WO2019103235A1 - Appareil de traitement de gaz et procédé associé - Google Patents

Appareil de traitement de gaz et procédé associé Download PDF

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Publication number
WO2019103235A1
WO2019103235A1 PCT/KR2017/015333 KR2017015333W WO2019103235A1 WO 2019103235 A1 WO2019103235 A1 WO 2019103235A1 KR 2017015333 W KR2017015333 W KR 2017015333W WO 2019103235 A1 WO2019103235 A1 WO 2019103235A1
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WO
WIPO (PCT)
Prior art keywords
gas
carbon dioxide
hydrogen sulfide
ammonia
solution
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PCT/KR2017/015333
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English (en)
Korean (ko)
Inventor
이승재
조문경
김병일
최재원
박경태
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주식회사 포스코
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Publication of WO2019103235A1 publication Critical patent/WO2019103235A1/fr

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    • 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
    • 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
    • C10B45/00—Other details
    • 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
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids

Definitions

  • the present invention relates to a gas processing apparatus and a method thereof, and more particularly, to a gas processing apparatus and a method thereof capable of efficiently separating hydrogen sulfide in an exhaust gas.
  • Coke oven gas contains various components when the coal is carbonized in the coke oven to produce coke.
  • acid gases such as carbon dioxide, hydrogen sulfide, ammonia, and hydrogen cyanide cause corrosion or clogging of gas pipelines.
  • the acid gas is used at a certain concentration or lower because it causes pollution.
  • hydrogen sulfide must be removed from sulfuric acid water as a substance that is highly polluted with air and odor.
  • the hydrogen sulfide absorbs hydrogen sulfide in the ammonia water by supplying ammonia water to the hydrogen sulfide collector, separates and removes the sulfur component from the acid gas by heating the ammonia water absorbed by the hydrogen sulfide and separating the acid gas.
  • the carbon dioxide contained in the coke oven gas causes hydrogen sulphide to be trapped in the hydrogen sulfide collector. That is, when the hydrogen sulfide is absorbed by the ammonia water, the absorption rate of the hydrogen sulfide decreases as the carbon dioxide is first absorbed by the competitive reaction.
  • ammonia water is generated in the process of carbonizing the coal in the coke oven, and this ammonia water is used to collect ammonia after being regenerated with water together with ammonia water used for collecting hydrogen sulfide.
  • a large amount of acid gas is generated during the regeneration of ammonia water.
  • the hydrogen sulfide and ammonia contained in the acid gas are converted into sulfur and produce and nitrogen through the purification process.
  • the unconverted gas contains a large amount of hydrogen sulfide and is mixed with the coke oven gas and sent back to the purification process.
  • the unconverted gas contains a large amount of carbon dioxide, the concentration of carbon dioxide in the coke oven gas supplied to the hydrogen sulfide collector is increased, thereby lowering the collection rate of the hydrogen sulfide.
  • the present invention provides a gas processing apparatus and method for efficiently separating and recycling carbon dioxide contained in an exhaust gas.
  • the present invention provides a gas processing apparatus and method capable of improving purification efficiency of hydrogen sulfide contained in an exhaust gas.
  • a gas processing method includes the steps of: preparing an exhaust gas; Providing an auxiliary gas having a lower carbon dioxide content than the exhaust gas; Separating the exhaust gas and hydrogen sulfide contained in the auxiliary gas; And separating the exhaust gas from ammonia contained in the auxiliary gas.
  • the step of separating the hydrogen sulfide may use an amine aqueous solution containing at least one of MEA (Mono-Ethanol Amine), DEA (Di-Ethanol Amine) and MDEA (Methyl Di-Ethanol Amine).
  • MEA Mono-Ethanol Amine
  • DEA Di-Ethanol Amine
  • MDEA Metal Di-Ethanol Amine
  • the step of treating the first solution includes a step of heating the first solution to separate an acid gas containing hydrogen sulfide into an amine aqueous solution and the separated amine aqueous solution includes a step of separating the hydrogen sulfide Can be reused.
  • the process of treating the second solution may include heating the second solution to separate it into water and ammonia gas; And a step of generating sulfur by heat treating a part of the separated ammonia gas and an acid gas generated in the process of treating the first solution.
  • the process of preparing the auxiliary gas may include separating carbon dioxide from a process gas generated in the process of producing sulfur and a mixed gas containing a part of the separated ammonia gas,
  • the processing gas from which the carbon dioxide is separated may be provided as the auxiliary gas.
  • the step of separating the carbon dioxide comprises the steps of: cooling the process gas and a mixed gas obtained by mixing a part of the separated ammonia gas to produce carbon dioxide contained in the mixed gas as an ammonium carbonate; And dissolving the ammonium carbonate salt in steam to produce an aqueous ammonium hydrogen carbonate solution.
  • the process of separating the carbon dioxide may be performed by using a plurality of carbon dioxide collectors, generating the ammonium carbonate salt in the plurality of carbon dioxide sorters, and producing the aqueous ammonium bicarbonate solution alternately.
  • the process of separating the carbon dioxide can be continuously performed using a plurality of carbon dioxide capture devices.
  • the step of separating the carbon dioxide may include the step of separating the ammonium bicarbonate aqueous solution into carbon dioxide gas and ammonia water by heating.
  • a gas processing apparatus includes a hydrogen sulfide sorter for separating hydrogen sulfide from an exhaust gas discharged from a reactor; An ammonia collector for separating ammonia from the exhaust gas passed through the hydrogen sulfide collector; A regenerator for treating the first solution discharged from the hydrogen sulfide collector; A distiller for treating the second solution discharged from the ammonia collector; And a carbon dioxide separator for separating the carbon dioxide from the mixed gas of the acid gas generated in the regenerator and the ammonia gas generated in the ammonia trapping unit and supplying the mixed gas in which the carbon dioxide is separated to the hydrogen sulfide trapping unit.
  • the carbon dioxide separator includes a carbon dioxide collector for cooling the mixed gas to produce carbon dioxide as an ammonium carbonate salt and dissolving the ammonium carbonate salt to produce an aqueous ammonium hydrogen carbonate solution; And a separator for separating the ammonium bicarbonate aqueous solution into carbon dioxide gas and ammonia water by heating.
  • the plurality of carbon dioxide collectors perform a process of producing the ammonium carbonate salt and a process of producing the aqueous ammonium bicarbonate solution and the plurality of carbon dioxide sorbents collects the carbonic acid ammonium salt And a process of producing the ammonium hydrogen carbonate aqueous solution alternately.
  • the carbon dioxide separator can supply separated carbon dioxide gas to the reactor.
  • the trapping rate of hydrogen sulfide in the exhaust gas can be improved by reducing the content of carbon dioxide in the exhaust gas and purifying it.
  • hydrogen sulfide contained in the coke oven gas can be collected using an amine-based aqueous solution having low reactivity with carbon dioxide. Therefore, the efficiency of collecting hydrogen sulfide contained in the exhaust gas can be improved without being greatly affected by the content of carbon dioxide contained in the exhaust gas.
  • carbon dioxide contained in the exhaust gas can be separated and used as a heat source in various operations.
  • carbon dioxide (CO 2 ) may be separated from the gas generated during the refining process of the coke oven gas and then supplied to the coke oven to be converted into carbon monoxide (CO), thereby being used as a heat source in the process of carbonizing the coke.
  • FIG. 1 is a block diagram conceptually showing a gas processing apparatus according to an embodiment of the present invention
  • FIG. 2 is a block diagram conceptually illustrating a process of treating a mixed gas of a process gas and an ammonia gas.
  • FIG. 3 is a block diagram conceptually illustrating a process of collecting carbon dioxide in a carbon dioxide collector.
  • FIG. 4 is a graph showing the collection rate of hydrogen sulfide according to the content of carbon dioxide in the coke oven gas.
  • FIG. 5 is a graph showing a comparison between the capturing ratio of hydrogen sulfide and carbon dioxide when the coke oven gas is treated using ammonia water and an aqueous MDEA solution.
  • the present invention relates to an apparatus and a method for purifying an exhaust gas generated in various industrial fields.
  • an apparatus and a method for purifying the coke oven gas generated in the process of manufacturing the coke will be described as an example.
  • FIG. 1 is a block diagram conceptually illustrating a gas processing apparatus according to an embodiment of the present invention.
  • FIG. 2 is a block diagram conceptually illustrating a process of processing a mixed gas of a process gas and an ammonia gas, The concept of CO2 capture is a conceptual block diagram.
  • a gas processing apparatus includes a hydrogen sulfide sorter 214 for separating hydrogen sulfide (H 2 S) from a coke oven gas discharged from a coke oven 10, a hydrogen sulfide sorter 214 An ammonia collector 216 for separating ammonia (NH 3 ) from the coke oven gas passed through the regenerator 224, a regenerator 224 for treating an aqueous amine solution containing a first solution, such as hydrogen sulfide, A distiller 226 for treating a second solution discharged from the ammonia collector 212, for example ammonia water, and a carbon dioxide separator 240 for separating carbon dioxide from the first solution and the gas generated during the treatment of the second solution can do.
  • a hydrogen sulfide sorter 214 for separating hydrogen sulfide (H 2 S) from a coke oven gas discharged from a coke oven 10
  • An ammonia collector 216 for separating ammonia (NH 3 ) from the coke oven
  • the gas processing apparatus includes an ammonia water reservoir 222 for storing the ammonia water generated in the coke oven 10, a cooler 210 for cooling the coke oven gas discharged from the coke oven 10, a cooler 210, A dust collector 212 for removing tar, dust, and the like from the coke oven gas discharged from the coke oven gas discharged from the ammonia collector 216; A gas reservoir 220 for storing the coke oven gas discharged from the light oil collecting unit 218 and a gas reservoir 220 for separating the sulfur from the gas generated in the process of treating the first solution and the second solution, A first reactor 228 and a second reactor 230.
  • the method for treating a gas includes the steps of providing an exhaust gas, providing an auxiliary gas having a lower carbon dioxide content than the exhaust gas, separating the hydrogen sulfide contained in the exhaust gas and the auxiliary gas, And separating the ammonia contained in the auxiliary gas.
  • the exhaust gas may be a coke oven gas
  • the auxiliary gas may be a gas in which carbon dioxide is removed from a mixed gas of ammonia gas and process gas.
  • the coke oven gas (COG) discharged from the coke oven 10 may be supplied to the hydrogen sulfide collector 214 through a pretreatment process such as cooling and dust collection.
  • the cooler 210 can cool the coke oven gas to about 25 to 30 ° C, and the dust collector 212 can collect and remove tar, dust, and the like contained in the coke oven gas.
  • the coke oven gas from which tar, dust, etc. have been removed may be purified through a hydrogen sulfide collector 214, an ammonia collector 216 and a light oil collector 218, and then stored in a gas reservoir 220.
  • the hydrogen sulfide sorter 214 supplies an amine aqueous solution to the hydrogen sulfide sorter 214 to collect hydrogen sulfide from the coke oven gas flowing into the hydrogen sulfide sorter 214. That is, the amine aqueous solution is brought into contact with the coke oven gas flowing into the hydrogen sulfide collector 214 to absorb the hydrogen sulfide contained in the coke oven gas into the amine aqueous solution and collect it.
  • An amine aqueous solution for example, an aqueous solution of MDEA (Methyl Di-Ethanol Amine) generates an aqueous solution of ((C 3 H 4 OH) 2 NHCH 3 ) SH) through ionic bonding with hydrogen sulfide as shown in the following Formula 1, absorbs hydrogen sulfide, It can be separated into MDEA aqueous solution and hydrogen sulfide.
  • the amine aqueous solution used herein may include at least one of MEA (Mono-Ethanol Amine), DEA (Di-Ethanol Amine) and MDEA (Methyl Di-Ethanol Amine).
  • Ammonia water (NH 4 OH) in the hydrogen sulfide and carbon dioxide capture mechanism in the coke oven gas forms an aqueous solution of (NH 4 ) SH and H 3 O type through ionic bonding with hydrogen sulfide through the reaction as shown in the following formula 2 and absorbs hydrogen sulfide can do.
  • this aqueous solution for example, ammonia water absorbed by hydrogen sulfide, is heated, it can be separated into ammonia water and hydrogen sulfide.
  • the carbon dioxide (CO 2 ) in the coke oven gas reacts with the N atom of the ammonia water through the reaction as shown in the following formula (3) to bind to the NH 2 COO component and interfere with the collection of hydrogen sulfide, thereby lowering the collection efficiency of hydrogen sulfide.
  • MDEA Metal Di-Ethanol Amine
  • C atom surrounds N atom and does not react with carbon dioxide rapidly.
  • generation of the amine aqueous solution such as MDEA (Methyl Di-Ethanol Amine) aqueous solution over the hydrogen sulfide and ionic bonding as Equation 1 below ((C 3 H 4 OH) 2 NHCH 3) SH) aqueous solution, and absorbing the hydrogen sulfide When heated, it can be separated into MDEA aqueous solution and hydrogen sulfide.
  • MDEA Metal Di-Ethanol Amine
  • hydrogen sulphide can be selectively removed from the coke oven gas containing carbon dioxide using the MDEA aqueous solution.
  • the ammonia collector 216 supplies water to the inside of the ammonia collector 216 to separate the ammonia gas from the coke oven gas flowing into the ammonia collector 216. That is, the ammonia gas contained in the coke oven gas can be absorbed and separated by contacting the coke oven gas flowing into the ammonia collector 216 with water. When the ammonia gas in the coke oven gas is separated in the ammonia collector 216 as described above, ammonia gas is absorbed in the water and ammonia water can be generated. At this time, the generated ammonia water can be sent to the ammonia water reservoir 222 and stored.
  • the diesel collector 218 separates benzene, toluene, xylene, and the like from the coke oven gas that has passed through the ammonia collector 216.
  • an aqueous amine solution e. G., The first solution, used to collect hydrogen sulphide in the hydrogen sulfide sorter 214 may be sent to the regenerator 224 and then regenerated as an aqueous amine solution to be fed to the hydrogen sulphide sorter 214 to re- .
  • the regenerator 224 can separate an aqueous amine solution containing hydrogen sulfide, which is introduced from the hydrogen sulfide collector 214, into hydrogen sulfide and an amine aqueous solution by heating the solution to about 110 to 130 ° C.
  • the separated hydrogen sulfide can be supplied to the first reactor 228, and the aqueous amine solution can be supplied to the hydrogen sulfide collector 214 and reused to collect hydrogen sulfide.
  • the gas supplied from the regenerator 224 to the first reactor 228 may include carbon dioxide, hydrogen cyanide, and the like in addition to hydrogen sulfide.
  • the gas is referred to as an acid gas.
  • the distiller 226 is supplied with a second solution, such as ammonia water, at the ammonia collector 216, and can separate the ammonia water into ammonia gas and water by heating it.
  • the distiller 226 is supplied with ammonia water from the ammonia water reservoir 222 storing the ammonia water generated in the coke oven and the ammonia water generated in the carbon dioxide sorter 242 and heated to a temperature of about 90 to 110 ° C., Water can be separated. Some of the water separated in the still 226 may be supplied to the ammonia collector 216 to collect the ammonia gas, and some of the water may be treated as wastewater. Some of the ammonia gas separated at the still 226 may be fed to the first reactor 228 and some may be fed to the carbon dioxide sorter 242 to be used to collect carbon dioxide.
  • a second solution such as ammonia water
  • the first reactor 228 heats the ammonia gas supplied from the distiller 226 and the acid gas supplied from the regenerator 224 at a temperature of about 1000 to 1200 ° C to thermally decompose them to produce nitrogen (N 2 ) and sulfur compounds (SO 2 Can be generated. At this time, a part of the hydrogen sulfide contained in the acid gas may react with the ammonia gas to form a sulfur compound.
  • the second reactor 230 can convert the sulfur compounds generated in the first reactor 228 into sulfur by reacting hydrogen sulfide. At this time, the second reactor 230 reacts the sulfur compound and hydrogen sulfide at a weight ratio of 1: 2 at a temperature of about 180 to 220 ° C to convert the sulfur into sulfur, and the remaining gas such as the process gas is supplied to the carbon dioxide sorter 242 . At this time, the process gas may contain about 70% by weight of nitrogen (N 2 ), about 15% by carbon dioxide, and 1% or more of hydrogen sulfide. Coke oven gas may cause increased carbon dioxide content.
  • the carbon dioxide in the coke oven gas can be reduced by reducing the carbon dioxide in the process gas and then used in the coke oven gas purification process, thereby preventing the reduction in the collection efficiency of the hydrogen sulfide.
  • the reaction furnace for separating carbon dioxide from the process gas and then treating the raw material, for example, as a heat source necessary for producing coke by feeding it to a coke oven for producing coke by carburizing the coal.
  • the carbon dioxide separator 240 separates carbon dioxide from the process gas supplied from the second reactor 230 and the ammonia gas supplied from the distillation unit 226.
  • the carbon dioxide separator 240 cools the mixed gas of the process gas supplied from the second reactor 230 and the ammonia gas supplied from the distillation unit 226 to produce carbon dioxide in the mixed gas as an ammonium carbonate salt and dissolves the ammonium carbonate salt,
  • a carbon dioxide sorter 242 to produce a hydrogen ammonium aqueous solution
  • a separator 244 to separate the aqueous ammonium bicarbonate solution into carbon dioxide and ammonia water by heating.
  • the carbon dioxide sorter 242 may include a plurality of, for example, a first carbon dioxide sorter 242a and a second carbon dioxide sorter 242b.
  • the carbon dioxide sorter 242 can separate the ammonia gas and the carbon dioxide gas by dissolving the ammonia gas and the processing gas into the ammonium carbonate after reacting it.
  • the carbon dioxide sorter 242 can produce an ammonium carbonate salt by reacting the ammonia gas and the process gas at a weight ratio of 1: 1.
  • the ammonia gas and the process gas may be supplied individually to the inside of the carbon dioxide sorter 242, or may be mixed before being supplied to the carbon dioxide sorter 242.
  • the carbon dioxide sorter 242 can selectively collect carbon dioxide in the mixed gas by cooling the mixed gas of the process gas and the ammonia gas to induce a reaction between carbon dioxide and ammonia in the mixed gas to generate an ammonium carbonate salt.
  • the internal temperature of the carbon dioxide sorter 242 is adjusted to 40 ° C or lower, more preferably 30 ° C or lower.
  • the reaction between carbon dioxide and ammonia gas occurs at a temperature of 40 DEG C or lower, and an ammonium carbonate salt is produced.
  • hydrogen sulfide or ammonia gas may condense together with carbon dioxide, which is the target component, and may be separated and removed together.
  • the temperature of the carbon dioxide sorter 242 can be adjusted to 40 ° C by using the indirect cooling method using the cooling water to cool the carbon dioxide sorter 242 to 40 ° C or less.
  • the mixed gas which is a process gas supplied into the carbon dioxide sorter 242
  • the mixed gas may be cooled indirectly rather than directly.
  • cooling water is supplied into the carbon dioxide sorter 242 to cool the mixed gas and the cooling water in direct contact with each other, the carbon dioxide is condensed in the salt or the separation efficiency is lowered due to dissolution of hydrogen sulfide or ammonia gas, Since the treatment process of the solution is accompanied, the indirect cooling method is efficient.
  • the carbon dioxide-removed mixed gas may be supplied to the cooler 210 together with the coke oven gas discharged from the coke oven.
  • the mixed gas from which the carbon dioxide has been removed may be supplied directly to the hydrogen sulfide collector ().
  • the carbon dioxide-free mixed gas can be used as an auxiliary gas to reduce the carbon dioxide concentration in the coke oven gas.
  • the carbon dioxide sorter 242 dissolves or melts the ammonium carbonate salt remaining therein.
  • the ammonium carbonate salt is easily dissolved and decomposed by moisture or heat.
  • An aqueous ammonium hydrogen carbonate (NH 4 HCO 3 ) aqueous solution can be produced by dissolving the ammonium carbonate salt by supplying steam containing both water and heat to the carbon dioxide sorter 242.
  • the resulting aqueous ammonium bicarbonate solution exits the carbon dioxide sorter 242.
  • the carbon dioxide sorter 242 cools the mixed gas of the process gas and the ammonia gas to produce an ammonium carbonate salt, and the generated ammonium carbonate salt is heated and melted.
  • a heating step for dissolving the ammonium carbonate salt can be alternately performed.
  • the process of collecting carbon dioxide from the process gas can be continuously performed without interruption.
  • the carbon dioxide gas supplied to the coke oven 10 is reduced to carbon monoxide (CO) gas through a Boudouard reaction with the coal charged in the coke oven, and can be used as a heat source for coal.
  • CO carbon monoxide
  • FIG. 4 is a graph showing the collection rate of hydrogen sulfide in accordance with the content of carbon dioxide in the coke oven gas
  • FIG. 5 is a graph comparing the collection rates of hydrogen sulfide and carbon dioxide when coke oven gas is treated using ammonia water and MDEA aqueous solution .
  • the carbon dioxide reduces the hydrogen sulfide capture rate in the coke oven gas, if the content of carbon dioxide in the coke oven gas is reduced, the collection rate of hydrogen sulfide in the coke oven gas can be increased.
  • the collection ratio of hydrogen sulfide can be further increased.
  • FIG. 5 shows the collection ratio of hydrogen sulfide when hydrogen sulfide in the coke oven gas was collected using ammonia water and MDEA aqueous solution.
  • the hydrogen sulfide capture ratio was measured to be about 27%.
  • the hydrogen sulfide in the coke oven gas was collected using the MDEA aqueous solution, the collection ratio of hydrogen sulfide increased to about 90%.
  • the gas processing apparatus and method according to the present invention can separate carbon dioxide contained in the exhaust gas and use it as a heat source in various operations.

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

Abstract

La présente invention concerne un appareil de traitement de gaz et un procédé associé, le procédé comprenant les étapes consistant à : préparer un gaz d'échappement ; préparer un gaz auxiliaire présentant une quantité de dioxyde de carbone inférieure à celle du gaz d'échappement ; séparer le sulfure d'hydrogène contenu dans le gaz d'échappement et le gaz auxiliaire ; et séparer l'ammoniac contenu dans le gaz d'échappement et le gaz auxiliaire, le sulfure d'hydrogène pouvant être séparé efficacement du gaz d'échappement.
PCT/KR2017/015333 2017-11-22 2017-12-22 Appareil de traitement de gaz et procédé associé WO2019103235A1 (fr)

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KR10-2017-0156808 2017-11-22
KR1020170156808A KR101981457B1 (ko) 2017-11-22 2017-11-22 가스처리장치 및 그 방법

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CN110141947A (zh) * 2019-05-27 2019-08-20 中冶焦耐(大连)工程技术有限公司 一种焦炉烟气二氧化碳减排工艺及系统
KR102325218B1 (ko) * 2019-12-11 2021-11-11 주식회사 포스코 우수한 시안화수소 분해능을 가지는 황 회수 장치 및 방법

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