KR20150133569A - Method for manufacturing adsorbent using coal mine drainage sludge - Google Patents

Method for manufacturing adsorbent using coal mine drainage sludge Download PDF

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KR20150133569A
KR20150133569A KR1020140060534A KR20140060534A KR20150133569A KR 20150133569 A KR20150133569 A KR 20150133569A KR 1020140060534 A KR1020140060534 A KR 1020140060534A KR 20140060534 A KR20140060534 A KR 20140060534A KR 20150133569 A KR20150133569 A KR 20150133569A
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sludge
mine drainage
coal mine
adsorbent
particle size
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KR1020140060534A
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Korean (ko)
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김덕민
이진수
홍지혜
김지형
최명찬
강경림
이용현
이상무
박남서
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한국광해관리공단
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Publication of KR20150133569A publication Critical patent/KR20150133569A/en

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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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3007—Moulding, shaping or extruding

Abstract

The present invention relates to a method for producing an absorbent by using a coal mine drainage sludge, and to an absorbent for treating rare-earth mine drainage produced thereby. The absorbent for absorbing pollutants such as a radioactive material, heavy metal, or the like, and removing the same is produced by using sludge included in by-products generated when coal mine drainage is treated as a starting material, thereby reducing costs for treating sludge which is waste, preventing environmental pollution, and creating a new added value according to resource recycling of the sludge. The method for producing an absorbent by using a coal mine drainage sludge according to the present invention comprises: a first step of selecting sludge having a particle size ranging from 1 to 3 μm through particle size separation from by-products generated when coal mine drainage is treated, and stirring and mixing the sludge, methylene diphenyl diisocyanate (MDI), and polyol in a weight ratio of 2:0.9-1.1: 0.9-1.1; a second step of drying the mixture obtained in the first step; and a third step of processing an absorbent material dried through the second step to have a predetermined particle size.

Description

석탄광산배수 슬러지를 이용한 흡착제 제조 방법 및 이 제조 방법에 의해 제조된 희토류 광산배수 처리용 흡착제{METHOD FOR MANUFACTURING ADSORBENT USING COAL MINE DRAINAGE SLUDGE}TECHNICAL FIELD The present invention relates to a method for producing an adsorbent using coal mine drainage sludge and an adsorbent for rare earth mine drainage produced by the method,

본 발명은 석탄광산배수 슬러지를 이용한 흡착제에 관한 것으로, 더욱 상세하게는 석탄광산배수의 처리시 발생되는 부산물에 포함된 입자상 슬러지를 이용하여 오염물 예컨대 방사성 물질을 흡착 제거하는 흡착제를 제조하는 석탄광산배수 슬러지를 이용한 흡착제 제조 방법 및 이 제조 방법에 의해 제조된 희토류 광산배수 처리용 흡착제에 관한 것이다.
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adsorbent using coal mine drainage sludge, and more particularly, to an adsorbent using coal mine drainage sludge to produce an adsorbent for adsorbing and removing contaminants such as radioactive substances using particulate sludge contained in by- The present invention relates to a method for producing an adsorbent using sludge and an adsorbent for treating rare earth mine drainage produced by the method.

흡착제는 각종 오염물을 흡착 제거하는 것으로서 흡착대상 물질에 따라 지질기원물질(점토광물 등), 활성탄, 합성물질 등의 다양한 종류가 개발되어 왔다.The adsorbent adsorbs and removes various contaminants, and various types of lipid-based materials (such as clay minerals), activated carbon, and synthetic materials have been developed depending on the substances to be adsorbed.

석탄 광산 배수는 높은 농도의 철을 함유하고 있다. 따라서 석탄 광산 배수처리 시스템은 철을 함유한 다량의 슬러지를 발생시킨다. 그러므로, 상기 슬러지를 처분하고, 재활용하는 것은 중요한 환경적 이슈가 되었다. Coal mine drainage contains high concentrations of iron. Thus, the coal mine drainage system generates a large amount of sludge containing iron. Therefore, disposing and recycling the sludge has become an important environmental issue.

이러한 실정에 맞춰 석탄광산배수에 포함된 슬러지를 자원화하는 기술들이 제안되고 있으나 상용화가 가능한 현실적인 기술이 제안되지 못하고 있는 실정이다.
According to this situation, technologies for recycling the sludge contained in the coal mine drainage have been proposed, but realistic technologies that can be commercialized have not been proposed.

등록특허 제10-0596943호Patent No. 10-0596943

본 발명은 전술한 바와 같은 문제점을 해결하기 위한 것으로, 석탄광산배수의 처리시 발생되는 부산물에 포함된 슬러지에 예를 들어 방사성 물질 등의 오염물을 흡착 제거할 수 있는 흡착능을 부여함으로써 슬러지 폐기물을 자원화할 수 있는 석탄광산배수 슬러지를 이용한 흡착제 제조 방법 및 이 제조 방법에 의해 제조된 희토류 광산배수 처리용 흡착제를 제공하려는 데에 그 목적이 있다.
Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made in view of the above problems, and it is an object of the present invention to provide an adsorbent capable of adsorbing and removing contaminants such as radioactive substances in sludge contained in byproducts generated during the treatment of coal mine drainage, The present invention has been made in view of the above problems, and it is an object of the present invention to provide a method for producing an adsorbent using coal mine drainage sludge and a sorbent for treating rare earth mine drainage produced by the method.

본 발명에 의한 석탄광산배수 슬러지를 이용한 흡착제 제조 방법은, 석탄광산 배수 처리시 발생되는 부산물로부터 입도 선별을 통해 1~3㎛ 입도의 슬러지를 구하고, 상기 슬러지와 메틸렌 디페닐 디이소시아네이트(Methylene Diphenyl diisocyanate, MDI) 및 폴리올을 중량비율로 2 : 0.9~1.1 : 0.9~1.1로 교반 혼합하는 제1단계와; 상기 제1단계에서 만들어진 혼합물을 건조하는 제2단계와; 상기 제2단계를 통해 건조된 흡착제 재료를 일정 입도로 가공하는 제3단계로 이루어지는 것을 특징으로 한다.
The method for producing an adsorbent using the coal mine drainage sludge according to the present invention is characterized in that sludge having a particle size of 1 to 3 μm is obtained from the byproducts generated during the coal mine drainage treatment and the sludge is mixed with the methylene diphenyl diisocyanate , MDI) and a polyol in a weight ratio of 2: 0.9 to 1.1: 0.9 to 1.1; A second step of drying the mixture produced in the first step; And a third step of processing the dried adsorbent material to a predetermined particle size through the second step.

본 발명에 의한 석탄광산배수 슬러지를 이용한 흡착제 제조 방법 및 이 제조 방법에 의해 제조된 희토류 광산배수 처리용 흡착제에 의하면, 석탄광산배수의 처리시 발생되는 부산물에 포함된 슬러지를 출발물질로 하여 방사성 물질, 중금속 등의 오염물을 흡착 제거하는 흡착제를 제조함으로써 폐기물인 슬러지의 처리 비용을 절감함과 아울러 환경오염을 방지할 수 있고 또한 슬러지의 자원화에 따른 부가가치를 창출할 수 있다.
According to the method for producing an adsorbent using the coal mine drainage sludge according to the present invention and the adsorbent for treatment of a rare earth mine drainage produced by the method, it is possible to use a sludge contained in the by- , And heavy metals, thereby reducing the disposal cost of the sludge as a waste, preventing environmental pollution, and creating value added due to resource utilization of the sludge.

본 발명에 따른 석탄광산배수 슬러지를 이용한 희토류 광산배수 처리용 흡착제 제조 방법은 다음과 같다.A method for producing an adsorbent for treatment of rare earth mine drainage using coal mine drainage sludge according to the present invention is as follows.

1. 재료 준비.1. Materials Preparation.

본 발명에 의한 흡착제(PUCMDS, Polyurethane Coal mine drainage sludge)는 우레탄 계열의 흡착제로서 1~3㎛ 입도의 석탄광산배수 슬러지, 메틸렌 디페닐 디이소시아네이트(Methylene Diphenyl diisocyanate, MDI) 및 폴리올을 재료로 하며 강도는 1GPa이다.The PU CMDS (Polyurethane Coal Mine drainage sludge) according to the present invention is a urethane-based adsorbent, which is made of coal mine drainage sludge having a particle size of 1 to 3 μm, methylene diphenyl diisocyanate (MDI) and polyol The strength is 1 GPa.

석탄광산배수 슬러지는 석탄광산배수 처리시 발생되는 부산물(Coal mine drainage sludge)에서 회수된다.Coal mine drainage sludge is recovered from coal mine drainage sludge.

상기 부산물에 대한 독성물질 용출시험(TCLP) 결과는 표 1과 같다.
Table 1 shows the results of toxic substance release test (TCLP) on the by-products.

유해물질Hazardous Substances
시험항목Test Items 기준standard 00광산00 mine 봄spring 여름summer 가을autumn 겨울winter PbPb 3 이하3 or less 0.0210.021 0.0920.092 0.0060.006 0.0110.011 CuCu 3 이하3 or less 0.0180.018 0.1230.123 0.0620.062 0.0230.023 AsAs 1.5 이하Not more than 1.5 0.0240.024 0.0580.058 0.0640.064 0.0350.035 HgHg 0.0. 005이하005 or less NDND NDND NDND NDND CNCN - - 1 이하1 or less NDND NDND NDND NDND Cr6Cr6 + + 1.5 이하Not more than 1.5 NDND 0.0050.005 0.0080.008 0.0060.006 유기인Organic phosphorus 1 이하1 or less NDND NDND NDND NDND TCETCE 0.1 이하0.1 or less NDND NDND NDND NDND PCEPCE 0.3 이하0.3 or less NDND NDND NDND NDND 기름성분 Oil component 5% 이하Less than 5% 5% 이하Less than 5% 5%이하 Less than 5% 5%이하 Less than 5% 5% 이하Less than 5%

표 1에서 보이는 바와 같이 석탄광산배수 처리시 발생되는 부산물은 기준치 이하이긴 하지만 중금속 등의 오염물이 포함되어 있다.As shown in Table 1, the byproducts generated during the coal mine drainage treatment contain contaminants such as heavy metals.

본 발명의 석탄광산배수 슬러지는 상기 부산물로부터 회수되며 선별공정을 통해 1~3㎛ 입도의 입자상 물질만으로 사용된다. 상기 입도는 흡착성능과 정화수의 생산성 등을 고려한 입도이며, 상기 입도 범위보다 입도가 작으면 흡착재의 손실량이 많고 입도가 너무 크면 정화수의 생산성 등이 떨어진다.The coal mine drainage sludge of the present invention is recovered from the by-product and used only as particulate matter having a particle size of 1 to 3 mu m through a sorting process. The particle size is a particle size in consideration of the adsorption performance and the productivity of the purified water. If the particle size is smaller than the particle size range, the loss of the adsorbent is large and the particle size is too large.

석탄광산배수 처리시 발생되는 부산물로부터 스크린에 의한 입도 선별만을 통해 본 발명의 출발물질인 입자상의 슬러지를 회수하여 자연 상태에서 건조하여 획득한다.The sludge as a starting material of the present invention is recovered from the byproducts generated in the coal mine drainage process only by screening by the screen, and dried and obtained in a natural state.

MDI와 폴리올은 슬러지의 공극률 확보와 우레탄 계열의 흡착제를 제조하기 위하여 사용되며, 입자상의 슬러지 : MDI : 폴리올이 2 : 0.9~1.1 : 0.9~1.1의 중량비율(권장조건 : 2 : 1 : 1)로 사용되며, 이는 최적의 공극률 및 흡착능을 위한 비율이다.
MDI and polyol are used for securing the porosity of the sludge and for producing urethane-based adsorbents. Particulate sludge: MDI: polyol in a weight ratio of 2: 0.9-1.1: 0.9-1.1 (recommended condition: 2: 1: , Which is the ratio for optimum porosity and adsorption capacity.

2. 재료 혼합 및 공극 형성.2. Material mixing and pore formation.

1~3㎛의 슬러지와 MDI 및 폴리올을 상기 비율로 교반기에 넣고 상온(20~25℃)에서 80-120 rpm의 속도로 20~40분(권장조건 : 100rpm)의 속도로 30분 동안 교반하며 이 과정을 통해 입자상의 슬러지에 있는 CO2가 배출되게 되어 공극이 형성된다.1 to 3 탆 sludge and MDI and polyol were added to the stirrer at the above ratios and stirred for 30 minutes at a rate of 80 to 120 rpm and 20 to 40 minutes (recommended condition: 100 rpm) at room temperature (20 to 25 ° C) Through this process, CO 2 in the particulate sludge is discharged and pores are formed.

상기 교반속도와 시간은 재료들의 균일한 혼합과 공극 형성을 위한 조건이며, 상기 조건을 벗어나면 공극률이 낮아 흡착성능이 떨어지거나 재료가 파괴된다.
The stirring speed and time are conditions for uniform mixing of materials and formation of voids. If the above conditions are not satisfied, the porosity is low and the adsorption performance is deteriorated or the material is destroyed.

3. 건조.3. Drying.

전 공정을 통해 공극을 형성한 흡착제 가공물의 안정화를 위하여 건조 공정을 거친다.A drying process is performed to stabilize the adsorbent workpieces that have formed voids through the whole process.

건조 조건은 상온(20~25℃)에서 2시간 30분~3시간 30분(권장조건 : 3시간)이다.
Drying conditions are 2 hours and 30 minutes to 3 hours and 30 minutes (recommended conditions: 3 hours) at room temperature (20 to 25 ° C).

4. 가공.4. Processing.

건조가 완료된 흡착제는 이전 공정을 거치면서 넓은 범위의 입도로 가공될 수 있으며 슬러지의 최초 입도인 1~3㎛ 입도이며 공극률이 0.5~0.6%인 흡착제로 가공하기 위하여 파쇄, 분쇄 및 입도선별 공정을 거친다. The dried adsorbent can be processed to a wide range of particle sizes through the previous process, and it can be crushed, pulverized and granulated to process the adsorbent having a particle size of 1 to 3 μm and a porosity of 0.5 to 0.6%, which is the initial particle size of the sludge It goes through.

이와 같이 제조된 흡착제의 특성은 표 2와 같다.
Table 2 shows the characteristics of the adsorbent thus prepared.

PropertiesProperties DataData Bulk density(g mL-1)Bulk density (g mL -1 ) 0.240.24 pHpH 7.687.68 pHzpcpHZPC 5.85.8 BET surface area(m2g-1)BET surface area (m 2 g -1 ) 23.023.0 Pore size(nm)Pore size (nm) 4848 Goethite(wt.%)
Calcite(wt.%)
SO4 2-(wt.%)Goethite (wt.%)
Calcite (wt.%)
SO 4 2- (wt.%) 60.67
16.33
5.1160.67
16.33
5.11 표면 강도Surface strength 1GPa1 GPa

이와 같은 조성의 흡착제는 오염도 등에 따라 달라지겠지만 공탁체류시간(EBCT)을 50분~70분(권장조건 : 60분)으로 하여 방사성 물질, 중금속 등을 제거한다.
The adsorbent of this composition will vary depending on the degree of contamination, but the radioactivity, heavy metals, etc. are removed with a deposit time (EBCT) of 50 to 70 minutes (recommended condition: 60 minutes).

<실시예><Examples>

석탄광산배수 처리시 발생된 부산물의 입도 선별(스크린)을 통해 2㎛의 슬러지를 획득하였고, 이 슬러지와 MDI 및 양이온의 폴리올을 중량 기준 2 : 1 : 1의 비율로 준비하여 교반기에 넣어 상온에서 100 rpm의 속도로 30분간 교반하였으며 이 과정을 통해 CO2 날려 공극을 형성하였다. 공극률(Porosity)은 0.57%이다. 활동량(activity volume)은 0.833L, 유량은 20L/day이다.2 ㎛ sludge was obtained by screening the byproducts generated in the coal mine drainage treatment. The sludge, MDI and cationic polyol were prepared at a ratio of 2: 1: 1 on the weight basis and placed in a stirrer at room temperature The mixture was stirred at a speed of 100 rpm for 30 minutes and CO 2 blown pores were formed through this process. The porosity is 0.57%. The activity volume is 0.833L and the flow rate is 20L / day.

이어서 상온에서 3시간 동안 건조한 후 입도 선별을 통해 2㎛ 입도의 흡착제를 준비하였다. Packing density 617kg/㎥이다.After drying at room temperature for 3 hours, the adsorbent having a particle size of 2 mu m was prepared through particle size selection. The packing density is 617 kg / m3.

이렇게 제조된 흡착제를 이용하여 희토류 광산배수로부터 오염물을 흡착 제거하였으며, 공탁체류시간을 1시간으로 하여 방사성 물질을 제거하였다. 또한 pH 5일 때 흡착 성능과 반응속도가 최대인 것으로 확인되어 공탁체류조건을 pH 5로 유지하였다. 표 3은 본 실시예에 의한 처리 결과를 보인 표이다.
The adsorbent was used to adsorb and remove contaminants from the rare earth mine drainage, and the radioactivity was removed with a deposit time of 1 hour. At pH 5, the adsorption performance and reaction rate were found to be the maximum, and the host suspension condition was maintained at pH 5. Table 3 shows the results of the processing according to the present embodiment.

ThTh UU PbPb CdCD CuCu ZnZn MnMn AsAs FF CODcrCODcr 유입inflow 0.920.92 0.090.09 0.090.09 0.070.07 0.110.11 0.100.10 0.070.07 1.851.85 8.08.0 182182 유출outflow 0.010.01 0.010.01 0.0020.002 0.050.05 0.060.06 0.050.05 0.010.01 0.020.02 0.50.5 8383

표 3에서 알 수 있듯이, 본 발명에 의해 희토류 광산배수를 처리한 결과 중금속과 방사성 물질 및 유기물 모두 유입수 대비 상당량 감소하였음을 알 수 있다.As can be seen from Table 3, the treatment of rare earth mine drainage according to the present invention shows that the heavy metals, radioactive substances and organic matters are considerably reduced compared to the influent water.

Claims (4)

석탄광산 배수 처리시 발생되는 부산물로부터 입도 분리를 통해 1~3㎛ 입도의 슬러지를 선별하고, 상기 슬러지와 메틸렌 디페닐 디이소시아네이트(Methylene Diphenyl diisocyanate, MDI) 및 폴리올을 중량비율로 2 : 0.9~1.1 : 0.9~1.1로 교반 혼합하는 제1단계와;
상기 제1단계에서 만들어진 혼합물을 건조하는 제2단계와;
상기 제2단계를 통해 건조된 흡착제 재료를 일정 입도로 가공하는 제3단계를 포함하는 것을 특징으로 하는 석탄광산배수 슬러지를 이용한 흡착제 제조 방법.Sludge having a particle size of 1 to 3 μm is separated from the byproducts generated during the coal mine drainage treatment and the sludge is mixed with methylene diphenyl diisocyanate (MDI) and polyol in a weight ratio of 2: 0.9 to 1.1 : 0.9 to 1.1;
A second step of drying the mixture produced in the first step;
And a third step of processing the dried adsorbent material to a predetermined particle size through the second step. 청구항 1에 있어서, 상기 제1단계는 상기 슬러지와 MDI 및 폴리올을 상온에서 80-120rpm의 속도로 20~40분간 교반 혼합하여 상기 슬러지에 있는 CO2를 배출하여 공극률을 0.5~0.6으로 유지하도록 하는 것을 특징으로 하는 석탄광산배수 슬러지를 이용한 흡착제 제조 방법.[2] The method of claim 1, wherein the first step comprises mixing the sludge, MDI, and polyol at a temperature of 80-120 rpm at a temperature of 20-100 rpm for 20-40 minutes to discharge CO 2 from the sludge to maintain a porosity of 0.5-0.6 Wherein the adsorbent is adsorbed to the adsorbent. 청구항 1 또는 청구항 2에 있어서, 상기 제2단계는 상기 제1단계에서 만들어진 혼합물을 상온에서 2시간 30분~3시간 30분간 건조하는 것을 특징으로 하는 석탄광산배수 슬러지를 이용한 흡착제 제조 방법.The method of claim 1 or 2, wherein the second step comprises drying the mixture prepared in the first step at room temperature for 2 hours to 30 minutes to 3 hours and 30 minutes. 청구항 3에 의한 석탄광산배수 슬러지를 이용한 흡착제 제조 방법에 의해 제조된 것을 특징으로 하는 석탄광산배수 슬러지를 이용한 희토류 광산배수 처리용 흡착제.A sorbent for the treatment of rare earth mine drainage using coal mine drainage sludge according to claim 3, which is produced by a method for producing an adsorbent using coal mine drainage sludge.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190034893A (en) * 2017-09-25 2019-04-03 주식회사 이앤켐솔루션 Manufacturing method of inorganic adsorbent for phosphorus removal using acid mine drainage sludge
CN110508243A (en) * 2019-08-14 2019-11-29 贵州大学 A kind of preparation method and application of biomass-based porous charcoal load iron wadding body adsorbent material

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190034893A (en) * 2017-09-25 2019-04-03 주식회사 이앤켐솔루션 Manufacturing method of inorganic adsorbent for phosphorus removal using acid mine drainage sludge
CN110508243A (en) * 2019-08-14 2019-11-29 贵州大学 A kind of preparation method and application of biomass-based porous charcoal load iron wadding body adsorbent material
CN110508243B (en) * 2019-08-14 2022-05-31 贵州大学 Preparation method and application of biomass-based porous carbon loaded iron floc adsorption material

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