KR20170070482A

KR20170070482A - Method and apparatus for eliminating tar emulsion in ammoina liquor

Info

Publication number: KR20170070482A
Application number: KR1020150178050A
Authority: KR
Inventors: 이현
Original assignee: 재단법인 포항산업과학연구원
Priority date: 2015-12-14
Filing date: 2015-12-14
Publication date: 2017-06-22
Also published as: KR101794623B1

Abstract

The present invention relates to a method for removing a tar emulsion from an ordinal water containing a tar emulsion, comprising the steps of: adsorbing a tar emulsion with the solid adsorbent by mixing and stirring the solid adsorbent with the ordinal water containing the tar emulsion; An extraction step of separating the solid adsorbent adsorbing the tar emulsion from the water, a dissolving step of dissolving and absorbing the tar emulsion adsorbed on the solid adsorbent by adding a solvent to the solid adsorbent adsorbing the tar emulsion, A solid adsorbent regeneration step of separating the solid adsorbent and the tar emulsion absorption solvent by a solvent, and a solvent absorbing the tar emulsion are supplied to a distillation step to separate the solvent from the tar emulsion, and the solvent is recovered by cooling And a solvent separation and recovery step.

Description

Technical Field [0001] The present invention relates to a method and apparatus for removing tar emulsion contained in an ordnance,

The present invention relates to a method for recovering an organic compound contained in an ordinal water, and more particularly, to a method for efficiently recovering organic compounds contained in an ordinal water by efficiently recovering benzene, toluene, xylene, naphthalene and various benzene ring organic compounds contained in ordinal water (ammonia water) Lt; / RTI >

Coke oven gas (COG) is generated in the process of producing coke by carbonizing coal in a coke oven. Such COG can be recovered and used as an energy source in the steelworks.

Meanwhile, the coke oven gas contains a part of carbon dioxide, sulfur dioxide and inflow oxygen that can not be utilized as fuel, thereby reducing the amount of heat generated by increasing the volume of the coke oven gas. When released into the atmosphere, Pollution and global warming due to carbon dioxide.

Accordingly, in order to solve the above-mentioned problems, the coke oven gas is subjected to a purification process to remove the above components. In order to remove these components, COG is injected with an ordinal water containing ammonia as an absorbent to absorb hydrogen sulfide, carbon dioxide and the like, and tar is removed.

On the other hand, it is desirable that the Ordnance sprayed on the COG is collected and reused by removing hydrogen sulfide, tar and the like adsorbed in the ordination. Benzene, toluene, xylene, naphthalene and various benzene ring organic compounds are present in the recycled water used for COG purification. Conventionally, only a part of the organic compounds contained in the ordnance are removed by a filter and then re-supplied to the process for reuse for coke oven gas purification.

However, when such ordinal water is used, benzene, toluene, xylene and naphthalene in the remaining organic compounds are vaporized or sublimated and adhere to the piping and distillation tower of the process in a solid state to cause clogging. As a result, Thereby deteriorating the efficiency of the process and causing a failure of the equipment.

Therefore, by efficiently recovering the benzene, toluene, xylene, naphthalene and various benzene ring organic compounds contained in the ordinal water generated in the process of manufacturing the coke, it is possible to prevent the process piping or the closure of the distillation column It is desirable to increase the efficiency of the process. To this end, a method of removing and recovering the organic compounds contained in the water sprayed to the COG is required.

The method according to one embodiment of the present invention is used for purification of COG to regenerate the ordinal water by removing the organic compounds contained in the recovered water, thereby preventing the closure of the process piping or the distillation column due to reuse of the ordination water Method.

Another object of the present invention is to solve the problem of equipment failure by removing and recovering the organic compounds contained in the ordination, to improve the efficiency of the process, and to improve the purification efficiency of the coke oven gas.

Another object of the present invention is to provide a method for recovering an organic compound contained in an ordinal water, which can recover economic benefits by selling an organic component in the waste water and selling the recovered organic component and naphthalene as a by-product I have to.

The present invention, in one aspect, provides a method for removing tar emulsion from an Ordnance including a tar emulsion, wherein, in one embodiment, mixing a solid adsorbent with an ordinal water containing a tar emulsion to adsorb the tar emulsion to the solid adsorbent An extraction step of separating the solid adsorbent adsorbing the tar emulsion from the water by solid-liquid separation, a solvent in the solid adsorbent adsorbing the tar emulsion, and dissolving the tar emulsion adsorbed in the solid adsorbent in a solvent A solid adsorbent separating step of separating the solid adsorbent and the tar emulsion absorbing solvent by solid-liquid separation, and a step of supplying the solvent absorbing the tar emulsion to the distillation step, separating the solvent from the tar emulsion, A solvent separating step for recovering the solvent by cooling and condensing the solvent The present invention provides a method for removing tar emulsion contained in the Ordnance.

The solid adsorbent is preferably gamma alumina, and the gamma alumina is preferably mixed in an amount of 1.67 times or more by weight based on the weight of the tar emulsion.

It is preferable that the solvent is at least one selected from quinoline and kerosene.

The distillation is preferably carried out at a temperature of 150 ° C or higher.

In at least one of the ordinal separation step and the solid absorbent separation step, the solid-liquid separation may be performed by a wet cyclone.

The solid adsorbent separated in the solid adsorbent separation step is preferably reused as the solid adsorbent in the adsorption step.

The solvent recovered in the solvent separation and recovery step is preferably reused as a solvent in the dissolution step.

In another aspect, the present invention provides a tar emulsion removal device contained in an ordinate, wherein, according to an embodiment, a tar emulsion-containing ordnance is provided, and the tar emulsion is supplied with a solid adsorbent for adsorbing the tar emulsion in the ordinate A first solid-liquid separating means for separating the solid adsorbent adsorbing the tar emulsion supplied from the tar emulsion adsorption tank from the ordinal number, a solid emitter for adsorbing the tar emulsion separated by the first solid-liquid separating means, A solid adsorbent regeneration tank for separating the tar emulsion from the solid adsorbent by dissolving the tar emulsion by the solvent, a solid adsorbent solid-liquid separator for separating the solid adsorbent from the tar emulsion containing solution supplied from the tar emulsion dissolution tank A second solid-liquid separating means and a second solid- I-containing solution by distillation to remove the solvent from the tar emulsion, and provides the tar contained in the emulsion removal device ordination comprising a distillation column for recovering tar emulsion.

At least one of the first and second solid-liquid separation means may be a wet cyclone.

Further, the apparatus may further include a condenser for condensing and recovering the solvent distilled in the distillation column.

According to the present invention, when recycling ordinal water is recovered by removing the tar emulsion from the waste water used to increase the collection ratio of hydrogen sulfide contained in the COG generated during the production of the coke, the tar emulsion contained in the ordinal water, It is possible to prevent closure and malfunction of the apparatus, and accordingly, it is considered that the cost to be used for maintenance and maintenance of the facility can be reduced according to the present invention.

Further, even when the regeneration ordnance is used, the tar emulsion content contained in the ordination is removed, so that the collection efficiency of hydrogen sulfide and the like can be increased during the reuse of the Ordnance. As a result, the content of hydrogen sulfide contained in the COG is reduced, Can be reduced.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a method for removing tar emulsion contained in ordnance according to an embodiment of the present invention and an apparatus applied thereto. Fig.
2 is a graph showing the adsorption rate of tar emulsion according to the amount of solid adsorbent used when the method according to one embodiment of the present invention is applied.
FIG. 3 is a graph showing the recovery rate of a solvent according to an operation temperature of a distillation column for regenerating a solvent absorbing tar emulsion according to an embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a method of recovering organic compounds contained in the ordnance according to the present invention and a device arrangement suitable therefor. Fig.

The present invention relates to a method for treating waste water generated during the treatment of COG generated by carbonization of coal in a coke oven in a chemical plant. Tar emulsion generated in a tar decanter for separating tar contained in the waste water is treated.

As shown in Fig. 1, the ordination water used for the purification of COG contains particulate solid matter together with hydrogen sulfide, tar, organic compounds and the like contained in COG. Therefore, these solid substances can be removed by filtration. The filtration is not particularly limited, and for example, a strainer may be used.

On the other hand, the filtration can be performed twice or more depending on the size of the solid particles contained in the ordnance. For example, the solid matter having a large particle size can be removed by primary filtration, and then the fine particles can be filtered by secondary filtration.

And adsorbing the tar emulsion contained in the ordinal water (filtrate ordinal number) from which solid particulate matter has been removed by the filtration. The adsorption is preferably carried out using a solid adsorbent. It is possible to further enhance the adsorption of the tar emulsion in the ordinance by bringing the chemical adsorption effect by the catalytic action on the solid surface upon contact with the solid adsorbent and further to separate the solid adsorbent adsorbing the tar emulsion from the ordinates . &Lt; / RTI >

As the solid adsorbent, it is preferable to use gamma alumina. Gamma alumina is particularly excellent in adsorption, but has a large effect of separating the tar emulsion into kerosene, and can be reused without recycling even when recycled, and can be reused more efficiently. In addition to the gamma alumina, active carbon having excellent adsorptivity can be used together.

Considering the content of the tar emulsion contained in the filtered ordinal water as the waste water to be treated as CO 2 generated during the dry distillation of the coke, about 95% or more of the tar emulsion must be removed, It does not cause problems such as closure of facilities. Therefore, it is preferable that the tar emulsion contained in the ordnance is adsorbed and removed by at least 95%.

In order to obtain such adsorption removal efficiency, the solid adsorbent is preferably used in an amount of 1.67 times or more based on the weight of the tar emulsion to be removed contained in the ordnance. When the amount of the solid adsorbent used is less than 1.67 times the amount of the tar emulsion, the adsorption efficiency of the tar emulsion is not sufficient and sufficient adsorption efficiency can not be obtained.

On the other hand, the upper limit of the solid adsorbent is not particularly limited as long as it exceeds the above range. However, when the solid adsorbent exceeds 3.33 times the weight of the tar emulsion, no further synergistic effect due to the addition of the solid adsorbent is obtained, The adsorption rate can be obtained.

The apparatus for mixing the tar-emulsion-containing filtrate ordinal water and the solid adsorbent for gamma-alumina is not particularly limited and may be suitably used as long as it can adsorb the tar emulsion from the tar emulsion contained in the ordinal water. For example, a tar-containing emulsion may be put into a tank such as a tar emulsion adsorption tank, and a solid adsorbent such as gamma-alumina as described above may be added to the emulsion and stirred to adsorb the tar emulsion to a solid adsorbent such as gamma alumina .

Adsorbing the tar emulsion to the solid adsorbent in the tar emulsion adsorption tank, and then separating the gamma alumina adsorbing the tar emulsion from the ordinal number. For the separation, the contents in the tar emulsion adsorption tank, that is, the gamma alumina adsorbed on the tar emulsion and the ordination water are transferred to the solid-liquid separating means. The conveyance is not particularly limited, and means such as a pump can be used.

The solid-liquid separating means is not particularly limited and may be suitably used in the present invention as long as it is generally used for separating solid phase and liquid phase. For example, a wet cyclone may be used as the solid-liquid separating means.

By applying the wet cyclone, the solid adsorbent adsorbing the solid tar emulsion to the lower part of the cyclone can be discharged and the liquid ointment can be discharged through the upper part.

The liquid oily water in which the tar emulsion has been removed by the solid-liquid separation can be recovered, and the recovered ordnance can be reused as an absorbing liquid for the removal of hydrogen sulfide and the like to COG. At this time, the recovered Ordnance may further include a step of removing impurities contained in the purified water through a purification process such as filtration if necessary, and then used in the COG purification process.

On the other hand, the solid adsorbent adsorbing the tar emulsion is discharged to the lower portion of the solid-liquid separating means such as the wet cyclone. In order to reuse the adsorbent, it is preferable to separate the tar emulsion adsorbed by the solid adsorbent to regenerate the solid adsorbent. To this end, the solid adsorbent adsorbing the tar emulsion is supplied to a solid adsorbent regeneration tank for regeneration of the adsorbent, and at the same time, a solvent having solubility in the tar emulsion is supplied to remove the tar emulsion from the solid adsorbent . The kerogen and other solvents can regenerate the adsorbent by dissolving the tar emulsion adsorbed in the adsorbent.

As the solvent, a tar emulsion can be dissolved. For example, kerogen or quinoline may be used, or they may be mixed and used. When the quinoline and kerogen are mixed with the solvent, they may be mixed at various mixing ratios. For example, quinoline and kerosene may be mixed at a ratio of 1: 1, although they are not particularly limited.

After dissolving the tar emulsion in the solid adsorbent regeneration tank, the recovered solid adsorbent can be recovered by separating the solid adsorbent, the liquid tar emulsion and the solvent. The separation can be performed by solid-liquid separation, and is not particularly limited. The same solid-liquid separation means as the first solid-liquid separation means used for solid-liquid separation of the solid adsorbent from the ordinal water can be applied as the second solid-liquid separation means For example, a wet cyclone.

The solid adsorbent can be recovered to the lower portion of the wet cyclone by the solid-liquid separating means. Thus, the recovered recovered solid adsorbent can be supplied to the tar emulsion adsorption tank to absorb the tar emulsion from the waste water.

On the other hand, a tar emulsion dissolved by the solvent is discharged to the upper part of the solid-liquid separating means together with a solvent such as kerosene. The liquid component includes a solvent such as kerosene and a tar emulsion. The solvent can be regenerated by separating them, and the tar emulsion can be separated and collected, and BTX (benzene, toluene, xylene) Various benzene ring organic compounds can be separated and recovered.

Therefore, it is preferable that the component discharged to the upper part of the solid-liquid separating means such as the wet cyclone be conveyed by the pump or the like. The solvent can be separated and recovered by distillation using the boiling point difference between the solvent and the tar emulsion in the distillation tower. By the distillation process in the distillation column, a solvent such as kerosene is discharged to the upper portion of the distillation column, and these components can be recovered as a liquid solvent by condensing by a condenser. These solvents can be stored in a storage tank and fed to a regeneration tank for regeneration of the solid adsorbent as needed to be reused.

On the other hand, the components remaining in the distillation column are tar emulsions, which can be collected and recovered as effective organic compounds by separate treatment.

Example

Hereinafter, the present invention will be described in more detail with reference to examples. However, the following embodiments are merely illustrative of one embodiment of the present invention, and thus the present invention is not limited thereto.

Example One

The tar emulsion adsorption rate in the Ordnance was measured by changing the amount of solid adsorbent depending on the amount of tar emulsion contained in the ordinal water passing through the strainer.

Specifically, gamma alumina in powder form was changed to 1, 3, 5, 7 and 10% by weight with respect to 100% of the ordinal ordnance water weight with respect to the ordinal ordinal water content of 3 wt% And the tar emulsion in the ordination was adsorbed.

Subsequently, solid-phase gamma alumina and liquid ointment were separated and recovered using a wet cyclone, and the recovered liquid ounce was analyzed, and the content of the remaining tar emulsion is shown in Fig.

As can be seen from FIG. 2, when the amount of gamma alumina used is 5% by weight, it can be seen that the adsorption rate of tar emulsion is about 95% or more. Therefore, it is preferable that the amount of the solid adsorbent to be added is 1.67 times or more of the weight of the tar emulsion contained in the ordnance for the adsorption and removal of tar emulsion during the ordnance.

On the other hand, when the content of the solid adsorbent is more than 5 wt%, it can be seen that the effect of the adsorbent is not increased even if the adsorbent is additionally used. Therefore, the solid adsorbent can obtain an adsorption rate of about 95% or more when the solid adsorbent contains 1.67 times or more of the weight of the tar emulsion contained in the ordnance

Example 2

The gamma alumina separated by solid-liquid separation in Example 1 was charged into a solid adsorbent regeneration tank, and then 500 ml of kerosene was added thereto and stirred so as to be sufficiently mixed.

Subsequently, the components contained in the solid adsorbent regeneration tank were transferred to a solid-liquid separator of a wet cyclone using a pump to perform solid-liquid separation. The liquid phase components were discharged to the upper layer of the wet cyclone and fed to the distillation column. The distillation process was carried out under the three temperature conditions of 125 ° C, 150 ° C and 175 ° C, as shown in Table 3.

Steam discharged to the upper part of the distillation tower was transferred to a condenser and condensed to collect kerosene in a liquid phase. The content of kerosene recovered according to the operating temperature in the distillation column was confirmed, and the results are shown in Fig.

As can be seen from FIG. 3, the recovered yield was about 70% at the distillation tower temperature of 125 ° C., but the total amount was recovered at 150 ° C. or higher.

Claims

CLAIMS What is claimed is: 1. A method for removing tar emulsion from an Ordnance containing tar emulsion,
An adsorption step of mixing the solid adsorbent with the ordinal water containing the tar emulsion to mix the tar emulsion with the solid adsorbent;
An ordinal water separation step of separating the solid adsorbent adsorbing the tar emulsion from the water by solid-liquid separation;
Adding a solvent to the solid adsorbent adsorbing the tar emulsion to dissolve and absorb the tar emulsion adsorbed on the solid adsorbent;
A solid adsorbent regeneration step of separating the solid adsorbent and the tar emulsion absorption solvent by solid-liquid separation; And
Separating the solvent from the tar emulsion by supplying the solvent absorbing the tar emulsion to the distillation step, separating the solvent from the tar emulsion, and recovering the solvent by cooling and condensing the solvent
Of the total amount of the tar emulsion.

The method of claim 1, wherein the solid adsorbent is gamma alumina.

3. The method of claim 2, further comprising activated carbon with the gamma alumina.

3. The method according to claim 2, wherein the gamma alumina is mixed in an amount of 1.67 times or more by weight with respect to the weight of the tar emulsion.

The method for removing tar emulsion according to claim 1, wherein the solvent is at least one selected from quinoline and kerosene.

The method according to claim 1, wherein the distillation is carried out at a temperature of 150 ° C or higher.

The method of claim 1, wherein the solid-liquid separation is performed by a wet cyclone.

The method according to claim 1, wherein the solid adsorbent separated in the solid adsorbent separation step is reused as a solid adsorbent in the adsorption step.

The method according to claim 1, wherein the solvent recovered in the solvent separation and recovery step is reused as a solvent in the dissolution step.

A tar emulsion adsorption tank supplied with a tar emulsion containing ordnance and supplied with a solid adsorbent for adsorbing the tar emulsion in the ordinate;
A first solid-liquid separating means for separating the solid adsorbent adsorbing the tar emulsion supplied from the tar emulsion adsorption tank from the ordinal water;
A solid adsorbent for adsorbing the tar emulsion separated by the first solid-liquid separating means, and a solid adsorbent for separating the tar emulsion from the solid adsorbent by dissolving the tar emulsion by the solvent, A regeneration tank;
A second solid-liquid separating means for solid-liquid separating the solid adsorbent from the tar emulsion-containing solution supplied from the tar emulsion dissolution tank; And
The solution containing the tar emulsion is distilled to separate the solvent from the tar emulsion, and the distillation tower
Wherein the tar emulsion is contained in the ordinal water.

11. The tar emulsion remover as claimed in claim 10, wherein at least one of the first and second solid-liquid separating means is a wet cyclone contained in the ordinal water.

11. The tar emulsion remover as claimed in claim 10, further comprising a condenser for condensing and recovering the solvent distilled in the distillation column.