KR100225047B1 - Method for manufacturing activated oyster shell powder for waste water treatment - Google Patents
Method for manufacturing activated oyster shell powder for waste water treatment Download PDFInfo
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- KR100225047B1 KR100225047B1 KR1019970013292A KR19970013292A KR100225047B1 KR 100225047 B1 KR100225047 B1 KR 100225047B1 KR 1019970013292 A KR1019970013292 A KR 1019970013292A KR 19970013292 A KR19970013292 A KR 19970013292A KR 100225047 B1 KR100225047 B1 KR 100225047B1
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 73
- 239000000843 powder Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000003463 adsorbent Substances 0.000 claims abstract description 10
- 230000003213 activating effect Effects 0.000 claims abstract description 3
- 241000237502 Ostreidae Species 0.000 claims description 13
- 235000020636 oyster Nutrition 0.000 claims description 13
- 238000000197 pyrolysis Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 32
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 32
- 239000011574 phosphorus Substances 0.000 abstract description 32
- 238000001179 sorption measurement Methods 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 10
- 238000001035 drying Methods 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 238000010298 pulverizing process Methods 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000010802 sludge Substances 0.000 description 9
- 239000000356 contaminant Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 244000005700 microbiome Species 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 239000010865 sewage Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000004075 wastewater filtration Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
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Classifications
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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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
-
- 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
- B01J20/3021—Milling, crushing or grinding
-
- 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
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
Abstract
본 발명은, 굴패각을 세척한 후 건조시키고, 상기 건조된 굴패각을 분쇄시키고, 얻어진 굴패각 분말을 활성화시키는 단계를 포함하는 폐수 처리용 활성 굴패각 분말의 제조방법 및 그 방법에 의해 제조된 활성 굴패각 분말에 관한 것이다. 본 발명에 따른 활성 굴패각 분말은 인을 포함한 오염물질의 흡착, 제거에 매우 효과적이어서 폐수처리용 흡착제 또는 생물막 공법용 메디아로 사용될 수 있다.The present invention provides a method for preparing active oyster shell powder for wastewater treatment and active oyster shell powder prepared by the method comprising washing and drying the oyster shell and then drying, pulverizing the dried oyster shell and activating the obtained oyster shell powder. It is about. The active oyster shell powder according to the present invention is very effective in the adsorption and removal of pollutants including phosphorus, and thus can be used as an adsorbent for wastewater treatment or as a media for biofilm process.
Description
본 발명은 폐수처리용 활성 굴패각 분말의 제조방법 및 그 방법에 따라 얻어진 활성 굴패각 분말에 관한 것으로 더욱 상세하게는 굴패각을 분쇄하여 활성화시킴으로써 폐수처리의 효율을 향상시킨 활성 굴패각 분말의 제조방법 및 그 방법에 의해 얻어진 활성 굴패각 분말에 관한 것이다.The present invention relates to a method for producing active oyster shell powder for wastewater treatment, and to an active oyster shell powder obtained according to the method. It relates to an active oyster shell powder obtained by.
생활 하수나 각종 공장의 폐수는 그대로 방류되는 경우 심각한 수질 오염을 일으키기 때문에, 자연의 정화능을 유지시킬 수 있는 정도까지 오염물질을 제거한 후 방류하여야 한다. 또한, 식수를 생산하기 위해 물을 정제하는 경우에도 오염물질을 분리, 제거하는 방법이 적용된다.Since the sewage of household sewage and various factories, if discharged as it is, causes serious water pollution, it must be discharged after removing the contaminants to the extent that natural purification ability can be maintained. In addition, when water is purified to produce drinking water, a method of separating and removing contaminants is applied.
그러나, 상하수 처리에서 난분해성 물질, 유해 독성물질, 부영양화 물질, 색소 성분 등은 일반적인 방법으로는 쉽게 제거되지 않는다. 이에 따라 여러 가지 방법이 시도되고 있으며, 그중에서 생물막 공법이나 흡착 처리방법이 가장 우수한 처리방법으로 알려져 있다.However, in the water and sewage treatment, hardly degradable substances, harmful toxic substances, eutrophic substances, pigment components and the like are not easily removed by a general method. Accordingly, various methods have been attempted, and among them, the biofilm method or the adsorption treatment method is known as the best treatment method.
생물막 공법은 메디아에 미생물이 부착되어 상대적으로 안정된 조건에서 미생물 체류시간이 증가하므로, 다양한 오염물질이 분해, 제거될 수 있다. 흡착법은 주로 활성탄에 의해 오염물질을 흡착시킴과 동시에 미생물이 서식하는 환경을 제공함으로써 오염물질을 제거하는 것이나, 다량의 폐수를 처리하려면 활성탄의 소모가 막대하여 경제성이 문제가 되고 있다.In the biofilm method, microorganisms are attached to the media to increase microorganism residence time under relatively stable conditions, so that various contaminants can be decomposed and removed. The adsorption method mainly removes pollutants by adsorbing pollutants by activated carbon and at the same time providing an environment where microorganisms live. However, in order to treat a large amount of wastewater, the consumption of activated carbon is enormous, resulting in economic problems.
한편, 폐수처리와 관련된 특허문헌으로, 한국 특허공개 제 96-37596 호는 원적외선 분말이 포함된 다공질 플레이트를 제시한다. 이 발명은 상기 원적외선 플레이트의 흡착력이 높고 7 내지 20 ㎛ 의 원적외선 에너지 방사에 의해 중금속을 분해하고 미생물의 성장을 촉진시킨다는 것이다.On the other hand, as a patent document related to wastewater treatment, Korean Patent Publication No. 96-37596 proposes a porous plate containing far-infrared powder. The present invention is that the far-infrared plate has a high adsorption force and decomposes heavy metals and promotes the growth of microorganisms by far-infrared energy radiation of 7-20 µm.
한국 특허공개 제 96-28965 호는 폐분말 활성탄 및 폐규산염을 주제로 한 복합 흡착제의 제조 및 폐수여과처리방법을 개시한다. 이 발명은 식료품 등의 생산공장에서 폐기되는 분말 활성탄 및 폐규산염을 복합 흡착제로 재생하여 폐수여과처리에 이용하는 것이다. 또한, 한국 특허공개 제 91-22644 호는 키토산을 중금속 흡착제와 폐수 응집제로 사용하는 방법을 기재하고 있다.Korean Patent Publication No. 96-28965 discloses a method for preparing a composite adsorbent based on waste powder activated carbon and waste silicate and a wastewater filtration process. The present invention is to recycle the powdered activated carbon and waste silicate, which are discarded in production plants such as foodstuffs, to be used for wastewater filtration by recycling the composite adsorbent. In addition, Korean Patent Publication No. 91-22644 discloses a method of using chitosan as a heavy metal adsorbent and a wastewater flocculant.
종래의 폐수처리방법 또는 상기 발명의 방법은 각각의 특성에 따라 폐수를 정화하는 기능을 가지고 있으나, 효율성과 경제성에서 많은 개선의 여지가 있으며, 특히 최근의 수질 오염 실태에 적합한 새로운 폐수처리방법이 요구되고 있다.The conventional wastewater treatment method or the method of the present invention has the function of purifying the wastewater according to each characteristic, but there is a lot of room for improvement in efficiency and economic efficiency, and in particular, a new wastewater treatment method suitable for the current water pollution situation is required. It is becoming.
따라서, 본 발명의 목적은 폐수의 처리 효율이 높고 경제성이 있는 폐수처리용 정화제를 제조하는 방법을 제공하는 것이다.Accordingly, an object of the present invention is to provide a method for producing a wastewater treatment purifier with high efficiency and economical efficiency.
본 발명의 다른 목적은 폐수처리용 흡착제 및 생물막 공법용 메디아를 제공하는 것이다.Another object of the present invention is to provide an adsorbent for wastewater treatment and a media for biofilm process.
도 1은 회화 또는 열분해에 의한 방법으로 본 발명에 따라 제조된 활성 굴패각 분말의 사진.1 is a photograph of an active oyster shell powder prepared according to the present invention by a process by incineration or pyrolysis.
도 2는 회화의 방법으로 본 발명에 따라 제조된 활성 굴패각 분말의 인 성분의 흡착 실험과 대조 실험에 따라 인 농도의 변화를 나타낸 그래프.Figure 2 is a graph showing the change in phosphorus concentration according to the adsorption experiment and the control experiment of the phosphorus component of the active oyster shell powder prepared according to the present invention by the method of incineration.
도 3은 열분해의 과정의 온도를 달리하여 각각 제조된 활성 굴패각 분말의 인 제거 흡착력 실험에 따라 인 농도의 변화를 나타낸 그래프.Figure 3 is a graph showing the change in phosphorus concentration according to the phosphorus removal adsorption force experiment of the active oyster shell powder produced by varying the temperature of the process of pyrolysis.
도 4는 활성오니 시스템에 본 발명의 활성 굴패각 분말을 투입하였을 때 난분해성 물질의 처리 결과를 보인 그래프.Figure 4 is a graph showing the results of treatment of hardly decomposable substances when the active oyster shell powder of the present invention is added to the activated sludge system.
도 5a 내지 c는 활성 굴패각 메디아에 부착된 활성오니의 양상을 전자현미경(Scanning Electron Micrograph)으로 촬영한 사진.Figures 5a to c is a photograph taken with the scanning electron microscope (Scanning Electron Micrograph) the aspect of the activated sludge attached to the active oyster shell media.
상기와 같은 본 발명의 목적은, 굴패각을 세척한 후 건조시키고, 상기 건조된 굴패각을 분쇄시키고, 얻어진 굴패각 분말을 활성화시키는 단계를 포함하는 폐수 처리용 활성 굴패각 분말의 제조방법에 의해 달성될 수 있다.The object of the present invention as described above, it can be achieved by the method of producing an active oyster shell powder for wastewater treatment comprising the step of washing and drying the oyster shell shell, pulverizing the dried oyster shell shell, and activating the obtained oyster shell powder. .
또한, 본 발명은 상기와 같은 본 발명의 방법에 따라 제조된 폐수처리용 활성 굴패각 분말를 제공한다.The present invention also provides an active oyster shell powder for wastewater treatment prepared according to the method of the present invention as described above.
본 발명은 바다에서 서식하는 굴의 껍질(이하, 굴패각 이라 한다)을 원료 물질로서 이용한다. 굴은 바다 생물로서 널리 분포하기 때문에 그 껍질의 입수는 매우 용이하며, 특히 해안에 널리 분포하여 야적, 방치되어 굴패각(oyster shell)을 사용할 수 있기 때문에 원료의 단가가 극히 저렴하다는 특징이 있다.The present invention uses the shell of oysters inhabiting the sea (hereinafter referred to as oyster shell) as a raw material. Oysters are widely distributed as sea creatures, and their shells are very easy to obtain. In particular, since they are widely distributed on the coast and can be used as oyster shells, they are extremely inexpensive.
해안에서 수집한 굴패각을 깨끗한 물로 세척하여 모래, 흙 기타 오염물질을 제거한다.Oyster shells collected offshore are washed with clean water to remove sand, soil and other contaminants.
오염물질을 제거한 굴패각은 자연 상태에서 수분을 제거하여 건조시킨다. 인위적으로 에너지를 가하여 물리적인 방법으로 건조시킬 수도 있으나, 경제성을 고려할 때 대기중에 노출시켜 물을 증발시키는 자연 건조 방법이 바람직하다.Oyster shells with contaminants removed and dried in nature. Although it may be dried by a physical method by artificially applying energy, a natural drying method of evaporating water by exposure to the atmosphere is preferable in view of economical efficiency.
상기 건조 굴패각을 분쇄하여 분말을 형성한다. 분말의 입자도가 너무 크거나 작으면 처리 효율이 달라지거나 현장 적용시 문제가 발생할 수 있다. 따라서, 본 발명의 목적에 적합한 범위 내에서 굴패각을 분쇄하며, 일반적으로는 30 내지 50 메시(mesh)의 크기로 분쇄시키는 것이 바람직하다.The dried oyster shell is pulverized to form a powder. If the particle size of the powder is too large or too small, the treatment efficiency may vary or problems may occur in field applications. Therefore, it is preferable to grind the oyster shell in a range suitable for the purpose of the present invention, and generally to a size of 30 to 50 mesh.
이와 같이 얻어진 굴패각 분말을 활성화시키는 단계가 필요하다. 굴패각의 원료 물질은 약 94%의 CaCO3와 미량의 Mg, Al, Si 성분으로 구성되어 있으며, 고온의 처리에 의한 활성화를 통해 CaO 로 성질전환이 일어나 폐수중의 인과 결합할 수 있는 성질을 갖는다. 또한, 다공성 구조로 전환됨으로써 흡착 및 미생물 성장을 위한 표면적을 제공한다.It is necessary to activate the oyster shell powder thus obtained. The raw material of oyster shell consists of about 94% of CaCO 3 and trace amounts of Mg, Al, and Si, and has the property of binding to phosphorus in the waste water due to the conversion of properties to CaO through activation by high temperature treatment. . In addition, conversion to a porous structure provides a surface area for adsorption and microbial growth.
굴패각 분말의 활성화를 위하여 회화와 열분해의 두가지 방법이 사용될 수 있다. 회화는 상기 굴패각 분말을 공기와의 접촉하에 450 ℃ 내지 650 ℃에서 10 내지 20 분 가열하는 것이고, 열분해는 상기 굴패각 분말을 산소와의 접촉을 차단한 상태로 300 ℃ 내지 600 ℃에서 30 분 내지 1 시간 가열하는 것이다.Two methods of incineration and pyrolysis can be used to activate the oyster shell powder. Incineration is heating the oyster shell powder at 450 ° C to 650 ° C for 10 to 20 minutes under contact with air, and pyrolysis is 30 minutes to 1 minute at 300 ° C to 600 ° C while blocking the contact with oxygen. It is time to heat.
이와 같이 활성화된 굴패각 분말은 흡착력이 높고 미생물 생존 환경을 제공하기 때문에, 폐수처리 정화제로서 사용할 수 있으며 고가의 활성탄을 데체할 수 있다. 따라서, 본 발명의 방법으로 제조된 굴패각 분말은 흡착제 또는 생물막 공법의 메디아로 사용될 수 있다. 활성화된 굴패각 분말은 흡착제 또는 생물막 공법의 메디아와 같이 구체적인 용도에 적합하도록 입자 크기별로 체분리(seive)하여 사용한다.Since the activated oyster shell powder has a high adsorption power and provides a microbial survival environment, it can be used as a wastewater treatment purifier and can replace expensive activated carbon. Therefore, the oyster shell powder produced by the method of the present invention can be used as a media of the adsorbent or biofilm process. Activated oyster shell powder is used by sieving by particle size to suit specific applications such as media of adsorbents or biofilm processes.
제조예 1: 회화에 의한 활성 굴패각의 제조Preparation Example 1 Preparation of Active Oyster Shells by Painting
해안에 야적되어 있는 굴패각을 수집하여 수돗물로 깨끗이 세척하였다. 굴패각을 상온에 방치하여 건조시켰다. 건조된 굴패각을 30 내지 50 메시로 분쇄시켜 건조 분말을 얻었다. 상기 건조 분말을 회화로를 사용해서 550 ℃ 로 10분간 가열하여 회화시켰다. 얻어진 분말을 상온에서 냉각하여 본 발명의 활성 굴패각 분말을 얻었다.Oyster shells piled up on the shore were collected and washed with tap water. The oyster shell was left to dry at room temperature. The dried oyster shells were ground to 30 to 50 mesh to obtain a dry powder. The dried powder was heated by heating at 550 ° C. for 10 minutes using an incineration furnace. The obtained powder was cooled at room temperature to obtain an active oyster shell powder of the present invention.
제조예 2: 열분해에 의한 활성 굴패각의 제조Preparation Example 2 Preparation of Active Oyster Shells by Pyrolysis
건조 굴패각 분말을 전기 가열로에서 산소와의 접촉없이 350 ℃에서 30분간 가열하여 열분해한 것을 제외하고는 제조예 1의 방법에 따라 본 발명의 활성 굴패각 분말을 제조하였다.The active oyster shell powder of the present invention was prepared according to the method of Preparation Example 1 except that the dried oyster shell powder was pyrolyzed by heating at 350 ° C. for 30 minutes without contact with oxygen in an electric heating furnace.
제조예 1 및 제조예 2의 분말을 촬영한 사진을 도 1로 제시한다.Photographs taken of the powders of Preparation Example 1 and Preparation Example 2 are shown in FIG. 1.
실시예 1: 회화의 방법을 제조된 활성 굴패각 분말의 인 제거 실험Example 1: Phosphorus removal experiment of active oyster shell powder prepared by the method of incineration
정제수에 인산이수소칼륨(KH2PO4)을 첨가하여 인 농도를 약 30㎎/ℓ로 조절하였다. 제조예 1에서 제조된 활성 굴패각 분말을 입자 크기별로 300 ㎛, 355 ㎛, 425 ㎛ 및 500 ㎛로 분류하였다. 이들 각각의 입자군을 상기 인 오염수에 0.3 g/ℓ 의 농도로 첨가하여 교반하면서 시간의 경과에 따라 인 농도의 변화를 측정하였다.Potassium dihydrogen phosphate (KH 2 PO 4 ) was added to the purified water to adjust the phosphorus concentration to about 30 mg / l. The active oyster shell powder prepared in Preparation Example 1 was classified into 300 μm, 355 μm, 425 μm, and 500 μm by particle size. Each of these particle groups was added to the phosphorus contaminated water at a concentration of 0.3 g / L and the change in phosphorus concentration was measured over time while stirring.
대조실험으로, 굴패각을 분쇄하여 활성화시키지 않은 분말을 입자 크기별로 300 ㎛, 355 ㎛, 425 ㎛ 및 500 ㎛로 분류하여 상기한 바와 같은 방법으로 제조된 인 오염수에 동일한 농도로 첨가하고 교반하면서 시간의 변화에 따라 인의 농도를 측정하였다.As a control experiment, powders that were not activated by crushing oyster shells were classified into 300 μm, 355 μm, 425 μm, and 500 μm by particle size, and added to the phosphorus-contaminated water prepared in the same manner as above, and stirred for a while. The concentration of phosphorus was measured according to the change of.
활성 분말의 첨가에 의해서 인 농도는 초기의 30 ㎎/ℓ에서 약 11 ㎎/ℓ으로 감소하였다. 활성화되지 않은 분말을 투입한 경우에 인의 농도는 26 ㎎/ℓ로 감소되는 경향을 나타냈다. 결과를 아래의 표 1 및 도 2의 그래프로 제시한다.By addition of the active powder, the phosphorus concentration decreased from the initial 30 mg / l to about 11 mg / l. When unactivated powder was added, the concentration of phosphorus tended to decrease to 26 mg / l. The results are presented in the graphs of Table 1 and FIG. 2 below.
(단위: mg/L)(Unit: mg / L)
A: 일반 분말 굴패각A: normal powder oyster shell
B: 활성 분말 굴패각B: active powder oyster shell
실시예 2: 활성 굴패각 분말의 인 흡착력 실험(Jar-Tester 시험)Example 2: Phosphorus adsorption test of active oyster shell powder (Jar-Tester test)
인 농도 50 ㎎/ℓ의 오염수에 제조예 1의 분말을 첨가하여 Jar-Tester(선미기술 제조, 모델명: SM-J10)에서 약 100 rpm 의 속도로 교반하였다. pH는 7.9, 수온은 22 ℃ 였다. 시간의 변화에 따라 인 농도를 측정한 결과를 다음 표 2에 표시한다.The powder of Preparation Example 1 was added to contaminated water having a phosphorus concentration of 50 mg / L, and stirred at a rate of about 100 rpm in a Jar-Tester (manufactured by Stern Technology, Model Name: SM-J10). pH was 7.9 and water temperature was 22 degreeC. The results of the measurement of phosphorus concentration over time are shown in Table 2 below.
상기 표에서 보는 바와 같이, 흡착이 평형상태에 이르렀을 때 최대 인 제거 흡착량은 0.5 g/ℓ를 투여하였을 경우 77 ㎎/(g 활성 굴패각 분말) 이었으며, 약 78%의 제거효율을 나타냈다. 활성 굴패각 분말을 흡착제로 사용하였을 때 Freundlich isotherm(Metcalf and Eddy, 1991, Wastewater Engineering)을 적용한 결과 Kf와 1/n 의 계수는 각각 4.413×10-4, 0.9264로 산술되었으며, 이 때의 상관계수는 0.71이었다.As shown in the table, when the adsorption reached equilibrium, the maximum phosphorus removal adsorption amount was 77 mg / (g active oyster shell powder) when 0.5 g / l was administered, indicating a removal efficiency of about 78%. Using the Freundlich isotherm (Metcalf and Eddy, 1991, Wastewater Engineering) when the active oyster shell powder was used as the adsorbent, the coefficients of K f and 1 / n were calculated to be 4.413 × 10 -4 and 0.9264, respectively. Was 0.71.
실시예 3: 열분해의 과정에서 온도를 달리하여 제조된 활성 굴패각 분말의Example 3: of active oyster shell powder prepared by varying the temperature in the process of pyrolysis
인 제거 흡착력 실험Phosphorus Removal Adsorption Force Experiment
굴패각의 활성 방법으로 열분해 과정에서 150 ℃, 250 ℃, 350 ℃, 450 ℃ 및 550 ℃ 의 온도에서 각각 열분해시킨 것을 제외하고는 제조예 2과 같은 방법에 따라 활성 굴패각 분말을 얻었다. 이들 각각의 활성 분말을 사용하여 실시예 2의 방법에 따라 인 제거 흡착력을 실험하였다. 결과를 아래의 표 3 및 도 3의 그래프로 나타낸다.An active oyster shell powder was obtained in the same manner as in Preparation Example 2, except that the pyrolysis was carried out at a temperature of 150 ° C., 250 ° C., 350 ° C., 450 ° C. and 550 ° C. in the pyrolysis process. Each of these active powders was used to test phosphorus removal adsorption according to the method of Example 2. The results are shown in Table 3 below and in the graphs of FIG. 3.
(단위: mg/L)(Unit: mg / L)
상기 결과로부터 알 수 있는 바와 같이, 300 ℃ 이상의 온도에서 열분해시켜 얻어진 활성 굴패각을 사용하는 경우에, 분말 투입 후 약 30분만에 수중의 인의 농도를 1 ㎎/ℓ 이하로 감소시킬 수 있었다. 이에 반하여, 150 ℃ 및 250 ℃에서 열분해시켜 제조된 굴패각 분말은 인의 제거능이 미미함을 알 수 있다.As can be seen from the above results, in the case of using an active oyster shell obtained by pyrolysis at a temperature of 300 ° C. or higher, the concentration of phosphorus in water can be reduced to 1 mg / l or less within about 30 minutes after powder injection. On the contrary, it can be seen that the oyster shell powder prepared by pyrolysis at 150 ° C. and 250 ° C. has a poor removal ability of phosphorus.
실시예 4: 생물학적 폐수처리 실험Example 4: Biological Wastewater Treatment Experiments
활성오니 시스템에 의한 생물학적 폐수처리에 있어서, 난분해성 물질(크롬법 COD 측정물질)의 처리 효율을 비교하였다. 즉, 본 발명의 굴패각 분말이 첨가된 활성오니를 메디아로 각각 첨가하여 COD cr를 1일부터 35일 경과시까지 계속적으로 측정하였다. 실험 개시 1일째 15g과, 18일째 20g의 활성 굴패각 분말을 첨가하였다. 대조 실험으로 활성 굴패각 분말의 첨가가 없이 통상의 활성오니를 메디아로 첨가하여 동일한 실험을 진행하였다. 결과를 아래의 표 4와 도 4의 그래프로 나타낸다.In the biological wastewater treatment by the activated sludge system, the treatment efficiency of the hardly decomposable substance (chromium method COD measurement substance) was compared. That is, the activated sludge to which the oyster shell powder of the present invention was added was added to the media, respectively, and the COD cr was continuously measured from 1 day to 35 days. 15 g of active oyster shell powder was added on
따라서, 유입수의 COD 농도가 210 ㎎/ℓ 로부터 유출수의 농도가 33 내지 55 ㎎/ℓ 로 감소되었다. 즉, 본 발명에 따른 활성 굴패각의 첨가로 난분해성 물질이 약 74 내지 84% 제거되었다.Therefore, the COD concentration of the influent was reduced from 210 mg / L to the concentration of the effluent from 33 to 55 mg / L. That is, the addition of the active oyster shell according to the present invention removed about 74-84% of the hardly degradable material.
F/M 비를 평균 0.259 g·COD/g·MLVSS·day로 일정하게 유지하면서 활성 굴패각 분말을 첨가한 시스템에서는 유출수의 오염물질의 농도가 낮을 뿐만 아니라 농도의 변화도 적어서 비교적 안정한 상태를 유지하였다. 이는 활성 굴패각 분말의 첨가에 의해 미생물의 부착성장이 안정화된 것을 의미하는 것이다.The F / M ratio was maintained at an average of 0.259 g · COD / g · MLVSS · day, and the active oyster shell powder added system maintained a relatively stable state due to the low concentration of contaminants in the effluent and the small change of concentration. . This means that the adhesion growth of microorganisms is stabilized by the addition of active oyster shell powder.
도 5는 활성 굴패각 메디아에 부착된 활성오니의 양상을 전자현미경(Scanning Electron Micrograph)으로 촬영한 것이다. 도 5(a)는 활성 굴패각 메디아이고, 도 5(b)는 활성 굴패각 메디아에 부착된 생물막의 형상이다. 도 5(c)는 생물막의 두께를 측정하기 위하여 2,000 배의 고배율로 확대한 것인데, 그 두께는 10 ㎛로 측정되었다.5 is a photograph of the activated sludge attached to the active oyster shell media by scanning electron microscopy (Scanning Electron Micrograph). Figure 5 (a) is the active oyster shell media, Figure 5 (b) is the shape of the biofilm attached to the active oyster shell media. Figure 5 (c) is to enlarge the magnification of 2,000 times in order to measure the thickness of the biofilm, the thickness was measured to 10 ㎛.
실시예 5: 활성오니 시스템에서 활성 굴패각 분말의 인 제거 실험Example 5 Phosphorus Removal Experiment of Active Oyster Shell Powder in Activated Sludge System
실시예 4에서와 같이, 본 발명의 활성 굴패각 분말을 첨가하여 실험한 경우와 첨가하지 않고 실시한 대조실험의 경우에서, 유입수와 유출수의 인 농도의 변화를 계속 측정하였다. 본 발명에 따른 활성 굴패각 분말을 투입하였을 때, 유입수의 인 농도가 0.25 ㎎/ℓ인 경우 유출수의 농도가 0.07 ㎎/ℓ 로 감소되어 최대 72%의 인 제거효율이 얻어졌고, 유출수의 인 농도가 낮은 상태로 안정되게 유지되었다(표 4 및 도 6참조). 도 6에서 y축의 T-P는 총 인을 의미한다.As in Example 4, in the case of the experiment with and without the active oyster shell powder of the present invention, the change in the phosphorus concentration of the influent and the effluent was continuously measured. When the active oyster shell powder according to the present invention was added, when the phosphorus concentration of the influent was 0.25 mg / l, the concentration of the effluent was reduced to 0.07 mg / l, resulting in up to 72% of phosphorus removal efficiency. It remained stable in the low state (see Table 4 and FIG. 6). In FIG. 6, T-P of the y-axis denotes total phosphorus.
반면에, 활성 굴패각 분말이 첨가되지 않은 활성오니를 적용하여 동일한 방법으로 실험한 경우에, 유출수의 인 농도의 변화가 심한 것으로 나타났다.On the other hand, when the activated sludge without the active oyster shell powder was tested by the same method, the phosphorus concentration of the effluent was shown to be severe.
(단위:mg/ℓ)(Unit: mg / ℓ)
이상의 설명으로부터 명백한 바와 같이, 본 발명에 따른 활성 굴패각 분말은 인을 포함한 오염물질의 흡착, 제거에 매우 효과적임을 알 수 있다. 따라서, 본 발명에 따른 활성 굴패각 분말은 폐수처리용 흡착제 또는 생물막 공법용 메디아로 사용될 수 있다. 굴패각은 해안에서 값싸게 얻을 수 있는 원료이기 때문에 단가가 저렴하여 고가의 활성탄을 대체할 수 있을 것으로 기대된다.As is apparent from the above description, it can be seen that the active oyster shell powder according to the present invention is very effective for adsorption and removal of contaminants including phosphorus. Therefore, the active oyster shell powder according to the present invention can be used as an adsorbent for wastewater treatment or as a media for biofilm process. Oyster shell is expected to be able to replace expensive activated carbon due to its low cost because it is a raw material that can be obtained cheaply from the coast.
더욱이, 본 발명에 따라 굴패각을 원료로 사용하게 되면, 해안에 방치되어 오염의 한 원인이 되고 있는 굴패각을 감소시키므로 해안가 오염을 줄일 수 있다는 장점도 있는 것이다.Moreover, when the oyster shell is used as a raw material according to the present invention, the oyster shell is left on the shore and thus reduces the coastal pollution since it reduces the oyster shell which causes one of the pollutions.
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KR1019970013292A KR100225047B1 (en) | 1997-04-10 | 1997-04-10 | Method for manufacturing activated oyster shell powder for waste water treatment |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100377968B1 (en) * | 2000-07-27 | 2003-03-29 | 이승목 | Preparation of Adsorbent for Removal of Heavy Metals by Seafood Processing Waste Sludge |
KR100402716B1 (en) * | 2000-12-01 | 2003-10-22 | 이찬원 | Preparation of activated oyster shell and use thereof |
KR100994781B1 (en) | 2010-04-20 | 2010-11-17 | 주식회사 성일엔텍 | Filling material having bottom ash of constructed wetland for the treatment of polluted water and preparation methods thereof |
KR20230121375A (en) * | 2022-02-11 | 2023-08-18 | 강원대학교산학협력단 | Method for manufacturing photocatalyst combined with calcined oyster shells, photocatalyst thereof, and method for removing pollutants using the same |
WO2024155172A1 (en) * | 2023-01-20 | 2024-07-25 | 주식회사 엘씨 | Composition for controlling green or red tides and method for controlling harmful algae using same |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
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KR100232578B1 (en) * | 1997-09-04 | 1999-12-01 | 왕창근 | Process for the removal of phosphous in sewage or waste water by using shell |
KR100413338B1 (en) * | 2001-02-15 | 2003-12-31 | 에코그린텍 (주) | Water processing system and processing material of high adsorption |
KR100431634B1 (en) * | 2001-09-19 | 2004-05-17 | 대우조선해양 주식회사 | Absorbing material using a granular acid white clay and a granular oyster shells |
KR101280803B1 (en) * | 2012-02-13 | 2013-07-01 | 김은혜 | Shell pound producing method for water clarification |
KR20210069366A (en) | 2019-12-03 | 2021-06-11 | 부경대학교 산학협력단 | Method for preparing sewage treatment material used for removing po4-p and nh3-n, sewage treatment material prepared thereby, and sewage treatment system comprising the same |
CN116199495B (en) * | 2023-01-18 | 2023-12-22 | 烟台大学 | Low-cost spinel hybridized gold mine tailings-based ceramic membrane and preparation process and application thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01224088A (en) * | 1988-03-03 | 1989-09-07 | Tokio Abe | Treatment of waste water with heat-treated oystershell |
-
1997
- 1997-04-10 KR KR1019970013292A patent/KR100225047B1/en not_active IP Right Cessation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01224088A (en) * | 1988-03-03 | 1989-09-07 | Tokio Abe | Treatment of waste water with heat-treated oystershell |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100377968B1 (en) * | 2000-07-27 | 2003-03-29 | 이승목 | Preparation of Adsorbent for Removal of Heavy Metals by Seafood Processing Waste Sludge |
KR100402716B1 (en) * | 2000-12-01 | 2003-10-22 | 이찬원 | Preparation of activated oyster shell and use thereof |
KR100994781B1 (en) | 2010-04-20 | 2010-11-17 | 주식회사 성일엔텍 | Filling material having bottom ash of constructed wetland for the treatment of polluted water and preparation methods thereof |
KR20230121375A (en) * | 2022-02-11 | 2023-08-18 | 강원대학교산학협력단 | Method for manufacturing photocatalyst combined with calcined oyster shells, photocatalyst thereof, and method for removing pollutants using the same |
KR102685603B1 (en) | 2022-02-11 | 2024-07-17 | 강원대학교 산학협력단 | Method for manufacturing photocatalyst combined with calcined oyster shells, photocatalyst thereof, and method for removing pollutants using the same |
WO2024155172A1 (en) * | 2023-01-20 | 2024-07-25 | 주식회사 엘씨 | Composition for controlling green or red tides and method for controlling harmful algae using same |
Also Published As
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KR19980076547A (en) | 1998-11-16 |
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