KR101798623B1 - the method for recycling BTX absorption oil in coke gas refining process - Google Patents

the method for recycling BTX absorption oil in coke gas refining process Download PDF

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KR101798623B1
KR101798623B1 KR1020150185932A KR20150185932A KR101798623B1 KR 101798623 B1 KR101798623 B1 KR 101798623B1 KR 1020150185932 A KR1020150185932 A KR 1020150185932A KR 20150185932 A KR20150185932 A KR 20150185932A KR 101798623 B1 KR101798623 B1 KR 101798623B1
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South Korea
Prior art keywords
oil
absorption
btx
viscosity
absorbing
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KR1020150185932A
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Korean (ko)
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KR20170076097A (en
Inventor
이종규
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주식회사 포스코
재단법인 포항산업과학연구원
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Priority to KR1020150185932A priority Critical patent/KR101798623B1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1425—Regeneration of liquid absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/96—Regeneration, reactivation or recycling of reactants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B27/00—Arrangements for withdrawal of the distillation gases
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B41/00—Safety devices, e.g. signalling or controlling devices for use in the discharge of coke
    • C10B41/08—Safety devices, e.g. signalling or controlling devices for use in the discharge of coke for the withdrawal of the distillation gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602

Abstract

According to an embodiment of the present invention, there is provided a method for regenerating an absorbing oil, comprising the steps of: injecting an absorbing oil into a COG gas flowing into an absorption tower to collect BTX contained in COG gas to form a mixed oil; Removing the BTX from the mixed oil to regenerate the absorption channel, and transferring the regenerated absorption oil to the separation column, and removing the polymeric substance from the regenerated absorption oil, wherein the removal of the polymeric substance The stripping column made is a pressure of 30 mmHg to 80 mmHg and a temperature of 100 ° C to 120 ° C.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for recycling an absorption oil used in a coke oven gas purification process,

The present invention relates to a method for regenerating an absorbing oil used in a coke oven gas purification process.

Benzene, toluene, and xylene contained in the coke oven gas are absorbed by the BTX absorption tower using the coal-based absorption oil as the absorption liquid.

The absorber that absorbs BTX is re-supplied to the BTX absorber after removing the BTX from the regeneration tower using high temperature steam.

At this time, the absorption oil to be supplied is accompanied by the polycondensation reaction of the absorption oil due to the reaction with the high temperature steam in the regeneration tower. Therefore, a high molecular weight compound is produced in the regeneration tower, and the viscosity of the absorption oil is increased due to the production of such a high molecular weight compound.

When the viscosity of the absorption oil is increased, the absorption rate of BTX in the BTX absorption tower is lowered, and the pipe of the heat exchanger is closed in the heat exchange step, which results in a disadvantage in the process stabilization.

Therefore, it is important to lower the viscosity of the recovered absorbent oil in the regeneration tower in order to reuse the absorber supplied again.

Disclosure of Invention Technical Problem [8] The present invention provides a method for reducing the viscosity of an absorption oil used in a coke oven gas purification process so as to be efficiently reused.

To solve these problems, a method of regenerating an absorbing oil according to an embodiment of the present invention includes the steps of injecting an absorbing oil into a COG gas flowing into an absorption tower to collect BTX contained in COG gas to form a mixed oil, Transporting the regenerated absorption oil to a separation tower, and removing the polymer material from the regenerated absorption oil, wherein the regenerated absorption oil is recovered from the regenerated absorption oil by removing BTX from the mixed oil, The stripping column from which the removal of the polymeric material occurs may be a pressure of 30 mmHg to 80 mmHg and a temperature of 100 ° C to 120 ° C.

And transferring the absorbing oil from which the polymer material is removed to the regeneration tower again.

The viscosity of the absorption oil from which the polymer material is removed may be less than 1.3 angular viscosity.

In the step of transferring the regenerated absorbing oil to the removing column and removing the polymer substance from the regenerated absorbing oil, the amount of the absorbing oil transferred to the removing column may be between 10% and 60%.

As described above, the regeneration method of the absorption oil according to the embodiment of the present invention effectively removes the polymer substances in the absorption oil using the steam at the reduced pressure and the low temperature condition and lowers the viscosity of the absorption oil.

1 shows a regeneration flow chart of an absorption oil according to an embodiment of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The above and other features and advantages of the present invention will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings in which: FIG. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Now, a method of controlling viscosity of an absorption oil used in a coke oven gas purification process according to an embodiment of the present invention will be described in detail.

1 shows a regeneration flow chart of an absorption oil according to an embodiment of the present invention. Referring to FIG. 1, a regeneration apparatus used in a method for regenerating an absorbing oil according to an embodiment of the present invention includes an absorption tower 10, a regeneration tower 20, and a removing apparatus 30. Hereinafter, the detailed configuration of each reproduction apparatus used in the method of regenerating the absorbing oil will be described.

Coke oven gas (COG) gas flows into the absorption tower 10. That is, in the coke process, coke oven gas (COG gas) may be generated as a by-product. The COG gas contains the BTX component. BTX refers to benzene, toluene, and xylene.

At this time, the COG gas generated in the coke process flows into the absorption tower 10, and the COG gas can flow into the lower side of the absorption tower 10. The absorption oil may be injected into the absorption tower 10. The absorbing oil is injected into the COG gas to capture the BTX contained in the COG gas. At this time, the absorption oil captures the BTX contained in the COG gas, and the COG gas from which the BTX is removed can be discharged to the upper side of the absorption tower 10. In the absorber 10, the absorption oil having a temperature of about 30 ° C and having captured BTX can be discharged. Hereinafter, the absorption oil in which BTX is captured will be referred to as mixed oil.

This mixed oil is conveyed to the regeneration tower 20 connected to the absorption tower 10. The regeneration tower 20 can supply steam to distill the BTX component contained in the mixed oil and discharge it to the outside. At this time, the steam supplied to the regeneration tower 20 may have a temperature of about 200 캜.

Although not shown, a heat exchanger may be located between the absorption tower 10 and the regeneration tower 20. [ This heat exchanger increases the temperature of the mixed oil. The temperature of the mixed oil heated by the heat exchanger may be about 180 ° C.

Accordingly, mixed oil of about 180 ° C is supplied to the regeneration tower 20, and about 200 ° C steam is supplied into the regeneration tower, so that a boiling temperature difference may be generated between the mixed oil and the steam. This boiling temperature difference can produce saturated steam from steam. The saturated steam can separate the BTX component contained in the mixed oil by the boiling temperature difference to the upper side of the regenerator 20. [ Therefore, in the regeneration tower 20, the BTX component and the mixed oil can be separated. Further, the BTX component separated in the regeneration tower 20 contains moisture (steam).

The separated BTX component may be separated from the regeneration tower 20 and stored in a storage tank or transferred to another facility.

Since the high-temperature steam is supplied in order to separate BTX from the regeneration tower 20, the high-temperature steam and the mixed oil react with each other to cause the polycondensation reaction of the mixed oil. By such polycondensation reaction, a high molecular weight compound can be produced in the mixed oil. These high molecular weight compounds cause viscosity increase of the mixed oil. Therefore, even after the BTX is removed from the mixed oil and the absorption channel is regenerated, the viscosity of the absorption oil is increased because the high molecular weight compound is contained in the absorption oil.

When the viscosity is increased, the absorption rate and the distillation rate of BTX are remarkably decreased when the absorption oil is reused thereafter. In addition, the viscosity of the absorbed oil is decreased due to the fluctuation of chemical components. Reuse of highly viscous absorbent oil can cause closure of the heat exchanger and absorption tower. Therefore, in such a case, it is necessary to replace the equipment with new equipment at a cost because the facility can not be operated. Therefore, in order to prevent the pipe of the absorption tower from being closed, the high molecular weight compound contained in the absorption oil is removed to lower the viscosity of the absorption oil desirable.

At this time, when the angular viscosity of the absorbing oil is less than 1.90, it is important to maintain the angular viscosity of the absorbing oil to be less than 1.90 because the amount of adhesion of the pipe is insignificant and the angular viscosity is increased sharply at an angle of 1.90 or more.

The recovery tower 20 is connected to a removal tower 30. The stripping chute 30 is supplied with a part of the high-viscosity absorbing oil recovered in the regeneration tower 20. In an embodiment of the present invention, the internal condition of the removing chute 30 is a pressure of 30 mmHg to 80 mmHg, and the temperature of the steam supplied to the removing chute is 100 ° C to 120 ° C.

That is, steam is supplied to the molten steel to remove the deteriorated polymer material contained in the absorbing oil. The deteriorated polymer material is discharged to the lower part of the removing column.

Thus, the steam supplied to the detached body reduces the viscosity of the absorption oil by removing the deteriorated polymer substance contained in the absorption oil. At this time, the amount of the absorption oil supplied from the regeneration tower to the stripping column may be between 10% and 60%. If the amount of the absorption oil supplied from the regeneration tower to the molten chute is 60% or more, the process recirculation absorption oil becomes small, and thus a new amount of new absorption oil must be replenished in a large amount. When the amount of the absorbing oil supplied from the regeneration tower to the removing column is less than 10%, the polymer material of circulating absorbing oil can not be sufficiently removed, which makes it difficult to control the viscosity of the absorbing oil.

In an embodiment of the present invention, the internal condition of the molten tooth 30 is a pressure of 30 mmHg to 80 mmHg, and the temperature of the steam supplied to the molten tooth 30 may be 100 ° C to 120 ° C. Generally, the high-temperature steam at 160 ° C or higher is used in the removing tower 30 to remove the polymer material. However, in this case, since the steam is used at a high temperature, the cost is excessively high. As the steam is at a high temperature, there is a problem that the absorption oil can react again with the polycondensation reaction during the removal process.

However, in an embodiment of the present invention, the inner pressure of the molten-metal chit was reduced to 30 mmHg to 80 mmHg, and the inner temperature of the molten metal was driven at a relatively low temperature of 100 to 120 ° C. By operating the internal pressure under reduced pressure, the recovery rate of BTX is increased and therefore the viscosity of the absorption oil can also be reduced.

Hereinafter, a method of regenerating the absorbing oil according to an embodiment of the present invention will be described. According to an embodiment of the present invention, there is provided a method for regenerating an absorbing oil, comprising the steps of: injecting an absorbing oil into a COG gas flowing into an absorption tower to collect BTX contained in COG gas to form a mixed oil; Removing the BTX from the mixed oil to regenerate the absorption channel, and transferring the regenerated absorption oil to the separation column, and removing the polymeric substance from the regenerated absorption oil, wherein the removal of the polymeric substance The resulting molten trough is operated at a pressure of 30 mmHg to 80 mmHg and a temperature of 100 ° C to 120 ° C.

First, the step of jetting an absorbing oil to the COG gas to collect BTX contained in the COG gas to form a mixed oil will be described. This step is carried out in the absorption tower 10. That is, as a by-product of the coke oven process, the COG gas containing the BTX component flows into the absorption tower 10, where the absorption oil is injected. This absorption oil captures the BTX contained in the COG gas, and the COG gas from which the BTX is removed is discharged to the upper side of the absorption tower 10. The BTX component is captured in the absorption oil, and thus the absorption oil containing BTX is referred to as a mixture oil.

Next, the mixed oil is transferred to the regeneration tower, and BTX is removed from the mixed oil to regenerate the absorption channel.

At this time, the removal of BTX from the mixed oil may be performed by supplying hot steam to the regeneration tower 20. The steam supplied to the regeneration tower 20 may have a temperature of about 200 ° C.

The mixed oil may be heated to about 180 [deg.] C before being fed to the regenerator 20. Therefore, saturated steam is generated due to the temperature difference between the mixed oil and steam in the regeneration tower 20, and the saturated steam separates the BTX component contained in the mixed oil into the upper side of the regenerator 20. In the mixed oil, the BTX component is removed and the absorption channel is regenerated again, but the mixed oil undergoes a polycondensation reaction due to the high temperature steam, and a high molecular weight compound is produced in the mixed oil. These high molecular weight compounds cause viscosity increase of the mixed oil. That is, BTX is removed and a high molecular weight compound remains in the regenerated absorbing oil, and the regenerated absorbing oil has higher viscosity than that before regeneration.

Next, the step of transferring the regenerated absorbing oil to the separating plate and removing the polymer material from the regenerated absorbing oil will be described. In the above step, the molten steel sheet from which the removal of the polymeric material is carried out is operated at a pressure of 30 mmHg to 80 mmHg and a temperature of 100 ° C to 120 ° C.

In the previous step, a portion of the regenerated absorbed oil having a higher viscosity is transferred to the molten tooth bed. At this time, the amount of the absorbing oil transferred to the transferred molten tooth may be between 10% and 60%.

When the amount of the absorption oil supplied from the regeneration tower to the absorption tower is 60% or more, the amount of process recycle absorption oil is reduced, so that a large amount of new absorption oil must be replenished newly. When the amount of the absorbing oil supplied from the regeneration tower to the removing column is less than 10%, the polymer material of circulating absorbing oil can not be sufficiently removed, which makes it difficult to control the viscosity of the absorbing oil.

The molten steel is supplied with steam to remove the deteriorated polymer material contained in the absorbing oil. The deteriorated polymer material is discharged to the lower part of the removing column.

The inside of the molten steel is 30 mmHg to 80 mmHg, and the temperature of the steam supplied to the molten steel is 100 ° C to 120 ° C. Since the inside of the molten steel is reduced in pressure from 30 mmHg to 80 mmHg at normal pressure, the polymer material of the absorption oil can be adsorbed even by using relatively low temperature steam.

At this time, the viscosity of the absorption oil from which the polymer substance is removed may be less than 1.3 angel viscosity.

The method for regenerating the absorbent oil according to an embodiment of the present invention may further include the step of transferring the regenerated absorbent oil to the absorbent core and removing the polymer material from the regenerated absorbent oil, To the tower. The absorption oil transferred to the regeneration tower again is injected into the absorption tower and can be reused in the BTX collection process in the absorption tower.

As described above, the method of regenerating the absorbing oil according to the embodiment of the present invention is characterized in that, in the removing step, steam is sucked into the absorber using steam at a reduced pressure and a low temperature (30 mmHg to 80 mmHg pressure, 100 ° C to 120 ° C steam) The existing deteriorated polymer material was removed, and the viscosity of the absorption oil was lowered. Therefore, the absorbing oil can be reused without being concerned with the piping being adsorbed to the process piping or the like. In addition, by operating the molten silica by using the low temperature steam under the reduced pressure condition, the cost can be reduced as compared with the case of using the high temperature steam, and the viscosity of the absorption oil can be effectively lowered.

Hereinafter, a method of regenerating the absorption oil according to an embodiment of the present invention and its effect will be described with reference to specific experimental examples.

Experimental Example  One

As the operating condition of the molten steel, the pressure was set to 80 mmHg and the temperature was operated at 120 ° C. As a result, the viscosity of the absorbent oil passed through the molten tooth was 1.1 angler viscosity, and the amount of absorbed oil loss was reduced by 30%.

Experimental Example  2

As the operating conditions of the molten steel sheet, the pressure was set to 30 mmHg and the temperature was operated at 100 ° C. As a result, the viscosity of the absorbent oil passed through the molten tooth was 1.2 angler viscosity, and the loss of absorption oil loss was 20%.

Comparative Example  One

As the operating condition of the molten steel, the pressure was set at atmospheric pressure and the temperature was operated at 160 ° C. As a result, the viscosity of the absorbent oil passed through the molt chute was 1.8 angler viscosity and the absorbed oil loss was 3 tons / day.

Comparative Example  2

As the operating condition of the molten steel, the pressure was set at normal pressure and the temperature was operated at 200 ° C. As a result, the viscosity of the absorbent oil passed through the molten tooth was 1.1 angler viscosity and the absorbed oil loss was 5 ton / day.

As described above, the method of regenerating the absorbing oil according to an embodiment of the present invention enables the viscosity of the absorbing oil to be controlled to be lowered and reusable by operating the absorbing chimney under the reduced-pressure low-temperature condition.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, Of the right.

10: Absorption tower 20: Reclaim tower
30: molting tooth

Claims (4)

Jetting an oil-absorbing oil into the COG gas flowing into the absorption tower to collect BTX contained in the COG gas to form a mixed oil,
Transferring the mixed oil to a regeneration tower, removing BTX from the mixed oil to regenerate an absorption channel, and
Transferring the regenerated absorbing oil to the removing column, and removing the polymer material from the regenerated absorbing oil,
The stripping column where the removal of the polymeric material is performed uses steam at a pressure of 30 mmHg to 80 mmHg and a temperature of 100 ° C to 120 ° C,
Wherein the viscosity of the absorbent oil from which the polymer material is removed is less than 1.3 angular viscosity. The method of claim 1,
And transferring the absorbing oil from which the polymer material has been removed to the regeneration tower again. delete 3. The method of claim 2,
In the step of transferring the regenerated absorbing oil to the removing column and removing the polymer material from the regenerated absorbing oil,
And the amount of the absorbing oil transferred to the removing tank is between 10% and 60%.
KR1020150185932A 2015-12-24 2015-12-24 the method for recycling BTX absorption oil in coke gas refining process KR101798623B1 (en)

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KR1020150185932A KR101798623B1 (en) 2015-12-24 2015-12-24 the method for recycling BTX absorption oil in coke gas refining process

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KR101798623B1 true KR101798623B1 (en) 2017-11-16

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