KR20200076617A - Apparatus and method for eliminating tar in ammoina liquor - Google Patents

Abstract

The present invention relates to an apparatus for removing tar included in ammonia liquor, comprising: a hollow tank; and an adsorbent embedded in the tank, wherein the adsorbent comprises coke breeze. According to the present invention, it is possible to remove tar contained in ammonia liquor by utilizing powder coke, which is a by-product of a coke manufacturing process, thereby contributing to the recycling of iron-making by-products. In addition, it is possible to contribute to the process stabilization of a gas purification process through the improvement of hydrogen sulfide purification efficiency among COG and the high quality realization of COG through the manufacture of high-quality ammonia liquor.

Description

Tar removal device and tar removal method included in ordination {APPARATUS AND METHOD FOR ELIMINATING TAR IN AMMOINA LIQUOR}

The present invention relates to a tar removal device and a tar removal method included in the ordination, more specifically, an apparatus for efficiently removing the tar component contained in the ordination (ammonia water) generated in the process of purifying the coke oven gas and It's about how.

In general, coke oven gas (COG) is generated in the process of preparing coke by distilling coal in a coke oven. The COG can be recovered and used as an energy source in the steel mill.

Some of the COG contains carbon dioxide, sulfur dioxide, and inlet oxygen that cannot be used as fuel, thereby reducing the amount of heat generated by increasing the volume of COG, and when released into the atmosphere, air pollution caused by sulfur dioxide contained in COG and earth caused by carbon dioxide It causes a warming phenomenon and the like.

In order to solve the above problems, COG sprays ordinal water containing ammonia as an absorbent to COG to remove these components, absorbs hydrogen sulfide, carbon dioxide, etc., and undergoes a purification process to remove tar.

On the other hand, the tar particles in the ordination contained from the COG have a problem that it is difficult to remove them because the fluidity increases as the temperature is higher than room temperature. The tar particles in the ordination are contained in a suspended state in the water, but the tar particles are sticky to each other, so that small ones gather to form larger and larger lumps. On the other hand, when the tar particles are attached to the filter, there is a problem that can cause the filter to be closed due to the adhesion of the tar, so the removal of tar contained in the ordination water is very high to improve the efficiency of the gas purification process and eliminate clogging of the purification equipment. It is an important factor.

In general, in order to remove tar contained in the ordination, tar is removed from the ordination using a filter sand (sand) filter. However, in the filter yarn filter, as the regeneration rate of the filter yarn decreases due to the tar attached to the filter yarn, the tar removal rate decreases over time and the quality of ordination decreases.

The present invention has been devised in view of the above circumstances, and to provide an apparatus and method for efficiently removing tar components included in ordination using coke breeze, a by-product of the coke production process.

According to one aspect of the invention, the hollow tank; And a first adsorbent embedded in the tank, wherein the first adsorbent comprises a coke breeze.

The bun coke may be a by-product generated in the coke manufacturing process.

The coke may be heat-treated at 400 to 700°C.

The specific surface area of the powder coke may be 5 to 10 m ² /g.

The adsorbent may further include sand.

The sand may be included in a volume ratio of 30% or less (but 0 is excluded) with respect to the total volume of the coke and sand.

The sand may be filled on top of the bun coke.

A solvent tank for supplying a solvent for backwashing the adsorbent to the tank may be further included.

The solvent may be at least one selected from quinoline, kerosene and hot water at 60 to 80°C.

According to another aspect of the present invention, in a method for removing tar contained in ordination, the step of adsorbing tar by supplying ordination containing tar to a tank containing an adsorbent, wherein the adsorbent is coke breeze) is provided.

The coke coke may be a by-product of the coke manufacturing process.

The coke may be heat-treated at 400 to 700°C.

The specific surface area of the powder coke may be 5 to 10 m ² /g.

The adsorbent may further include sand.

The sand may be included in a volume ratio of 30% or less (but 0 is excluded) with respect to the total volume of the coke and sand.

The sand may be filled on top of the bun coke.

The method may further include regenerating an adsorbent dissolving the adsorbed tar by supplying a solvent to the adsorbent adsorbed by the tar.

The solvent may be at least one selected from quinoline, kerosene and hot water at 60 to 80°C.

According to the present invention, by using bun coke as a by-product of the coke manufacturing process, it is possible to remove the tar contained in the ordination, it can contribute to the recycling of steel by-products.

In addition, it is possible to contribute to the stabilization of the process of the gas refining process by improving the efficiency of hydrogen sulfide purification in COG and improving the quality of COG by manufacturing high-quality ordination.

1 schematically shows a tar removal apparatus according to an embodiment of the present invention.
Figure 2 schematically shows a hollow tank included in the tar removal device according to an embodiment of the present invention.
Figure 3 schematically shows a hollow tank included in the tar removal device according to another embodiment of the present invention.
4 is a graph showing the change of the tar removal rate and regeneration rate according to the heat treatment temperature of the bun coke.
5 is a graph showing the results of the tar removal test in ordination according to Example 2 of the present invention.

Hereinafter, preferred embodiments of the present invention will be described with reference to various examples. However, the embodiments of the present invention may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below.

The present invention relates to an apparatus and method for efficiently removing the tar component contained in the ordination (ammonia water) generated in the process of purifying coke, Figure 1 schematically shows a tar removal apparatus according to an embodiment of the present invention will be. Hereinafter, the present invention will be described in more detail with reference to FIG. 1.

According to one aspect of the invention, the hollow tank; And an adsorbent embedded in the tank, wherein the adsorbent comprises a coke breeze.

Inside the hollow tank, an adsorbent for adsorbing the tar component contained in the ordination water is filled. FIG. 2 schematically shows a hollow tank included in a tar removal device according to an embodiment of the present invention. Referring to FIG. 2, the adsorbent is located in a central region inside the tank by a mesh structured mesh. It may be arranged and filled, the hollow tank constituting the tar removal device may be a fixed bed adsorption tower.

From the top of the tank, used in the COG purification process, ordination water containing the tar component is supplied, and the tar contained in the ordination water is adsorbed and removed by the adsorbent. In the present invention, coke breeze may be used as the adsorbent.

Coke is a basic raw material that is essentially used in blast furnace steel mills and is made by distilling coal, and coke is produced as a by-product of powdered powder coke by impact and vibration in the process of manufacturing, transportation, cooling, and transportation. Bone coke used as an adsorbent in the present invention may be a by-product generated in the coke manufacturing process as described above.

On the other hand, since the tar contained in the ordination fluid is a viscous fluid, the larger the specific surface area of the adsorbent, the higher the adsorption performance of the tar is, whereas the larger the specific surface area, the more the specific surface area is due to the development of fine pores, which has a side that is difficult to detach the adsorbed tar. . In general, in the case of sand used as an adsorbent, the specific surface area is very small (less than 1 m ² /g), and accordingly, the amount of tar that can adhere to the sand surface is small. On the other hand, in the case of activated carbon having a large specific surface area (500 to 1000 m ² /g), there is a disadvantage that it is not easy to detach and attach the attached tar due to the development of micropores.

The specific surface area of the powder coke used as an adsorbent for tar in the present invention is preferably 5 to 10 m ² /g. If it is less than 5 m ² /g, the amount of tar adsorbed is too small, whereas if it is more than 10 m ² /g, the adsorption rate of adsorbed tar is difficult and the regeneration rate of the adsorbent decreases, so the specific surface area of Buncokes is 5 to 10 m ² /g. It is preferred.

Bone coke used in the present invention may be used as an adsorbent after heat treatment at a temperature of 400 to 700° C. of powdered coke obtained as a by-product generated during coke production. Bone coke used in the present invention has physical properties similar to coke for blast furnace produced by heat treating coal under an oxygen-free atmosphere at a temperature of 1300° C., and contains a small amount of volatile powder. As the heat removal of the coke is increased, the tar removal performance increases, but if the micropore is too developed, there is a problem that the regeneration rate of the adsorbent may decrease, so at a temperature of 400 to 700°C, more preferably at a temperature of 500 to 600°C. The coke can be heat treated.

According to another embodiment of the present invention, the tar removal device is an adsorbent built into the tank, and may further include sand. Bunk coke contains pores and has a specific gravity lower than that of water. Accordingly, sand can be used to suppress the floating phenomenon of the coke and to prevent a phenomenon in which the position of the coke is fluctuated. Sand has the advantage of being easy to obtain and inexpensive.

Meanwhile, the sand may be included in a volume ratio of 30% or less (but 0 is excluded) with respect to the total volume of the coke and sand. That is, it is preferable that the powdered coke is filled to 70% by volume or more and sand to 30% by volume or less. When the above range is satisfied, as described later, when backwashing the adsorbent buncox with hot water, the tar attached to the buncoke surface is desorbed by hot water, so that the hot water containing tar is easily top of the tank. Can be discharged. When outside the above range, for example, when the powdered coke and sand are each filled with 50% by volume, the tar contained in the hot water used for backwashing is trapped in the air gap between the sand particles located at the top, causing the backwashing efficiency to decrease. do. In addition, when only the bunk coke is filled in the filling tower, the bunk coke is accompanied by a back-washing hot water flow, resulting in a loss of the bunk coke, which may cause a problem of additionally supplementing the bunk coke.

In addition, as described above, since the minute coke adsorbing tar in ordinal water has a lower specific gravity than water, in order to suppress the floating phenomenon of the minute coke that may be caused by hot water during backwashing, the sand is higher than the minute coke in the tank. It is preferably filled in. FIG. 3 schematically shows a hollow tank included in a tar removal apparatus according to another embodiment of the present invention. Referring to FIG. 3, sand is supported on the top of the net on which the bunk cokes are supported. It may consist of a structure in which a network is arranged.

When the ordination water containing tar is supplied to the tank containing the adsorbent as described above, the tar is adsorbed on the surface of the adsorbent, and the ordination water is discharged through the upper portion of the tank. According to the present invention, after adsorbing tar by the adsorbent, the adsorbed adsorbent is dissolved in a solvent to regenerate the adsorbent, and for this purpose, a solvent tank for supplying a solvent for backwashing the adsorbent to the tank is added. It can contain as.

The solvent supplied to the tank is not particularly limited, but, for example, quinoline, kerosene, and hot water at 60 to 80° C. may be used, and these may be used in combination. When using a mixture of quinoline and hot water at 60 to 80°C, kerosene and hot water at 60 to 80°C as the solvent, it is not particularly limited as being usable by mixing at various mixing ratios, for example, quinoline and 60 to 80 It can be used by mixing hot water of ℃ or kerosene and hot water of 60 to 80 ℃ at a ratio of 0.1:1. In order to promote the fluidity of the attached tar, the temperature of the hot water is preferably 60° C. or higher, but when it exceeds 80° C., it is not economical due to an increase in the production cost of hot water, so the temperature of the hot water is preferably 60 to 80° C. .

According to another aspect of the present invention, in a method for removing tar contained in ordination, the step of adsorbing tar by supplying ordination containing tar to a tank containing an adsorbent, wherein the adsorbent is coke breeze) is provided. In addition, the adsorbent may further include sand, and since it has been described above, detailed description thereof will be omitted.

As described above, according to the present invention, by utilizing bun coke as a by-product of the coke production process, it is possible to remove tar contained in the ordination water, as well as contributing to the recycling of steel by-products, and also the tar removal rate and regeneration rate as an adsorbent are also excellent. Do.

Example

Hereinafter, the present invention will be described in more detail with reference to examples. The following examples are intended to illustrate the present invention more specifically, but the present invention is not limited thereby.

1. Tar removal amount and adsorbent regeneration experiment according to adsorbent

Example 1

As shown in FIG. 1, a fixed bed adsorption column filled with bunk cokes as an adsorbent is used for ordination water having a tar content of 50 g/L in the ordination tank filled in the ordination tank, and the ordination is supplied to the upper portion of the fixed bed adsorption column to adsorb tar in the sorbent and the lower part. The tar removal rate was measured as a percentage by measuring the amount of tar contained in the discharged water.

On the other hand, after supplying 80° C. hot water filled in the hot water tank to the bottom of the fixed bed adsorption column to desorb the tar adsorbed on the adsorbent, the weight of the adsorbent before and after desorbing the tar adsorbed on the adsorbent was measured to measure the regeneration rate.

Example 2

The adsorption of tar and regeneration of the adsorbent were carried out in the same manner as in Example 1, except that sand was additionally filled on the top of the buncoke, and at this time, the buncoke was filled at 80 vol% and sand at 20 vol%. Did.

Example 3

Buncoke was subjected to adsorption of tar and regeneration of the adsorbent in the same manner as in Example 2, except that 70% by volume and 30% by volume of sand were filled.

Comparative Example 1

Buncoke was subjected to adsorption of tar and regeneration of the adsorbent in the same manner as in Example 2, except that 50% by volume and 50% by volume of sand were filled.

Comparative Example 2

Buncoke was subjected to adsorption of tar and regeneration of the adsorbent in the same manner as in Example 2, except that 60% by volume and 40% by volume of sand were filled.

The results according to Examples 1 to 3 and Comparative Examples 1 and 2 are shown in Table 1 below.

Item Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Tar removal rate (%) 80 96 95 55 62 Refresh rate (%) 93 99 98 50 60

Referring to Table 1, it can be seen that in Examples 1 to 3, the tar removal rate and regeneration rate were remarkably superior to those of Comparative Examples 1 and 2. In addition, it can be seen that in Examples 2 and 3 in which the powdered coke was 70% by volume or more and the sand was 30% by volume or less, the tar removal rate was 95% or more, and the regeneration rate was 98% or more when backwashing.

2. Buncokes Tar removal performance and adsorbent according to heat treatment temperature Refresh rate Evaluation experiment

Example 4

The adsorption of tar and regeneration of the adsorbent were performed in the same manner as in Example 2, except that the powder coke heat-treated at a temperature of 500°C was used.

Example 5

The adsorption of tar and regeneration of the adsorbent were performed in the same manner as in Example 2, except that the powder coke heat-treated at a temperature of 600°C was used.

Comparative Example 3

The adsorption of tar and regeneration of the adsorbent were performed in the same manner as in Example 1, except that the powder coke heat-treated at a temperature of 300°C was used.

Comparative Example 4

The adsorption of tar and regeneration of the adsorbent were performed in the same manner as in Example 1, except that the powder coke heat-treated at a temperature of 800°C was used.

의 범위에서 열처리하는 것이 바람직하다는 것을 확인할 수 있다.The graph showing the experimental results is shown in FIG. 4. Referring to FIG. 4, the tar removal performance increases as the heat treatment of the coke is increased, but as in Comparative Example 4, when the temperature exceeds 700°C, the tar removal performance is rather deteriorated, and the regeneration rate tends to decrease due to the development of micropores. , You can check. Accordingly, when considering the overall aspects of tar removal rate and regeneration rate, the powder coke is 400 to 700.

It can be seen that it is preferable to heat-treat in the range of.

On the other hand, Figure 5 shows the results of the continuous experiment of removing tar from ordination according to Example 2 of the present invention using a fixed bed adsorption column having a volume of 20 m ³ , the tar content (intake tar) in ordination flowing into a tank filled with filler. Content) and the tar content (outlet tar content) in the effluent after passing through the tank. On the other hand, the graph included at the top of FIG. 5 represents the percentage of the outlet tar content compared to the inlet tar content. It can be confirmed that the tar removal rate is 90% or more through the tar content in the inlet and outlet of the tank.

Although the embodiments of the present invention have been described in detail above, the scope of rights of the present invention is not limited to this, and various modifications and variations are possible without departing from the technical spirit of the present invention as set forth in the claims. It will be obvious to those of ordinary skill in the field.

Claims (18)

Hollow tank; And
Contains an adsorbent built into the tank,
The adsorbent comprises a coke breeze (coke breeze), tar removal device included in the ordination.
According to claim 1,
Tar removal apparatus contained in the ordination, characterized in that the coke coke is a by-product of the coke manufacturing process.
According to claim 1,
Tar removal apparatus included in the ordination, characterized in that the blast coke is heat-treated at 400 to 700 ℃.
According to claim 1,
Tar removal apparatus included in the ordination, characterized in that the specific surface area of the Bunk coke is 5 to 10m ² /g.
According to claim 1,
Tar removal device contained in the ordination, characterized in that it further comprises sand as an adsorbent.
The method of claim 5,
The sand removal apparatus included in the ordination, characterized in that contained in a volume ratio of less than 30% (but 0 is excluded) with respect to the total volume of the coke and sand.
The method of claim 5,
The sand is tar removal apparatus included in the ordination, characterized in that filled in the upper portion of the coke.
According to claim 1,
A tar removal device further comprising a solvent tank for supplying a solvent for backwashing the adsorbent to the tank.
The method of claim 8,
The solvent is at least one selected from quinoline, kerosene and hot water at 60 to 80 ℃ tar removal device.
In the method of removing tar contained in the ordination,
The step of adsorbing tar by supplying the ordination water containing the tar to the tank containing the adsorbent,
The adsorbent is a coke breeze, a method for removing tar contained in ordination.
The method of claim 10,
Method for removing tar contained in ordination, characterized in that the coke coke is a by-product of the coke manufacturing process.
The method of claim 10,
Method for removing tar contained in ordination, characterized in that the coke is heat-treated at 400 to 700°C.
The method of claim 10,
Method for removing tar contained in the ordination, characterized in that the specific surface area of the coke is 5 to 10 m ² /g.
The method of claim 10,
A method for removing tar contained in ordination, further comprising sand as an adsorbent.
The method of claim 14,
The sand is a method for removing tar contained in ordination, characterized in that it is included in a volume ratio of 30% or less (but 0 is excluded) relative to the total volume of the coke and sand.
The method of claim 14,
The sand is a tar removal method included in the ordination, characterized in that filled in the upper portion of the coke.
The method of claim 10,
A method for removing tar, further comprising regenerating an adsorbent dissolving the adsorbed tar by supplying a solvent to the adsorbent adsorbed by the tar.
The method of claim 17,
Wherein the solvent is quinoline, kerosene and tar removal method characterized in that at least one selected from 60 to 80 ℃ hot water.

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