizing coal and a combustion chamber (not shown) for supplying heat to the carbonization chamber 2 are alternately sandwiched. It is arranged and configured. The size of the carbonization chamber 2 is, for example, 6 to 7 in height h.
m, length 1 is 15 to 17 m, and width (not shown) is 0.45 m
Basically, all of them are constructed by stacking fine bricks. In the coke oven 1, for example, an amount of about 20 to 40 tons of coal is charged as a raw material into the inside of the carbonization chamber 2 at one time, and is calcined to about 1000 ° C. in a dry distillation time of about 24 hours. As a result, about 75% of the charged coal is converted to coke 3, about 10% is converted to tar and ammonium hydroxide 4, and the remaining about 15% is converted to gas 5.

Of these, the coke 3 is discharged from the coke oven 1 in a red heat state, and then, in many cases, is introduced into a CDQ (Coke Dry Quencher), which is a heat exchange equipment, to generate heat. Replaced and cooled. On the other hand, other than the coke 3, the carbonization product gas (coke oven gas) 6 containing a large amount of cheap water and tar vapor is used in the carbonization chamber 2
It is discharged to the outside of the furnace through an ascending pipe 7 provided at the ceiling part of and is guided to an air collecting main pipe (dry main) 8. At this time, although the dry-distilled product gas 6 has a sensible heat of about 800 ° C., cold and cold water 9 is sprayed at the bent pipe portion 7a at the outlet of the rising pipe 7 and rapidly cooled to 100 ° C. or less. That is, up to now, the sensible heat of these dry-distilled product gases 6 has hardly been effectively reused and has been simply discarded.

That is, the carbonization product gas 6 produced by the carbonization reaction of coal flows through the upper space 2a in the carbonization chamber 2 toward the ascending pipe 7 usually located on the pusher side (P / S). After ascending inside the rising pipe 7, cold and cold water 9 is sprayed and cooled in the curved pipe portion 7a. here,
Since the temperature of the upper space 2a is usually about 800 to 1000 ° C,
The dry distillation product gas 6 passing through the upper space 2a has also been heated to a temperature close to this, and although it has a sufficient sensible heat, the sensible heat has hardly been recovered so far.

The reason for this is that the gas 6 produced by carbonization contains a large amount of tar vapor containing hydrocarbon as a main component. In other words, tar vapor does not cause any particular problems because it exists as vapor at high temperatures exceeding 500 ° C, but it recondenses when the temperature drops to around 500 ° C or less, and it becomes oily bituminous matter such as in pipes. This is because it adheres to the inner surface and the like and causes problems such as blockage of the gas flow path and reduction of the thermal efficiency of the heat exchanger.

Therefore, in order to effectively recover and utilize the sensible heat of the dry distillation gas 6 without causing such a problem, various inventions have been proposed in the past. For example, in Japanese Unexamined Patent Publication No. 8-134456, the outer surface of the heat transfer tube of the heat exchanger is
An invention has been disclosed in which a catalyst capable of decomposing tar or the like such as crystalline aluminosilicate is applied in advance to suppress the adhesion of tar and recover the sensible heat of the gas produced by carbonization.

Further, in Japanese Patent Laid-Open No. 58-76487, a heat exchanger is arranged between an ascending pipe and a main air collecting pipe, and the temperature becomes about 500 ° C. near the heat exchanger due to cold and cold water. The temperature of the dry-distilled product gas is controlled by using low-temperature water, and heat is recovered in two steps: primary heat exchange to recover heat at a temperature of 500 ° C or higher and secondary heat exchange to recover the sensible heat of the dry-distilled product gas at a temperature of 500 ° C or lower. An invention for recovering is disclosed. According to this invention, since the temperature of the gas produced by carbonization is maintained at about 500 ° C., the tar adhering to each part is collected in the air collecting main pipe while being kept in a flowable state without sticking.

[0008]

However, none of these conventional inventions can effectively recover the sensible heat of the gas produced by dry distillation.

That is, in order to carry out the invention proposed by Japanese Patent Application Laid-Open No. 8-134456, crystalline aluminosilicate or the like is applied to the surface of a device having a complicated three-dimensional shape such as piping of a heat exchanger. It was necessary to do the difficult work of doing. Even if the coating could be managed, the coating had to be peeled off and recoated when the life of the coating was reached, and the coating operation had to be repeated.
Therefore, it was extremely difficult to carry out the present invention on an industrial scale.

According to the invention proposed in Japanese Patent Laid-Open No. 58-76487, it is certainly possible to recover a part of the sensible heat of the gas produced by dry distillation. However, in other words, the present invention utilizes only about half (500 to 1000 ° C.) of the sensible heat of the carbonization product gas, which is usually about 800 to 1000 ° C. Further, in order to carry out the present invention, it is not only necessary to newly dispose a heat exchanger between the existing riser pipe and the main air collecting pipe, but also a disposition of a secondary recovery device for heat-exchanged heat, Further, it is necessary to lay a large-scale pipe for connecting the recovery device and the heat exchanger, and a large amount of equipment modification cannot be avoided, so that the cost required for the equipment modification increases significantly. Further, it is not easy to accurately control the temperature of the dry-distilled product gas so that the temperature will be about 500 ° C in the vicinity of this heat exchanger by cold and cold water. Therefore, the present invention has not been widely implemented in reality.

It is an object of the present invention to provide a coke oven and a method of operating the coke oven. Specifically, the sensible heat of the carbonization product gas, which has been mostly discarded until now, is not recovered. The purpose is to provide a coke oven that can be effectively recovered and a method of operating the coke oven.

[0012]

Means for Solving the Problems The present inventors directly recover the sensible heat of the dry-distilled product gas as heat energy by heat exchange, which is a problem caused by tar vapor contained in a large amount in the dry-distilled product gas. Based on the basic recognition that it cannot be realized because it cannot be prevented, and as a result of diligent study on other means different in fundamental idea from such means, for example, it is formed by carbonization product gas and moisture By contacting the mixed gas with water vapor with the metal catalyst, it is reformed into a reformed gas having higher energy than the carbonization product gas, and by recovering this reformed gas, any of the above-mentioned problems are solved. It was discovered that the sensible heat of the carbonized product gas can be truly recovered on an industrial scale.
The present invention has been completed through further studies.

According to the present invention, a carbonization chamber, a communication channel provided in communication with the carbonization chamber, a communication channel provided in communication with the communication channel, and generated during carbonization of coal loaded inside the carbonization chamber And a recovery flow path for guiding the carbonized product gas flowing above the coal to a recovery device, and further, the carbonized product that reforms the carbonized product gas into a reformed gas having higher energy than the carbonized product gas. The coke oven is characterized by comprising a produced gas reforming device.

In the coke oven according to the present invention, the carbonization product gas flowing above the coal is provided in a part of the communication passage,
It is exemplified that a metal catalyst that is in contact with a mixed gas with water vapor formed by the added water is provided.

In the coke oven according to the present invention, the dry distillation produced gas reforming device is exemplified by a water addition device for adding moisture to the dry distillation produced gas and a metal catalyst. It is desirable that this metal catalyst be (i) detachably provided in the communication channel and (ii) be a Ni-based metal catalyst.

From another point of view, the present invention converts a carbonization product gas flowing above coal disposed inside a coking furnace of a coke oven into a reformed gas having higher energy than the carbonization product gas. A method of operating a coke oven, characterized in that the reformed reformed gas is recovered after the qualification.

In the coke oven operating method according to the present invention, the reforming of the carbonized product gas to the reformed gas is carried out by adding water to the carbonized product gas, (v) the carbonized product gas, Desirably, it is carried out by forming a mixed gas of water vapor and steam, and (vi) by contacting the mixed gas with a metal catalyst.

In these coke oven operating methods according to the present invention, it is desirable that the reformed gas be recovered after the carryover due to the coal charging into the carbonization chamber has been subsided.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of a coke oven and a method for operating the coke oven according to the present invention will be described in detail below with reference to the accompanying drawings. In the following description, the case where the coke oven is a so-called horizontal chamber furnace coke oven that produces blast furnace coke is taken as an example.

FIG. 1 is an explanatory view schematically showing the structure of a horizontal chamber type coke oven 10 of the present embodiment in the furnace length direction. In the following description of the horizontal chamber coke oven 10, the conventional horizontal chamber coke oven 1 shown in FIG.
Constituent parts similar to those are denoted by the same reference numerals, and redundant description will be appropriately omitted.

Horizontal chamber furnace type coke oven 10 of the present embodiment
Has a carbonization chamber 2, a communication flow path 7, a recovery flow path 8, a carbonization product gas reformer 12, and a metal catalyst 13. Hereinafter, these components of the horizontal chamber coke oven 10 will be sequentially described.

(Carbonizing Chamber 2) The carbonizing chamber 2 in the horizontal chamber coke oven 10 of the present embodiment is the same as the known horizontal chamber coke oven, and the carbonizing chamber 2 itself has no special feature. There is no feature. That is, the carbonization chamber 2 is for carbonizing the coal loaded in the internal space 2a of the carbonization chamber 2 from the coal car 11 running on the furnace, and the combustion chamber for supplying heat to the carbonization chamber 2 (shown in the figure). No)) and are arranged alternately in a sandwich.

The size of the carbonization chamber 2 is about normal, for example, the height h is 6 to 7 m, the length l is 15 to 17 m, and the width (not shown) is about 0.45 m. Brick is piled up and built.

Also in the horizontal chamber coke oven 10 of the present embodiment, for example, about 20 to 40 tons of coal is charged as a raw material from the coal car 11 into the internal space 2a of the carbonization chamber 2 at a time, and 24 It is baked up to about 1000 ° C in the dry distillation time before and after the time. As a result, about 75% of the charged coal is converted to coke 3, about 10% is converted to tar and ammonium hydroxide 4, and the remaining about 15% is converted to gas 5. As a result, the carbonization product gas 6 is generated in the internal space 2a of the carbonization chamber 2.

The coke 3 thus produced is discharged from the coke oven 10 in a red heat state after the completion of the dry distillation, and then, in many cases, it is introduced into a CDQ (not shown) for heat exchange and cooling. Since the structure of the carbonization chamber 2 other than this is the same as that of the conventional carbonization chamber, further description of the carbonization chamber 2 will be omitted.

The carbonization chamber 2 of this embodiment is constructed as described above. (Communication flow path) In the horizontal chamber coke oven 10 of the present embodiment, a communication flow path is provided in communication with both the carbonization chamber 2 described above and a recovery flow path 8 described later. In this embodiment,
Pusher side (P / S) of carbonization chamber 2 as a communication channel
The ascending pipe 7 arranged on the ceiling part of was used.

The carbonization product gas 6 generated during carbonization of the coal charged in the carbonization chamber 2 and containing a large amount of ammonium hydroxide and tar vapor other than the coke 3 is as shown by an outline arrow in FIG. Flows above the charged coal or coke 3 and is discharged to the outside of the furnace through the rising pipe 7 to collect the air.
Be led to.

In the present embodiment also, the rising pipe 7
A curved pipe portion 7a is formed at the outlet of the curved pipe portion 7a.
At a, cold cold water 9 is sprayed and quenched. Since the structure of the rising pipe 7 other than this is the same as that of the conventional rising pipe, further description of the rising pipe 7 will be omitted.

The communication channel of this embodiment is configured as described above. (Recovery flow path) The horizontal chamber furnace type coke oven 10 of the present embodiment is
A communication channel is provided in communication with the recovery channel described above.
The recovery flow path is formed by the dry distillation generated gas 6 sent through the rising pipe 7.
The air collecting main tube 8 is used in the present embodiment.

Since the structure of the air collecting main 8 is the same as that of a conventional air collecting main, further description of the air collecting main will be omitted. The recovery channel of this embodiment is configured as described above.

(Carbon Distillation Product Gas Reforming Device) The horizontal chamber furnace coke oven 10 of the present embodiment has a carbonization product gas reforming device. The dry-distillation product gas reforming device is a device for reforming the dry-distillation product gas 6 flowing in the furnace space 2a into a reformed gas having higher energy than the dry-distillation product gas 6.

In the present embodiment, a water addition device 12 for adding water vapor formed by water and a metal catalyst 13 are used as a carbonization product gas reforming device. This water addition device 12
In order to reform the dry-distilled product gas 6, the steam 12a formed by water is added to the dry-distilled product gas 6 flowing in the inner space 2a of the carbonization chamber 2.

That is, the carbonization product gas 6 flowing in the internal space 2a of the carbonization chamber 2 is composed of gas and tar converted from coal by carbonization in the carbonization chamber 2, and mainly contains hydrocarbons such as methane. To do. This hydrocarbon is generally highly reactive and reacts with steam at high temperatures to produce carbon monoxide and hydrogen. For example, methane reacts with steam at high temperature as shown in the following formula (1).

CH ₄ + H ₂ O → CO + 3H ₂ −49.3 kcal / mol (1) As is apparent from the equation (1), it is produced by adding steam to the dry distillation product gas 6, The energy of the reformed gas, which is a mixed gas of carbon monoxide and hydrogen, is higher by 49.3 (kcal / mol) than the energy of the dry-distillation product gas 6 containing methane as a main component, in other words, the dry-distillation product gas. By adding water to 6 to reform the dry-distilled product gas 6 to a reformed gas, the energy of the reformed gas composed of carbon monoxide and hydrogen is increased more than the energy of the dry-distilled product gas 6. be able to.

Here, since the temperature of the internal space 2a of the carbonization chamber 2 during the carbonization is about 800 to 1000 ° C., water is added to the carbonized product gas 6 existing in the internal space 2a, and the generated mixed gas is converted into metal. When brought into contact with the catalyst 13, the above-mentioned reaction of the formula (1) effectively occurs.

The form of water supply may be spraying of liquid at high pressure, or steam of gas, without any limitation. In the present embodiment, it is added as gas steam.

The amount of water added is not particularly limited, but it is preferably added so as to be 2 to 15 mass% with respect to the amount of coal charged. If the addition amount is less than 2% by mass, the above (1)
The reaction shown in the formula may not occur sufficiently, while if the addition amount exceeds 15 mass%, the temperature drop in the carbonization chamber 2 due to the endotherm becomes remarkable, which may hinder the carbonization reaction itself. Because.

The water addition device 12 is a space inside the carbonization chamber 2.
Any device may be used as long as it can supply water to 2a, and is not limited to a specific type of water addition device.

The water addition device 12 of this embodiment is configured as described above. (Metal catalyst 13) Horizontal chamber furnace type coke oven 10 of the present embodiment
The metal catalyst 13 is attached to the lowermost part of the rising pipe 7. The metal catalyst 13 is a carbonization product gas 6 flowing above coal,
By sufficiently contacting the mixed gas 6 ′ mixed with the water vapor formed by the added water,
It promotes the reaction represented by the formula (1).

As described above, in the present embodiment, the above
Although it is necessary to cause the reaction of formula (1), it is generally difficult to take a long reaction time in the carbonization chamber 2 including the riser pipe 7. Therefore, a metal catalyst is used as the gas reforming catalyst in order to enhance the reaction efficiency and accelerate the reaction of the above formula (1).

In this embodiment, the metal catalyst 13 is stored in, for example, a cassette type storage container so that the metal catalyst 13 can be easily detached from the rising pipe 7 while forming a fixed layer.
It is arranged. In addition, since the metal catalyst 13 is brought into sufficient contact with the mixed gas 6'which rises due to the high temperature,
Although it is provided in a portion of the ascending pipe 7 that is vertically arranged upward, the present invention is not limited to such a form.
It may be loaded in a portion other than the upper space 2a of the carbonization chamber 2 or the lower portion of the rising pipe 7.

Further, in the present embodiment, the shape and size of the metal catalyst 13 are not particularly limited, but it is preferable that the metal catalyst 13 is formed in a granular shape or the like, because the pressure loss can be suppressed rather than a powder shape. Further, in the present embodiment, Ni is used as the metal catalyst.
A Ni-based metal catalyst having a content of 50 mass% or more was used. However, it is not limited to this Ni-based metal catalyst, but Co
It is also possible to use a metal-based catalyst or a Mo-based metal catalyst.
The normal operating temperature of this Ni-based metal catalyst is 600-90.
It is about 0 ° C. Also, since the environment of use is not clean, it is desirable that it can be basically recycled and repeatedly used.

When the mixed gas 6'of the dry-distilled product gas 6 and the added water vapor 12a of water passes through the metal catalyst 13 in contact with it, the reaction of the formula (1) occurs rapidly. This reaction is 49.3 kcal per mole of methane (or per 1 Nm ³
Since it is an endothermic reaction of 2200 kcal), the sensible heat of the carbonization product gas 6 is used depending on the reaction rate of methane or hydrocarbon. In this case, the sensible heat used is converted into a product of CO gas or H ₂ gas and is recovered. Therefore, if methane reacts with 1 Nm ^3, for example,
2200 kcal of thermal energy will be converted into chemical substances.

In order to suppress the deactivation of the catalyst performance, it is important to carry out a sulfurizing treatment in advance. In addition, a guard reactor may be installed in front of the metal catalyst to suppress deterioration of catalyst performance.

The metal catalyst 13 of this embodiment is configured as described above. Carbonization chamber 2, communication channel 7, recovery channel 8
The horizontal chamber furnace type coke oven 10 according to the present embodiment, which includes the water addition device 12 and the metal catalyst 13, is configured as described above. Next, a situation in which an operation for carbonizing carbon is carried out by using this horizontal chamber type coke oven 10 will be described.

First, in the horizontal-chamber coke oven 10 of the present embodiment, a coal car is installed in the internal space 2a of the carbonization chamber 2 in the empty kiln state.
From 11 to, for example, 20 to 40 tons of raw coal is charged at a time, and this carbonization chamber 2 is used for 10 hours in the dry distillation time of around 24 hours.
It is carbonized to about 00 ℃. As a result, about 75% of the charged coal is converted into coke 3. In addition, about 10% of the charged coal is converted to tar and cheap water 4, and the remaining about 15% is converted to gas 5. As a result, in the internal space 2a of the carbonization chamber 2, a dry distillation produced gas 6 containing a large amount of noble water and tar vapor other than the coke 3 is produced, and the dry distillation produced gas 6 directs this internal space 2a to the rising pipe 7. And flows above the coal arranged inside the carbonization chamber 2.

At this time, in this embodiment, the water addition device is used.
Moisture is supplied to the internal space 2a by 12. For this reason,
Moisture is added to the dry distillation product gas 6 existing in the internal space 2a to form a mixed gas 6 ′ of the dry distillation product gas 6 and steam.

The formed mixed gas 6'passes while contacting the metal catalyst 13 arranged at the lowermost portion of the rising pipe 7, whereby the reaction of the formula (1) is immediately generated and reformed, and the dry distillation is carried out. A reformed gas composed of carbon monoxide and hydrogen is generated from methane gas which is a main component of the gas 6.

As described above, this reaction is an endothermic reaction of 49.3 kcal per 1 mol of methane (or 2200 kcal per 1 Nm ³ ). Therefore, the energy contained in the reformed gas composed of carbon monoxide and hydrogen is methane or the like. It is increased more than the energy of the carbonization product gas 6 containing as a main component.

Therefore, according to the present embodiment, the reformed gas rising in the rising pipe 7 is guided to the collecting main pipe 8 and collected, so that the reforming gas is collected depending on the reaction rate of methane or hydrocarbons.
The sensible heat of the dry distillation gas 6 can be efficiently used.

Further, according to the present embodiment, instead of directly recovering the sensible heat from the carbonization product gas 6 containing a large amount of tar vapor, the sensible heat is reformed into the reformed gas and the sensible heat is reformed from the reformed gas. Since it is recovered, various problems caused by the large amount of tar vapor can be eliminated.

Therefore, according to the present embodiment, for example, a complicated outer surface shape such as piping of a heat exchanger, which is necessary for carrying out the invention proposed by Japanese Patent Laid-Open No. 8-134456, is used. Coating operation of crystalline aluminosilicate or the like on the surface of the apparatus having the above, recoating operation, and further, the gas temperature at the time of recovery processing, which was indispensable in the invention proposed by JP-A-58-76487. Neither management nor installation of heat exchangers is necessary at all.

Therefore, according to the present embodiment, the sensible heat of the dry-distilled product gas 6 which could not be recovered and had to be discarded so far is effectively and truly on an industrial scale. Can be collected at.

Incidentally, also in the carbonization chamber 2 of the coke oven 10 of the present embodiment, like the known carbonization chamber of the coke oven,
In accordance with the carbonization cycle, for example, a large amount of coal is charged from the coal car 11 by gravity fall every 24 hours. For this reason,
Immediately after charging into the carbonization chamber 2 (usually 0.2 to 1 hour after the start of carbonization), a large amount of dust, mainly pulverized coal, rises in the carbonization chamber 2. Therefore, if an attempt is made to recover the dry-distillation product gas 6 during this time, a so-called carry-over will occur, in which the pulverized coal accompanies the gas flow of the mixed gas 6 ′ and flows out of the carbonization chamber 2. If the metal catalyst 13 is exposed to the flow of the pulverized coal at the time of this carryover, the pulverized coal becomes the metal catalyst.
There is a risk that the surface of 13 will be covered up and the catalytic ability of the metal catalyst 13 will be lost in a short time.

Therefore, in the operating method of the present embodiment, the dry distillation product gas is recovered after the carryover due to the charging of the raw material coal into the carbonization chamber is suppressed, and then the mixed gas 6 '
It is desirable to pass the gas flow of the above into the metal catalyst 13.

For example, having two gas extraction systems,
A so-called double-main type coke oven can be easily realized. Even in the case of a so-called single-main type coke oven in which the gas extraction is one system, for example, as shown in FIG. Part 7-1 without catalyst 13 and part 7-2 with metal catalyst 13
Split into two. Immediately after carbonization, the flow path control valve
When the mixed gas 6'is made to flow in the portion 7-1 where the metal catalyst 13 is not loaded by rotating 15 so that the carryover at the time of 0.2 to 1 hour after the start of carburizing is calmed down to some extent. The mixed gas 6 ′ may be caused to flow through the portion 7-2 loaded with the metal catalyst 13 by reversing the flow passage control valve 15. Thus, the metal catalyst
It is desirable that 13 be provided in a part of the plurality of flow paths provided in the communication flow path. For example, a branch pipe may be provided in parallel with the rising pipe 7 in addition to the present embodiment. Good.

In this way, according to the present embodiment,
The sensible heat of the dry distillation produced gas 6 can be effectively and stably recovered on an industrial scale. Further, the present invention will be described in detail with reference to examples.

[0058]

EXAMPLE Using the coke oven 10 according to the present invention shown in FIG. 1, coal carbonization operation was carried out. That is, as shown in FIG. 1, 37 tons of coal whose water content has been adjusted to 6 mass% is charged into the internal space 2a of the carbonization chamber 2 from the coal car 11 on the upper side of the carbonization chamber 2 by the gravity drop method, and thereafter. The steam was circulated from the water addition device 12 at a constant rate of 2 kg / min until the end of the carbonization. Further, 300 kg of the Ni-based metal catalyst 13 was loaded at the base of the ascending pipe 7 as shown in FIG. 2, so that the mixed gas 6'of the carbonization product gas 6 and the steam would flow through the catalyst loading side 7-2. The flow path control valve 15 was controlled. In this state, dry distillation of coal was performed for about 22 hours, and the generated coke 3 was extruded and discharged.

During this carbonization, the gas at the outlet 7-3 of the rising pipe 7
(g) was sampled and its composition was measured by gas chromatography. A total of 10 samples were obtained about every 2 hours, and Table 1 shows the gas composition as an average value thereof. Such one cycle of dry distillation was repeated 5 times in total, and this was set as Example 1. In addition, in Table 1 described later,
The gas composition for the second time is also shown.

After replacing the metal catalyst 13 with a fresh one, the same test as in Example 1 was conducted. However, at this time, the operation of the flow path control valve 15 is controlled so that the mixed gas 6 ′ does not pass through the catalyst loading side 7-2 for 1 hour after the carbonization, and at the time when 1 hour of carbonization has elapsed. The flow path control valve 15 was reversed, and the mixed gas 6 ′ was circulated through the catalyst loading side 7-2 until the end of dry distillation. One cycle of dry distillation was repeated 5 times to obtain Example 2. In addition, the gas composition of the 5th time is shown in Table 1 mentioned later.

Also, the catalyst loading side 7-2
Dry distillation was carried out under the same conditions as in Example 1 except that the mixed gas 6 ′ was not passed through, and this was designated as Comparative Example 1. Furthermore, during the entire dry distillation period, dry distillation was carried out without performing steam supply from the dry distillation product gas reformer 12 and utilization of the metal catalyst 13, and this was set as Comparative Example 2.

The results of Examples 1 and 2 and Comparative Examples 1 and 2 described above are summarized in Table 1.

[0063]

[Table 1]

The reaction rate (%) in Table 1 means each test when the methane reduction amount (volume% ,: methane concentration of comparative example-methane concentration before test) in Example 1-1 was 100. Shows the amount of methane reduction in

From Table 1, as compared with the reaction rate of 100% in Example 1-1, the reaction rate was 4.6% only by introducing steam as in Comparative Example 1, and the reaction hardly progressed. I understand.

Further, it can be seen from Example 1 that the performance is lowered when the catalyst is repeatedly used, and the reaction rate is lowered to 22% at the fifth time. On the other hand, from Example 2,
When the metal catalyst 13 is protected from the initial carryover immediately after carbonization, the reaction rate is 98% even after repeated use 5 times.
Therefore, it is understood that the life of the metal catalyst 13 can be extended.

Further, comparing the total calorific value of the gas in Examples 1 and 2 and Comparative Examples 1 and 2 in Table 1, the methane gas and steam react with each other to generate the reformed gas. It can be seen that the amount of generated gas per unit increases and the energy of the recovered gas as a whole (total calorific value per coking coal) increases.

(Modification) In the above description, the case where the carbonization reformed gas reforming apparatus is the water addition apparatus for adding the water vapor consisting of moisture to the carbonization produced gas and the metal catalyst is taken as an example. However, the carbonization product gas reforming device in the present invention is not limited to this example, and any device that can reform the carbonization product gas into a reformed gas having higher energy than the carbonization product gas can be applied. Is.

In the above description, the case where the coke oven is the horizontal chamber type coke oven is taken as an example. However, the present invention is not limited to the horizontal chamber coke oven, and is similarly applied to coke ovens other than the horizontal chamber coke oven.

In the above description, the Ni-based metal catalyst is used as an example of the metal catalyst. However, the present invention is not limited to this Ni-based metal catalyst, and is similarly applied to metal catalysts other than Ni-based metal catalysts such as Co-based metal catalysts and Mo-based metal catalysts.

[0071]

As described above in detail, according to the present invention, the coke which can effectively recover the sensible heat of the carbonization product gas, which has been mostly discarded until now without being recovered. A furnace and its operating method could be provided.

The significance of the present invention having such an effect is extremely remarkable.

[Brief description of drawings]

FIG. 1 is an explanatory view schematically showing a longitudinal sectional structure of a horizontal chamber coke oven according to an embodiment in a furnace length direction.

FIG. 2 is an explanatory view showing a base portion of an ascending pipe of the horizontal chamber furnace type coke oven according to the embodiment.

FIG. 3 is an explanatory view schematically showing a longitudinal sectional structure of a horizontal chamber furnace type coke for producing a coke which is a blast furnace charging raw material in a furnace length direction.

[Explanation of symbols]

2 carbonization chamber 6 Carbonization product gas 7 riser 8 Main air collection 10 coke oven 12 Water addition device 13 Metal catalyst

Claims (7)

[Claims] 1. A carbonization chamber, a communication channel provided in communication with the carbonization chamber, a communication channel provided in communication with the communication channel, and generated during carbonization of coal loaded in the carbonization chamber. And a recovery passage for guiding the dry-distilled product gas to a recovery device, and further comprising a dry-distilled product gas reformer for reforming the dry-distilled product gas into a reformed gas having higher energy than the dry-distilled product gas. Coke oven characterized by. 2. A metal catalyst, which is in contact with a mixed gas of the carbonization product gas flowing above the coal and steam formed by the added water, is provided in a part of the communication channel. Coke oven described in. 3. The coke oven according to claim 2, wherein the metal catalyst is detachably provided in the communication channel. 4. The coke oven according to claim 2, wherein the metal catalyst is a Ni-based metal catalyst. 5. The reforming is performed after the carbonization product gas flowing above coal disposed inside the carbonization chamber of the coke oven is reformed into a reformed gas having higher energy than the carbonization product gas. A method for operating a coke oven, comprising recovering the reformed gas thus produced. 6. The method according to claim 5, wherein the reforming is carried out by bringing a mixed gas obtained by mixing the dry-distilled product gas and steam formed by the added water into contact with a metal catalyst. How to operate a coke oven. 7. The coke oven operating method according to claim 5, wherein the reformed gas is recovered after the carry-over caused by the coal charging into the carbonization chamber has been subsided. .