KR100797284B1 - A method for improving hydrogen sulfide distillation efficiency of disociator - Google Patents

A method for improving hydrogen sulfide distillation efficiency of disociator Download PDF

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KR100797284B1
KR100797284B1 KR1020010083372A KR20010083372A KR100797284B1 KR 100797284 B1 KR100797284 B1 KR 100797284B1 KR 1020010083372 A KR1020010083372 A KR 1020010083372A KR 20010083372 A KR20010083372 A KR 20010083372A KR 100797284 B1 KR100797284 B1 KR 100797284B1
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tower
hydrogen sulfide
absorption liquid
regeneration tower
coke oven
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KR20030053615A (en
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이광우
곽호남
박양주
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주식회사 포스코
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J1/00—Production of fuel gases by carburetting air or other gases without pyrolysis
    • C10J1/24—Controlling humidity of the air or gas to be carburetted
    • 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
    • B01D53/1456—Removing acid components
    • B01D53/1475—Removing carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/002—Removal of contaminants
    • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Industrial Gases (AREA)

Abstract

본 발명은 코크스오븐가스중 황화수소 흡수액에 포함된 이산화탄소 및 황화수소의 분리효율을 향상시키도록 황화수소 증류효율을 향상시키는 방법을 제공하는데, 이를 위한 기술적 구성요소는 흡수액 재생탑에 열원으로써 스팀을 직접 주입하지 않고 스팀이 공급되는 재비기에 의한 간접열원 공급과 불활성가스를 공급하는 데에 있다.The present invention provides a method for improving the hydrogen sulfide distillation efficiency to improve the separation efficiency of the carbon dioxide and hydrogen sulfide contained in the hydrogen sulfide absorption liquid in the coke oven gas, the technical component for this does not directly inject steam as a heat source to the absorption liquid regeneration tower. Indirect heat source supply and inert gas by the reboiler is supplied without steam.

따라서, 본 발명에 의하면, 흡수액재생탑의 압력과 온도를 조정함으로써 흡수액에 공존하는 황화수소 및 이산화탄소에 대한 분리효율을 증대시켜 코크스오븐가스 정제용 흡수액 재생탑의 황화수소 증류효율을 향상시키는 것이다.Therefore, according to the present invention, by adjusting the pressure and temperature of the absorption liquid regeneration tower, the separation efficiency of hydrogen sulfide and carbon dioxide coexisting in the absorption liquid is increased to improve the hydrogen sulfide distillation efficiency of the absorption liquid regeneration tower for coke oven gas purification.

화성공정, 코크스오븐가스, 황화수소 포집탑, 흡수액 재생탑, 암모니아 증류탑Chemical Process, Coke Oven Gas, Hydrogen Sulfide Collection Tower, Absorbent Regeneration Tower, Ammonia Distillation Tower

Description

코크스오븐가스 정제용 흡수액 재생탑의 황화수소 증류효율 향상방법{A METHOD FOR IMPROVING HYDROGEN SULFIDE DISTILLATION EFFICIENCY OF DISOCIATOR} Method for improving the distillation efficiency of hydrogen sulfide in the regeneration tower for coke oven gas purification {A METHOD FOR IMPROVING HYDROGEN SULFIDE DISTILLATION EFFICIENCY OF DISOCIATOR}             

도 1은 종래의 코크스오븐가스 처리공정인 화성공정을 도시한 공정도1 is a process chart showing a chemical conversion process of a conventional coke oven gas treatment process

도 2는 본 발명에 따른 황화수소 증류를 위하여 재비기를 설치하여 간접방식으로 황화수소를 증류하고, 재비기에서 발생되는 응축수는 암모니아 포집탑으로 공급하는 공정을 도시한 공정도이다2 is a process diagram illustrating a process of distilling hydrogen sulfide in an indirect manner by installing a reboiler for distilling hydrogen sulfide according to the present invention, and supplying the condensed water generated in the reboiler to an ammonia collection tower.

도 3은 본 발명에서 사용되는 재비기를 도시한 개략도Figure 3 is a schematic diagram showing a reboiler used in the present invention

* 도면의 주요부분에 대한 부호의 설명 * Explanation of symbols on the main parts of the drawings

1.... 재비기 10.... 불활성가스 공급관1 .... Reboiler 10 .... Inert gas supply line

110.... 황화수소 포집탑 120.... 암모니아 포집탑110 .... Hydrogen Sulfide Collection Tower 120 .... Ammonia Collection Tower

170.... 흡수액 재생탑 180.... 암모니아 증류탑
170 .... Absorbent Regeneration Tower 180 .... Ammonia Distillation Tower

본 발명은 제철소의 코크스오븐에서 발생되는 코크스오븐가스를 처리하는 화 성공정에서 코크스오븐가스 정제용 흡수액중 황화수소의 증류효율을 향상시키는 방법에 관한 것으로 이는 특히, 흡수액 재생탑 및 암모니아증류탑에 열원으로써 스팀을 직접 주입하지 않고 스팀이 공급되는 재비기에 의한 간접열원 공급과 불활성가스를 공급함으로써 흡수액재생탑의 압력과 온도를 조정함으로써 흡수액에 공존하는 황화수소 및 이산화탄소에 대한 분리효율을 증대시켜 코크스오븐가스 정제용 흡수액 재생탑의 황화수소 증류효율 향상방법에 관한 것이다.
The present invention relates to a method for improving the distillation efficiency of hydrogen sulfide in the absorption liquid for the coke oven gas purification in the successful treatment of the coke oven gas generated in the coke oven of the steelworks. Coke oven gas purification by increasing the separation efficiency of hydrogen sulfide and carbon dioxide in the absorbent liquid by adjusting the pressure and temperature of the absorbent liquid regeneration tower by supplying indirect heat source and inert gas by reboiler steam supplied without directly injecting steam. The present invention relates to a method for improving distillation efficiency of hydrogen sulfide in an absorption liquid regeneration tower.

일반적으로 제철소의 코크스오븐에서 발생되는 코크스오븐가스(COKE OVEN GAS)(COG)를 처리하기 위한 화성공정은 도 1에서 도시한 바와 같이, 코크스오븐 (100)에서 순환안수로서 냉각기와 집진기를 거쳐 냉각된 COG가스는 황화수소 포집탑(110)과 암모니아 포집탑(120)을 거쳐 가스홀더(130)로 보내진다.In general, a chemical conversion process for treating COKE OVEN GAS (COG) generated in a coke oven of a steel mill is cooled through a cooler and a dust collector as a circulating water in the coke oven 100, as shown in FIG. The COG gas is sent to the gas holder 130 through the hydrogen sulfide collecting tower 110 and the ammonia collecting tower 120.

이때, 상기 황화수소 포집탑(110)에는 다음에 설명하는 황화수소 포집용 흡수액(안수) 재생탑(170)에서 증기(S1)로서 농축된 농축안수와 암모니아 포집탑 (120)을 거친 연수로서 황화수소(H2S)가 포집되고, 상기 포집탑(110)의 하부에서 배출되는 안수는 순환되거나 저장탱크(160)로 보내지고, 상기 암모니아 포집탑(120)에서는 연수로서 암모니아를 포집한다.At this time, the hydrogen sulfide collection tower 110 includes hydrogen sulfide (H) as soft water that has been concentrated through the concentrated ordination and ammonia collection tower 120 as steam (S1) in the absorption solution (ordination) regeneration tower 170 for hydrogen sulfide collection described below. 2 S) is collected, the ordination water discharged from the lower portion of the collecting tower 110 is circulated or sent to the storage tank 160, and the ammonia collecting tower 120 collects ammonia as soft water.

이때, COG가스를 냉각하는 데에 사용한 순환안수중에는 다량의 타르(TAR)가 함유되어 있어, 이 타르는 타르데칸트(140)에서 침적과정을 거쳐 통상 도로포장시 사용되는 타르제품을 부산물로 생산한다.At this time, a large amount of tar (TAR) is contained in the circulating ordination used to cool the COG gas, and this tar is produced as a by-product of tar products normally used for road paving through the deposition process in the tardecant (140). do.

또한, 코크스오븐(100)에서 석탄을 건류하면서 발생하는 흡수액인 암모니아 수용액 즉, 안수(순환안수)는 COG가스중에 포함된 황화수소를 포집하기 위해서 여과기(150)와 저장탱크(160)를 통하여 펀프(P)로서 황화수소포집용 흡수액 재생탑 (Disociator)(170)으로 보내져 흡수액(안수)으로 재순환되기도 한다.In addition, an aqueous ammonia solution, namely, ordination (circulating water), which is an absorbent liquid generated by coking coal in the coke oven 100, collects a pulp through a filter 150 and a storage tank 160 to collect hydrogen sulfide contained in COG gas. As P), it may be sent to an absorption liquid regeneration tower 170 for collecting hydrogen sulfide and recycled to the absorption liquid (ordination).

그리고, 상기 황화수소포집용 흡수액 재생탑(170)에서 발생되는 황화수소와 이산화탄소는 암모니아 증류탑(180)에서 암모니아가스를 분리한 후 그 상부를 통하여 열교환기(172)를 거쳐 탈황설비인 촉매연소반응기(210)에서 완전연소에 의하여 질소 및 수소로 분해 처리되는 것이다. Hydrogen sulfide and carbon dioxide generated in the absorption recovery regeneration tower 170 for collecting hydrogen sulfide are separated from the ammonia gas in the ammonia distillation tower 180 and then through the heat exchanger 172 through the upper portion of the catalytic combustion reactor 210. ) Is decomposed into nitrogen and hydrogen by complete combustion.

또한, 상기 황화수소 포집용 흡수액 재생탑(170)과 하부로 탈안수가 배출되는 암모니아증류탑(180)에서는 스팀(S1)(S2)을 각각의 탑의 하부로 직접 주입함으로써 황화수소 및 암모니아성분을 분리하고 있다.In addition, the hydrogen sulfide and ammonia components are separated by directly injecting steam (S1) (S2) into the lower portion of each tower in the ammonia distillation tower 180 in which the absorption solution regeneration tower 170 for collecting hydrogen sulfide and deionized water are discharged downward. have.

이때, 상기 암모니아 증류탑(180) 하부로 배출되는 미증류물인 탈안수는 열교환기를 거쳐 냉각처리된후 폐수처리설비(190)로 보내져 탈안수중 암모니아성분을 미생물활성화로 제거하기 위하여 정화단계를 거치게 된다. At this time, the undistilled water which is undistilled water discharged to the lower part of the ammonia distillation tower 180 is cooled through a heat exchanger and then sent to the wastewater treatment facility 190 to undergo a purification step to remove the ammonia component in the desalinated water by activating microorganisms.

그러나, 이와 같은 종래의 화성공정에서는 상기 황화수소포집용 흡수액재생탑(170)에 공급되는 타르테칸트(140)를 거친 흡수액(안수)중에는 이산화탄소와 황화수소가 함께 공존하기 때문에, 상기 황화수소포집용 흡수액 재생탑(170)에 직접적으로 스팀을 주입하는 경우에는, 상기 흡수액 재생탑(170)내의 온도 및 압력조정이 상당히 어려운 것이다.However, in the conventional chemical conversion process, since carbon dioxide and hydrogen sulfide coexist in the absorbent liquid (ordination) passed through the tartecant 140 supplied to the absorbent liquid regeneration tower 170 for collecting hydrogen sulfide, the hydrogen sulfide absorption absorbent liquid is regenerated. In the case of directly injecting steam to the tower 170, it is difficult to adjust the temperature and pressure in the absorption liquid regeneration tower 170.

따라서, 타트데칸트(140)를 거친 흡수액(안수)중에 함유된 이산화탄소 및 황화수소가스성분이 함께 흡수액 재생탑(170)의 상부로 배출될 수 밖에 없어, 후공정 인 탈류공정에서 이상운전이 발생되고, 가스처리시 용량초과를 초래하는 것이다. Therefore, the carbon dioxide and hydrogen sulfide gas components contained in the absorbent liquid (ordination) passing through the tart decant 140 must be discharged together with the upper part of the absorbent liquid regeneration tower 170, so that abnormal operation occurs in the post-reflow process. This results in overcapacity during gas treatment.

또한, 상기 흡수액재생탑(170)에 직접 공급되는 스팀은 응축하여 폐수발생량의 증가시키기 때문에, 이의 처리를 위한 별도의 설비가 필요한 문제가 있는 것이다.
In addition, since the steam supplied directly to the absorption liquid regeneration tower 170 increases the amount of wastewater generated by condensation, there is a problem that a separate facility for the treatment thereof is required.

본 발명은 상기와 같은 종래의 문제점을 해결하기 위한 것으로 안출된 것으로서 그 목적은, 황화수소 포집탑에 농안수인 황화수소 포집액을 제조하는 흡수액재생탑 및 암모니아를 증류시키어 안수를 발생시키는 암모니아증류탑의 열원을 직접 스팀공급방식에서 스팀이 공급되는 재비기에 의한 간접열원공급방식으로 교체하여, 황화수소포집용 흡수액 재생탑에서의 압력과 온도 조정이 용이하게 됨으로 인하여, 흡수액(안수)에 공존하는 황화수소 및 이산화탄소에 대한 분리효율을 가일층 증대시킬 수 있도록 한 코크스오븐가스 정제용 흡수액 재생탑의 황화수소 증류효율 향상방법을 제공하는 데에 있다.The present invention has been made to solve the conventional problems as described above, the object is, the heat source of the absorption liquid regeneration tower for producing hydrogen sulfide capture liquid in the hydrogen sulfide collection tower and the ammonia distillation tower to generate ordination by distilling ammonia Is changed from direct steam supply method to indirect heat source supply method by re-boiler with steam supply, and it is easy to adjust pressure and temperature in absorbent regeneration tower for collecting hydrogen sulfide, so that hydrogen sulfide and carbon dioxide coexist in absorbent liquid (ordination) It is to provide a method for improving the hydrogen sulfide distillation efficiency of the absorption liquid regeneration tower for the coke oven gas refining to further increase the separation efficiency.

또한, 본 발명의 다른 목적은, 황화수소 포집용 흡수액 재생탑에 열원을 제공하는 간접 스팀방식의 재비기에서 발생되는 스팀응축수를 암모니아 포집탑에 보내어 암모니나 포집을 위하여 사용하게 함으로서, 폐수발생량이 감소하여 공정운전비용을 감소시키도록 한 코크스오븐가스 정제용 흡수액 재생탑의 황화수소 증류효율 향상방법을 제공하는 데에 있다.In addition, another object of the present invention is to reduce the amount of waste water generated by sending the steam condensed water generated in the reboiler of the indirect steam method for providing a heat source to the absorption liquid regeneration tower for collecting hydrogen sulfide to be used for ammonia or collection. It is to provide a method for improving the hydrogen sulfide distillation efficiency of the absorption liquid regeneration tower for coke oven gas purification to reduce the process operating cost.

상기와 같은 목적을 달성하기 위한 기술적인 구성으로서 본 발명은, 코크스오븐에서 발생된 코크스오븐가스의 처리를 위한 화성공정에서 황화수소 포집탑에 흡수액을 보내도록 제조하는 흡수액 재생탑과 연수로서 암모니아를 포집하는 암모니아 포집탑 및, 탈안수를 배출하는 암모니아 증류탑에 의한 코크스오븐가스 정제용 흡수액중 황화수소 증류효율을 높이는 방법에 있어서, As a technical configuration for achieving the above object, the present invention, the absorption liquid regeneration tower for producing the absorption liquid to the hydrogen sulfide collection tower in the chemical conversion process for the treatment of the coke oven gas generated in the coke oven to collect ammonia as soft water In the method of increasing the distillation efficiency of hydrogen sulfide in the absorption liquid for the coke oven gas purification by the ammonia collection tower and the ammonia distillation column to discharge the desorption water,

상기 황화수소 포집용 흡수액 재생탑에는 탑내부의 온도 및 압력을 용이하게 조정토록 스팀이 열원인 재비기로서 간접 열원이 제공되고, The absorption liquid regeneration tower for collecting hydrogen sulfide is provided with an indirect heat source as a reboiler in which steam is a heat source to easily adjust the temperature and pressure inside the tower.

상기 재생탑에는 탑내부의 압력조정을 위한 일정압의 불활성가스가 공급되며, The regeneration tower is supplied with an inert gas of a constant pressure for adjusting the pressure inside the tower,

상기 재비기에서 발생된 응축수는 상기 암모니아 포집탑에 보내는 코크스오븐가스 정제용 흡수액 재생탑의 황화수소 증류효율 향상방법을 마련함에 의한다.The condensate generated in the reboiler is to provide a method for improving the hydrogen sulfide distillation efficiency of the absorption liquid regeneration tower for coke oven gas purification sent to the ammonia collection tower.

이하, 첨부된 도면에 의거하여 본 발명을 보다 상세하게 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

도 2에서는 본 발명에 따른 황화수소증류를 위하여 재비기를 설치하여 간접방식으로 황화수소를 증류하고, 재비기에서 발생되는 응축수는 암모니아흡수탑으로 공급하는 공정을 도시하고 있다.2 shows a process of distilling hydrogen sulfide in an indirect manner by installing a reboiler for distillation of hydrogen sulfide according to the present invention, and supplying the condensed water generated in the reboiler to an ammonia absorption tower.

이때, 이하에서는 종래의 구성과 동일한 구성은 동일부호로 나나내고 그 작용설명은 생략한다.In this case, hereinafter, the same components as the conventional components will be denoted by the same reference numerals and the description thereof will be omitted.

안수가 공급되어 코크스오븐가스(COG)중에 포함된 황화수소를 포집하기 위한 황화수소 포집탑(100)에 황화수소 포집용인 흡수액 즉, 농안수를 제조하는 흡수액 재생탑(170)의 하부에 재비기(1)를 설치하고, 또한 암모니아 증유탑(180)에도 재비기(1)를 설치한다.Re-absorbing the absorbent liquid for hydrogen sulfide collection, namely, the absorbent liquid regeneration tower 170 for producing the farmed water, to the hydrogen sulfide collection tower 100 for collecting the hydrogen sulfide contained in the coke oven gas (COG) with ordination (1) And install the reboiler 1 in the ammonia filling tower 180.

한편, 도 3에서는 본 발명의 재비기(1)를 개략적으로 도시하고 있는데, 안수가 공급되는 흡수액 재생탑(170)의 하부에 연결관(3)으로 스팀관이 통과하는 보조탱크(2)가 설치되어 안수가 순환되면서 스팀관에 의하여 승온되는 것이다.On the other hand, Figure 3 schematically shows a reboiler 1 of the present invention, the auxiliary tank (2) through which the steam pipe passes through the connection pipe (3) in the lower portion of the absorbent liquid regeneration tower 170 is supplied Installed and ordination is to be heated up by the steam pipe while circulating.

따라서, 종래 스팀이 직접 흡수액 재생탑(170)에 주입되지 않고 본 발명에서는 재비기(1)로서 흡수액 재생탑(170)에 간접방식으로 안수를 승온시키는 열원을 제공하는 것이다.Therefore, conventional steam is not directly injected into the absorbent liquid regeneration tower 170, and in the present invention, the reheater 1 provides a heat source for raising the ordinal water in an indirect manner to the absorbent liquid regeneration tower 170.

즉, 도 2에서 도시한 바와 같이, 본 발명에서는 흡수액 재생탑(170)에 재비기(1)를 사용하여 종래 스팀을 직접공급함에 따른 스팀 응축수로 인한 페수발생을 감소시키는 것이다.That is, as shown in Figure 2, in the present invention, by using the reboiler (1) to the absorption liquid regeneration tower 170 to reduce the generation of waste water due to steam condensed water by direct supply of conventional steam.

또한, 상기 흡수액 재생탑(170)과 암모니아 증류탑(180)에는 가스공급관(10)을 연결하여 상기 흡수액 재생탑(170)내의 압력조정을 위하여 3~4 기압의 불활성가스를 주입하는데, 이때 사용되는 불활성 가스로는 질소, 아르곤 또는 헬륨 등으로 반응성이 전혀 없는 가스를 사용한다.In addition, the absorption liquid regeneration tower 170 and the ammonia distillation tower 180 is connected to the gas supply pipe 10 to inject an inert gas of 3 to 4 atm for pressure adjustment in the absorption liquid regeneration tower 170, which is used As an inert gas, a gas having no reactivity such as nitrogen, argon or helium is used.

이때, 상기 흡수액 재생탑(170)에 공급되는 불활성가스의 공급압력을 3~4기압으로 한정하는 이유는 불활성가스는 가스공급에 따른 경비와 관계있는 것으로써 위에서 제시한 공급압력이 최소의 경비를 유지할수 있는 수준이기 때문이다. In this case, the reason why the supply pressure of the inert gas supplied to the absorption liquid regeneration tower 170 is limited to 3 to 4 atm is that the inert gas is related to the cost of supplying the gas. This is because it is a sustainable level.

그런데, 상기 불활성가스의 공급압력이 3 기압 보다 낮은 경우에는, 상기 재 생탑(170)의 내부 압력조정이 곤란하고, 동시에 황화수소 증류효율이 감소하게 된다. However, when the supply pressure of the inert gas is lower than 3 atm, it is difficult to adjust the internal pressure of the regeneration tower 170, and at the same time the hydrogen sulfide distillation efficiency is reduced.

또한, 상기 흡수액 재생탑(170)의 온도는 재비기(1)에 공급되는 스팀관의 온도를 조정하여 70-80℃로, 그리고 탑의 내부압력은 2500~3000mmH2O을 유지하는 것이 바람직하다. In addition, the temperature of the absorption liquid regeneration tower 170 is adjusted to 70-80 ℃ by adjusting the temperature of the steam pipe supplied to the reboiler 1, and the internal pressure of the tower is preferably maintained at 2500 ~ 3000mmH 2 O. .

즉, 상기 재생탑(170)의 내부온도는 70-80℃가 적정한데, 이는 흡수액 즉, 안수중 이산화탄소와 황화수소의 증기압과 관계가 있기 때문이고, 만약 상기 온도보다 재생탑(170)의 내부온도가 낮을 경우에는 이산화탄소만 증류되는 현상이 나타내게 되고, 반대로 상기 온도보다 높을 때에는 흡수액 재생시 열원인 재비기(1)의 스팀관을 통하는 스팀의 공급량을 증대시켜야 하기 때문이데, 이는 설비의 가동비용을 증대시키는 문제가 있는 것이다.That is, the internal temperature of the regeneration tower 170 is suitable for 70-80 ℃, because it is related to the vapor pressure of the absorption liquid, that is, carbon dioxide and hydrogen sulfide in the water, if the internal temperature of the regeneration tower 170 than the temperature If it is low, only carbon dioxide is distilled. On the contrary, when the carbon dioxide is higher than the above temperature, the supply amount of steam through the steam pipe of the reboiler 1, which is a heat source during regeneration of the absorbent liquid, must be increased, which increases the operating cost of the equipment. There is a problem to increase.

따라서, 상기 공정조건이 최소의 비용으로 최대의 효과를 거둘수 있는 최적의 조건이 된다. Therefore, the process conditions are the optimum conditions that can achieve the maximum effect at the minimum cost.

다음, 상기 흡수액 재생탑(170)에 공급되는 흡수액의 온도는 70~75℃을 유지하는 것이 바람직한데, 이는 공급되는 흡수액의 온도에 따른 황화수소 증류효율이 좌우되는 변수로써, 위에서 제시한 온도보다 낮을시에는 황화수소증류효율이 감소하게 되고, 보다 높은 온도로 공급하여도 증류효율은 크게 증가하기 않았다. Next, the temperature of the absorbent liquid supplied to the absorbent liquid regeneration tower 170 is preferably maintained at 70 ~ 75 ℃, which is a variable depending on the hydrogen sulfide distillation efficiency depending on the temperature of the supplied absorbent liquid, it is lower than the temperature suggested above At the time of distillation, hydrogen sulfide distillation efficiency decreased, and the distillation efficiency did not increase significantly even at higher temperature.

이는 공급되는 흡수액의 온도에 따라 탑내에서의 흡수액중 성분들의 증기압변화로 인하여 응축되는 현상을 보이므로 공급온도의 조건을 조절함으로써 흡수액중의 황화수소성분에 대한 응축현상을 최소화시킬수 있는 조건이 된다. Since the condensation occurs due to the change in the vapor pressure of the components in the absorbent liquid in the column according to the temperature of the absorbent liquid to be supplied, the condensation phenomenon of the hydrogen sulfide component in the absorbent liquid is minimized by adjusting the conditions of the supply temperature.                     

다음, 재비기(1)에 공급되는 스팀의 응축수를 암모니아 포집탑(120)에 공급하면, 흡수액 재생탑(170)에서 흡수액중의 황화수소를 증류하는데 있어서, 재비기 (1)를 이용한 간접 스팀을 사용함에 따라 흡수액과 스팀과의 열교환으로 스팀의 응축수가 생성되는데 , 이와 같은 스팀의 응축수는 경도성분이 제거된 순수한 물인 연수의 특성을 가지고 있으므로 이를 암모니아 포집탑(120)에 공급하여 코크스오븐가스중의 암모니아가스를 포집하도록 하는데 재활용할 수 있는 것이다. Next, when the condensed water of steam supplied to the reboiler 1 is supplied to the ammonia collection tower 120, indirect distillation using the reboiler 1 in distilling hydrogen sulfide in the absorbent liquid from the absorption liquid regeneration tower 170 is performed. As it is used, condensate of steam is generated by heat exchange between absorbent and steam. Since the condensate of steam has characteristics of soft water, which is pure water from which hardness components have been removed, it is supplied to the ammonia collection tower 120 to provide coke oven gas. To collect ammonia gas, which can be recycled.

따라서, 상기 암모니아 증류탑(120)에 공급되는 연수의 양도 감소되기 때문에, 제조설비에서 연수제조를 위한 경비절감을 추구할 수가 있는 것이다.Therefore, since the amount of soft water supplied to the ammonia distillation column 120 is also reduced, it is possible to seek cost savings for soft water production in a manufacturing facility.

한편, 앞에서 설명한 흡수액 재생탑(170)의 온도와 불화성가스의 공급압력 및 탑내압력에 따른 황화수소 증류효율 결과를 다음의 표 1에서 나타내었다.On the other hand, the hydrogen sulfide distillation efficiency according to the temperature of the absorption liquid regeneration tower 170, the supply pressure of the fluorinated gas and the internal pressure of the column are shown in Table 1 below.

탑내 온도 (℃)Temperature in tower (℃) 불활성가스 유입압력(bar)Inert gas inlet pressure (bar) 탑내압력 (mmH2O)Tower Inner Pressure (mmH 2 O) 증류효율(%)Distillation efficiency (%) 5050 1One 12001200 8080 6060 22 15001500 8282 7070 33 26402640 9292 8080 44 28902890 9595 100100 55 32003200 8484

즉, 상기 표 1에서 알수 있듯이, 흡수액 재생탑(170)의 탑내온도 70-80℃로 하고, 그 내부에 공급되는 불화성가스의 공급압력을 3-4bar로 하며, 탑내압력 2500~3000 mmH2O 일때 황화수소의 증류효율은 90%이상임을 알 수 있는 것이다. That is, as can be seen in Table 1, the internal temperature of the absorption liquid regeneration tower 170 is 70-80 ℃, the supply pressure of the fluorinated gas supplied therein is 3-4bar, the internal pressure 2500 ~ 3000 mmH 2 When O is distillation efficiency of hydrogen sulfide is 90% or more will be seen.

다음, 탑내압력조정을 위하여 불화성가스의 유입압력을 일정하게 유지하였을 때, 탑내온도 및 탑내압력에 따른 황화수소 증류효율을 표 2에서 나타내었다.
Next, Table 2 shows the hydrogen sulfide distillation efficiency according to the tower temperature and the tower pressure when the inflow pressure of the fluorinated gas is kept constant for the tower pressure adjustment.

탑내 온도 (℃)Temperature in tower (℃) 불활성가스 유입압력(bar)Inert gas inlet pressure (bar) 탑내압력 (mmH2O)Tower Inner Pressure (mmH2O) 증류효율(%)Distillation efficiency (%) 5050 33 19001900 8585 6060 33 21802180 8787 7070 33 26402640 9292 8080 33 27902790 9595 100100 33 30103010 8888

. .

즉, 상기 표 2에서 알수 있듯이, 불활성가스의 공급압력을 3기압으로 일정하게 하였을때, 탑내온도는 70-80℃ 이고, 탑내압력은 2500~3000 mmH2O 일때 황화수소의 증류효율이 90%이상임을 알 수 있는 것이다.That is, as can be seen in Table 2, when the supply pressure of the inert gas is constant at 3 atmospheres, the distillation efficiency of hydrogen sulfide is 90% or more when the tower inside temperature is 70-80 ℃, the inside pressure is 2500 ~ 3000 mmH 2 O You can see that.

그리고, 탑내온도 및 불화성가스의 공급압력을 일정하게 유지하고, 탑내압력을 변화시켰을때의 황화수소 증류효율을 표 3 에서 나타내고 있다.Table 3 shows the hydrogen sulfide distillation efficiency when the column temperature and the supply pressure of the fluorinated gas are kept constant and the column pressure is changed.

탑내 온도 (℃)Temperature in tower (℃) 불활성가스 유입압력(bar)Inert gas inlet pressure (bar) 탑내압력 (mmH2O)Tower Inner Pressure (mmH 2 O) 증류효율(%)Distillation efficiency (%) 7070 33 15001500 8282 7070 33 20002000 8686 8080 33 25002500 9393 8080 33 30003000 9595 8080 33 35003500 8787

따라서, 상기 표 3에서 알수 있듯이, 압력증가에 따라 황화수소 증류효율은 증류효율은 증가하는 경향을 보여주고 있지만. 탑내압력이 3000mmH2O 보다 클경우에는 오히려 증류효율이 감소하는 것을 알수가 있었다.Therefore, as can be seen in Table 3, the hydrogen sulfide distillation efficiency shows a tendency to increase as the pressure increases. Distillation efficiency decreased when the column pressure was greater than 3000mmH2O.

즉, 증기상의 황화수소성분이 압력상승으로 인하여 흡수액중에 함유되어 있는 수분증기상에 흡수되는 역전현상으로 인한 것이다.In other words, the hydrogen sulfide component in the vapor phase is caused by the reverse phenomenon of being absorbed by the water vapor contained in the absorbent liquid due to the pressure increase.

다음, 표 4에서는 탑내온도를 일정한 경우에 대하여 나타내고 있다.
Next, Table 4 shows the case where the tower internal temperature is constant.

탑내 온도 (℃)Temperature in tower (℃) 불활성가스 유입압력(bar)Inert gas inlet pressure (bar) 탑내압력 (mmH2O)Tower Inner Pressure (mmH 2 O) 증류효율(%)Distillation efficiency (%) 5050 33 25002500 8282 6060 33 25002500 8585 7070 33 25002500 9393 8080 33 25002500 9797 100100 33 25002500 8585

즉, 상기 표 4에서는 탑내온도변화에 따른 황화수소 증류효율을 보여주고 있는데, 탑내온도가 증가함에 따라 황화수소 증류효율이 증가하는 경향을 보여주고 있지만, 탑내온도가 100℃인 경우 즉, 80도 보다 높은 경우에는 오히려 황화수소 증류효율이 감소하는 것을 보여주고 있다. That is, Table 4 shows the hydrogen sulfide distillation efficiency according to the change in the tower temperature, the hydrogen sulfide distillation efficiency shows a tendency to increase as the tower temperature increases, but when the tower temperature is 100 ℃, that is, higher than 80 degrees In this case, the hydrogen sulfide distillation efficiency is shown to decrease.

이는, 탑내온도가 낮은 경우에는 흡수액중의 황화수소에 대한 증기압이 크지가 못하여 증류효율이 낮게 나타나고 있고, 지나친 온도의 상승은 증기상의 황화수소에 대한 이슬점이 낮아짐으로 인하여 증류효율이 감소하기 때문이다.
This is because, when the temperature in the tower is low, the distillation efficiency is low because the vapor pressure of hydrogen sulfide in the absorbent liquid is not large, and the excessive increase in temperature decreases the distillation efficiency due to the low dew point of the vaporized hydrogen sulfide.

이와 같이 본 발명인 코크스오븐가스 정제용 흡수액 재생탑의 황화수소 증류효율 향상방법에 의하면, 황화수소 포집탑에 농안수인 황화수소 포집액을 제조하는 흡수액재생탑 및 암모니아를 증류시키어 안수를 발생시키는 암모니아증류탑의 열원을 직접 스팀공급방식에서 스팀이 공급되는 재비기에 의한 간접열원공급방식으로 교체하여, 황화수소포집용 흡수액 재생탑에서의 압력과 온도 조정이 용이하게 됨으로 인하여, 흡수액(안수)에 공존하는 황화수소 및 이산화탄소에 대한 분리효율을 가일층 증대시키는 우수한 효과를 제공한다.Thus, according to the method for improving the hydrogen sulfide distillation efficiency of the absorption liquid regeneration tower for coke oven gas purification of the present invention, the heat source of the absorption liquid regeneration tower for producing hydrogen sulfide collection liquid, which is a concentrated water in the hydrogen sulfide collection tower, and the ammonia distillation column that generates ordination by distilling ammonia Is changed from direct steam supply method to indirect heat source supply method by re-boiler with steam supply, and it is easy to adjust pressure and temperature in absorbent regeneration tower for collecting hydrogen sulfide, so that hydrogen sulfide and carbon dioxide coexist in absorbent liquid (ordination) It provides an excellent effect to further increase the separation efficiency for.

더하여, 황화수소 포집용 흡수액 재생탑에 열원을 제공하는 간접 스팀방식의 재비기에서 발생되는 스팀응축수를 암모니아 포집탑에 보내어 암모니나 포집을 위하여 사용하게 함으로서, 폐수발생량이 감소하여 공정운전비용을 감소시키는 잇점을 추가로 제공하는 것이다.In addition, the steam condensed water generated in the indirect steam reboiler, which provides the heat source to the absorption liquor recovery tower for collecting hydrogen sulfide, is sent to the ammonia collection tower for use in ammonia or collection. It provides additional benefits.

본 발명은 특정한 실시예에 관련하여 도시하고 설명하였지만, 이하의 특허청구범위에 의해 마련되는 본 발명의 정신이나 분야를 벗어나지 않는 한도내에서 본 발명이 다양하게 개조 및 변화될수 있다는 것을 당업계에서 통상의 지식을 가진자는 용이하게 알수 있음을 밝혀두고자 한다.While the invention has been shown and described with respect to specific embodiments thereof, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit or scope of the invention as set forth in the claims below. I would like to know that those who have knowledge of this can easily know.

Claims (2)

코크스오븐(100)에서 발생된 코크스오븐가스의 처리를 위한 화성공정에서 황화수소 포집탑(110)에 흡수액을 보내도록 제조하는 흡수액 재생탑(170)과 연수로서 암모니아를 포집하는 암모니아 포집탑(120) 및, 탈안수를 배출하는 암모니아 증류탑 (180)에 의한 코크스오븐가스 정제용 흡수액중 황화수소 증류효율을 높이는 방법에 있어서, Absorption liquid regeneration tower 170 for producing an absorption liquid to the hydrogen sulfide collection tower 110 in the chemical conversion process for the treatment of coke oven gas generated in the coke oven 100 and ammonia collection tower 120 to collect ammonia as soft water And, in the method for increasing the hydrogen sulfide distillation efficiency in the absorption liquid for coke oven gas purification by the ammonia distillation tower 180 for discharging de-anhydration, 상기 황화수소 포집용 흡수액 재생탑(170)에는 탑내부의 온도 및 압력을 용이하게 조정토록 스팀이 열원인 재비기(1)로서 간접 열원이 제공되고, The absorption liquid regeneration tower 170 for collecting hydrogen sulfide is provided with an indirect heat source as a reboiler 1 in which steam is a heat source to easily adjust the temperature and pressure inside the tower. 상기 재생탑(170)에는 탑내부의 압력조정을 위한 일정압의 불활성가스가 공급되며, The regeneration tower 170 is supplied with an inert gas of a constant pressure for adjusting the pressure inside the tower, 상기 재비기(1)에서 발생된 응축수는 상기 암모니아 포집탑(120)에 보내는 것을 특징으로 하는 코크스오븐가스 정제용 흡수액 재생탑의 황화수소 증류효율 향상방법.The condensate generated in the reboiler (1) is sent to the ammonia collection tower 120, characterized in that the hydrogen sulfide distillation efficiency improvement method of the absorption liquid regeneration tower for coke oven gas purification. 제 1항에 있어서, 상기 흡수액 재생탑(170)의 온도는 상기 재비기(1)에 공급되는 스팀의 유량을 조정하여 70-80℃로 유지하고, According to claim 1, wherein the temperature of the absorption liquid regeneration tower 170 is maintained at 70-80 ℃ by adjusting the flow rate of steam supplied to the reboiler (1), 상기 재생탑(170)의 내부 압력은 2500~3000mmH2O로 유지되며, The internal pressure of the regeneration tower 170 is maintained at 2500 ~ 3000mmH 2 O, 상기 흡수액 재생탑(170)에 공급되는 불활성가스는 3-4 기압으로 공급되는 것을 특징으로 하는 코크스오븐가스 정제용 흡수액 재생탑의 황화수소 증류효율 향 상방법Inert gas supplied to the absorption liquid regeneration tower 170 is hydrogen sulfide distillation efficiency improvement method of the absorption liquid regeneration tower for refining coke oven gas, characterized in that supplied to 3-4 atm pressure
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US5260047A (en) * 1990-10-05 1993-11-09 Linde Aktiengesellschaft Process for purifying waste gases containing polyhalogenated compounds
KR20000040398A (en) * 1998-12-18 2000-07-05 이구택 Method for excluding capture of carbon dioxide in purifying coke gas
JP2000239673A (en) * 1999-02-17 2000-09-05 Nippon Steel Corp Method for purifying coke oven gas
JP2001081479A (en) * 1999-09-16 2001-03-27 Kawasaki Steel Corp Method and apparatus for purifying coke oven gas

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Publication number Priority date Publication date Assignee Title
US5260047A (en) * 1990-10-05 1993-11-09 Linde Aktiengesellschaft Process for purifying waste gases containing polyhalogenated compounds
KR20000040398A (en) * 1998-12-18 2000-07-05 이구택 Method for excluding capture of carbon dioxide in purifying coke gas
JP2000239673A (en) * 1999-02-17 2000-09-05 Nippon Steel Corp Method for purifying coke oven gas
JP2001081479A (en) * 1999-09-16 2001-03-27 Kawasaki Steel Corp Method and apparatus for purifying coke oven gas

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