KR102653354B1 - Manufacturing method of bead-type arsenic adsorbent using iron hydroxide-based waste - Google Patents
Manufacturing method of bead-type arsenic adsorbent using iron hydroxide-based waste Download PDFInfo
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- iron hydroxide
- bead
- based waste
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- inorganic binder
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- 239000002699 waste material Substances 0.000 title claims abstract description 67
- 235000014413 iron hydroxide Nutrition 0.000 title claims abstract description 61
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 title claims abstract description 61
- 239000003463 adsorbent Substances 0.000 title claims abstract description 49
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 49
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 62
- 239000011230 binding agent Substances 0.000 claims abstract description 30
- 239000011324 bead Substances 0.000 claims abstract description 29
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 28
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000292 calcium oxide Substances 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 238000000465 moulding Methods 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000005507 spraying Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 5
- 238000003914 acid mine drainage Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- 238000005054 agglomeration Methods 0.000 abstract description 7
- 230000002776 aggregation Effects 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 239000010419 fine particle Substances 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 238000001179 sorption measurement Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000007602 hot air drying Methods 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000001932 seasonal effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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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
- B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
-
- 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
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
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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
- B01J20/3007—Moulding, shaping or extruding
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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
- B01J20/3014—Kneading
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
본 발명은 수산화철계열 폐기물 분말과 산화칼슘 분말을 비드 성형기에서 혼합하는 동안에 액상 무기바인더를 분무하여 뭉침 방지와 미립자 형성의 크기가 제어하면서 입자의 크기가 고른 비드형상의 비소흡착제를 제조할 수 있는 비소흡착제의 제조방법에 관한 것이다.
본 발명은 수산화철계열 폐기물을 이용한 수산화철계열 폐기물 분말을 생성하는 단계와; 수산화철계열 폐기물 분말과 산화칼슘 분말을 혼합하는 단계와; 비드성형기에서 수산화철계열 폐기물 분말과 산화칼슘 분말을 교반하면서 액상 무기바인더를 분무하여 반죽물을 생성하면서 입상 비드 형태의 비소흡착제로 성형하는 단계와, 생성된 비드형상의 비소흡착제를 입경이 4~6mm을 갖는 것으로 선별하는 단계를 포함하는 것을 특징으로 한다.The present invention is to prevent agglomeration and control the size of fine particle formation by spraying a liquid inorganic binder while mixing iron hydroxide-based waste powder and calcium oxide powder in a bead molding machine, and to produce an arsenic adsorbent in the form of beads with uniform particle size. It relates to the manufacturing method of adsorbent.
The present invention includes the steps of producing iron hydroxide-based waste powder using iron hydroxide-based waste; mixing iron hydroxide-based waste powder and calcium oxide powder; A step of forming a granular bead-shaped arsenic adsorbent by spraying a liquid inorganic binder while stirring the iron hydroxide-based waste powder and calcium oxide powder in a bead molding machine to create a paste, and forming the arsenic adsorbent in the form of a granular bead with a particle size of 4 to 6 mm. It is characterized in that it includes the step of selecting as having.
Description
본 발명은 수산화철계열 폐기물 분말과 산화칼슘 분말을 비드 성형기에서 혼합하는 동안에 액상 무기바인더를 분무하여 뭉침 방지와 미립자 형성의 크기가 제어하면서 입자의 크기가 고른 비드형상의 비소흡착제를 제조할 수 있는 수산화철계열 폐기물을 이용한 비드형 비소흡착제의 제조방법에 관한 것이다.The present invention is an iron hydroxide that sprays a liquid inorganic binder while mixing iron hydroxide-based waste powder and calcium oxide powder in a bead molding machine to prevent agglomeration and control the size of fine particle formation while producing a bead-shaped arsenic adsorbent with uniform particle size. This relates to a method of manufacturing a bead-type arsenic adsorbent using series waste.
국내에서 발생되는 모든 수산화철계열 폐기물는「폐기물관리법■ 제 2조에 의거 사업장폐기물(지정외폐기물 무기성 오니류)로 분류되어 철 성분을 다량 함유하고 있는 무기성 소재임에도 불구하고 연간 약 6천톤(2018년 수질정화시설 연간 수산화철계열 폐기물 처리량 기준) 가량의 수산화철계열 폐기물이 매립하여 처분되거나 일부는 시멘트 부원료로 사용되고 있는 실정이다.All iron hydroxide-based waste generated in Korea is classified as industrial waste (non-designated waste, inorganic sludge) in accordance with Article 2 of the Waste Management Act, and although it is an inorganic material containing a large amount of iron, it is approximately 6,000 tons per year (2018 water quality). (Based on the annual iron hydroxide waste treatment volume of purification facilities), iron hydroxide waste is landfilled and disposed of, or some of it is used as cement auxiliary raw materials.
수산화철계열 폐기물에 다량 함유되어 있는 철 성분은 수산화철계 재제로 활용가치가 매우 높으며, 이미 국외에서는 이를 활용할 수 있는 다양한 연구개발들이 이루어져 활용되고 있다.The iron component contained in large quantities in iron hydroxide-based waste has great utility as an iron hydroxide-based material, and various research and developments have already been conducted overseas to utilize it.
이와 같이 처리되고 있는 수산화철계열 폐기물은 처리공정 및 계절별 오염부하량(유입수질, 유량등)에 따라 성분에 변동성은 있지만 전반적으로 주요 성분 및 구조, 물성이 공통적인 부분을 활용하여 표준화 및 목적사업용 제품화가 가능하다는 연구결과들이 나오고 있다. Iron hydroxide-based waste being treated in this way has variations in composition depending on the treatment process and seasonal pollutant load (inflow water quality, flow rate, etc.), but is standardized and commercialized by utilizing the common main components, structure, and physical properties. Research results are showing that it is possible.
철 성분은 비소나 인 등 중금속 원소류와의 반응성이 높은 특성을 지닌다. 수산화철계열 폐기물에 다량 포함되어 있는 수산화철계 성분은 이러한 환경상의 중금속 오염물질등과 반응하여 화학적 또는 물리적 흡착을 통해 제거하기위한 제품의 소재로 활용하기에 아주 적합하다고 볼 수 있다. The iron component has the characteristic of being highly reactive with heavy metal elements such as arsenic and phosphorus. Iron hydroxide-based components, which are contained in large quantities in iron hydroxide-based waste, can be considered to be very suitable for use as a material for products that react with environmental heavy metal pollutants and remove them through chemical or physical adsorption.
그 중에서도 효율이 우수한 비소 제거제로 알려져있는 GFH는 독일 Wasserchemie사의 GEH가 대표적인 제품으로, 대부분의 수처리 시설에서 비소 및 인을 제거하기 위한 제재로 사용되고 있으며 1mm~2mm 범위 내의 규격을 가지는 그래뉼 형태의 수산화철, 산화철 복합 베이스 흡착제로 다양한 물 속 중금속도 함께 흡착 제거할 수 있는 제품으로 알려져 있으나 수입 의존도가 높으며, 교체 주기 대비 교체 비용이 매우 고가이므로 처리에 소비되는 비용이 매우 높아 GFH를 대체할 수 있는 흡착제의 발굴이 매우 중요한 실정이다.Among them, GFH, which is known as an efficient arsenic remover, is a representative product of GEH from Wasserchemie, Germany. It is used as a material to remove arsenic and phosphorus in most water treatment facilities. It is made of granular iron hydroxide with a size in the range of 1mm to 2mm, It is known as an iron oxide complex base adsorbent that can adsorb and remove a variety of heavy metals from water, but it is highly dependent on imports and the replacement cost is very high compared to the replacement cycle. Therefore, the cost of treatment is very high, so it is difficult to find an adsorbent that can replace GFH. Excavation is very important.
기존의 대표적인 비소제거용 흡착제로 사용되고 있던 GFH는 비소 제거 효율이 매우 높은 비소제거용 흡착제로 알려져 있는데, 그래뉼 형태이기는 하나 그 입자의 규격 범위가 1mm~2mm에서 불균일한 입자 형태를 보인다.GFH, which has been used as a representative existing adsorbent for arsenic removal, is known as an adsorbent for arsenic removal with very high arsenic removal efficiency. Although it is in granule form, the particle size is in the range of 1mm to 2mm and has a non-uniform particle shape.
수산화철계열 폐기물을 재활용한 수산화철계 비소제거용 흡착제의 제조방법의 개발을 통하여 시멘트의 부자재로 활용되거나 버려지고 있던 수산화철계열 폐기물을 비소제거용 비드형 흡착제로 사용하므로 인해 효율적이고 합리적인 비용으로 비소를 제거할 수 있다. 정화 시설에서 발생하는 슬러지는 많은 양의 철분 및 기타 금속물질, 칼슘 및 마그네슘 등을 함유하고 있다. 전술한 성분들이 포함되어 있는 슬러지는 회수하여 바인더류 등과 혼합하여 비드 성형기를 통하여 성형과정을 거쳐 비드형태로 제조되는데 기존의 펠릿형태 또는 그래뉼 형태의 흡착제들에 비하여 비드형태의 비소 제거용 흡착제는 규격범위 내에서 크기와 모양이 균일하고 투입과 회수가 용이하게 사용될 수 있다. 폐기물을 재활용하여 만들어진 비드형상의 흡착제는 원 부자재의 제조원가가 저렴하고 제조 공정이 용이하여 매우 경제적이다. Through the development of a manufacturing method for iron hydroxide-based arsenic removal adsorbent using recycled iron hydroxide-based waste, iron hydroxide-based waste that was used as an auxiliary material for cement or discarded is used as a bead-type adsorbent for arsenic removal, thereby removing arsenic efficiently and at a reasonable cost. can do. Sludge generated from purification facilities contains large amounts of iron and other metal substances, calcium and magnesium. Sludge containing the above-mentioned ingredients is recovered, mixed with binders, etc., and processed into a bead shape through a bead molding machine. Compared to the existing pellet- or granule-type adsorbents, the bead-type arsenic removal adsorbent has a standard. The size and shape are uniform within the range and can be easily used for input and recovery. Bead-shaped adsorbents made by recycling waste are very economical because the manufacturing cost of raw materials is low and the manufacturing process is easy.
이에 따라 본 발명자는 철을 함유하는 광산배수를 이용하여 산업적으로 이용할 수 있는 비소흡착제를 제조하여 광산배수를 정화시키면서 슬러지 배출량을 절감시킬 수 있는 기술을 개발하게 되었다.Accordingly, the present inventor developed a technology that can reduce sludge discharge while purifying mine drainage by producing an industrially usable arsenic adsorbent using iron-containing mine drainage.
본 발명이 해결하고자 하는 과제는 수산화철계열 폐기물 분말과 산화칼슘 분말을 비드 성형기에서 혼합하는 동안에 액상 무기바인더를 분무하여 뭉침 방지와 미립자 형성의 크기가 제어하면서 입자의 크기가 고른 비드형상의 비소흡착제를 제조할 수 있는 수산화철계열 폐기물을 이용한 비드형 비소흡착제의 제조방법을 제공하는 데 있다.The problem to be solved by the present invention is to prevent agglomeration and control the size of fine particle formation by spraying a liquid inorganic binder while mixing iron hydroxide-based waste powder and calcium oxide powder in a bead molding machine, and to provide a bead-shaped arsenic adsorbent with uniform particle size. The aim is to provide a method for manufacturing a bead-type arsenic adsorbent using manufacturable iron hydroxide-based waste.
본 발명에 따른 수산화철계열 폐기물을 이용한 비드형 비소흡착제의 제조방법은 수산화철계열 폐기물을 이용한 수산화철계열 폐기물 분말을 생성하는 단계와; 수산화철계열 폐기물 분말과 산화칼슘 분말을 혼합하는 단계와; 비드성형기에서 수산화철계열 폐기물 분말과 산화칼슘 분말을 교반하면서 액상 무기바인더를 분무하여 반죽물을 생성하면서 입상 비드 형태의 비소흡착제로 성형하는 단계와, 생성된 비드형상의 비소흡착제를 입경이 4~6mm을 갖는 것으로 선별하는 단계를 포함하는 것을 특징으로 한다.The method for producing a bead-type arsenic adsorbent using iron hydroxide-based waste according to the present invention includes the steps of producing iron hydroxide-based waste powder using iron hydroxide-based waste; mixing iron hydroxide-based waste powder and calcium oxide powder; A step of forming a granular bead-shaped arsenic adsorbent by spraying a liquid inorganic binder while stirring the iron hydroxide-based waste powder and calcium oxide powder in a bead molding machine to create a paste, and forming the arsenic adsorbent in the form of a granular bead with a particle size of 4 to 6 mm. It is characterized in that it includes the step of selecting as having.
바람직하게, 수산화철계열 폐기물 분말은 산성광산배수를 처리하는 수질정화시설에서 발생되는 폐기물을 건조하고, 평균 입경이 0.3 내지 2.0 ㎛로 분쇄된 것으로, 전체 중량에 대하여 45~65중량%로 혼합되는 것을 특징으로 한다.Preferably, the iron hydroxide-based waste powder is obtained by drying waste generated in a water purification facility that treats acid mine drainage and grinding it to an average particle size of 0.3 to 2.0 ㎛, and is mixed at 45 to 65% by weight based on the total weight. It is characterized by
바람직하게, 산화칼슘 분말은 입자 크기가 10㎛ 이하이며, 전체 중량에 대하여 5~10중량%로 혼합되는 것을 특징으로 한다.Preferably, the calcium oxide powder has a particle size of 10㎛ or less and is mixed at 5 to 10% by weight based on the total weight.
바람직하게, 액상 무기바인더는 실리콘계 무기바인더 또는 알루미늄계 무기바인더이며, 전체 중량에 대하여 30~40중량%로 혼합되는 것을 특징으로 한다.Preferably, the liquid inorganic binder is a silicon-based inorganic binder or an aluminum-based inorganic binder, and is mixed at 30 to 40% by weight based on the total weight.
바람직하게, 비드 성형기는 원통형의 혼합조 내부에 회전형을 갖는 교반날개가 구비되고, 측면에 액상 무기바인더를 분무하는 토출노즐이 형성된 것을 특징으로 한다.Preferably, the bead molding machine is characterized in that a stirring blade having a rotating type is provided inside a cylindrical mixing tank, and a discharge nozzle for spraying a liquid inorganic binder is formed on the side.
본 발명은 수산화철계열 폐기물 분말, 산화칼슘 분말을 비드 성형기에서 혼합하는 동안에 포졸란 유도하는 액상 무기바인더를 노즐을 통해 분사하기 때문에 각 혼합물이 뭉치는 것을 방지하여 입자의 크기가 고른 비드형상의 비소흡착제를 제조할 수 있는 장점이 있다. The present invention sprays a pozzolan-inducing liquid inorganic binder through a nozzle while mixing iron hydroxide-based waste powder and calcium oxide powder in a bead molding machine, thereby preventing each mixture from agglomerating and creating a bead-shaped arsenic adsorbent with uniform particle size. There are advantages to manufacturing it.
도 1은 본 발명에 따른 수산화철계열 폐기물을 이용한 비드형 비소흡착제의 제조과정에 대한 플로차트.
도 2는 본 발명에 의해 제조된 실시예1, 실시예2의 비드형 비소흡착제에 대한 등온흡착 실험 결과 그래프.
도 3은 본 발명에 의해 제조된 실시예1, 실시예2의 비드형 비소흡착제에 대한 반응속도상수 실험 결과 그래프.Figure 1 is a flow chart of the manufacturing process of a bead-type arsenic adsorbent using iron hydroxide-based waste according to the present invention.
Figure 2 is a graph showing the results of isothermal adsorption experiments on the bead-type arsenic adsorbents of Examples 1 and 2 prepared according to the present invention.
Figure 3 is a graph showing the results of reaction rate constant experiments for the bead-type arsenic adsorbents of Examples 1 and 2 prepared according to the present invention.
이하, 첨부된 도면을 참조하여 본 발명의 실시예를 설명한다.Hereinafter, embodiments of the present invention will be described with reference to the attached drawings.
도 1을 참조하면, 본 발명에 따른 수산화철계열 폐기물을 이용한 수산화철계열 폐기물 분말을 생성하는 단계(S10)와; 수산화철계열 폐기물 분말과 산화칼슘 분말을 고르게 혼합하는 단계(S20)와; 비드성형기에서 수산화철계열 폐기물 분말과 산화칼슘 분말을 교반하면서 액상 무기바인더를 분무하여 반죽물을 생성하면서 입상 비드 형태의 비소흡착제로 성형하는 단계(S30)와, 생성된 비드형상의 비소흡착제를 소정 입경을 갖는 것으로 분리하는 단계(S30)를 포함하다.Referring to Figure 1, generating iron hydroxide-based waste powder using iron hydroxide-based waste according to the present invention (S10); Evenly mixing iron hydroxide-based waste powder and calcium oxide powder (S20); A step (S30) of forming a granular bead-shaped arsenic adsorbent by spraying a liquid inorganic binder while stirring the iron hydroxide-based waste powder and calcium oxide powder in a bead molding machine to create a dough, and forming the arsenic adsorbent in the form of a granular bead with a predetermined particle size. It includes a separation step (S30).
수산화철계열 폐기물 분말 생성단계(S10)는 철을 함유하는 광산배수를 처리하는 수질정화시설에서 발생되는 폐기물을 자연건조, 열풍건조 등으로 건조하고 소정크기로 분쇄하여 생성하게 된다. 수산화철계열 폐기물 분말의 평균 입경은 0.3 내지 2.0 ㎛ 인 것이 바람직하다. 이때, 수산화철계열 폐기물은 산성광산배수에 Ca(OH)2를 혼합하여 철 등의 성분이 침전되는 폐기물이다.The iron hydroxide-based waste powder generation step (S10) is generated by drying waste generated in a water purification facility that treats iron-containing mine drainage by natural drying, hot air drying, etc., and pulverizing it to a predetermined size. The average particle size of the iron hydroxide-based waste powder is preferably 0.3 to 2.0 ㎛. At this time, iron hydroxide-based waste is a waste in which components such as iron are precipitated by mixing Ca(OH) 2 with acid mine drainage.
산화칼슘 분말 혼합단계(S20)는 수산화철계열 폐기물 분말에 산화칼슘 분말이 고르게 분포되도록 혼합한다. 이러한 산화칼슘 분말은 수산화철계열 폐기물 분말에 함유된 철성분과 함께 액상 무기바인더와 반응하여 포졸란 반응을 형성하게 된다. 이러한 산화칼슘 분말은 수산화철계열 폐기물 분말에 고르게 혼합되도록 입자 크기가 10㎛ 이하인 것이 바람직하다. 이때, 수산화철계열 폐기물 분말과 산화칼슘 분말의 혼합은 비드성형기에서 이루어지는 것이 바람직하다.In the calcium oxide powder mixing step (S20), the calcium oxide powder is mixed so that the iron hydroxide-based waste powder is evenly distributed. This calcium oxide powder reacts with the liquid inorganic binder along with the iron contained in the iron hydroxide-based waste powder to form a pozzolanic reaction. This calcium oxide powder preferably has a particle size of 10㎛ or less so that it is evenly mixed with the iron hydroxide-based waste powder. At this time, it is preferable that the mixing of iron hydroxide-based waste powder and calcium oxide powder is performed in a bead molding machine.
한편, 수산화철계열 폐기물 분말은 전체 중량에 대하여 45~65중량%, 산화칼슘 분말은 5~10중량%로 혼합되는 것이 바람직하다. 수산화철계열 폐기물 분말의 함량이 45 중량% 미만이면 비소 흡착능이 감소할 수 있고, 65 중량% 초과인 경우 비드형성이 어려울 수 있다. 또한, 산화칼슘 분말의 함량이 5중량% 미만이면 포졸란 반응의 유도가 어렵고, 10 중량% 초과인 경우 뭉침현상으로 비드형성이 어려울 수 있다.Meanwhile, it is desirable to mix 45 to 65% by weight of iron hydroxide-based waste powder and 5 to 10% by weight of calcium oxide powder based on the total weight. If the content of iron hydroxide-based waste powder is less than 45% by weight, arsenic adsorption capacity may be reduced, and if it is more than 65% by weight, bead formation may be difficult. In addition, if the content of calcium oxide powder is less than 5% by weight, it is difficult to induce a pozzolanic reaction, and if it is more than 10% by weight, bead formation may be difficult due to agglomeration.
액상 무기바인더 분무단계(S30)는 비드 성형기에서 수산화철계열 폐기물 분말, 산화칼슘이 교반되면서 고르게 혼합되는 동안에 노즐을 통해 분사되어 수산화철계열 폐기물 분말에 포함된 철성분, 산화칼슘과 반응하면서 포졸란(Pozzolan) 반응을 유도하여 혼합물을 견고하게 유지시킨다. 액상 무기바인더는 포졸란 반응이 용이한 실리콘계 무기바인더, 알루미늄계 무기바인더인 것이 바람직하다. 액상 무기바인더는 전체 중량에 대하여 30~40중량%로 혼합되는 것이 바람직하다. 이때, 액상 무기바인더의 함량이 30중량% 미만이면 포졸란 반응의 유도가 어렵고, 40중량% 초과인 경우 뭉침현상으로 비드형성이 어려울 수 있다. 또한, 액상 무기바인더를 한 번에 투입하여 혼합하면 포졸란 반응이 일시에 일어나게 되어 비드성형이 어려운 문제가 발생되기 때문에 액상 무기바인더는 비드 성형기에 수산화철계열 폐기물 분말, 산화칼슘 분말이 교반되는 동안에 분무방식으로 혼합되는 것이 바람직하다.In the liquid inorganic binder spraying step (S30), while the iron hydroxide-based waste powder and calcium oxide are stirred and evenly mixed in the bead molding machine, it is sprayed through a nozzle and reacts with the iron and calcium oxide contained in the iron hydroxide-based waste powder to form pozzolan. It induces a reaction and keeps the mixture strong. The liquid inorganic binder is preferably a silicon-based inorganic binder or an aluminum-based inorganic binder that is prone to pozzolanic reaction. The liquid inorganic binder is preferably mixed at 30 to 40% by weight based on the total weight. At this time, if the content of the liquid inorganic binder is less than 30% by weight, it is difficult to induce a pozzolanic reaction, and if it is more than 40% by weight, bead formation may be difficult due to agglomeration. In addition, if the liquid inorganic binder is added and mixed at once, a pozzolanic reaction occurs at once, making bead molding difficult. Therefore, the liquid inorganic binder is sprayed while the iron hydroxide-based waste powder and calcium oxide powder are stirred in the bead molding machine. It is preferable to mix.
한편, 비드 성형기는 원통형의 혼합조 내부에 회전형을 갖는 교반날개가 구비되어서 수산화철계열 폐기물 분말과 산화칼슘 분말을 고르게 혼합하고 측면에 노즐이 형성되어서 액상 바인더를 분무방식으로 투입하여 수산화철계열 폐기물 분말, 산화칼슘 분말과 함께 반죽되면서 비드형 흡착제를 형성하게 된다. 이러한 비드 성형기는 일정량으로 투입되는 액상 바인더에 의하여 뭉침이 발생할 수 있으나, 이는 성형기 내부 원통 혼합조에 설치된 고속회전 교반날개에 의하여 뭉침 방지와 미립자 형성의 크기가 제어될 수 있다. Meanwhile, the bead molding machine is equipped with a rotating stirring blade inside a cylindrical mixing tank to evenly mix the iron hydroxide-based waste powder and calcium oxide powder, and a nozzle is formed on the side to inject the liquid binder by spraying to powder the iron hydroxide-based waste powder. , it is kneaded with calcium oxide powder to form a bead-type adsorbent. In such bead molding machines, agglomeration may occur due to the liquid binder introduced in a certain amount, but this can be prevented by agglomeration and the size of fine particle formation can be controlled by the high-speed rotating stirring blade installed in the cylindrical mixing tank inside the molding machine.
비드형 비소흡착제 선별단계(S40)는 비드 성형기에서 생성된 흡착제의 입경이 약 4~6mm을 갖는 것으로 선별한다. In the bead-type arsenic adsorbent selection step (S40), the adsorbent produced in the bead molder is selected to have a particle diameter of about 4 to 6 mm.
이와 같이 생성된 비드형 흡착제는 높은 비표면적을 보이는 구형의 형상을 갖기 때문에 동일부피대비 높은 비소제거 효율을 나타낼 수 있으며, 수상에 머무르며 오래도록 형상이 변형되거나 파손되지 않고 유지될 수 있다. 또한, 기존의 펠릿형 흡착제와 비교하였을 때 보다 세밀하고 균일한 크기를 가짐으로써 흡착 베드(용기)에 충진 시 일정한 공극률 확보할 수 있으며, 구형상의 특성상 투입과 배출이 용이하다는 장점을 가짐과 동시에 펠릿형태의 가장자리의 충격에 의한 파편발생 부분에 대한 단점도 감소할 수 있다.The bead-type adsorbent produced in this way has a spherical shape with a high specific surface area, so it can exhibit high arsenic removal efficiency compared to the same volume, and can remain in the water phase for a long time without being deformed or damaged. In addition, compared to existing pellet-type adsorbents, it has a finer and more uniform size, enabling a constant porosity to be secured when filling the adsorption bed (container), and has the advantage of being easy to input and discharge due to the spherical nature of the pellet. The disadvantage of fragmentation due to impact at the edge of the shape can also be reduced.
<제조예><Manufacturing example>
<실시예1><Example 1>
영동지역의 탄광에서 배출되는 산성광산배수를 처리하여 배출되는 폐기물을 열풍건조하였으며, 24메쉬체를 통과시켜 수산화철계열 폐기물 분말을 생성하였다. 그 후, 비드 성형기의 원통형 혼합조에 수산화철계열 폐기물 분말 60중량%와 산화칼슘 분말 5중량%를 투입하고 교반하면서 혼합하는 동안에 혼합조에 형성된 노즐을 통해서 액상 무기바인더인 알루미나 35중량%를 분사하여 수산화철계열 폐기물 분말, 산화칼슘 및 액상 무기바인더가 뭉치지 않으면서 고르게 경화되도록 하면서 비드형상으로 제작하였고, 그 중에서 약 2~5mm의 입경을 갖는 것을 선별하여 비드형 비소흡착제(CMDS-YD)를 분리하였다.The waste discharged from the coal mines in the Yeongdong area was treated with hot air, dried, and passed through a 24 mesh sieve to produce iron hydroxide waste powder. Afterwards, 60% by weight of iron hydroxide-based waste powder and 5% by weight of calcium oxide powder were added to the cylindrical mixing tank of the bead molding machine, and while stirring and mixing, 35% by weight of alumina, a liquid inorganic binder, was sprayed through the nozzle formed in the mixing tank to form iron hydroxide-based waste powder. Waste powder, calcium oxide, and liquid inorganic binder were manufactured into a bead shape while curing evenly without agglomerating, and among them, those with a particle size of about 2 to 5 mm were selected to separate the bead-type arsenic adsorbent (CMDS-YD).
<실시예2><Example 2>
나전지역의 탄광에서 배출되는 산성광산배수를 처리하여 배출되는 폐기물을 열풍건조시켜 생성된 수산화철계열 폐기물 분말을 이용하면서 실시예1과 동일한 방법을 사용하여 2~5mm 직경을 갖는 입경을 갖는 상체로 실시예 2의 비드형 비소흡착제(CMDS-NJ)를 제조하였다.Using iron hydroxide waste powder generated by hot air drying the waste discharged from treating acid mine drainage discharged from a coal mine in the Najeon area, the same method as Example 1 was used to produce an upper body having a particle size of 2 to 5 mm in diameter. The bead-type arsenic adsorbent (CMDS-NJ) of Example 2 was prepared.
<실험예1><Experimental Example 1>
<등온흡착 실험><Isothermal adsorption experiment>
실시예 1로 제조된 비드형 비소흡착제를 이용하여 pH에 따른 등온 흡착 실험을 As(III), As(V)에 대하여 실시하여 그 결과를 도 2의 그래프로 나타내었다.Isothermal adsorption experiments depending on pH were performed on As(III) and As(V) using the bead-type arsenic adsorbent prepared in Example 1, and the results are shown in the graph in FIG. 2.
도 2의 그래프에 나타난 바와 같이, 실시예 1의 비드형 비소흡착제는 As(III)와 As(V)를 막론하고 pH에 관계없이 비소를 흡착할 수 있었다. 특히, As(III)의 경우 As(V)보다 높은 흡착능을 갖는 것을 확인할 수 있다.As shown in the graph of FIG. 2, the bead-type arsenic adsorbent of Example 1 was able to adsorb arsenic regardless of pH, regardless of As(III) and As(V). In particular, it can be seen that As(III) has a higher adsorption capacity than As(V).
<반응속도상수 실험><Reaction rate constant experiment>
실시예 1 및 실시예2로 제조된 비드형 비소흡착제를 이용하여 pH 6.5, 온도 250C, 흡착제 3g/L의 조건으로 비소흡착 반응속도를 실험을 As(III), As(V)에 대하여 실시하여 그 결과를 도 3a, 도 3b의 그래프로 나타내었다.Using the bead-type arsenic adsorbent prepared in Example 1 and Example 2, the arsenic adsorption reaction rate was tested for As(III) and As(V) under the conditions of pH 6.5, temperature 250C, and adsorbent 3g/L. The results are shown in the graphs of Figures 3A and 3B.
도 3a, 도 3b의 그래프에 나타난 바와 같이, 실시예1 및 실시예2의 비소흡착제는 반응속도상수는 As(III)의 경우 실시예1는 24×10-3, 실시예2는 15×10-3이었고, As(V)의 경우 실시예1는 455×10-3, 실시예2는 2.31×10-3이다. 이는 본 발명의 비소흡착제가 높은 반응속도로 비소를 제거하는 것을 알 수 있었다. As shown in the graphs of Figures 3a and 3b, the reaction rate constant of the arsenic adsorbent of Example 1 and Example 2 is 24 × 10 -3 for As(III) in Example 1 and 15 × 10 in Example 2. It was -3 , and in the case of As(V), Example 1 was 455×10 -3 and Example 2 was 2.31×10 -3 . It was found that the arsenic adsorbent of the present invention removes arsenic at a high reaction rate.
<비소흡착 메커니즘><Arsenic adsorption mechanism>
실시예1과 실시예2로 제조된 비드형 비소흡착제 대한 Dubinin-Radushkevich (D-R)모델을 이용한 흡착에너지값을 계산한 결과 두 흡착제 모두 8 kJ/mol 이하였다. 때문에 물리적 흡착이었다. 이는 에너지 값이 E<8 kJ/mol 일 때 물리적 흡착, E>16 kJ/mol 일 때 화학적 흡착, 8 kJ/mol <E<16 kJ/mol 일 때는 이온교환 이라는 (Redl et al., 1996) 보고에 따른 것이다. As a result of calculating the adsorption energy values using the Dubinin-Radushkevich (D-R) model for the bead-type arsenic adsorbents prepared in Examples 1 and 2, both adsorbents were 8 kJ/mol or less. Because it was physical adsorption. This is called physical adsorption when the energy value is E<8 kJ/mol, chemical adsorption when E>16 kJ/mol, and ion exchange when 8 kJ/mol <E<16 kJ/mol (Redl et al., 1996). This is according to the report.
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.As described above, although the present invention has been described with limited examples and drawings, the present invention is not limited thereto, and the technical idea of the present invention and the following will be understood by those skilled in the art to which the present invention pertains. Of course, various modifications and variations are possible within the scope of equivalence of the claims to be described.
Claims (5)
수산화철계열 폐기물 분말과 산화칼슘 분말을 혼합하는 단계와;
비드성형기에서 수산화철계열 폐기물 분말과 산화칼슘 분말을 교반하면서 액상 무기바인더를 분무하여 반죽물을 생성하면서 입상 비드 형태의 비소흡착제로 성형하는 단계와,
생성된 비드형상의 비소흡착제를 입경이 4~6mm을 갖는 것으로 선별하는 단계를 포함하는 것을 특징으로 하는 수산화철계열 폐기물을 이용한 비드형 비소흡착제의 제조방법.
generating iron hydroxide-based waste powder using iron hydroxide-based waste;
mixing iron hydroxide-based waste powder and calcium oxide powder;
A step of spraying a liquid inorganic binder while stirring iron hydroxide-based waste powder and calcium oxide powder in a bead molding machine to create a dough and molding it into an arsenic adsorbent in the form of granular beads;
A method for producing a bead-shaped arsenic adsorbent using iron hydroxide-based waste, comprising the step of selecting the produced bead-shaped arsenic adsorbent as having a particle size of 4 to 6 mm.
The method of claim 1, wherein the iron hydroxide-based waste powder is obtained by drying waste generated in a water purification facility that treats acid mine drainage and grinding it to an average particle size of 0.3 to 2.0 ㎛, and is mixed at 45 to 65% by weight based on the total weight. A method for manufacturing a bead-type arsenic adsorbent using iron hydroxide-based waste.
The method for producing a bead-type arsenic adsorbent using iron hydroxide-based waste according to claim 1, wherein the calcium oxide powder has a particle size of 10㎛ or less and is mixed at 5 to 10% by weight based on the total weight.
The method of claim 1, wherein the liquid inorganic binder is a silicon-based inorganic binder or an aluminum-based inorganic binder, and is mixed in an amount of 30 to 40% by weight based on the total weight.
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| KR100788120B1 (en) | 2000-09-26 | 2007-12-21 | 란세스 도이치란트 게엠베하 | Contact and adsorber granulates |
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| JP2005270933A (en) | 2004-03-26 | 2005-10-06 | Nittetsu Mining Co Ltd | Anion adsorbent, elimination method of anion, recycle method of anion adsorbent, and recovery method of elements |
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