KR100961394B1 - Manufacturing Method of Zn-ferrite for removing H2S in Coke oven gas - Google Patents
Manufacturing Method of Zn-ferrite for removing H2S in Coke oven gas Download PDFInfo
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- KR100961394B1 KR100961394B1 KR1020070135660A KR20070135660A KR100961394B1 KR 100961394 B1 KR100961394 B1 KR 100961394B1 KR 1020070135660 A KR1020070135660 A KR 1020070135660A KR 20070135660 A KR20070135660 A KR 20070135660A KR 100961394 B1 KR100961394 B1 KR 100961394B1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
Abstract
본 발명은 COG(coke oven gas)에 함유된 황화수소를 제거하기 위한 건식반응의 제거 방법에 사용되는 촉매에 관한 것으로, COG내의 함유된 황화수소를 제철 냉연공정에서 생산되는 산화철(Fe2O3)과 산화아연(ZnO)를 혼합하여 반응시켜 아연페라이트(Zn-ferrite) 결정의 촉매를 제조하는 방법에 관한 것이다.The present invention relates to a catalyst used in a method of removing a dry reaction for removing hydrogen sulfide contained in a coke oven gas (COG), wherein the iron sulfide contained in the COG is produced in a cold rolling process of iron and iron (Fe 2 O 3 ) and The present invention relates to a method for preparing a catalyst for zinc ferrite (Zn-ferrite) crystals by mixing and reacting zinc oxide (ZnO).
본 발명의 방법은 COG중에 함유된 황화수소를 제거하기 위한 건식반응에 사용되는 촉매를 제조하는 방법에 관한 것으로, COG중에 함유된 황화수소로 인한 연소시에 발생되는 SOx가 대기 환경 오염을 증대시키는 문제를 해결 가능하고, 건식 반응법에 의해서 황화수소를 제거하기 때문에 폐수의 발생이 없어서 환경적으로 적정한 방법임을 알 수 있으며, 황화수소 제거효율 또한 우수함을 확인할 수 있고 조업에 직접활용이 가능한 방법이다.The method of the present invention relates to a method for preparing a catalyst for use in a dry reaction for removing hydrogen sulfide contained in COG, and the problem that SOx generated during combustion due to hydrogen sulfide contained in COG increases pollution of the air. It can be solved, and by removing the hydrogen sulfide by the dry reaction method, it can be seen that it is an environmentally appropriate method because there is no generation of waste water, it can be confirmed that the hydrogen sulfide removal efficiency is also excellent and can be utilized directly in the operation.
COG, 코크오븐가스, 황화수소, 제거, 건식반응, 촉매, 제조방법 COG, coke oven gas, hydrogen sulfide, removal, dry reaction, catalyst, manufacturing method
Description
본 발명은 COG(coke oven gas, 코크오븐가스, 이하 'COG'라고 한다 )에 함유된 황화수소를 제거하기 위한 건식반응의 제거 방법에 사용되는 촉매에 관한 것으로, 보다 상세하게는 COG내의 함유된 황화수소를 제철냉연공정에서 생산되는 산화철(Fe2O3)과 산화아연(ZnO)를 혼합하여 반응시켜 아연페라이트(Zn-ferrite) 결정의 촉매를 제조하는 방법에 관한 것이다.The present invention relates to a catalyst used in a method of removing a dry reaction for removing hydrogen sulfide contained in a coke oven gas (coke oven gas, hereinafter referred to as 'COG'), and more particularly, hydrogen sulfide contained in COG. The present invention relates to a method of preparing a catalyst for zinc ferrite (Zn-ferrite) crystals by mixing and reacting iron oxide (Fe 2 O 3 ) and zinc oxide (ZnO) produced in a steelmaking cold rolling process.
본 발명의 방법은 COG중에 함유된 황화수소로 인한 연소시에 발생되는 SOx가 대기 환경 오염을 증대시키는 문제를 해결 가능하고, 건식 반응법에 의해서 황화수소를 제거하기 때문에 폐수의 발생이 없어서 환경적으로 적정한 방법임을 알 수 있으며, 황화수소 제거효율 또한 우수함을 확인할 수 있고 조업에 직접활용이 가능한 방법이다.The method of the present invention can solve the problem that SOx generated during combustion due to hydrogen sulfide contained in COG increases pollution of the air environment, and since it removes hydrogen sulfide by dry reaction method, there is no waste water generation, which is environmentally appropriate. It can be seen that the method, the hydrogen sulfide removal efficiency is also excellent and can be used directly in the operation.
석탄을 배합하여 건류공정으로 코크스를 제조하는 과정에서 발생되는 COG, 타르 및 수분이 존재하는데, 이러한 생성물 중에서 타르 및 수분은 액상 상태로 회수 처리되며, 가스 상태인 COG는 포집하고 일부 정제공정을 거쳐서 제철소내의 에너지원으로 사용된다. 그러나, COG 중에는 황화수소가 일부 함유되어 있어서 연소시에 대기 환경의 오염을 일으키는 SOx를 방출시키는 원인 물질이다.COG, tar, and water generated during the coking process by mixing coal are present in the coking process. Among these products, tar and water are recovered in a liquid state, and gaseous COG is collected and subjected to some purification processes. Used as an energy source in steel mills. However, COG contains some hydrogen sulfide, which is a causative substance for releasing SOx which causes pollution of the atmospheric environment during combustion.
또한 대기환경공해를 해소하기 위해서 COG를 정제하는 공정을 거치게 되는데 이는 공정에서 발생한 안수(암모니아수)를 사용하여 황화수소를 제거하는데 제거의 효율이 저하되는 단점이 있다. In addition, the COG is purified to solve the air pollution, which has a disadvantage in that the removal efficiency is lowered to remove hydrogen sulfide using ordination (ammonia water) generated in the process.
대한민국 공개특허 2002-0088688(2002.11.29)에서는 암모니아용액의 농도를 조절하여 습식방법으로 황화수소를 제거하는 것으로 농도의 증가분만큼 유량을 감소시키는 것으로 일반적인 습식 제거방법과 유사한 발명이다. Korean Patent Laid-Open Publication No. 2002-0088688 (2002.11.29) is an invention similar to a general wet removal method in which the flow rate is reduced by an increase in concentration by removing hydrogen sulfide by a wet method by adjusting the concentration of ammonia solution.
또한 대한민국 공개특허 2002-0016136 (2002.03.04)에서는 흡수탑에서 안수와 접촉시킴으로써 코크스오븐가스의 황화수소를 안수에 선택적으로 흡수시켜 제거하는 코크스오븐가스를 0.5 내지 0.6의 기액접촉 비율로 농도가 2 내지 5 g/l인 메틸디에탄올아민(MDEA; Methyldiethanolamine) 수용액과 접촉시켜서 코크스오븐가스의 황화수소 제거 방법을 제공하는데, 습식방법에 의해서 공정을 진행되므로 함유된 메틸디에탄올아민을 안수중에서 제거하는 공정을 포함하지 않고는 어려운 문제점이 존재한다. In addition, Korean Patent Laid-Open Publication No. 2002-001613603 (2002.03.04) has a concentration of 2 to 2 at a gas-liquid contact ratio of 0.5 to 0.6 for coke oven gas, which selectively absorbs and removes hydrogen sulfide of coke oven gas to ordination by contacting with ordination in an absorption tower. It provides a method of removing hydrogen sulfide from coke oven gas by contacting with 5 g / l of methyldiethanolamine (MDEA) aqueous solution, and the process by wet method removes the contained methyldiethanolamine in ordination. If not included, difficult problems exist.
또한 본 발명의 전단계로서 발명자의 선출원인 대한민국 공개특허 2006-071537(2006.6.27)에서는 수산화철 특히 괴타이트(α-FeOOH) 와 수산화제이철(Fe(OH)3)의 분말을 펠렛으로 제조하여 황화수소와 건식 화학반응을 진행시켜 황화수소를 효과적으로 건식화학 반응시켜 제거하는 방법이 제안되어 있다. In addition, Korean Patent Laid-Open Publication No. 2006-071537 (2006.6.27), which is a prior application of the present invention, prepares powders of iron hydroxide, in particular, gothite (α-FeOOH) and ferric hydroxide (Fe (OH) 3 ) as pellets, and There has been proposed a method of effectively drying and removing hydrogen sulfide by performing a dry chemical reaction.
따라서 본 발명에서는 COG중의 황화수소를 효율적으로 제거하기 위한 건식반응에 사용되는 촉매를 제조하는 방법으로서, 대기 환경 오염을 증대시키는 문제를 해결하고, 폐수의 발생이 없어서 환경적으로 적정한 방법이며, 황화수소 제거효율 또한 우수하고 조업에 직접활용이 가능한 방법을 제공하고자 한다. Therefore, the present invention is a method for producing a catalyst used in the dry reaction for the efficient removal of hydrogen sulfide in COG, solving the problem of increasing the environmental pollution of the air, there is no generation of waste water, it is an environmentally appropriate method, removing hydrogen sulfide It is also intended to provide a method that is highly efficient and can be used directly in operation.
이에 본 발명의 목적은 COG에 함유된 황화수소를 제거하기 위해서 건식반응에 의한 제거 방법에 사용되는 촉매로서, COG내의 함유된 황화수소를 제철 냉연공정에서 생산되는 산화철(Fe2O3)과 산화아연(ZnO)를 혼합하여 반응시켜 아연페라이트 결정의 촉매를 제조하는 방법을 제공하는 것이다.Accordingly, an object of the present invention is a catalyst used in a dry method for removing hydrogen sulfide contained in COG, and the hydrogen sulfide contained in COG (Fe 2 O 3 ) and zinc oxide ( It is to provide a method for producing a catalyst of zinc ferrite crystals by mixing and reacting ZnO).
본 발명의 방법은 COG중에 함유된 황화수소로 인한 연소시에 발생되는 SOx가 대기 환경 오염을 증대시키는 문제를 해결 가능하고, 건식 반응법에 의해서 황화수소를 제거하기 때문에 폐수의 발생이 없어서 환경적으로 적정한 방법임을 알 수 있으며, 황화수소 제거효율 또한 우수함을 확인할 수 있고 조업에 직접활용이 가능한 방법이다. The method of the present invention can solve the problem that SOx generated during combustion due to hydrogen sulfide contained in COG increases pollution of the air environment, and since it removes hydrogen sulfide by dry reaction method, there is no waste water generation, which is environmentally appropriate. It can be seen that the method, the hydrogen sulfide removal efficiency is also excellent and can be used directly in the operation.
본 발명은 코크스 제조과정에서 발생하는 COG중의 황화수소를 제거하기 위한 건식반응의 촉매를 제조하는 방법에 있어서, 산화철 분말과 산화아연 분말에 탄산나트륨 분말을 혼합하여 통상의 방법으로 펠렛을 제조하는 단계; 및 제조된 펠렛을 열처리로에서 질소분위기에서 950-1050℃로 열처리하여 아연페라이트 펠렛을 제조 하는 단계;를 포함하는 것을 특징으로 한다. The present invention provides a method for producing a dry reaction catalyst for removing hydrogen sulfide in COG generated during the coke production process, comprising: preparing a pellet in a conventional manner by mixing sodium carbonate powder with iron oxide powder and zinc oxide powder; And heat-treating the prepared pellets at 950-1050 ° C. in a nitrogen atmosphere in a heat treatment furnace to produce zinc ferrite pellets.
또한, 본 발명은 상기 펠렛을 제조하는 단계에서 Fe/Zn비를 2로 한 전체 중량에 탄산나트륨 분말을 2% 이상을 첨가하는 것을 특징으로 한다.In addition, the present invention is characterized in that at least 2% of the sodium carbonate powder is added to the total weight of the Fe / Zn ratio in the step of producing the pellet.
본 발명에서는 COG중에 함유된 황화수소 제거를 위해서 제조된 펠렛을 반응탑에 장착시키고 COG량을 공간속도를 25,000/시간 이하로 통과시켜 황화수소를 건식 반응 시키는 단계의 실시예를 통하여 증명하였다In the present invention, the pellets prepared for removing hydrogen sulfide contained in COG were installed in a reaction tower, and the COG amount was passed through an example of a step of dry reaction of hydrogen sulfide by passing a space velocity of 25,000 / hour or less.
* 공간속도(Space Velocity, SV): 반응탑의 펠렛층을 통과하는 1시간당 처리 COG량을 펠렛 용량으로 나눈값. 즉, 1시간에 충진된 펠렛량의 몇 배의 COG를 처리하는가의 통기량.Space Velocity (SV): The amount of COG treated per hour passing through the pellet bed of the reaction column divided by the pellet capacity. That is, how many times the COG to process the amount of pellets filled in one hour.
이하, 본 발명에 대하여 좀더 상세히 설명한다. Hereinafter, the present invention will be described in more detail.
본 발명은 코크스 제조과정에서 발생되는 COG중에 함유되어 있는 황화수소를 건식 화학반응에 의해서 효과적으로 제거하기 위한 촉매의 제조 방법에 관한 것으로, 본 발명자는 여러 가지 시험을 거쳐서 황화수소를 아연페라이트 촉매와 반응시키면 산화철 부분은 화학적으로 반응시켜 황화철이 생성되고, 산화아연 부분은 황화아연이 생성되어 효과적으로 화학흡착 제거가 가능하며, 환원분위기가 유지되면, 원소유황으로 석출되어 이 방법을 통하여 COG중에 함유된 황화수소를 건식으로 화학반응에 의해서 제거 가능한 것이다. The present invention relates to a method for preparing a catalyst for effectively removing hydrogen sulfide contained in COG generated during the coke production process by a dry chemical reaction. The present inventors have undergone various tests to react iron sulfide with a zinc ferrite catalyst. The part is chemically reacted to produce iron sulfide, and the zinc oxide part is formed of zinc sulfide to effectively remove chemical adsorption.If the reducing atmosphere is maintained, elemental sulfur is precipitated to dry hydrogen sulfide contained in COG through this method. It can be removed by chemical reaction.
COG중에 함유된 황화수소를 건식 반응에 의해서 촉매를 통하여 제거가 가능한 화학반응은 하기 반응식 1과 같다. A chemical reaction capable of removing hydrogen sulfide contained in COG through a catalyst by a dry reaction is shown in Scheme 1 below.
[반응식 1]Scheme 1
3H2S + ZnFe2O4 →2FeS + ZnS + 3H2O + [O] 3H 2 S + ZnFe 2 O 4 → 2FeS + ZnS + 3H 2 O + [O]
즉, 황화수소 중의 수소이온이 아연페라이트와 건식 반응하여 물분자 3개를 생성하고, 이중의 황이온은 전기적으로 안정한 산화금속황 상태로 산화되어 COG중의 황화수소를 촉매에 석출시켜서 제거하는 관계를 나타낸 화학 반응이다.In other words, hydrogen ions in hydrogen sulfide dry react with zinc ferrite to form three water molecules, and double sulfur ions are oxidized to an electrically stable metal oxide state to precipitate and remove hydrogen sulfide in COG by catalyst. Reaction.
본 발명의 전체적인 황화수소 촉매를 장착하고 처리시험을 한 공정을 도 1에 나타내었다.1 shows a process in which the entire hydrogen sulfide catalyst of the present invention is equipped and subjected to a treatment test.
이하, 실시예를 통해 본 발명을 좀더 상세히 설명한다. Hereinafter, the present invention will be described in more detail with reference to Examples.
실시예 1 Example 1
본 실시예에서는 산화철 분말 과 산화아연 분말에 탄산나트륨 분말을 혼합하여 통상의 방법으로 펠렛을 제조하는 방법에 대한 시험으로, 산화철 분말과 산화아연분말을 Fe/Zn 몰비로 2를 유지하는 조건에 이론적으로 아연페라이트가 생성되므로 이 조건을 유지하면서 탄산나트륨을 첨가량을 조절하여 열처리시의 적정강도를 유지하도록 하는 시험을 실시하였다. In this embodiment, a test for preparing pellets by mixing sodium carbonate powder and zinc oxide powder with sodium carbonate powder in a conventional manner, and theoretically under the condition that the iron oxide powder and zinc oxide powder are kept at a Fe / Zn molar ratio of 2. Since zinc ferrite was produced, a test was conducted to maintain the appropriate strength during heat treatment by adjusting the amount of sodium carbonate while maintaining this condition.
탄산나트륨을 각 0, 1, 2, 3, 4, 5 중량 %를 첨가하여 펠렛을 제조하고 얻어진 펠렛을 질소분위기 열처리로에서 1,000℃에서 처리한 펠렛의 압축 강도를 측정하였다0, 1, 2, 3, 4, 5 wt% of sodium carbonate was added to prepare pellets, and the compressive strength of the pellets treated at 1,000 ° C. in a nitrogen atmosphere heat treatment furnace was measured.
그 결과를 도 2에 나타냈다. The result is shown in FIG.
도 2에 있어서, 촉매제의 펠렛의 강도는 일반적으로 50kgf/Cm2를 유지하는 것이 바람직한데 탄산나트륨 첨가량이 2% 이상에서 제대로 강도가 나오나, 그 이하에서는 바람직한 강도 조건을 갖지 못한다. 따라서 본 발명에서는 탄산나트륨 첨가량이 2% 이상의 조건을 바람직한 조건으로 한다. In Fig. 2, the strength of the pellets of the catalyst is generally preferably maintained at 50 kgf / Cm 2 , but the amount of sodium carbonate added is well obtained at 2% or more, but below, it does not have desirable strength conditions. Therefore, in this invention, the condition of sodium carbonate addition amount shall be 2% or more as preferable conditions.
실시예 2Example 2
본 실시예에서는 산화철 분말과 산화아연 분말에 탄산나트륨 분말을 혼합하여 통상의 방법으로 펠렛을 제조하는 방법에 대한 시험으로, 산화철 분말과 산화아연 분말을 Fe/Zn 몰비로 2를 유지하는 조건에 이론적으로 아연페라이트가 생성되므로 이 조건을 유지하면서 탄산나트륨을 3중량 % 첨가하여 펠렛을 제조하고 얻어진 펠렛을 질소분위기 열처리로에서 900, 950, 1000, 1050, 1100℃에서 처리한 펠렛의 황화수소 제거율 시험을 실시하였다. 촉매 제조시에 열처리온도는 촉매의 활성에 영향을 미치므로 온도 조건을 선정하고자 하였다. In this embodiment, a test for producing pellets by mixing sodium carbonate powder and zinc oxide powder with sodium carbonate powder in a conventional manner, and theoretically under the conditions of maintaining the iron oxide powder and zinc oxide powder at a Fe / Zn molar ratio of 2 Since zinc ferrite was produced, pellets were prepared by adding 3% by weight of sodium carbonate while maintaining this condition, and the obtained pellets were subjected to hydrogen sulfide removal test of the pellets treated at 900, 950, 1000, 1050, and 1100 ° C. in a nitrogen atmosphere heat treatment furnace. . Since the heat treatment temperature affects the activity of the catalyst in preparing the catalyst, the temperature condition was selected.
3-5mm의 펠렛을 제조하고 이 펠렛을 반응탑에 장착시키고 장착된 펠렛양 대비 COG처리량을 공간속도 개념으로 정립하기 위해서 30℃ 온도에서 반응탑 입구에 COG중에서 함유된 황화수소 농도 0.80mg/Nm3인 COG를 공간속도 25,000 h- 1 에서 시험을 실시하였다.Hydrogen sulfide concentration 0.80mg / Nm 3 contained in COG at the entrance of reaction tower at 30 ℃ to prepare pellets of 3-5mm and install them in the reaction column and to establish the COG throughput compared to the amount of installed pellets in terms of space velocity. Phosphorus COG was tested at a space velocity of 25,000 h - 1 .
가스크로마토그래피로 측정하여 황화수소의 반응제거율로 환산하여 그 결과를 구분하여 도 3에 나타내었다. 도 3에 나타낸 바와 같이, 공간속도 25,000 h- 1 에서 열처리 촉매의 조건을 설정하는데 온도에 따른 반응제거율의 도면에서 보면 1,100℃이상에서는 반응제거율이 90% 이하를 유지하고 제거율이 감소하는 것을 알 수 있다. 따라서, 본 발명에서 제거효율이 90%를 상회하는 조건과 적정강도를 유지하는 열처리 조건인 950-1,050℃에서 열처리하는 것이 바람직함을 알 수 있다.Measured by gas chromatography and converted to the reaction removal rate of hydrogen sulfide, the results are shown in FIG. 3. As shown in Figure 3, the conditions of the heat treatment catalyst to set the conditions of the heat treatment catalyst at the space velocity 25,000 h - 1 It can be seen that the reaction removal rate is maintained at 90% or less and the removal rate is reduced at 1,100 ℃ or more. have. Therefore, in the present invention, it can be seen that the heat treatment is preferably performed at 950-1,050 ° C., which is a condition in which the removal efficiency exceeds 90% and a heat treatment condition for maintaining an appropriate strength.
도 1은 본 발명의 전체적인 황화수소 촉매를 장착하고 처리시험을 한 공정도Figure 1 is a process chart equipped with the entire hydrogen sulfide catalyst of the present invention and the treatment test
도 2는 탄산나트륨 첨가량에 따른 강도의 변화를 나타낸 그래프2 is a graph showing the change in strength according to the amount of sodium carbonate added
도 3은 열처리 온도의 변화에 따른 반응제거율을 나타낸 그래프3 is a graph showing the reaction removal rate according to the change of the heat treatment temperature
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| US9068128B2 (en) | 2011-10-18 | 2015-06-30 | Baker Hughes Incorporated | Method for reducing hydrogen sulfide evolution from asphalt and heavy fuel oils |
| KR101403805B1 (en) * | 2012-09-04 | 2014-06-11 | 재단법인 포항산업과학연구원 | Catalyst for removing acidic gas contained in coke oven gas and method for producing the same |
| KR102119503B1 (en) * | 2018-12-12 | 2020-06-16 | 주식회사 포스코 | Manufacturing method of Catalysts For Removal of Hydrogen Sulfide in COG |
| KR102482248B1 (en) * | 2020-12-15 | 2022-12-28 | 재단법인 포항산업과학연구원 | Method for removing h2s and hcn species contained in deacidified water |
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| KR20170111478A (en) | 2016-03-28 | 2017-10-12 | 주식회사 엘지화학 | Mehtod of prepararing zinc ferrite catalysts |
| US10456775B2 (en) | 2016-03-28 | 2019-10-29 | Lg Chem, Ltd. | Method of preparing zinc ferrite catalyst |
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