JP3899020B2 - Method for reducing sulfur compounds in gas in coke dry fire extinguishing equipment - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a technique for reducing sulfur compounds in a gas by introducing lime in a coke dry fire extinguishing equipment (hereinafter also simply referred to as CDQ).
[0002]
[Prior art]
The coke oven is an external heating furnace, which is inevitably increased in size to improve thermal efficiency, and has become a very advanced facility for energy recovery due to past energy-saving technology development. The main method of energy recovery technology is to use a coke dry fire extinguishing system, which cools the coke with a large volume of circulating gas (almost nitrogen) and generates steam with the heat obtained from the circulating gas to operate the steam turbine. And recovered as electricity.
[0003]
In such a coke dry fire extinguishing system, red hot coke discharged from the coke oven is put into a pre-chamber and the circulating gas is supplied to the cooling chamber as a cooling gas while passing through the lower cooling chamber. As described above, the sensible heat obtained from the high-temperature circulating gas discharged from the cooling chamber is exchanged by a heat exchanger such as a boiler to generate steam and operate the steam turbine to generate electric power. The two purposes of efficient recovery are achieved. And the cooling coke discharged | emitted from the said cooling chamber is charged into a blast furnace. That is, it is charged into a blast furnace and used as a fuel for heating and reducing the sintered ore.
[0004]
In such a coke dry fire extinguishing equipment, a technique for introducing air into a pre-chamber has been proposed for the purpose of stabilizing gas components or increasing the amount of sensible heat recovery by coke combustion (for example, Patent Document 1). -3)).
[0005]
In the conventional method of producing quick lime by causing thermal decomposition reaction of lime (mainly calcium carbonate, slaked lime), fuel is used in addition to decomposition of lime and generation of carbon dioxide by using fuel such as heavy oil burner. It was an inefficient, large-scale carbon dioxide generation process that also generates carbon dioxide derived from it (see, for example, Non-Patent Document 1).
[0006]
[Patent Document 1]
JP-A-6-336588
[Patent Document 2]
JP-A-7-145377
[Patent Document 3]
JP-A-7-242879
[Non-Patent Document 1]
Industrial Furnace Handbook (Edited by Japan Industrial Furnace Association), p352, 2nd edition, issued April 20, 1982
[0007]
[Problems to be solved by the invention]
What is proposed in the above Patent Documents 1 to 3 relates to a technique for stabilizing gas components by introducing air and a technique for increasing the amount of sensible heat recovery by circulating gas by burning coke by introducing air, The fact is that no attention has been paid to the minute amount of sulfur compounds produced by the combustion of coke by the air present in the pre-chamber.
[0008]
However, sulfur compounds generated by coke combustion are transported to the coke dry fire extinguishing system as a circulating gas component, and are cooled at the low temperature part (exit) of the boiler (heat exchanger), so that part of the sulfur compound is sulfuric acid. (H ₂ SO _Four ) Or sulfurous acid (H ₂ SO _Three ) Condensation. Therefore, metal corrosion due to acid condensed on the metal surface in the apparatus proceeds. Therefore, during maintenance performed with the equipment shut down periodically, repair work on the corroded metal parts found in the relevant part (mainly repair work by polishing the corroded metal surface, etc. If it gets worse, the device parts need to be replaced). Therefore, if the number of maintenance operations associated with the corrosion can be reduced, it can be expected that it can greatly contribute to the reduction of valuable time, labor, and cost for the maintenance. Nonetheless, no effective measures to prevent metal corrosion (corrosion prevention technology) at the low temperature section (exit) of the coke dry fire extinguishing equipment, especially the boiler (heat exchanger), have been proposed. Currently.
[0009]
Accordingly, an object of the present invention is to provide a method for reducing sulfur compounds in a gas in a coke dry fire extinguishing facility, which is generated by burning coke by air existing in a pre-chamber.
[0010]
[Means for Solving the Problems]
Therefore, the present inventors can obtain sufficient temperature and residence time for decomposition, and only use coke sensible heat, compared to the use of fuel such as conventional heavy oil burners even when lime is charged into the pre-chamber. Therefore, it has been found that heat sources do not contribute to the increase in carbon dioxide, and that there are advantages such as high recovery efficiency, and by utilizing the sensible heat of red hot coke, decomposition of lime and desulfurization reaction are caused. , Sulfur compounds generated by combustion (SO _X ) Can be removed and recovered from the gas, the sulfur compound can be greatly reduced, and the present invention has been completed.
[0011]
That is, this invention can be achieved by the sulfur compound reduction method in the gas in the coke dry fire extinguishing equipment of following (1)-(10).
[0012]
(1) A method for reducing sulfur compounds in a gas in a coke dry fire extinguishing facility, wherein lime is charged into the coke dry fire extinguishing facility.
[0013]
(2) The method for reducing sulfur compounds in the gas in the coke dry fire extinguishing facility according to (1), wherein the lime is put into a pre-chamber which is a charging space for red hot coke in the coke dry fire extinguishing facility.
[0014]
(3) Coke dry fire extinguishing equipment according to (1) or (2), wherein the lime is put into a bucket and / or bucket car that is a moving and charging equipment for red hot coke in a coke dry fire extinguishing equipment. Of reducing sulfur compounds in gas inside.
[0015]
(4) The coke dry fire extinguishing equipment according to any one of (1) to (3) above, wherein a part or all of the space inside the pre-chamber is an atmospheric temperature of 1000 to 1100 ° C. Of reducing sulfur compounds in gas inside.
[0016]
(5) The lime contains 10% by mass or more of lime having a particle size of 10 mm or less. The gas in the coke dry fire extinguishing facility according to any one of (1) to (4), Method for reducing sulfur compounds.
[0017]
(6) The sulfur in the gas in the coke dry fire extinguishing facility according to any one of the above (1) to (5), wherein the lime is charged in a range of 30 to 650 g per ton of coke. Compound reduction method.
[0018]
(7) The above lime, wherein the lime is charged into a pre-chamber between and / or when red hot coke is charged into a coke dry fire extinguishing apparatus that is made intermittently and / or simultaneously with red hot coke. The method for reducing sulfur compounds in the gas in the coke dry fire extinguishing facility according to any one of 1) to (6).
[0019]
(8) Any one of the above (1) to (7), wherein the lime is introduced from a coke inlet at the top of the coke dry fire extinguishing equipment and / or one or more inlets installed in the pre-chamber. The method for reducing sulfur compounds in the gas in the coke dry fire extinguishing facility according to claim 1.
[0020]
(9) Inside the coke dry fire extinguishing facility according to any one of the above (1) to (8), wherein the lime is introduced by air flow conveyance using nitrogen and / or circulating gas as a carrier gas To reduce sulfur compounds in gas.
[0021]
(10) The above-mentioned (1) to (1), wherein the lime is charged before, during and / or after loading of red hot coke on a bucket and / or bucket car intermittently made from a coke oven. 9) The method for reducing sulfur compounds in the gas in the coke dry fire extinguishing equipment according to any one of 9).
[0022]
DETAILED DESCRIPTION OF THE INVENTION
The method for reducing sulfur compounds in the gas in the coke dry fire extinguishing facility of the present invention is characterized in that lime is introduced into the coke dry fire extinguishing facility to reduce sulfur compounds in the gas.
[0023]
According to the present invention, sulfur present in coke is converted into sulfur compounds (SO _X ) And move into the gas. Also, the lime introduced into the pre-chamber (directly or indirectly via a bucket truck) is subjected to a pyrolysis reaction (CaCO) due to sensible heat of red hot coke. _Three → CaO + CO ₂ Reaction temperature; 700-900 ° C) proceeds. In addition, sulfur compounds (SO ₂ Or H ₂ (1) CaO + SO with CaO produced by pyrolysis of lime. ₂ + 1 / 2O ₂ → CaSO _Four , ▲ 2 ▼ CaO + H ₂ S → CaS + H ₂ O, CaS + 2O ₂ → CaSO _Four As a result of the progress of each reaction (the time required for the introduced lime (CaO) to pass (retain) in the temperature range of 800 to 1000 ° C. in the CDQ is about 1 hour, the reaction proceeds sufficiently). SO in the gas phase ₂ Or H ₂ S is a stone (CaSO _Four ) Is attached (immobilized) to the coke surface (solid phase). As a result, the sulfur compounds in the gas are significantly reduced (in the examples, SO in the gas is reduced). _X The concentration can be reduced by 92%), and acid corrosion in the system can be greatly suppressed (closer to a maintenance-free state). Furthermore, in the present invention, the sulfur compound in the gas is immobilized by charging lime, but the CaCO that did not react _Three , CaO can be used as a lime substitute material in the sintering process, and can exhibit a desulfurization effect in either the CDQ or the sintering process.
[0024]
Here, as lime used in the present invention, calcium carbonate (CaCO _Three ), Slaked lime (calcium hydroxide; Ca (OH) ₂ ), Or a mixture of one or more of these and quicklime (calcium oxide; CaO). Natural limestone mainly composed of calcium carbonate also falls within the category of lime as referred to in the present invention.
[0025]
Further, the particle size of the lime used in the present invention is not particularly limited, but it is desirable to contain 10% by mass or more of lime having a particle size of 10 mm or less. More specifically, lime having a particle size of 10 mm or less is in the range of 10 to 100% by mass, preferably 50 to 100% by mass, and lime having a particle size of more than 10 mm and 200 mm or less is 0 to 90% by mass, preferably 0. What is contained in the range of ˜50 mass% is desirable. This is because if large sized particles are added to the lime to be added, there is a risk that the effect of immobilizing the sulfur compound may be deteriorated because some of the lime will be subjected to a thermal decomposition reaction and a desulfurization reaction inside the CDQ. This is because it is necessary to increase the amount of lime to be added. Usually, the lime put into the pre-chamber is sufficiently advanced in about 1 hour to pass (exit) the temperature range of 700 ° C. or higher necessary for the thermal decomposition reaction and desulfurization reaction. It can be said that a suitable particle size (particle size distribution) capable of satisfying the above is the range specified above. That is, the particle size of the lime to be introduced is too large, and a thermal decomposition reaction (part of the lime is CO 2 from the particle surface toward the center). ₂ As a result of gasification, the pyrolysis part becomes brittle and becomes finer. ), The thermal decomposition reaction by using coke sensible heat becomes difficult, and if there is an unreacted part in the part of the particles, it becomes difficult to proceed with the circulating gas. This is because the reaction with the sulfur compound in the gas does not proceed sufficiently even by contact, and it becomes difficult to obtain the effect of reducing the sulfur compound by immobilization.
[0026]
However, in the present invention, lime having a particle diameter exceeding 200 mm may be included. Such large lime is refined to an appropriate size by friction applied during the passage through the CDQ, increased weight, etc., and enters the particle size distribution range defined above. This is because even the particles are sufficiently finely divided before passing through the high temperature range and are subjected to thermal decomposition and desulfurization reaction, which can contribute to the achievement of the object of the present invention. In addition, even if the amount of lime is increased by assuming that a part of the lime is not pyrolyzed, the coke after passing through the CDQ has an average particle size of about 45 to 55 mm and is sized. Therefore, if lumps are crushed with a coke cutter and refined to the extent that they are sent to the sintering process together with the powder coke in the classification process (nodal 25 to 30 mm), the lime in the sintering process There is no problem because it can be used effectively as an alternative material.
[0027]
The reason why 10% by mass or more, preferably 50 to 100% by mass (total amount) of lime having a particle size of 10 mm or less is usually included because the particle size of lime or the like in sintering is 10 mm or less. This is because it is convenient in handling that the size is equal to or less than the size of. From the above, in the present invention, for example, the particle size of lime or the like in sintering is not 10 mm or less, and for example, a particle having a diameter of 15 mm or less may be used. In a broad sense, the particle size of the lime used in the sintering is less than or equal to the particle size of the lime used (for example, if the lime used in the sintering is 10 mm or less, the lime used in the sintering is 15 mm or less. If the particle size of the lime is in the range of 10 to 100% by mass, preferably 50 to 100% by mass, the particle size of the lime is 200 mm or less. It is desirable that the lime is contained in the range of 0 to 90 mass%, preferably 0 to 50 mass%.
[0028]
The particle size of lime here can be defined as follows.
[0029]
The size of the sieve opening when the lime, which has been reduced in particle size by a crusher, crusher, etc., is separated on the sieve and below the sieve with a screen or other sieving equipment (the "opening" of the sieve such as the screen) 2 (B) to 2 (E) regarding the form, however, it is not limited to these forms, and in other forms as in FIG. The arrow range in the middle) may be the opening size.) Is defined as the particle size of lime in the present invention.
[0030]
The pulverizer, crusher, etc. are usually finely sized by impact, friction, cutting or the like. The representative of the impact system is a hammer mill or ball mill, the representative of the friction system is a grind mill, and the representative of the cutting system is a cutter type. In the case of lime, as in the case of pulverization of coal and foods, there are many spheres and cubes, and the concept of particle size = particle size is relatively clear. Therefore, it is easy to use concepts such as the representative diameter and the average diameter, but in the present invention, evaluation and definition are performed by sieving equipment used in most practical crushing processes, particularly through the passage of openings such as screens. The screen used for evaluation and definition in the present invention is not the screen attached to the crusher shown in FIG. 2, but, for example, a screen when the crushed material that has passed through the crusher screen is separately sieved. By suppressing the vibration in the direction perpendicular to the screen as much as possible (vibrating in the horizontal direction when the inclination is 0), the size in the major axis direction is used as the passage diameter (where the crushed material is separately added). The form of the “opening” of the screen when sieving is the same as the form of the “opening” of the screen attached to the crusher etc. shown in FIGS. 2 (B) to (E). See this.)
[0031]
In addition, in order to obtain the lime reduced in particle size by a pulverizer, a crusher, etc., for example, as shown in FIG. 2 (A), a lime raw material (for example, limestone etc.) 301 is crushed (in the figure, An example of a hammer-type crusher is shown.) The material is charged from the charging port 302 as shown by the thick arrow in the figure. When the lime is rotated in the rotation direction 305 of the thin line arrow by the rotating body 303 in the pulverizer, when the lime is collided with one or more hammers (parts) 304 installed in the pulverizer or between the hammer and the rotating body 303 When passing through the gap, the lime is crushed to reduce the particle size. The lime having a small particle size comes out to the outside due to centrifugal force during rotation. Therefore, the size of the appropriate opening 308 (see FIGS. 2B to 2E) on the outer surface side of the rotation path of the pulverizer (the arrow in the enlarged view of FIGS. 2B to 2E). By installing a screen 307 having a range (length) corresponding to the size of the apertures) and a shape, lime (lime) reduced to a size (particle size) that passes through the apertures Only the crushed material 306) is taken out through the screen 307.
[0032]
Hereinafter, a specific example of sieving will be described in detail.
[0033]
Hammer type crusher: 100 kg / h crushing amount, 200 rpm, hammer width 10 mm, number of hammers 12, outlet screen size □ 50 mm (opening, square), vibration sieve: □ 10 mm screen (opening, square ), When sieving at a tilt angle of 5 °, a vibration amplitude of 10 mm horizontally and at right angles to the tilt direction, and the number of vibrations of 30 times / minute, the undersieving is 10, 9, 10% by mass (3 trials). It shall contain 10% by mass of lime having a particle size of 10 mm or less (average rounded off). Similarly, if the crusher exit side screen size is □ 30 mm and the vibration sieve screen is □ 10 mm, if the screen size is 20, 20, 20% by mass, it shall contain 20% by mass of lime having a particle size of 10 mm or less, If the crusher-side screen size is □ 10 mm and the vibration sieve screen is □ 10 mm, if the screen size is 80, 79, or 79% by mass, it will contain 80% by mass of lime having a particle size of 10 mm or less.
[0034]
The above figures are for the crusher A. In this method, the crusher B (50 kg / h crush, 200 rpm, hammer width 10 mm, number of hammers 12, slightly smaller than crusher A) data is also used. The reliability of data may be improved.
[0035]
As described above, the ratio (content) of “lime with a particle size of 10 mm or less” in the present invention is the sieving mass% based on the sieving screen size, and in order to change the sieving mass%, The screen size of the crusher screen has been changed. As a method of changing the particle size, in addition to the size of the screen of the crusher screen of the specific example shown above, the shape of the hammer, the width, the number of rotations, the screen position, etc. Any method can be used, but the numerical value can be defined by sieving with a sieving screen. In addition, the sieve can be changed depending on the vibration type and vibration method (impact by cam, circle / ellipticalization in the sieving direction, number of vibrations, etc.), screen eye shape (rectangle, circle, ellipse, etc.) It can be defined as a common numerical value by sieving by the vibration method in the specific example shown above.
[0036]
Next, the input amount of the coal is not particularly limited, and the amount of sulfur compound in the gas can be reduced in proportion to the input amount of lime. Corresponding to the above, it is desirable to add lime in the range of 50 to 500 g per ton of coke. When the input amount of lime is less than 50 g per ton of coke, there is a possibility that the removal of sulfur compounds may be insufficient. On the other hand, when the input amount of the lime exceeds 500 g per ton of coke, the sulfur compound is sufficiently removed and recovered, and a further removal and recovery effect cannot be expected. However, there is no particular problem as long as the amount of unreacted lime remaining by being charged in excess of the upper limit is within the range that can be used as the lime material used in the sintering process as described above.
[0037]
This is the amount of coke that is burned by the amount of air per ton of coke (the amount of air that is introduced for other purposes in addition to the amount of air that enters from the opening, etc. when the coke is charged), and thus coke. This is because the amount (concentration) of sulfur compounds generated by combustion differs.
[0038]
For example, 5-20Nm per ton of coke ^Three If the air enters the pre-chamber, 1.13 to 4.5 kg of coke will burn. By burning the coke, 4.5-18 g of sulfur in the coke moves into the gas (gas phase), and 3.2-13 liters of SO _X (This is based on the results of demonstration experiments using actual equipment, _X It corresponds to a concentration of 13 to 52 ppm. ).
[0039]
Here, (1) When it is assumed that the fluidized state of lime and its thermal decomposition product (CaO) in coke by circulating gas is in a fluidized bed state, Ca / S = 2 or more (that is, circulation) Efficient desulfurization is possible with the Ca content of the input lime with respect to the sulfur (S) content in the gas being at least twice (see FIG. 3). Therefore, the lime per ton of coke is CaCO. _Three 30 to 130 g (fluidized bed) in terms of conversion is an appropriate amount.
[0040]
(2) Assuming that the fluidized state of the lime in the coke by the circulating gas and its thermal decomposition product (CaO) is in a packed bed state, it is considered that the contact opportunity is insufficient, so Ca / S = 10 or more (see FIG. 3). Therefore, the lime per ton of coke is CaCO. _Three An appropriate amount is 160 to 650 g (filled layer) in terms of conversion.
[0041]
Since the coke in the CDQ of this system is a moving bed, it can be in an intermediate contact state between the above (1) and (2), so it can be said that lime should be charged in the range of 30 to 650 g per ton of coke. However, it is desirable to determine the optimum input amount of lime under the moving bed with respect to the air amount change, preferably by conducting a preliminary experiment with an actual machine.
[0042]
In addition to coke, for example, the applicant has already proposed a technology for introducing biomass into a pre-chamber to perform alternative combustion. When using other alternative fuels such as biomass, in addition to changing the air amount, It can be said that the amount of sulfur compound generated in the gas should be determined in consideration of changes in the amount of input such as, etc., and the amount of lime input should be determined, but preferably, by conducting a demonstration experiment with an actual machine, It is desirable to determine the optimum input amount of lime for changes in the air amount and changes in the input amount of biomass and the like.
[0043]
The lime is not necessarily charged into the prechamber. In the present invention, lime, in particular limestone, calcium carbonate, slaked lime, etc., is thermally decomposed (the reaction proceeds at 700 ° C. or higher) to be converted into calcium oxide (CaO), and this and the sulfur compound in the CDQ gas. The main purpose is to fix the sulfur content by reaction. Among these, in order to advance the thermal decomposition reaction of lime, in addition to utilizing the sensible heat of red hot coke (about 1000 ° C) charged into the pre-chamber, it is pushed out of the coke oven into a bucket / bucket car. This is because the sensible heat of red hot coke can also be used. That is, the sensible heat of the red coke before being put into the pre-chamber is not used, and the sensible heat of the red coke is dissipated to the atmosphere while it is loaded on a bucket / bucket car and moved to the CDQ (about 5 minutes). However, the sensible heat of reddish coke that has been dissipated into the atmosphere can be used effectively for preheating (thermal decomposition) of lime by mixing lime input.
[0044]
In order to clarify the above requirements of the present invention, a description will be given with reference to the drawings. FIG. 1 is a schematic diagram schematically showing a typical CDQ that can be used in the present invention.
[0045]
First, an example of normal operation of CDQ is shown based on FIG. About 1000 ° C. red hot coke 151 produced in the coke oven 201 is extruded to a bucket / bucket vehicle (hereinafter simply referred to as a bucket vehicle 102) by an extruder (not shown) and conveyed to the CDQ 101. The upper lid 103 at the top is opened and the prechamber (space portion) 105 is charged. The portion that has been blocked by the upper lid 103 is the upper coke inlet 104. After the red hot coke 151 is charged, the upper lid 103 is closed, and the amount of air that naturally flows in is limited. In addition, the bucket car 102 and the like which have been emptied are sent to the coke oven 201 to load the next lot of red hot coke.
[0046]
The hot red hot coke 151 that has entered the pre-chamber 105 is cooled to about 200 ° C. while being gradually cooled by the circulating gas 107 while passing through the lower cooling chamber 106, and the outlet 108 at the lower portion of the cooling chamber 106 is cooled. Is taken out of. In the figure, the red hot coke put into the CDQ is represented by a thick arrow with a reference numeral 151. The coke in the CDQ is denoted by reference numeral 153 and the moving direction is indicated by a thick arrow (no reference numeral). In addition, coke taken out from the CDQ (in the present invention, lime and lime and the like, which are fixed by reaction with sulfur content, are also included) are represented by thick arrows with a reference numeral 155.
[0047]
On the other hand, for example, heat is recovered in a heat exchanger (boiler) 109 by a circulating gas 107 mainly composed of nitrogen or the like, and power is generated by moving the steam turbine 113 with the steam 111 generated by the heat. At this time, residual volatile matter and powdered coke (and, in the present invention, lime powder and a part of stone powder that is fixed by reaction with sulfur and decomposed lime) reach the heat exchanger 109 and coke. In order to prevent the problem of heat transfer inhibition, air (outside air) 117 is added and completely burned in the vicinity of the ring duct 115, which is a gas discharge port after exiting the pre-chamber 105. Furthermore, a dust catcher 123 is provided on the circulation path 121 from the ring duct 115 to the heat exchanger 109, and the above-mentioned powder coke (in the present invention, lime powder and lime are decomposed and immobilized by reaction with sulfur content). It is desirable to make effective use in the next sintering process. The circulating gas 107 recovered by the heat exchanger (boiler) 109 is adjusted to an appropriate pressure by the circulating gas blower 125 provided on the circulation path 121 and then introduced into the cooling chamber 106 from the circulating gas inlet 127. do it. Further, in order to keep the circulation gas supply flow rate into the CDQ 101 constant, for example, a diffusion for releasing a part of the circulation gas 107 from the circulation path 121 between the circulation gas blower 125 and the circulation gas inlet 127. A gas extraction path 129 may be provided and diffused through the path 129. Therefore, it goes without saying that a flow rate adjusting valve, a flow meter, an exhaust gas purifying device (all not shown and omitted) and the like may be provided on the path 129 as necessary. In the figure, the movement of coke is indicated by a thick line, and the movement of gas is indicated by a thin line.
[0048]
The method for reducing sulfur compounds in the gas in the CDQ according to the present invention will be further described with reference to FIG.
[0049]
In the present invention, as shown in FIG. 1, (A) lime 181a may be (directly) charged into a pre-chamber 105 that is a charging space for red hot coke 151 in a coke dry fire extinguishing equipment (CDQ) 101. (B) The lime 181b may be charged into a bucket and / or bucket vehicle 103, which is a moving and charging facility for the red-hot coke 151 in the coke dry fire extinguishing facility (CDQ) 101, or (A) and ( B) may be used in both cases.
[0050]
Hereinafter, the above-described (A) charging mode and (B) charging mode will be described separately.
[0051]
<In the case of the charging mode (A)>
Next, the case where lime is charged according to the charging mode (A) of the present invention will be described with reference to FIG.
[0052]
(A-1) Since charging of the red hot coke 151 is batch charging performed at intervals of several minutes to several tens of minutes, the lime charging mode of the present invention is red hot from the viewpoint of ease of charging timing. It can be said that the lime 181a may be charged into the pre-chamber 105 via the appropriate charging device 183 between the charging of the coke 151, but is preferably charged immediately after the red hot coke 151 is charged. Is. As described above, it is sufficient that the lime 181a charged can be subjected to a pyrolysis reaction and a desulfurization reaction using the sensible heat of red hot coke. Is in a temperature atmosphere of 1000 to 1100 ° C., and thus does not have to be uniformly mixed with coke. Furthermore, since the residence time in the temperature range of 800 to 1000 ° C. is about 1 hour while passing through the inside of CDQ101, sufficient reaction proceeds while passing through this region. It can be said that it is not restricted. However, if lime is introduced into the pre-chamber 105 immediately after the red hot coke 151 is introduced, the amount of sulfur compounds in the gas that can be immobilized before being sucked into the circulation path can be increased. It is possible to further reduce the condensation of sulfur at the boiler outlet and the like, and to suppress the degree of acid corrosion in the system to a lighter level.
[0053]
Here, the period between the charging of the red hot coke 151 is the time when the red hot coke 151 of the next lot starts from the time when the coke disappears in the bucket car 102 or the like when the red hot coke of a certain lot is charged into the pre-chamber 105. This refers to the period immediately before the opening of the lower part of the bucket wheel 102 or the like when the chamber 105 is loaded.
[0054]
When lime is charged between red hot coke, the charged coke layer and the charged lime layer are alternately lowered in the CDQ while sandwiched, and from the lower outlet 108 Before being discharged, the lime layer undergoes thermal decomposition reaction and desulfurization reaction, is fixed as stone and is discharged in the form of adhering to the nearby granulated coke surface.
[0055]
(A-2) As another charging mode of the biomass of the present invention, the lime 181a may be charged into the prechamber 105 via the charging device 183 (or the charging device 163) simultaneously with the charging of the red hot coke 151. . Since this is a form in which lime is mixed and dispersed in the red hot coke layer by simultaneous charging, it can be said that it is one of the preferable aspects in that it is easy to receive the sensible heat of the red hot coke surrounding the lime and the thermal decomposition is promoted. The pyrolyzed lime has good contact efficiency with the sulfur compound in the circulating gas passing through the gaps between the cokes, and can efficiently fix the sulfur content.
[0056]
Here, “to put in at the same time” means to start and end the charging of the lime 181a between the time when the red hot coke 151 of a certain lot starts dropping from the bucket truck 102 or the like and the time when dropping ends. , By introducing at the same time, by utilizing the diffusion of coke and mixing with coke on average, promote contact opportunities between lime and coke (promote thermal decomposition reaction by improving heat transfer efficiency of coke sensible heat) Further, it is possible to promote contact with the circulating gas (promoting the fixation of sulfur by improving the reaction efficiency between the sulfur compound in the gas and CaO).
[0057]
When the coke is charged at the same time as the red hot coke is added, the mixed layer of red hot coke 151 and lime 181a simultaneously added is stacked for each lot, descends in the CDQ, and is discharged from the lower outlet 108. Is subjected to thermal decomposition reaction and desulfurization reaction, and is fixed as stone and discharged in the form of adhering to the surface of coking coke nearby.
[0058]
(A-3) As other forms of lime of the present invention, the forms of lime input of (A-1) and (A-2) may be combined. That is, lime may be charged into the pre-chamber between charging of red hot coke and simultaneously with charging of red hot coke. This is useful in that a necessary amount of lime can be charged into the coke layer or the coke surface layer according to the purpose of use.
[0059]
In the methods (A-1) to (A-3) described above, lime 181a corresponding to the amount of red hot coke for each charged lot is introduced between red hot coke 151 and / or simultaneously with red hot coke 151. There is no particular limitation such that the entire amount may be charged at a time, may be continuously charged within a certain period, or may be intermittently charged. In the case of continuously or intermittently charging within a certain period, the charging amount may be made constant, or the charging amount may be charged so as to change with time.
[0060]
Further, in the above (A), the lime 181a is particularly limited, for example, it may be charged from the coke inlet 104 above the CDQ 101 and / or one or more lime inlets 185 installed in the pre-chamber 105. It is not a thing.
[0061]
That is, the lime 181a is introduced into the pre-chamber 105 from the coke inlet 104, or from one or more lime inlets 185 and biomass inlets 165 newly installed in the pre-chamber 105. In some cases, these may be used in combination.
[0062]
Here, the number of lime inlets 185 installed in the pre-chamber 105 is not particularly limited, but is diffused evenly in the pre-chamber 105 and deposited in the pre-chamber 105 as uniformly as possible. Since it is desirable to increase the contact efficiency (and thus the reaction efficiency) with the sulfur compound in the circulating gas, the inner circumference of the pre-chamber 105 is at two or more, preferably three or more, more preferably four to four at equal intervals. It is desirable to provide about 16 locations. However, there is no problem with 17 or more, but the apparatus configuration and control become complicated, so 17 or less is sufficient from the viewpoint of simplification. Also, when providing a plurality of lime inlets 185, they are installed on the same circumference (that is, at the same height) on the inner peripheral surface so that the input amount or flow rate of lime 181a from each input port, the amount of carrier gas or the flow rate It is easy to control or determine the charging flow rate, charging angle, and the like.
[0063]
In addition, when a plurality of input ports 185 are provided, the lime 181a may be input by synchronizing the input amount from each input port, the input timing, the input flow rate, etc. (same). The amount of lime input, the input timing, the input flow rate, etc. may be changed for each input port. In any case, the sensible heat of coke can be effectively used, so long as it can efficiently achieve the purpose of fixing and reducing sulfur compounds in the gas phase by thermal decomposition and desulfurization of lime. It is not something. For example, locally, there is a shortage of lime by changing the input amount, input timing, and input flow rate for each input port so that the distribution of lime does not vary between the central part and the side part of the prechamber. And it is desirable to adjust so that lime may be injected | thrown-in uniformly throughout so that reaction efficiency with the sulfur compound in circulating gas may not fall. Furthermore, it goes without saying that the type of lime and the method of blending may be changed depending on the timing of input, if necessary.
[0064]
Further, as shown in FIG. 1, the installation height of the lime charging port 185 is preferably provided in a portion where the pre-chamber 105 at the upper part of the ring duct 115 is expanded in diameter toward the lower part. The upper lid 103 may be provided.
[0065]
In addition, with respect to the input amount of lime from each input port, the input flow velocity (flow rate), the input angle, and the like in the method (A), the total input amount of lime, the input timing, the input position (upper or inner periphery) Should be determined as appropriate according to the number of inputs, etc., so that optimal conditions can be determined in advance by conducting preliminary experiments or simulations with a computer or the like so that the purpose of lime input can be achieved. Good. More preferably, the final adjustment is performed by conducting a demonstration experiment using an actual machine. In particular, the lime input amount, input flow rate (flow rate), and input angle from each of these input ports are adjusted so that the lime is uniformly distributed in the pre-chamber by, for example, changing the carrier gas amount described later. Is desirable.
[0066]
In the method (A), when lime 181a is charged from the coke charging port 104 or the coke upper lid 103, depending on the charging time, when performing between the charging of the red hot coke 151, The coke charging port 104 does not need to be fully opened, and may be opened slightly to the extent that lime can be charged. Further, a separate inlet (not shown) may be provided for charging lime in a part of the upper lid 103, and it may be introduced (dropped) through the inlet. Therefore, a plurality of lime charging ports can be provided even when lime is charged from the coke charging port. However, since the apparatus configuration may be complicated, it is easy to open the upper lid 103 even when lime is added.
[0067]
In the method (A), when the lime 181a is introduced from the upper coke inlet 104 or the lime inlet 185 provided on the inner peripheral surface of the pre-chamber 105, the lime 181a is evenly diffused (distributed) in the pre-chamber 105. These inlets can be easily expanded by expanding their diameters or by providing a movable mechanism or nozzle at the tip of the inlet. It is more desirable to diffuse. This is because the ambient temperature at the inlet becomes high, and even if an existing drive device or mechanism can be used, a highly heat-resistant member is required for the member to be used. is there.
[0068]
In addition, when the lime 181a is charged at the same time when the red hot coke 151 of (A-2) is charged, the lime 181a is dropped even if it is charged from the lime charging port 185 provided on the inner peripheral surface of the pre-chamber 105 toward the central portion. In this case, it is more suitable to drop the lime 181a together with the red hot coke 151 from the coke inlet 104 because it is difficult to uniformly distribute the lime.
[0069]
As a method for charging (conveying) lime in the above method (A), at each charging position, an appropriate charging device 183, for example, a dropping device such as a screw feeder, a table feeder or the like, is dropped by its own weight, and nitrogen and There is a method in which (or a part of) the circulating gas is used as a carrier gas and is introduced (injected) by airflow conveyance.
[0070]
Of the latter methods, in which nitrogen and / or (a part of) the circulating gas is used as a carrier gas and introduced (injected) by airflow transportation, when the circulation gas is used, the gas temperature is as shown in FIG. At the time of lowering, for example, a part of the gas after the circulating gas blower 125 for circulation is branched, and is drawn by a pipe 186 to a cutting device such as a table feeder, for example, a table feeder, from the cutting device to the lime charging port 185 The circulating gas is used in combination with the cutting equipment so that the circulating gas can be supplied into the lime conveying pipe 187 as the conveying gas. In the case of nitrogen gas as well, nitrogen is drawn from the outside through piping 188 to a cutting device 186, for example, a cutting facility such as a table feeder, and the nitrogen gas is similarly introduced into the lime conveying piping 187 from the cutting facility to the lime charging port 185. Used in combination with cutting equipment so that it can be supplied as carrier gas. Furthermore, when both nitrogen gas and circulating gas are used as the carrier gas, both the above-described piping paths may be provided. In this way, if necessary, nitrogen gas and circulating gas can be used at the same time, or the opening and closing of each piping path can be switched so that they can be used alternately. Supply becomes possible.
[0071]
In the present invention, what can be used as the carrier gas should not be limited to the nitrogen gas and the circulation gas described above, but inert gas (such as argon gas), air (especially other than natural inflow) (Alternatively, some of the air that is actively input for other purposes may be used), various oxygen gas produced in steelmaking facilities, such as coke oven gas, blast furnace gas, converter gas, etc. What can be utilized as etc. can be used conveniently.
[0072]
The superiority of the air current transport is that the dispersion range can be expanded with a smaller number of input ports, and therefore the uniformity of the layer thickness is increased compared to the case of falling by its own weight (in the case of coke input, the dispersibility is improved). Further, by using the circulating gas 107 as the carrier gas, it is possible to minimize the cost disadvantage of using nitrogen gas.
[0073]
Moreover, the method of dropping by its own weight is that no carrier gas is required and the running cost can be suppressed. In particular, when lime is charged from the coke charging port 104, the gas in the pre-chamber 105 is moderately dispersed because of thermal convection even when falling due to its own weight, which is preferable.
[0074]
<About the method (B)>
First, the bucket and the bucket car are distinguished as follows. The bucket refers to a red hot coke transfer container, and the bucket vehicle includes an appropriate carriage (with wheels or the like) for easy transportation as shown in FIG. It should be noted that the present invention should not be limited to these, and it is needless to say that other movement and input equipment can be used.
[0075]
Further, if there is no misunderstanding regarding the method (B), the sensible heat of red hot coke can be used as described above for the bucket and / or bucket car 102 which is the lime movement and charging facility. The red hot coke 151 needs to be loaded either before, simultaneously with and / or after the charging of the lime 181b. Therefore, the bucket and / or bucket wheel 102 is transported to the pre-chamber 105 (specifically, above the coke inlet 104) of the CDQ 101 in a state where the red hot coke 151 and the lime 181b are loaded. Therefore, only the lime 181b may be put into the dedicated bucket and / or bucket car 102 and transported to the pre-chamber 105, and in that case, it is substantially within the category of the method (A). It can be said that it is included. In addition, the method of “putting lime into the coke dry fire extinguishing equipment” includes the above-described charging modes (A) and / or (B). This is because the bucket and / or bucket vehicle 102 can also be regarded as an incidental facility of the CDQ 101. Even if the bucket and / or bucket vehicle is not included in the CDQ 101, the charging mode of (B) “loading lime into the bucket and / or bucket vehicle” is thereafter in the bucket and / or bucket vehicle 102. As a result, it is necessary to put the red hot coke 151 and lime 181b into the pre-chamber 105 of the CDQ101. As a result, the "lime 181b (using the bucket and / or bucket car 102) is put into the CDQ101. Therefore, the charging mode of (B) is also included as one of the methods of “loading lime into the coke dry fire extinguishing equipment”.
[0076]
In addition, as described above, the timing of charging lime into the bucket and / or bucket car (also simply referred to as a bucket car) is not particularly limited, and red-hot coke 151 from the coke oven 201 to the bucket car 102 or the like is not limited. May be performed either before, simultaneously with loading and / or after loading. This is because lime can be preheated by effectively utilizing the sensible heat of coke.
[0077]
{Circle around (1)} Before loading the red hot coke 151, the lime 181b is put into the bucket car 102 or the like in advance. For example, from the relationship between the arrangement of the lime charging device to the bucket car 102 and the ease of charging, the lime charging device is in the middle of returning the red bucket coke 151 to the coke oven 102 after charging the red hot coke 151 into the CDQ 101. (In the same manner as described in the charging mode (A) above, an appropriate charging device 183, for example, a cutting device such as a screw feeder or a table feeder can be used, and a rotary feeder or the like may be used. ), And the lime 181b is thrown into the empty bucket truck 102 or the like by a method of dropping by its own weight from the lime throwing device or a method of blowing (blowing) air or the like by using air or the like as a carrier gas. Thereafter, the red hot coke 151 may be pushed out and loaded.
[0078]
(2) The lime 181b is put into the bucket car 102 loaded with the red hot coke 151. For example, after the red hot coke 151 is pushed out of the coke oven 201 by an extruder and loaded on the bucket truck 102, the bucket truck 102 is moved to just below the lime inlet (not shown) of the lime charging apparatus, and the lime is charged. In the same manner as described in the charging mode of the device (A), a suitable charging device 183, for example, a cutting device such as a screw feeder or a table feeder can be used, and a rotary feeder or the like may be used. ) 181b, and the lime 181b is thrown (dropped) onto the loaded red coke by a method of dropping by its own weight or a method of blowing (blowing) by air flow using air or the like as a carrier gas. You may do it. Both are advantageous in that the operation is simple and the lime charging apparatus does not interfere with other coke extruders and CDQ equipment.
[0079]
In the above (1), it can be transported to the CDQ 101 without taking extra time after the red hot coke 151 is loaded on the bucket car 102 or the like. In (2) above, the surface of the red hot coke 151 loaded on the bucket wheel 102 or the like can be covered with lime 181b, the thermal decomposition of the lime 181b can be promoted while suppressing the sensible heat of the red hot coke 151 to the atmosphere, and air (outside air) ) And the red hot coke 151 can be cut off, and it is possible to effectively prevent the red hot coke 151 from burning during conveyance.
[0080]
Further, in the present invention, the charging modes (A) and (B) can be combined. That is, in the charging mode of (B), only the amount of lime input sufficient to promote the thermal decomposition of lime 181b while suppressing the sensible heat of reddish coke 151 sensible heat by the above (2) is added. It can be said that it is desirable to input the lime input amount remaining depending on the input form so as to be mixed and dispersed evenly in the red hot coke as much as possible.
[0081]
Further, when the lime is finally charged into the pre-chamber 105 according to any of the above-described charging forms (A) and / or (B), a part or all of the internal space of the pre-chamber 105 is 1000 It is desirable that the ambient temperature is ˜1100 ° C. This uses coke sensible heat for the reaction, but by increasing the reaction temperature (= atmosphere temperature in the pre-chamber internal space), lime pyrolysis reaction, pyrolysis product (CaO) and gas Sulfur content is fixed in the form of stone-cow by reaction with sulfur compounds in it, and removed from the gas and recovered (attached to the coke surface, which is a solid layer), but the reaction rate at this time becomes faster and desulfurization This is advantageous in that the effect is high. In addition, CaSO fixed and adhered to the coke surface _Four The powder is unreacted CaCO _Three After being taken out with the coke 155 cooled from the outlet 108 at the bottom of the CDQ together with CaO, etc., the large mass is crushed with a coke cutter, classified, and then subjected to the sintering process, which is the next process, together with the powder coke under the sieve. Sent. The sieved coke on the sieve is supplied to the blast furnace. Here, usually lime is added to iron ore together with powdered coke and sintered, and CaO (generally limestone powder) is previously added to the sintered ore (especially so as not to add a solvent agent to the blast furnace). In the present invention, the CaCO contained in the coke breeze is produced. _Three The CaO powder can be effectively used as a lime substitute material as it is, and is extremely efficient in that it has an effect of reducing lime in the sintering process. CaSO in either CDQ or sintering process _Four Even so, it is effectively used as a desulfurizing agent in the iron making process.
[0082]
When the atmospheric temperature of the space inside the pre-chamber is less than 1000 ° C., CaCO by thermal decomposition _Three → CaO + CO ₂ The reaction hardly occurs (decomposes at 900 ° C. or more), and the desulfurization reaction efficiency cannot be increased, so that the sulfur compound removal rate (desulfurization rate) may not be increased. On the other hand, when the temperature exceeds 1100 ° C., the cooling efficiency of the CDQ is lowered due to an increase in heat loss such as dissipated heat, so that the overall thermal efficiency is lowered.
[0083]
Here, the reason why the space inside the pre-chamber is part or all is that the entire pre-chamber interior does not have a uniform temperature distribution, and there is no particular problem even if the temperature is locally outside the temperature range.
[0084]
【Example】
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, it cannot be overemphasized that this invention should not be restrict | limited to these.
[0085]
Comparative Example 1 (Example where lime is not charged)
First, about 5 Nm per ton of red hot coke ^Three The normal operation was performed using the CDQ shown in FIG. The amount of air that naturally flows when the top lid 103 is opened when red coke is charged is 5 Nm. ^Three (This point was assumed by estimating an almost accurate natural inflow from the actual CDQ operation results.) Moreover, the sulfur content in the coke used in this comparative example was 0.4 mass% (dry), and the volatile substance (VM) was 3%. Moreover, the space part inside a pre chamber was the atmospheric temperature of 1000-1100 degreeC during operation. This ambient temperature was measured by installing a temperature sensor 191 at the position shown in FIG. Moreover, the particle size of the charging coal of the coke oven 201 was 10 mm or less.
[0086]
Introduced air 5Nm ^Three Oxygen gas (O ₂ ) The amount is 1.05Nm ^Three It burns with red hot coke (1.13 kg), and 4.5 g of sulfur (S) is transferred to gas. Thus, 3.2 Nl of SO _X Will occur. This is the SO gas in the emitted gas that is emitted through the emission gas extraction path 129 of FIG. _X Measured as concentration. As a result, SO in the emitted gas when lime is not input. _X The amount is 13 ppm (SO in the gas released during CDQ operation) _X Average concentration).
[0087]
Example 1 (Lime input example)
On the other hand, as in Comparative Example 1, approximately 5 Nm per ton of red hot coke. ^Three Of air entered the prechamber. Further, from the four lime inlets 185 installed at equal intervals around the pre-chamber 105 in FIG. Using air as a carrier gas and blowing in by airflow conveyance (specifically, by adjusting (fluctuating) the flow rate of lime and carrier gas from the cutting equipment, the same amount of lime from each input port 185 at the same time. And adjusted so that a uniform lime layer is formed on the surface of the coke.) 300 g per ton of red hot coke between the input of red hot coke 151 to the CDQ101 intermittently. Except that lime was added, a normal operation was performed using the CDQ shown in FIG. In addition, the sulfur content in the coke used in the present Example was 0.4 mass% (dry), and the volatile substance (VM) was 3%. In addition, the lime used in this example is the total amount of calcium carbonate (CaCO _Three ) Was used. Further, in this example, since the coal having a particle size of 10 mm or less was used for the charging coal of the coke oven 201, the particle size of lime used in this example was lime having a particle size of 10 mm or less. Containing 10% by mass. Specifically, as shown in FIG. 2, hammer type crusher: 100 kg / h crushing amount, 200 rpm, hammer width 10 mm, number of hammers 12, outlet screen size □ 50 mm (opening, square) : □ 10 mm screen (opening, square; using the screen of FIG. 2B), the result of sieving at a tilt of 5 °, a horizontal and vertical vibration amplitude of 10 mm, and a vibration frequency of 30 times / minute, Since the sieving was 10, 9, and 10% by mass (3 trials), these were used in this example assuming that the lime having a particle size of 10 mm or less was 10% by mass.
[0088]
In this example, 300 g of lime (CaCO) per ton of red hot coke is used. _Three ) And operating the CDQ, the SO in the emitted gas is emitted through the emission gas extraction path 129 of FIG. _X Concentration was measured. As a result, SO in the emitted gas _X Amount of 1 ppm (SO in gas released during CDQ operation) _X It was confirmed that the concentration was reduced to an average value. From this, SO _X It was confirmed that the removal / recovery rate (desulfurization rate) by immobilization of the product reached 92%.
[0089]
As a result, sulfur compounds are H on the outer surface of the heat exchange pipe (water / steam circulation pipe) inside the boiler 109 and the outlet of the boiler. ₂ SO _Four Or H ₂ SO _Three The problem due to acid corrosion of the metal surface due to condensation in the form of can be greatly reduced, and from the state of such condensation, Example 1 relative to Comparative Example 1 was much better.
[0090]
Example 2
300 g of lime 181b per ton of red hot coke (the same lime used in Example 1 was used) was put into the bucket wheel 103 loaded with red hot coke 151. In this case, the thermal decomposition reaction (CaCO _Three → CaO + CO ₂ ) Occurs, and the amount of steam that is considered to correspond to the heat of decomposition increases (0.5 t / h). 7.5% from the amount of heat decomposed before CDQ101 {steam increase = (0.64-0.635) / (0.702-0.635) x 100} and was conventionally dissipated in the atmosphere. The sensible heat of reddish coke could be recovered as the heat of decomposition of lime.
[0091]
【The invention's effect】
According to the present invention, sulfur compounds in the gas in the CDQ can be reduced. Specifically, 5Nm per ton of coke ^Three In the case where the air (air that naturally entered when coke is added, etc.) enters the pre-chamber, the sulfur compound SO _X The amount is reduced by about 92% from 13 ppm to 1 ppm. For this reason, the number of times of maintenance associated with acid corrosion has been reduced to at least once every 3 years, but it can be reduced to at least once every 5 years. Therefore, valuable time, labor, and cost required for repairing or repairing the corroded portion can be reduced. It can be greatly reduced. Also, in the past, due to polishing by refurbishment, the metal corrosion part would fall below the design allowable thickness earlier than expected, so replacement of parts including that part was necessary, but by adopting the present invention The life of the device can be greatly extended. Also, the emitted SO _X Since the amount can be greatly reduced, the running cost of the emission gas purifier installed in the emission path can be greatly reduced.
[0092]
Also, the coke cooled by CDQ is sieved and the sized coke on the sieve is sent to a blast furnace, while the powder coke under the sieve is sent to the sintering process and used to form sintered ore. That is, in the sintering process, powdered coke and lime are added to iron ore and sintered to form a sintered ore having a particle size of 10 to 20 mm. In the present invention, the lime added to the CDQ converts the sulfur content to stone (CaSO _Four ) And is taken out from the CDQ and collected by sieving together with the powder coke. Therefore, the stone koji (CaSO _Four ) Is also used in the sintering process, the derivative effect that the amount of lime used in the sintering process is greatly reduced or lime is not required is obtained. In addition, since the sulfur content is originally contained in the coke, and this is only partially transferred to the sintered ore side, there is no significant difference in the amount of sulfur brought into the blast furnace, so it is from the CDQ gas. The removed and recovered sulfur content is also excellent in that it does not require any extra processing or operation such as separate removal in a subsequent process.
[Brief description of the drawings]
FIG. 1 is a schematic view schematically showing a typical CDQ that can be used in the present invention.
FIG. 2 (A) is a schematic view of a pulverizer used for pulverizing biomass, and FIGS. 2 (B) to (E) pass only lime that has been reduced in particle size by the pulverizer. FIG. 2 is a drawing schematically showing the form and size of the sieve openings provided at the pulverizer outlet used for making the pulverized lime that has passed through the sieve of the pulverizer. In order to be able to define the proportion of lime having a particle diameter of 10 mm or less as defined in the present invention, particles larger than 10 mm are separated on a sieve and particles of 10 mm or less are separated under a sieve with a separate sieving equipment. It can also be a drawing schematically showing the form of the sieve opening and the size of the opening.
FIG. 3 is a drawing excerpted from Chemical Engineering Handbook 5th edition, page 279, wherein (1) to (5) in FIG. 3 (A) are diagrams showing fluidization state diagrams of the gas-system fluidized bed, FIG. 3B is a graph showing the relationship between the gas superficial velocity and the particle diameter in the above (1) to (5).
[Explanation of symbols]
101 ... CDQ, 102 ... bucket car, etc.
103 ... Upper lid of CDQ, 104 ... Upper coke inlet,
105 ... pre-chamber (space part), 106 ... cooling chamber,
107… Circulating gas, 108… Take out port under CDQ
109 ... heat exchanger (boiler), 111 ... steam,
113 ... steam turbine, 115 ... ring duct,
117 ... Air (outside air), 121 ... Circulation route,
123 ... Dust catcher, 125 ... Circulating gas blower,
127… Circulating gas inlet, 129… Exhaust gas extraction route,
151 ... Red hot coke, 153 ... Coke in CDQ,
155 ... Coke extracted from CDQ, 181 ... Lime,
183 ... Lime charging device, 185 ... Lime charging port,
191 ... Temperature sensor, 201 ... Coke oven,
301 ... Lime raw material, 302 ... Hammer type crusher,
303 ... Rotating body, 304 ... Hammer (part),
305 ... hammer rotation direction, 306 ... crushed lime,
307 ... Screen, 308 ... Opening.

Claims (10)

A method for reducing sulfur compounds in a gas in a coke dry fire extinguishing facility, wherein lime is charged into the coke dry fire extinguishing facility. 2. The method for reducing sulfur compounds in a gas in a coke dry fire extinguishing facility according to claim 1, wherein the lime is put into a pre-chamber which is a charging space for red hot coke in the coke dry fire extinguishing facility. The sulfur in the gas in the coke dry fire extinguishing equipment according to claim 1 or 2, wherein the lime is put into a bucket and / or a bucket car which is a moving and throwing equipment of red hot coke in the coke dry fire extinguishing equipment. Compound reduction method. The sulfur in the gas in the coke dry fire extinguishing equipment according to any one of claims 1 to 3, wherein a part or all of the space inside the pre-chamber is an atmospheric temperature of 1000 to 1100 ° C. Compound reduction method. The said lime contains 10 mass% or more of lime with a particle size of 10 mm or less, The sulfur compound reduction method in the gas in the coke dry fire extinguishing equipment of any one of Claims 1-4 characterized by the above-mentioned. The method for reducing sulfur compounds in a gas in a coke dry fire extinguishing facility according to any one of claims 1 to 5, wherein the lime is charged in a range of 30 to 650 g per ton of coke. The lime is introduced into the pre-chamber between and / or during the introduction of red hot coke into an intermittent coke dry fire extinguishing apparatus. The sulfur compound reduction method in the gas in the coke dry fire extinguishing equipment of any one of these. The said lime is supplied from the coke inlet of the upper part of a coke dry-type fire extinguishing equipment, and / or one or two or more inlets installed in the pre chamber, The one of Claims 1-7 characterized by the above-mentioned. A method for reducing sulfur compounds in gases in coke dry fire extinguishing equipment. The sulfur compound in the gas in the coke dry fire extinguishing equipment according to any one of claims 1 to 8, wherein the lime is introduced by air flow conveyance using nitrogen and / or circulating gas as a carrier gas. Reduction method. The lime is charged before, during and / or after loading of red hot coke on a bucket and / or bucket truck intermittently made from a coke oven. The method for reducing sulfur compounds in the gas in the coke dry fire extinguishing facility according to the item.

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