KR20190023459A - Preparation of adsorbent for removal of sulfur compounds using acid mine drainage - Google Patents
Preparation of adsorbent for removal of sulfur compounds using acid mine drainage Download PDFInfo
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- KR20190023459A KR20190023459A KR1020170109262A KR20170109262A KR20190023459A KR 20190023459 A KR20190023459 A KR 20190023459A KR 1020170109262 A KR1020170109262 A KR 1020170109262A KR 20170109262 A KR20170109262 A KR 20170109262A KR 20190023459 A KR20190023459 A KR 20190023459A
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
Description
본 발명은 산성광산배수를 이용하여 황화합물을 고효율로 제거할 수 있는 흡착제의 제조방법에 관한 것이다.The present invention relates to a method for producing an adsorbent capable of removing sulfur compounds with high efficiency using acid mine drainage.
산성광산배수(acid mine drainage, AMD)는 가행탄광 또는 폐광지에서 지속적으로 수질 및 토양 환경오염을 일으키는 오염원이다. 이러한 산성광산배수를 처리하기 위한 많은 공법들이 연구되고 개발되었다.Acid mine drainage (AMD) is a pollutant that causes continuous pollution of water quality and soil in mine or mine. Many methods for treating such acidic mine drainage have been researched and developed.
산성광산배수는 대기 중에 노출된 황철석(FeS2), 백철석 (FeS) 등의 황화광물이 산소 및 물과 반응하여 산화되면서 형성되며, pH가 낮아 산성을 띠고 있으며, 황산염을 비롯한 철, 알루미늄, 망간 등 금속함량이 높은 것이 특징이다.Acid mine drainage is formed by oxidation of sulfide minerals such as pyrite (FeS 2 ) and white iron (FeS) exposed to the atmosphere by reacting with oxygen and water, and it is acidic due to its low pH, and iron, aluminum, manganese And the like.
이러한 산성광산배수의 처리방법은 크게 적극적 처리법(active treatment)과 소극적 처리법(passive treatment)으로 나누어진다. 적극적 처리법은 중화제를 이용한 pH조절, 이온교환과 흡착, 응집, 여과 등의 방식을 이용하는 방법으로서, 대표적인 적극적 처리법으로는 역삼투압법, 이온교환법, 전기투석법 등이 있다. 소극적 처리법은 유기물과 석회석 등을 이용하여 동력을 투여하지 않는 방식으로 대표적인 소극적 처리법으로는 SAPS(successive alkalinity-producing systems) 등이 있다. The treatment methods of acid mine drainage are divided into active treatment and passive treatment. Aggressive treatment methods are methods using pH control, ion exchange and adsorption, coagulation, and filtration using a neutralizing agent. Typical active treatment methods include reverse osmosis, ion exchange, and electrodialysis. The passive treatment method is a method in which power is not administered by using organic materials and limestone, and typical passive treatment methods include successive alkalinity-producing systems (SAPS).
그러나, 이러한 산성광산배수의 처리방법은 산성광산배수에 포함된 금속들을 슬러지로 침전시킨 후에 방류하고, 슬러지는 폐기물로 처리되어 폐기물 처리비용이 추가로 소요될 수밖에 없었다.However, in the method of treating acidic mine drainage, the metals contained in the acidic mine drainage are discharged after sedimentation with sludge, and the sludge is treated as waste, so that the waste treatment cost has to be further increased.
이에 따라 본 발명자는 산성광산배수를 이용하여 산업적으로 이용할 수 있는 흡착제를 제조하여 산성광산배수를 정화시키면서 슬러지 배출량을 절감시킬 수 있는 기술을 개발하게 되었다.Accordingly, the present inventors have developed a technology capable of reducing the amount of sludge discharged while purifying acidic mine drainage by preparing an adsorbent which can be industrially used by using acid mine drainage.
본 발명이 해결하고자 하는 과제는 산성광산배수를 이용하여 황화합물을 고효율로 제거할 수 있는 흡착제의 제조방법을 제공하는 데 있다.The object of the present invention is to provide a method for producing an adsorbent capable of removing sulfur compounds with high efficiency by using acid mine drainage.
본 발명에 따른 산성광산배수를 이용한 황화합물 제거용 흡착제 제조방법은, 산성광산배수에 가성소다(NaOH) 또는 액상소석회(Ca(OH)2)와, 무기질 바인더를 투입·교반하여 3차원 망상구조의 무기질 바인더-수산화철의 혼합 슬러지를 침전시키는 무기질 바인더-수산화철의 혼합 슬러지 생성공정과; 침전된 무기질 바인더-수산화철의 혼합 슬러지를 탈수시키는 슬러지 탈수공정과; 슬러지 탈수공정을 통해서 탈수된 무기질 바인더-수산화철의 혼합 슬러지를 펠렛형상으로 압출 성형하고 건조시켜 흡착제로 성형하는 흡착제 성형공정;을 포함하는 것을 특징으로 한다.The method for producing an adsorbent for removing sulfur compounds using acidic mine drainage according to the present invention comprises the steps of adding sodium hydroxide (NaOH) or calcium hydroxide (Ca (OH) 2 ) and inorganic binder to an acidic mine drainage, A mixed sludge-producing step of an inorganic binder-iron hydroxide precipitating a mixed sludge of an inorganic binder-iron hydroxide; A sludge dewatering step of dewatering the mixed sludge of the precipitated inorganic binder-iron hydroxide; And an adsorbent forming step of extruding and sintering the mixed sludge of the inorganic binder-iron hydroxide dehydrated through the sludge dewatering process into a pellet, and drying the same to form an adsorbent.
바람직하게, 무기질 바인더-수산화철의 혼합 슬러지 생성공정은 산성광산배수가 pH 8~9.5로 유지되도록 가성소다(NaOH) 또는 액상소석회(Ca(OH)2)를 첨가하는 것을 특징으로 한다.Preferably, the process for producing an inorganic binder-iron hydroxide mixed sludge is characterized by adding caustic soda (NaOH) or liquid calcium hydroxide (Ca (OH) 2 ) so that the acid mine drainage is maintained at a pH of 8 to 9.5.
바람직하게, 무기질 바인더는 실리카졸, 벤토나이트, 점토, 운모, 고령토, 몬모릴로나이트, 변성 실리케이트 중에서 선택된 어느 하나 이상인 것을 특징으로 한다.Preferably, the inorganic binder is at least one selected from silica sol, bentonite, clay, mica, kaolin, montmorillonite, and modified silicate.
바람직하게, 무기질 바인더는 산상광산배수 13L를 기준으로 0.1~0.5중량(g) 혼합되는 것을 특징으로 한다.Preferably, the inorganic binder is mixed 0.1 to 0.5 wt.% (G) based on 13 L of acid mine drainage.
바람직하게, 무기질 바인더-수산화철의 혼합 슬러지 생성공정은 수산화철의 침전이 신속하게 진행되도록 응집제를 5-10ppm으로 더 첨가하는 것을 특징으로 한다.Preferably, the mixed binder-iron hydroxide mixed sludge production process is characterized in that the coagulant is further added at 5-10 ppm so that precipitation of the iron hydroxide rapidly proceeds.
바람직하게, 흡착제 성형공정은 압출 성형 후에 100℃-120℃의 온도에서 3-6시간 동안 건조시키는 것을 특징으로 한다.Preferably, the adsorbent molding process is characterized in that after extrusion molding, it is dried at a temperature of 100 ° C to 120 ° C for 3-6 hours.
본 발명의 산성광산배수를 이용하여 제조된 흡착제는 황화수소를 포함하는 황화합물의 흡착율이 우수하여 배수로 처리되는 산성광산배수를 산업용 흡착제로 재활용할 수 있는 효과가 있다.The adsorbent produced by using the acidic mine drainage of the present invention has an excellent adsorption rate of sulfur compounds including hydrogen sulfide and is effective for recycling acidic mine drainage treated with drainage as an industrial adsorbent.
또한, NaOH 또는 가격면에서 경제적인 Ca(OH)2를 사용하면서도 높은 황화수소 흡착능을 갖는 흡착제를 제조할 수 있는 장점이 있다.In addition, there is an advantage in that an adsorbent having a high hydrogen sulfide adsorbing ability can be produced while using NaOH or a cost-effective Ca (OH) 2 .
도 1은 본 발명에 따른 산성광산배수를 이용한 황화합물 제거용 흡착제 제조방법의 공정도.
도 2는 본 발명에 따른 흡착제를 이용한 흡착탑에서 배출되는 황화수소의 흡착능 그래프(파과곡선).1 is a process diagram of a method for producing an adsorbent for removing sulfur compounds using acid mine drainage according to the present invention.
2 is a graph of adsorption capacity (breakthrough curve) of hydrogen sulfide discharged from an adsorption tower using an adsorbent according to the present invention.
이하 본 발명을 구체적으로 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명에 따른 산성광산배수를 이용한 황화합물 제거용 흡착제 제조방법은 산성광산배수 저장공정(S10)과, 무기질 바인더-수산화철의 혼합 슬러지 생성공정(S20)과, 슬러지 탈수공정(S30), 흡착제 성형공정(S40)을 포함한다.The method for producing an adsorbent for removing sulfur compounds using acidic mine drainage according to the present invention comprises a step of storing an acidic mine drainage (S10), a step (S20) of producing an inorganic binder-iron hydroxide mixed sludge, a sludge dewatering step (S30) (S40).
산성광산배수 저장공정(S10)은 저류조를 이용하여 산성광산배수를 공급받아 저장한다. 저류조에서 산성광산배수에 포함도 고형의 이물질이 분리되어 침전된다.The acidic mine drainage storage process (S10) receives and stores acidic mine drainage using a storage tank. In the reservoir, solid foreign matter contained in the acid mine drainage is separated and settled.
무기질 바인더-수산화철의 혼합 슬러지 생성공정(S20)은 슬러지 반응조를 이용하여 저류조에 저장된 산성광산배수를 공급받고 가성소다(NaOH) 또는 액상소석회(Ca(OH)2)와 무기질 바인더를 투입·교반하여 무기질 바인더-수산화철의 혼합 슬러지를 생성한다.Inorganic binder-mixed sludge formation step (S20) of the iron hydroxide is received by a sludge tank supplying the acid mine drainage are stored in the storage bath of caustic soda (NaOH) or liquid calcium hydroxide (Ca (OH) 2) and stirred added, the inorganic binder To produce a mixed sludge of inorganic binder-iron hydroxide.
NaOH 또는 Ca(OH)2는 산상광산배수에 존재하는 철화합물을 FeO(OH), Fe2O3, Fe(OH)3 등의 수산화철을 생성하여 침전시키게 된다. 이때, NaOH 또는 Ca(OH)2는 슬러지 반응조의 pH가 8~9.5로 유지되도록 첨가되는 것이 바람직하다. pH가 8 미만인 경우 산성광산배수서 미반응된 철화합물이 존재할 수 있고, pH가 9.5를 초과하는 경우 슬러지 반응조에서 배출되는 배출수를 중화시키기 위한 약품이 다량 필요한 문제가 있다.NaOH or Ca (OH) 2 precipitates iron hydroxide such as FeO (OH), Fe 2 O 3 , Fe (OH) 3 and the like, which are present in acid mine drainage. At this time, NaOH or Ca (OH) 2 is preferably added so that the pH of the sludge reaction tank is maintained at 8 to 9.5. If the pH is less than 8, unreacted iron compounds may exist in the acid mine drainage, and if the pH is more than 9.5, there is a problem that a large amount of chemicals are required to neutralize the effluent discharged from the sludge reactor.
한편, 초기 응집되는 수산화철이 신속하게 조대화되어 용이하게 침전되도록 수산화철 미립자의 표면전하를 변화시키는 응집제를 추가로 첨가할 수 있다. 이러한 응집제는 2-프로펜산나트륨 2-프로펜아마이드 중합체(SODIUM 2-PROPENOATE 2- PROPENAMIDE POLYMER)을 사용하는 것이 바람직하고, 응집제는 5-10ppm으로 첨가되는 것이 바랍니다. 이대, 5ppm 미만이면 수산화철의 침전시간이 길어지는 문제가 있고, 10ppm 초과되면 수산화철을 빠르게 침전시킬 수 있지만 황화합물의 흡착율이 낮아지며 고가의 응집제 사용으로 인한 경제적인 비용이 증가되는 문제가 있다.On the other hand, a flocculant for changing the surface charge of the iron hydroxide fine particles may be added so that the initially coagulated iron hydroxide rapidly coagulates and precipitates easily. Such flocculant is preferably a 2-propenoic acid sodium 2-propenamide polymer (SODIUM 2-PROPENOATE 2-PROPENAMIDE POLYMER), and the flocculant is added at 5-10 ppm. If it is less than 5 ppm, the precipitation time of the iron hydroxide becomes long. If it exceeds 10 ppm, the iron hydroxide can be precipitated quickly, but the adsorption rate of the sulfur compound is low and the economical cost due to the use of the expensive coagulant is increased.
또한, 무기질 바인더는 침전되는 수산화철과 반응하여 3차원 망상구조를 형성하면서 높은 비표면적(specific surface area)을 갖는 무기질 바인더-수산화철의 혼합 슬러지를 형성하게 된다. 무기질 바인더는 Si- 또는 Al-를 포함하는 무기질 바인더가 바람직하다. 특히, 실리카졸, 벤토나이트, 점토, 운모, 고령토, 몬모릴로나이트, 변성실리케이트 중에서 선택된 어느 하나 이상을 사용한다. 무기질 바인더는 산상광산배수 13 L를 기준으로 0.1~0.5중량(g)을 사용할 수 있다. 이때, 무기 바인더의 함유량이 0.1중량(g) 미만이면 생성되는 무기질 바인더-수산화철의 혼합 슬러지의 3차원 망상구조가 유지되기 어려운 문제가 있을 수 있고, 또한 성형 후에 일정한 형상을 유지하는 것이 어렵다. 0.5중량(g) 초과이면 생성되는 무기질 바인더-수산화철의 혼합 슬러지에 무기질 바인더의 함유량이 불필요하게 높은 문제가 있다.In addition, the inorganic binder reacts with precipitated iron hydroxide to form a three-dimensional network structure, and forms a mixed sludge of an inorganic binder-iron hydroxide having a high specific surface area. The inorganic binder is preferably an inorganic binder containing Si- or Al-. In particular, at least one selected from silica sol, bentonite, clay, mica, kaolin, montmorillonite, and modified silicate is used. The inorganic binder may be used in an amount of 0.1 to 0.5 wt.% (G) based on 13 L of acid mine drainage. At this time, if the content of the inorganic binder is less than 0.1 weight (g), there may be a problem that the three-dimensional network structure of the resulting inorganic binder-iron hydroxide mixed sludge is difficult to maintain, and it is difficult to maintain a constant shape after molding. If the amount is more than 0.5 weight (g), there is a problem that the content of the inorganic binder in the mixed sludge of the inorganic binder-iron hydroxide is unnecessarily high.
슬러지 탈수공정(S30)은 탈수장치를 슬러지 반응조에서 침전된 무기질 바인더-수산화철의 혼합 슬러지를 70-80%의 함수율을 갖도록 탈수시킨다. 이때, 탈수장치는 필터 프레스를 이용하는 것이 바람직하다. 이때, 무기질 바인더-수산화철의 혼합 슬러지의 함수률이 80% 초과하면 높은 함수율로 펠렛으로 성형하기 어려운 문제가 있다.In the sludge dewatering process (S30), the dewatering device dehydrates the mixed sludge of the inorganic binder-iron hydroxide precipitated in the sludge reaction tank to have a water content of 70-80%. At this time, it is preferable to use a filter press as the dewatering device. At this time, when the water content of the mixed sludge of the inorganic binder-iron hydroxide exceeds 80%, there is a problem that it is difficult to form pellets with a high water content.
흡착제 성형공정(S40)은 슬러지 탈수공정을 통해서 탈수된 무기질 바인더-수산화철의 혼합 슬러지를 소정 형상의 성형틀에 넣고 펠렛형상의 흡착제로 압출 성형하고 100℃-120℃의 온도에서 3-6시간 동안 건조한다. 이때, 100 ℃ 미만에서는 펠렛의 강도가 저하되는 문제가 있으며, 120℃를 초과하는 온도에서 수행되는 경우에는 펠렛이 갈라질 수도 있는 문제가 있다.In the adsorbent forming step (S40), the mixed sludge of the inorganic binder-iron hydroxide dehydrated through the sludge dewatering process is extruded into a pellet-shaped adsorbent into a molding die of a predetermined shape, and the mixture is extruded at a temperature of 100 ° C to 120 ° C for 3-6 hours Dry. At this time, there is a problem that the strength of the pellets is lowered at a temperature lower than 100 ° C, and there is a problem that the pellets may be cracked when the temperature is higher than 120 ° C.
이와 같은 공정을 거쳐 산성광산배수로부터 제조된 흡착제는 높은 황화수소 흡착능을 갖는 흡착제로 사용할 수 있다.The adsorbent prepared from acidic mine drainage through such a process can be used as an adsorbent having a high hydrogen sulfide adsorbing ability.
<실험예><Experimental Example>
영동탄광에서 배출하는 산성광산배수 약 13 L에 표 1과 같이 NaOH을 포함하는 성분들을 첨가하여 pH 9(약 8.69g 사용)로 유지하면서 1 시간동안 유지하여 무기질 바인더-수산화철의 혼합 슬러지를 침전시켰다. 그 후, 무기질 바인더-수산화철의 혼합 슬러지를 필터프레스로 함수율이 80% 이하가 되도록 탈수하였다. 그리고 탈수된 무기질 바인더-수산화철의 혼합 슬러지를 펠렛으로 압출성형하고, 110℃에서 5시간 건조하여 각각의 흡착제를 제작하였다. 또한, 비교예로 산성광산배수에서 무기바인더를 첨가하지 않고 Ca(OH)2를 첨가하여 약 pH 9로 유지하면서 1 시간동안 유지하여 생성된 슬러지를 탈수하여 펠렛으로 압출성형하여 사용하였다.About 13 L of acidic mine drainage discharged from Yeongdong coal mine was added NaOH-containing components as shown in Table 1, and maintained at pH 9 (about 8.69 g) for 1 hour to precipitate a mixed sludge of inorganic binder-iron hydroxide . Thereafter, the mixed sludge of the inorganic binder-iron hydroxide was dewatered to a water content of 80% or less with a filter press. The mixed sludge of dehydrated mineral binder and iron hydroxide was extruded into pellets and dried at 110 ° C for 5 hours to prepare each adsorbent. In addition, as a comparative example, Ca (OH) 2 was added to the acidic mine drainage without adding an inorganic binder, and the resulting sludge was maintained at about pH 9 for 1 hour.
실시예 1
Example 1
실시예 2
Example 2
실시예1, 2와 비교예의 흡착제 2.141g을 건식 흡착탑에 설치하고 표 2와 같은 조건으로 황화수소가 포함된 가스를 통과시켜 흡착탑에서 배출되는 가스에 황화수소가 포함되어 있는지를 확인하여 도 2의 그래프로 나타내었다. 그리고, 흡착제에 흡착된 황화수소의 흡착량을 분석하여 표 3로 나타내었으며 흡착능을 확인하였다.2.141 g of the adsorbent of Examples 1 and 2 and the comparative example were placed in a dry adsorption tower and a gas containing hydrogen sulfide was passed under the same conditions as in Table 2 to confirm whether or not hydrogen sulfide was contained in the gas discharged from the adsorption tower. Respectively. The adsorption amount of hydrogen sulfide adsorbed on the adsorbent was analyzed and shown in Table 3, and the adsorption capacity was confirmed.
도 2의 그래프에서 확인할 수 있듯이 흡착탑으로 유입된 가스에 포함된 황화수소는 흡착시간이 약 250~350분이 경과될 때까지 거의 모든 황화수소가 흡착되어 황화수소(H2S)의 제거율도 99.9% 이상임을 확인할 수 있다.As can be seen from the graph of FIG. 2, the hydrogen sulfide contained in the gas flowing into the adsorption tower was found to adsorb almost all of the hydrogen sulfide until the adsorption time of about 250 to 350 minutes elapsed, and the removal rate of hydrogen sulfide (H 2 S) was 99.9% or more .
또한, 표 3에 도시된 바와 같이, 흡착제에 흡착된 황화수소의 흡착성능은 무게비로 20.5, 23.9 중량비의 우수한 흡착성능을 갖는 것으로 확인할 수 있었다.In addition, as shown in Table 3, it was confirmed that the adsorption performance of hydrogen sulfide adsorbed on the adsorbent had an excellent adsorption performance of 20.5 and 23.9 weight ratio by weight.
이상과 같이, 본 발명은 비록 한정된 실시예와 도면에 의해 설명되었으나, 본 발명은 이것에 의해 한정되지 않으며, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에 의해 본 발명의 기술사상과 아래에 기재될 청구범위의 균등범위 내에서 다양한 수정 및 변형이 가능함은 물론이다.While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Various modifications and variations are possible within the scope of the appended claims.
Claims (7)
산성광산배수에 가성소다(NaOH) 또는 액상소석회(Ca(OH)2)와, 무기질 바인더를 투입·교반하여 3차원 망상구조의 무기질 바인더-수산화철의 혼합 슬러지를 침전시키는 무기질 바인더-수산화철의 혼합 슬러지 생성공정과;
침전된 무기질 바인더-수산화철의 혼합 슬러지를 탈수시키는 슬러지 탈수공정과;
슬러지 탈수공정을 통해서 탈수된 무기질 바인더-수산화철의 혼합 슬러지를 펠렛형상으로 압출 성형하고 건조시켜 흡착제로 성형하는 흡착제 성형공정;을 포함하는 것을 특징으로 하는 산성광산배수를 이용한 황화합물 제거용 흡착제 제조방법.An acidic mine drainage storing process for receiving and storing the acidic mine drainage;
An inorganic binder for precipitating mixed sludge of an inorganic binder-iron hydroxide in a three-dimensional network structure by adding caustic soda (NaOH) or liquid caustic soda (Ca (OH) 2 ) and an inorganic binder to an acid mine drainage and stirring the mixed sludge; A production process;
A sludge dewatering step of dewatering the mixed sludge of the precipitated inorganic binder-iron hydroxide;
A process for producing an adsorbent for removing sulfur compounds using acidic mine drainage, comprising the step of extruding and drying a mixed sludge of an inorganic binder-iron hydroxide dehydrated through a sludge dewatering process into a pellet, and drying the same to form an adsorbent.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR102230845B1 (en) * | 2019-12-26 | 2021-03-23 | 한국광해관리공단 | Manufacturing method of bead type absorbent for eleminating fluoriine in mine drainage from water treatment sludge and bead type absorbent made by the same |
| KR20210148669A (en) * | 2020-06-01 | 2021-12-08 | 한국광해관리공단 | Preparation method of arsenic adsorbent using iron-containing mine drainage |
| KR102348305B1 (en) * | 2020-08-21 | 2022-01-11 | 한국과학기술연구원 | Formaldehyde removal adsorption comprising coffee waste and acid mine drainage sludge, and method for manufacturing the same |
| KR102453854B1 (en) * | 2022-01-12 | 2022-10-12 | 주식회사 태성공영 | Method for manufacturing an adsorbent comprising mine drainage sludge and water treatment sludge and adsorbent manufactured through the same |
| KR20220153759A (en) * | 2021-05-12 | 2022-11-21 | 지원현 | Adsorbent for removing hydrogen sulfide using mine drainage sludge and red mud |
| CN117138547A (en) * | 2023-08-30 | 2023-12-01 | 北京予知环保科技有限公司 | Calcium-based desulfurization powder and preparation method thereof |
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| KR102230845B1 (en) * | 2019-12-26 | 2021-03-23 | 한국광해관리공단 | Manufacturing method of bead type absorbent for eleminating fluoriine in mine drainage from water treatment sludge and bead type absorbent made by the same |
| KR20210148669A (en) * | 2020-06-01 | 2021-12-08 | 한국광해관리공단 | Preparation method of arsenic adsorbent using iron-containing mine drainage |
| KR102348305B1 (en) * | 2020-08-21 | 2022-01-11 | 한국과학기술연구원 | Formaldehyde removal adsorption comprising coffee waste and acid mine drainage sludge, and method for manufacturing the same |
| KR20220153759A (en) * | 2021-05-12 | 2022-11-21 | 지원현 | Adsorbent for removing hydrogen sulfide using mine drainage sludge and red mud |
| KR102453854B1 (en) * | 2022-01-12 | 2022-10-12 | 주식회사 태성공영 | Method for manufacturing an adsorbent comprising mine drainage sludge and water treatment sludge and adsorbent manufactured through the same |
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