KR20020044254A - Method for treating tail gas in sintering process - Google Patents

Method for treating tail gas in sintering process Download PDF

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KR20020044254A
KR20020044254A KR1020000073246A KR20000073246A KR20020044254A KR 20020044254 A KR20020044254 A KR 20020044254A KR 1020000073246 A KR1020000073246 A KR 1020000073246A KR 20000073246 A KR20000073246 A KR 20000073246A KR 20020044254 A KR20020044254 A KR 20020044254A
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tail gas
hydrogen sulfide
sulfur
limestone
fluidized bed
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KR1020000073246A
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Korean (ko)
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KR100494135B1 (en
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정동철
백남철
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이구택
주식회사 포스코
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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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/52—Hydrogen sulfide
    • B01D53/523—Mixtures of hydrogen sulfide and sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D45/00—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces
    • B01D45/12—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces by centrifugal forces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/02—Particle separators, e.g. dust precipitators, having hollow filters made of flexible material
    • B01D46/023—Pockets filters, i.e. multiple bag filters mounted on a common frame
    • 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/75—Multi-step processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/12—Methods and means for introducing reactants
    • B01D2259/126—Semi-solid reactants, e.g. slurries

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Gas Separation By Absorption (AREA)
  • Treating Waste Gases (AREA)
  • Industrial Gases (AREA)

Abstract

PURPOSE: Provided is a method for treating tail gas from sintering process which can prevent corrosion and clogging in pipe arrangement by neutralizing tail gas containing sulfur dioxide and hydrogen sulfide by using limestone/lime slurry generated from steelmaking industries as byproduct. CONSTITUTION: The method includes the steps of recovery of liquid sulfur in desulfurizing device(130); spraying ammonia water to hot tail gas(31) so that the temperature of tail gas is lowered to 110-130deg.C; feeding the cooled tail gas into fluidized reactor(10); reacting the tail gas and limewater(12) in the fluidized reactor in such a manner that the ratio of sulfur in the tail gas and calcium in limewater become 1:3; maintenance of the temperature of tail gas in which sulfur dioxide and hydrogen sulfide are removed by reacting with limestone liquid in the fluidized reactor with 30 to 35deg.C; passing tail gas through cyclone(20) and back filter(30) for removing limestone dust after absorbing sulfur compound in tail gas and feeding that in absorbing tower(110).

Description

화성 테일가스 처리방법{METHOD FOR TREATING TAIL GAS IN SINTERING PROCESS}Hwaseong tail gas treatment method {METHOD FOR TREATING TAIL GAS IN SINTERING PROCESS}

본 발명은 황화수소를 포함한 가스를 탈황공정에서 액체 황으로 생산하고, 미 반응한 황화수소와 이산화황을 포함한 테일가스(Tail Gas)를 처리하는 공정에관한 것으로, 보다 상세히는 제철소에서 부산물로 생산되는 석회석/석회슬러리를 이용하여 이를 효과적으로 중화 처리함으로써 열교환기와 같은 배관에서의 부식 및 폐쇄를 최대한 억제할 수 있고, 제철소에서 부산물로 취급하고 있는 석회석/석회슬러리를 효과적으로 재활용하여 원가절감을 이룰 수 있는 화성 테일가스 처리방법에 관한 것이다.The present invention relates to a process for producing gas containing hydrogen sulfide as liquid sulfur in a desulfurization process and treating tail gas containing unreacted hydrogen sulfide and sulfur dioxide, and more specifically, limestone / By neutralizing this effectively using lime slurry, it is possible to minimize corrosion and closure in pipes such as heat exchangers, and to reduce costs by effectively recycling limestone / lime slurry, which is treated as a by-product in steel mills. It relates to a treatment method.

일반적으로 코크스 오븐가스(COG)중에 함유되어 있는 황화수소는 도 2에 도시된 바와 같이, 가스 냉각기(100)를 거쳐 황화수소 흡수탑(110)으로 진행되고, 상기 흡수탑(110)에서 흡수액에 의하여 흡수된 후, 증류탑(120)으로 진행되며, 상기 증류탑(120)에서는 흡수액으로부터 황화수소가 분리되어 탈황장치(130)로 보내진다.In general, hydrogen sulfide contained in coke oven gas (COG) is passed to the hydrogen sulfide absorption tower 110 through the gas cooler 100, as shown in FIG. 2, and is absorbed by the absorption liquid in the absorption tower 110. After that, the process proceeds to the distillation tower 120, in which the hydrogen sulfide is separated from the absorbent liquid and sent to the desulfurization apparatus 130.

그리고, 상기 황화수소를 분리시킨 흡수액은 다시 흡수탑(110)으로 재 공급되어 활용된다. 상기 탈황장치(130)에서는 일부분의 황화수소을 이산화황으로 전환한 후, 가스중의 황화수소와 이산화황의 비율을 2;1로 조절하여 고온의 내장된 촉매반응기에서 액체황으로 전환하고 있다. 이때, 고온의 촉매반응기에서 미반응한 황화수소와 이산화황을 포함한 고온의 테일가스는 탈황장치(130) 후방의 테일가스 냉각기(140)에서 분사되는 75oC의 안수를 통과하면서 냉각되어 재차 가스 냉각기(100)측의 순환되고, 코크스 오븐가스와 합하여져 처리되고 있다. 여기서 테일가스는 대략 그 조성이 질소 80.5%, 이산화탄소 10.5%, 일산화탄소 5%, 황화수소 1%, 이산화황 0.5%, 기타 2.5%인 유독성분의 가스이다.In addition, the absorbing liquid from which the hydrogen sulfide is separated is re-supplied to the absorption tower 110 to be utilized. The desulfurization apparatus 130 converts a part of hydrogen sulfide into sulfur dioxide, and then adjusts the ratio of hydrogen sulfide and sulfur dioxide in the gas to 2: 1 to convert the sulfur sulfide into liquid sulfur in a high temperature embedded catalytic reactor. At this time, the high temperature tail gas including the unreacted hydrogen sulfide and sulfur dioxide in the high temperature catalytic reactor is cooled while passing through 75 o C ordination sprayed from the tail gas cooler 140 behind the desulfurization unit 130 and the gas cooler again ( It is circulated on the 100) side, and is processed in combination with coke oven gas. The tail gas is a toxic component gas of approximately 80.5% nitrogen, 10.5% carbon dioxide, 5% carbon monoxide, 1% hydrogen sulfide, 0.5% sulfur dioxide, and 2.5%.

그러나, 이러한 처리과정에서 테일가스중에 함유된 황화수소는 상기 황화수소 흡수탑(110)에서 흡수액에 의하여 흡수되어 탈황장치(130)에서 액체황을 생산하도록 되어 있지만, 황화수소도 흡수액으로부터 완전 분리되지 않고 흡수되어 흡수액중에 황산으로 존재하여 탈황장치(130)로부터 빠져 나감으로서 열교환기와 같은 배관을 부식시키거나, 폐쇄시키는 주요 원인으로 작용하고 있다.However, the hydrogen sulfide contained in the tail gas in this process is absorbed by the absorption liquid in the hydrogen sulfide absorption tower 110 to produce liquid sulfur in the desulfurization apparatus 130, but hydrogen sulfide is also absorbed without being completely separated from the absorption liquid. It exists as sulfuric acid in the absorbent liquid and exits from the desulfurization unit 130, which acts as a major cause of corroding or closing a pipe such as a heat exchanger.

또한, 탈황설비의 대수리 시에는 증류탑(120)에서 분리된 이산화황을 함유한 가스를 소각로로 유도하여 전량 소각처리 함에 따라 심각한 대기오염의 주범이 되기도 한다.In addition, during the repair of the desulfurization facility, the gas containing sulfur dioxide separated from the distillation column 120 is led to an incinerator, thereby causing the entire amount of incineration to become a major culprit of serious air pollution.

본 발명은 상기와 같은 종래의 문제점을 해소하고자 한 것으로서, 그 목적은 이에 이산화황과 황화수소을 함유한 테일가스을 석회석/석회슬러리을 이용하여 효과적으로 중화 처리함으로써 열교환기와 같은 배관에서의 부식 및 폐쇄를 최대한 억제할 수 있고, 제철소에서 부산물로 취급하고 있는 석회석/석회슬러리를 효과적으로 재활용하여 원가절감을 이룰 수 있는 화성 테일가스 처리방법을 제공하고자 하는 것이다.The present invention has been made to solve the conventional problems as described above, and its purpose is to effectively neutralize the tail gas containing sulfur dioxide and hydrogen sulfide using limestone / lime slurry to effectively suppress corrosion and closure in piping such as heat exchangers. In addition, the present invention aims to provide a method of treating Mars tail gas that can reduce costs by effectively recycling limestone / lime slurry, which is treated as a by-product of steel mills.

도 1은 본 발명에 따른 화성 테일가스 처리방법을 구현하기 위한 공정도;1 is a process chart for implementing the method of treating the Mars tail gas according to the present invention;

도 2는 종래의 기술에 따른 화성 테일가스 처리방법을 도시한 공정흐름도이다.Figure 2 is a process flow diagram showing a method of treating the Mars tail gas according to the prior art.

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

10..... 유동층 반응기 12..... 석회석 용액10 ..... Fluidized Bed Reactor 12 ..... Limestone Solution

20..... 싸이클론 30..... 백필터20 ..... cyclone 30 ..... bag filter

31..... 테일 가스 40..... 석회석용액 회수탱크31 ... Tail gas 40 ..... Limestone solution recovery tank

100.... 가스 냉각기 110.... 황화수소 흡수탑100 .... Gas Cooler 110 .... Hydrogen Sulfide Absorption Tower

120.... 증류탑 130.... 탈황장치120 ... Distillation column 130 ... Desulfurization

140.... 테일가스 냉각기140 .... Tail Gas Cooler

상기와 같은 목적을 달성하기 위하여 본 발명은, 황화수소를 포함한 코크스 오븐가스를 탈황공정에서 액체 황으로 생산하고, 미 반응한 황화수소와 이산화황을 포함한 테일가스(Tail Gas)를 코크스 오븐가스에 재도입하여 처리하는 공정에 있어서,In order to achieve the above object, the present invention, the coke oven gas containing hydrogen sulfide produced as liquid sulfur in the desulfurization process, by reintroducing tail gas containing unreacted hydrogen sulfide and sulfur dioxide into the coke oven gas In the process of processing,

탈황설비에서 액체황을 회수하고 고온의 테일가스를 테일가스냉각기에서 안수를 분사하여 테일가스의 온도를 110-130oC로 조정한 후 유동층반응기로 급송하는 단계;Recovering the liquid sulfur from the desulfurization system and adjusting the temperature of the tail gas to 110-130 ° C. by spraying hot water on the tail gas cooler in the tail gas cooler, and then feeding the liquid sulfur to a fluidized bed reactor;

상기 유동층 반응기에서 테일가스중의 황과, 석회석용액의 칼슘비율을 1;3으로 반응시키는 단계;Reacting sulfur in the tail gas with a calcium ratio of the limestone solution in the fluidized bed reactor to 1; 3;

상기 유동층 반응기에서 석회석용액과 반응하여 이산화황과 황화수소가 제거된 테일가스의 온도를 30-35oC로 유지하는 단계; 및Reacting with the limestone solution in the fluidized bed reactor to maintain the temperature of the tail gas from which sulfur dioxide and hydrogen sulfide are removed at 30-35 o C; And

상기 유동층 반응기에서 테일가스중의 황화합물을 흡수한 후, 미량의 석회석 더스트 제거를 위하여 사이클론과 백필터를 통과시키고, 황화수소 흡수탑 전단으로 급송하는 단계;를 포함함을 특징으로 하는 화성 테일가스 처리방법을 마련함에 의한다.After absorbing the sulfur compound in the tail gas in the fluidized bed reactor, passing through a cyclone and a bag filter to remove traces of limestone dust, feeding to the front of the hydrogen sulfide absorption tower; Hwaseong tail gas treatment method comprising the By providing.

이하, 본 발명을 도면을 참조하여 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail with reference to the drawings.

본 발명에 따른 화성 테일가스 처리방법은 도 1에 도시된 바와 같이, 황화수소를 포함한 코크스 오븐가스를 탈황공정에서 액체 황으로 생산하고, 미 반응한 황화수소와 이산화황을 포함한 테일가스(Tail Gas)를 황화수소 흡수탑(110) 전단의 코크스 오븐가스에 재도입하여 처리하는 공정에 관련된다.As shown in FIG. 1, the method for treating petroleum tail gas according to the present invention produces coke oven gas including hydrogen sulfide as liquid sulfur in a desulfurization process, and tail gas containing unreacted hydrogen sulfide and sulfur dioxide (Tail Gas) to hydrogen sulfide. It relates to a process of reintroducing and treating the coke oven gas in front of the absorption tower 110.

본 발명은, 탈황장치(130)에서 액체황을 회수하고 고온의 테일가스를 테일가스 냉각기(140)에서 안수를 분사하여 테일가스의 온도를 110-130oC로 조정한 다음, 이를 유동층 반응기(10)로 급송하게 된다. 이 단계에서 유동층 반응기(10)에 유입되는 테일가스의 온도를 110-130oC로 조정하는 이유는 테일가스의 온도가 높을수록 액적은 빨리 건조되어 기-액반응을 저해하게 된다. 따라서 테일가스의 온도가 낮아 액적이 석회석주변을 둘러싸여 있는 시간이 길수록 황화합물은 액적에만 잔존하여 석회석과 반응하지 않은 상태로 됨으로써 황화합물의 제거효율이 떨어지게 된다.The present invention recovers the liquid sulfur from the desulfurization apparatus 130, and the hot tail gas is sprayed in the tail gas cooler 140 to the ordination to adjust the temperature of the tail gas to 110-130 ° C, and then the fluidized bed reactor ( 10). The reason for adjusting the temperature of the tail gas flowing into the fluidized bed reactor 10 at 110-130 ° C. is that the higher the tail gas temperature is, the faster the droplets are dried to inhibit the gas-liquid reaction. Therefore, the lower the temperature of the tail gas, the longer the time the droplet is surrounded by limestone, the sulfur compound remains only in the droplet and becomes unreacted with the limestone, thereby reducing the removal efficiency of the sulfur compound.

따라서, 적절한 온도로 조정하게 되며, 만일 상기에서 제시한 온도보다 높을 시에는 액적에 흡수된 황화합물의 잔존시간이 짧아지고, 석회석과 테일가스중의 황화합물의 반응시간이 짧아져 황화합물 제거효율이 낮아진다.Therefore, it is adjusted to an appropriate temperature. If the temperature is higher than the above, the remaining time of sulfur compounds absorbed in the droplets is shortened, and the reaction time of sulfur compounds in limestone and tail gas is shortened, thereby reducing sulfur compound removal efficiency.

그 다음으로는, 상기 유동층 반응기(10)에서 테일가스중의 황과, 석회석용액의 칼슘비율을 1;3으로 반응시키는 단계가 이루어지며, 상기 석회석 용액은 석회석/석회슬러리을 이용하여 제조된 것이고, 석회석 용액탱크(5)로부터 이송되며, 석회석용액을 유동층 반응기(10)에서 테일가스중에 분사시켜 반응시키며, 석회석용액의 칼슘 농도는 0.3-0.5wt%로 유지하는 것이 바람직하다.Next, the step of reacting sulfur in the tail gas and the calcium ratio of the limestone solution to 1 in the fluidized bed reactor 10, wherein the limestone solution is prepared by using limestone / lime slurry, The limestone solution is transferred from the limestone tank 5 and reacted by spraying the limestone solution into the tail gas in the fluidized bed reactor 10, and the calcium concentration of the limestone solution is preferably maintained at 0.3-0.5 wt%.

상기에서 석회석용액(12)의 칼슘 농도를 0.3-0.5wt%로 유지하는 이유는 유동층 반응기(10)에서 칼슘과 황화합물의 반응속도는 위에서 제시한 농도이상에서는 더 이상 높아지지 않고 일정하게 된다. 그러므로 상기에서 제시한 칼슘의 농도보다 높을 시에는 석회석이 과량으로 존재하여 경제적인 부담을 초래할 뿐만 아니라, 가스흐름에 동반하여 이후에 설명되는 사이클론(20) 및 백필터(30)에 가서 누적되어 폐쇄현상을 일으키게 된다.The reason why the calcium concentration of the limestone solution 12 is maintained at 0.3-0.5wt% is because the reaction rate of calcium and sulfur compounds in the fluidized bed reactor 10 is not increased any more than the above concentration. Therefore, when the concentration of calcium is higher than the above, limestone is present in excess, resulting in an economic burden, and accumulating and closing in the cyclone 20 and the bag filter 30 which will be described later accompanying the gas flow. It causes a phenomenon.

만일, 상기와는 다르게 칼슘의 농도가 낮을 시에는 황화합물의 반응속도가 낮아서 황화합물 제거에는 비효율적이다. 그리고, 유동층 반응기(10)에서 황화합물의 황과 석회석의 칼슘비율은 기-액반응에 있어서 기-액접촉시간과 상관성이 있는 것으로써 기액 접촉시간이 길수록 황화합물의 제거효율이 높아지기는 하지만, 최적의 황과 칼슘비율이상에서는 더 이상 높아지지 않는다. 또한 황과 칼슘의 비율이 낮아지게되면 제거효율이 떨어지게 된다.Unlike the above, when the concentration of calcium is low, the reaction rate of the sulfur compound is low, which is inefficient for removing the sulfur compound. In addition, the calcium ratio of sulfur to limestone of the sulfur compound in the fluidized bed reactor 10 is correlated with the gas-liquid contact time in the gas-liquid reaction. It no longer rises above the sulfur and calcium ratios. In addition, when the ratio of sulfur and calcium is lowered, the removal efficiency is lowered.

상기의 단계 다음으로는 상기 유동층 반응기(10)에서 석회석용액(12)과 반응하여 이산화황과 황화수소가 제거된 테일가스의 온도를 30-35oC로 유지하는 단계가 이루어진다.The above step is followed by a step of maintaining the temperature of the tail gas from which sulfur dioxide and hydrogen sulfide are removed by reacting with the limestone solution 12 in the fluidized bed reactor 10 at 30-35 ° C.

이는 상기 유동층 반응기(10)에서 황화합물을 제거한 테일가스의 온도를 30-35oC로 유지하는 이유는 유동층 반응기(10)에서 테일가스중에 잔존하는 황화합물을 처리하여 위하여 황화수소 흡수탑(110) 전단으로 도입되는데, 상기 30-35oC의 테일가스(31)의 온도가 황화수소 흡수탑(110)의 반응온도이다.The reason for maintaining the temperature of the tail gas to remove the sulfur compound in the fluidized bed reactor 10 at 30-35 o C is the front end of the hydrogen sulfide absorption tower 110 to process the sulfur compound remaining in the tail gas in the fluidized bed reactor (10) It is introduced, the temperature of the tail gas 31 of 30-35 ° C is the reaction temperature of the hydrogen sulfide absorption tower (110).

만일 상기에서 제시한 온도보다 높을 시에는 황화수소 흡수탑(110)에서 코크스오븐가스중의 황화수소 흡수효율이 저하하여 코크스오븐가스 정제효율이 떨어지게 된다.If the temperature is higher than the above-mentioned temperature, the hydrogen sulfide absorption efficiency in the coke oven gas decreases in the hydrogen sulfide absorption tower 110, thereby reducing the coke oven gas purification efficiency.

그리고, 상기 유동층 반응기(10)에서 테일가스중의 황화합물을 흡수한 후, 미량의 석회석 더스트 제거를 위하여 사이클론(20)과 백필터(30)를 통과시키고, 황화수소 흡수탑(110) 전단으로 급송하는 단계를 포함하는 것이다.Then, after absorbing the sulfur compound in the tail gas in the fluidized bed reactor 10, the cyclone 20 and the bag filter 30 to pass through the removal of trace limestone dust, and the hydrogen sulfide absorption tower 110 is fed to the front end To include the steps.

또한, 상기 유동층 반응기(10)로부터 그리고 사이클론(20)과 백필터(30)로부터 석회석용액과 황화합물의 혼합물(33)을 석회석 용액회수 탱크(40)로 회수하는 단계가 이루어지는 것이다.In addition, a step of recovering the mixture 33 of limestone solution and sulfur compound 33 from the fluidized bed reactor 10 and from the cyclone 20 and the bag filter 30 is performed in the limestone solution recovery tank 40.

이하의 본 발명의 실시예 및 비교예들을 통하여 본 발명을 더욱 상세하게 설명한다.The present invention will be described in more detail with reference to the following Examples and Comparative Examples.

단, 실시예는 본 발명을 예시하는 것이지 이들만으로 한정하는 것은 아니다.However, the Examples illustrate the present invention and do not limit the present invention.

[실시예 1]Example 1

이산화황은 0.8vol%이고, 황화수소는 0.1vol%인 테일가스(31)의 온도를 130oC로 유동층 반응기(10)로 도입하고, 석회석용액(12)중의 칼슘농도를 0.5wt%로 하였을 때 황화수소 흡수탑(110) 전단에 도입되는 테일가스중의 제거효율은 이산화황은 96%, 황화수소는 91%이었다.Hydrogen sulfide was introduced into the fluidized bed reactor 10 at 130 ° C. with the temperature of tail gas 31 of 0.8 vol% sulfur and 0.1 vol% hydrogen sulfide, and 0.5 wt% calcium concentration in the limestone solution 12. Removal efficiency in the tail gas introduced in front of the absorption tower 110 was 96% for sulfur dioxide and 91% for hydrogen sulfide.

[비교예 1]Comparative Example 1

이산화황은 0.8vol%이고, 황화수소는 0.1vol%인 테일가스(31)의 온도를 90oC로 유동층 반응기(10)로 도입하고, 석회석용액(12)중의 칼슘농도를 0.5wt%로 하였을 때 황화수소 흡수탑(110) 전단에 도입되는 테일가스(31)중의 제거효율은 이산화황은 84%, 황화수소는 79%이었다.Hydrogen sulfide was introduced into the fluidized bed reactor 10 at a temperature of tail gas 31 of 90 vol% sulfur dioxide and 0.1 vol% hydrogen sulfide at 90 ° C., and the calcium concentration in the limestone solution 12 was 0.5 wt%. Removal efficiency in the tail gas 31 introduced to the front of the absorption tower 110 was 84% for sulfur dioxide and 79% for hydrogen sulfide.

[비교예 2]Comparative Example 2

이산화황은 0.8vol%이고, 황화수소는 0.1vol%인 테일가스(31)의 온도를 150oC로 유동층 반응기(10)로 도입하고, 석회석용액(12)중의 칼슘농도를 0.3wt%로 하였을 때 황화수소 흡수탑(110) 전단에 도입되는 테일가스(31)중의 제거효율은 이산화황은 87%, 황화수소는 82%이었다.Hydrogen sulfide was introduced into the fluidized bed reactor 10 at a temperature of 150 ° C. of tail gas 31 having a sulfur dioxide of 0.8 vol% and hydrogen sulfide of 0.1 vol%, and the concentration of calcium in the limestone solution 12 was 0.3 wt%. The removal efficiency in the tail gas 31 introduced to the front of the absorption tower 110 was 87% for sulfur dioxide and 82% for hydrogen sulfide.

[비교예 3]Comparative Example 3

이산화황은 0.8vol%이고, 황화수소는 0.1vol%인 테일가스(31)의 온도를 130oC로유동층 반응기(10)로 도입하고, 석회석용액(12)중의 칼슘농도를 0.2wt%로 하였을 때 황화수소 흡수탑(110) 전단에 도입되는 테일가스(31)중의 제거효율은 이산화황은 79%, 황화수소는 75%이었다.Hydrogen sulfide is introduced into the fluidized bed reactor (10) at 130 ° C. with the temperature of tail gas (31 vol) of 0.8 vol% sulfur and 0.1 vol% hydrogen sulfide and 0.2 wt% calcium concentration in the limestone solution (12). The removal efficiency in the tail gas 31 introduced into the front of the absorption tower 110 was 79% for sulfur dioxide and 75% for hydrogen sulfide.

상기에서와 같이, 본 발명에 의하면 석회석/석회슬러리을 이용하여 제조된 석회석용액(12)을 유동층 반응기(10)에서 테일가스(31)중에 분사시켜 테일가스중의 황화수소 및 이산화황을 중화 처리함에 따라 열교환기와 같은 배관에서의 부식 및 폐쇄를 최대한 억제할 수 있으며, 제철소에서 부산물로 취급하고 있는 석회석/석회슬러리를 재활용하여 원가절감을 이룰 수 있는 효과가 있다.As described above, according to the present invention, the limestone solution 12 prepared by using limestone / lime slurry is injected into the tail gas 31 in the fluidized bed reactor 10 to neutralize hydrogen sulfide and sulfur dioxide in the tail gas. Corrosion and closure can be minimized in pipes such as air, and the cost can be reduced by recycling limestone / lime slurry, which is treated as a by-product in steel mills.

Claims (2)

황화수소를 포함한 코크스 오븐가스를 탈황공정에서 액체 황으로 생산하고, 미 반응한 황화수소와 이산화황을 포함한 테일가스(Tail Gas)를 코크스 오븐가스에 재도입하여 처리하는 공정에 있어서,In the process of producing coke oven gas containing hydrogen sulfide as liquid sulfur in the desulfurization process, re-introduced tail gas containing unreacted hydrogen sulfide and sulfur dioxide into the coke oven gas, 탈황장치(130)에서 액체황을 회수하고 고온의 테일가스(31)를 테일가스 냉각기(140)에서 안수을 분사하여 테일가스(31)의 온도를 110-130oC로 조정한 후 유동층반응기(10)로 급송하는 단계;The liquid sulfur is recovered from the desulfurization apparatus 130 and the hot tail gas 31 is sprayed with tail water from the tail gas cooler 140 to adjust the temperature of the tail gas 31 to 110-130 ° C., followed by a fluidized bed reactor 10 Feeding); 상기 유동층 반응기(10)에서 테일가스(31)중의 황과, 석회석용액(12)의 칼슘비율을 1;3으로 반응시키는 단계;Reacting sulfur in the tail gas 31 and the calcium ratio of the limestone solution 12 in the fluidized bed reactor 10 to 1; 3; 상기 유동층 반응기(10)에서 석회석용액(12)과 반응하여 이산화황과 황화수소가 제거된 테일가스(31)의 온도를 30-35oC로 유지하는 단계; 및Reacting with the limestone solution 12 in the fluidized bed reactor 10 to maintain a temperature of the tail gas 31 from which sulfur dioxide and hydrogen sulfide are removed at 30-35 ° C .; And 상기 유동층 반응기(10)에서 테일가스(31)중의 황화합물을 흡수한 후, 미량의 석회석 더스트 제거를 위하여 사이클론(20)과 백필터(30)를 통과시키고, 황화수소 흡수탑(110) 전단으로 급송하는 단계;를 포함함을 특징으로 하는 화성 테일가스 처리방법.After absorbing the sulfur compound in the tail gas 31 in the fluidized bed reactor 10, the cyclone 20 and the bag filter 30 to pass through to remove the trace limestone dust, and is fed to the front of the hydrogen sulfide absorption tower 110 Mars tail gas treatment method comprising the ;. 제 1항에 있어서, 상기 석회석용액(12)의 칼슘 농도는 0.3-0.5wt%임을 특징으로 하는 화성 테일가스 처리방법.The method according to claim 1, wherein the calcium concentration of the limestone solution (12) is 0.3-0.5wt%.
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KR20020037005A (en) * 2002-04-22 2002-05-17 안준홍 pure lime collectional method by cyclone in flue gas desulfurization and its apparatus
KR100905617B1 (en) * 2002-12-10 2009-07-02 주식회사 포스코 Rotary duct device for tail gas
CN101429070B (en) * 2008-12-05 2011-05-04 聊城鲁西化工第四化肥厂 Method for producing azophoska complex fertilizer with boiler flue gas and sulphuric acid tail gas
US7996039B2 (en) 2003-02-19 2011-08-09 Samsung Electronics Co., Ltd. Method for reselling content
CN116332533A (en) * 2023-05-30 2023-06-27 山西富渊通科技有限公司 Opposite firing type sleeve lime kiln and operation method thereof

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JPS60118220A (en) * 1983-11-29 1985-06-25 Mitsui Miike Kakoki Kk Tail gas treating method
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JP2745099B2 (en) * 1993-03-23 1998-04-28 三菱化工機株式会社 Klaus tail gas treatment equipment
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US6027704A (en) * 1997-11-25 2000-02-22 Mobil Oil Corporation Process for the reduction of SO2 from wet lime/limestone tailgas in power plant desulfurization processes
KR100342696B1 (en) * 1999-08-14 2002-07-04 정종현 Ca-based absorbent for acid gas treatment and method for preparing the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20020037005A (en) * 2002-04-22 2002-05-17 안준홍 pure lime collectional method by cyclone in flue gas desulfurization and its apparatus
KR100905617B1 (en) * 2002-12-10 2009-07-02 주식회사 포스코 Rotary duct device for tail gas
US7996039B2 (en) 2003-02-19 2011-08-09 Samsung Electronics Co., Ltd. Method for reselling content
CN101429070B (en) * 2008-12-05 2011-05-04 聊城鲁西化工第四化肥厂 Method for producing azophoska complex fertilizer with boiler flue gas and sulphuric acid tail gas
CN116332533A (en) * 2023-05-30 2023-06-27 山西富渊通科技有限公司 Opposite firing type sleeve lime kiln and operation method thereof

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