KR100297928B1 - Method of nitrogen removal in wastewater with photocatalytic technology - Google Patents
Method of nitrogen removal in wastewater with photocatalytic technology Download PDFInfo
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- KR100297928B1 KR100297928B1 KR1019990007739A KR19990007739A KR100297928B1 KR 100297928 B1 KR100297928 B1 KR 100297928B1 KR 1019990007739 A KR1019990007739 A KR 1019990007739A KR 19990007739 A KR19990007739 A KR 19990007739A KR 100297928 B1 KR100297928 B1 KR 100297928B1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000002351 wastewater Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 31
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 23
- 238000005516 engineering process Methods 0.000 title claims abstract description 11
- 230000001699 photocatalysis Effects 0.000 title claims description 21
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims description 24
- 238000007254 oxidation reaction Methods 0.000 claims description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 8
- -1 CaCO 3 Chemical compound 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 239000011941 photocatalyst Substances 0.000 abstract description 26
- 238000005273 aeration Methods 0.000 abstract description 9
- 230000033116 oxidation-reduction process Effects 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 28
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 20
- 239000002002 slurry Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000002378 acidificating effect Effects 0.000 description 5
- 238000007872 degassing Methods 0.000 description 5
- 238000013032 photocatalytic reaction Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000009303 advanced oxidation process reaction Methods 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- JVMRPSJZNHXORP-UHFFFAOYSA-N ON=O.ON=O.ON=O.N Chemical compound ON=O.ON=O.ON=O.N JVMRPSJZNHXORP-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical group [N].N CVTZKFWZDBJAHE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- CKMXBZGNNVIXHC-UHFFFAOYSA-L ammonium magnesium phosphate hexahydrate Chemical compound [NH4+].O.O.O.O.O.O.[Mg+2].[O-]P([O-])([O-])=O CKMXBZGNNVIXHC-UHFFFAOYSA-L 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 238000009297 electrocoagulation Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052567 struvite Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Materials Engineering (AREA)
- Physical Water Treatments (AREA)
- Catalysts (AREA)
Abstract
본 발명은 UV/TiO2광촉매기술을 이용하여 폐수내 질소함유량의 대부분을 차지하고 있는 암모니아성 질소를 제거하는 방법에 관한 것이다. 좀 더 상세하게는 강력한 산화환원 능력을 지닌 UV/TiO2광촉매를 이용하여 폐수내 암모니아성 질소 성분을 pH 및 용존산소(DO) 조절을 위한 폭기 등의 조업조건을 변화시켜가며 NO2 -1, NO3 -1생성을 억제하며 효과적으로 제거할 수 있는 광촉매기술을 이용한 폐수내 질소성분의 제거방법에 관한 것이다.The present invention relates to a method for removing ammonia nitrogen, which occupies most of the nitrogen content in wastewater using UV / TiO 2 photocatalyst technology. Gamyeo to more specifically to using a UV / TiO 2 photocatalyst having a strong oxidation-reduction ability wastewater ammonium nitrogen component changes the operating conditions of aeration or the like for the pH and dissolved oxygen (DO) control NO 2 -1, The present invention relates to a method for removing nitrogen components in wastewater using photocatalyst technology that can effectively remove NO 3 -1 and effectively remove it.
Description
본 발명은 광촉매기술을 이용한 폐수내 질소성분의 제거방법에 관한 것으로, 좀 더 상세하게는 생물학적 폐수처리로는 한계가 있는 난분해성 유기물질의 제거를 위하여 강력한 OH 라디칼을 이용하는 고도산화법(Advanced Oxidation Processes, AOPs)의 한 방법인 광촉매기술을 이용하여 폐수내 질소성분을 효율적으로 제거하는 방법에 관한 것이다.The present invention relates to a method for removing nitrogen components in wastewater using photocatalyst technology, and more particularly, Advanced Oxidation Processes using strong OH radicals for the removal of hardly degradable organic substances, which are limited by biological wastewater treatment. , AOPs) is a method of efficiently removing nitrogen components in wastewater using a photocatalyst technique.
일반적으로, AOPs에는 펜톤(Fenton) 처리법, 과산화수소·오존·자외선의 단독 사용 또는 조합하여 사용하는 방법이 있다. 현재 국내에서 광촉매산화에 관한 연구가 많이 진행되고 있으나, 실재에 적용한 바는 아직 없다. 그러나, 캐나다, 일본 등지에서는 실재에 적용하고 있으며, 캐나다 퓨리픽스 인크(Purifics Inc.)사에서 광촉매 산화장치를 개발하여 생산하고 있다. 그러나, 이 시스템(system)은 가격이 비싸고 광촉매 회수율이 낮으며 운영비가 높다는 단점을 지니고 있다.In general, AOPs include a Fenton treatment method, a hydrogen peroxide, ozone, and ultraviolet light alone or in combination. Currently, a lot of research on photocatalytic oxidation has been conducted in Korea, but it has not been applied to reality yet. However, in Canada, Japan, etc., the present invention is applied to reality, and photocatalytic oxidizer is developed and produced by Purifics Inc. of Canada. However, this system has the disadvantages of high price, low photocatalyst recovery and high operating cost.
광촉매로서는 TiO2을 주로 사용하며 TiO2이외에 광여기(exciting)가 가능한 촉매를 개발 중에 있으며 광여기 후 재결합(recombination)을 저지시키기 위하여 촉매 표면에 금속물질을 도핑(doping)시키는 촉매개질 연구도 진행되고 있다. 광촉매 기술은 주로 연구실 범위에서 단일물질을 대상으로 연구하고 있으며, 침출수와 같이 성상이 까다로운 대상에 대해서도 근래들어 연구가 시작되었다. 국내에서의 연구는 페놀, 시안 화합물, 염소계 화합물 등 생물학적 처리가 어려운 물질을 대상으로 연구되고 있다. 대개 실험은 TiO2/UV에 의한 산화방식 이외에 과산화수소 등의 산화보조제를 가하여 처리효율의 극대화를 꾀하였다. 캐나다 퓨리픽스사의 국내 특약점인 (주)바투 엔지니어링에서 수도권 위생매립지에서 발생되는 침출수를 전기응집 과정을 거친 후 광촉매 기술로 처리한 연구보고서 (대한환경공학회지, Vol. 19 No. 3, 1997)에 의하면 15ℓ의 침출수를 0.2wt%의 TiO2와 혼합하고 1,000mg/ℓ의 과산화수소를 첨가한 결과, 14분만에 약 70%의 CODMn제거율을 나타내었다고 보고하였다.As a photocatalyst, TiO 2 is mainly used. In addition to TiO 2 , we are developing a catalyst capable of photo-exciting. Also, a catalyst reforming study is conducted to dope a metal material on the surface of a catalyst to prevent recombination after photo-excitation. It is becoming. Photocatalyst technology is mainly researched on a single substance in the laboratory scope, and research has recently begun on difficult objects such as leachate. Domestic research has been conducted on materials that are difficult to biologically treat, such as phenols, cyanide compounds, and chlorine compounds. In general, experiments were conducted to maximize the treatment efficiency by adding oxidation aids such as hydrogen peroxide in addition to the oxidation by TiO 2 / UV. According to a research report (Battery Engineering Co., Ltd., a domestic dealer in Canada), the leachate from sanitary landfills in the metropolitan area was treated with photocatalytic technology after undergoing electrocoagulation (Korean Journal of Environmental Engineering, Vol. 19 No. 3, 1997). It was reported that 15 L of leachate was mixed with 0.2 wt% of TiO 2 and 1,000 mg / L of hydrogen peroxide added, resulting in about 70% COD Mn removal in 14 minutes.
이와 같이, UV/TiO2광촉매기술에 대한 연구는 주로 유기화합물을 중심으로 이루어져 있어 이에 대한 연구가 많이 진행되어 있으나, 축산폐수 또는 염료폐수와 같은 암모니아성 폐수에 대한 질소의 제거는 아직 미개척 분야이다. 즉, UV/TiO2광촉매기술을 암모니아성 폐수에 대한 질소의 제거에 적용된바는 없는 실정이다.As described above, research on UV / TiO 2 photocatalyst technology mainly consists of organic compounds, and much research has been conducted. However, the removal of nitrogen to ammonia wastewater such as livestock wastewater or dye wastewater is still unexplored. . That is, the UV / TiO 2 photocatalyst technology has not been applied to the removal of nitrogen to the ammonia wastewater.
한편, 고농도의 질소화합물이 정체수역으로 방류될 경우 부영양화 및 적조현상, 어류에 대한 독성, 수계의 용존산소 소비 등 생태계에 미치는 악영향이 매우 위협적이므로 이를 방지하기 위해서 질소제거공정은 필수적이다. 1996년 이후 총질소와 총인에 대한 규제가 시작되었으나, 주로 생물학적 처리 방법을 이용한 국내 폐수는 적정처리 수준에 다다르지 못한 채 방류되고 있다.On the other hand, when high concentrations of nitrogen compounds are discharged into the stagnant water, adverse effects on the ecosystem, such as eutrophication and red tide, toxicity to fish, and dissolved oxygen consumption in water systems, are very threatening. Since 1996, the regulation of total nitrogen and total phosphorus has begun, but domestic wastewaters, mainly biological treatment methods, are being discharged without reaching the proper level of treatment.
특히, 침출수와 같이 조성이 매우 불균일한 수질에 대해서는 더욱 더 어려움을 겪고있다. 침출수의 경우 총질소의 대부분이 암모니아성 질소로 구성되어 있어이에 대한 방안으로 스티리핑(Stripping), 분화석(Struvite) 침전, 제올라이트 (Zeolite) 흡착 등이 이용되고 있다. 스트리핑은 스트리핑 타워(Stripping Tower)를 이용해야 한다는 단점을 지니고 있으며, 분화석 침전법은 약품비 및 침전물의 재활용의 제약이 있으며, 제올라이트 흡착은 전처리 및 재생 등이 문제가 될 수 있다. 가장 많이 이용하고 있는 생물학적 질산화 및 탈질은 미생물을 이용하여 유기물과 질소를 동시에 제거할 수 있어 경제적이나 넓은 부지를 요하는 시스템으로서 국토 이용에 비효율적이다.In particular, there are more and more difficulties for the water quality having a very uneven composition such as leachate. In the case of leachate, most of the total nitrogen is composed of ammonia nitrogen, and as a countermeasure, stipping, struvite precipitation, and zeolite adsorption are used. Stripping has the disadvantage of using a stripping tower, and the sedimentation method of the crater has limitations in chemical costs and recycling of the precipitate, and zeolite adsorption may be a problem such as pretreatment and regeneration. The most commonly used biological nitrification and denitrification is an inefficient way to use the land as a system that requires the removal of organic matter and nitrogen at the same time using microorganisms, which requires economical and large land.
한편, 광촉매기술을 이용한 선행기술로서 미국특허 제 5,174,877호에서는 슬러리 전체를 탱크 반응기 속에서 한번에 광촉매 반응시키는 방법을 개시하고 있다. 상기 특허에서는 탱크 반응기 저부의 슬러리는 슬러리가 모두 광촉매적으로 반응될때 까지 연속적으로 탱크 반응기의 최상부로 이동된다. 상기 방법은 촉매가 현탁되고 슬러리 전체에 균일하게 분산되도록 슬러리를 연속적으로 혼합하는데 너무 오랜 시간이 걸린다. 미국특허 제 5,118,422호에서는 광촉매적 반응이 일어나고 오염물이 오염 유체로부터 파괴되면 폴리프로필렌과 같은 중합체성 물질로 제조된 막을 이용하여 광반응성 촉매를 분리시키는 방법을 개시하고 있다. 그러나, 상기 중합체성 물질로 제조된 막은 승온 뿐만 아니라 승압에도 견딜 수 없다. 미국특허 제 5,462,674호에서는 오염된 유체를 광촉매와 혼합하여 슬러리를 형성시키고, 슬러리를 자외선 광이 조사되는 공간을 통해 통과시켜 슬러리의 광촉매 반응을 유발시킴으로써 슬러리에 오염제거된 유출물을 제공하고, 다수의 세라믹 필터 부재를 통과시켜 여과시킴으로써 슬러리로부터 오염제거된 유출물을 분리시키고, 다수의세라믹 필터 부재내의 광촉매 수집물에 충격파를 통과시킴으로써 광촉매 수집물을 간헐적으로 제거시키고, 광촉매를 실질적으로 일정하게 충전시키면서 상기 과정을 반복 수행하는 오염된 유체를 정화시키는 방법으로 상술한 문제점을 해결할 수 있다고 개시하고 있으나, 만족할 만한 수준은 아니다.On the other hand, US Patent No. 5,174,877 as a prior art using a photocatalyst technology discloses a method for photocatalytic reaction of the entire slurry at once in a tank reactor. In this patent, the slurry at the bottom of the tank reactor is continuously moved to the top of the tank reactor until all of the slurry is photocatalytically reacted. The process takes too long to continuously mix the slurry so that the catalyst is suspended and uniformly dispersed throughout the slurry. U. S. Patent No. 5,118, 422 discloses a method for separating a photoreactive catalyst using a membrane made of a polymeric material such as polypropylene when the photocatalytic reaction occurs and the contaminants are destroyed from the contaminating fluid. However, membranes made of such polymeric materials cannot withstand elevated temperatures as well as elevated pressures. U.S. Patent No. 5,462,674 discloses a decontaminated effluent in a slurry by mixing contaminated fluid with a photocatalyst to form a slurry and passing the slurry through a space irradiated with ultraviolet light to induce a photocatalytic reaction of the slurry. Filtration of the ceramic filter member through the ceramic filter member to separate the decontaminated effluent from the slurry, passing the shock wave through the photocatalyst collection in the plurality of ceramic filter members, intermittently removing the photocatalyst collection, and substantially constant filling of the photocatalyst. While it is disclosed that the above-mentioned problem can be solved by the method of purifying the contaminated fluid repeatedly performing the above process, but it is not satisfactory.
이에 비해 본 발명에 따른 광촉매 기술은 장치가 기계적으로 비교적 작다는 장점과 함께 난분해성 유기물질과 질소화합물에 대해서 고효율의 산화가 가능하고, 생물학적 처리나 펜톤산화 처리에서 발생되는 슬러지가 발생되지 않는다는 장점을 지니고 있다.On the other hand, the photocatalyst technology according to the present invention has the advantage that the device is mechanically relatively small, and it is possible to efficiently oxidize hardly decomposable organic substances and nitrogen compounds, and does not generate sludge generated in biological treatment or fenton oxidation treatment. It has
따라서, 본 발명의 목적은 기존의 물리화학적 처리 공정으로 효과적이지 못한 폐수내의 질소성분의 대부분을 차지하는 암모니아성 질소를 효율적으로 제거할 수 있는 광촉매기술을 이용한 폐수내 질소성분의 제거방법을 제공하는데 있다.Accordingly, an object of the present invention is to provide a method for removing nitrogen components in wastewater using a photocatalytic technique capable of efficiently removing ammonia nitrogen, which occupies most of the nitrogen components in wastewater, which is ineffective by conventional physicochemical treatment processes. .
상기 목적을 달성하기 위한 본 발명의 방법은 UV/TiO2광촉매 산화법을 이용하여 폐수를 처리하는 방법에 있어서, 암모니아성 폐수에 공기를 불어 넣어 용존산소를 4∼10㎎/ℓ 및 pH를 8∼10으로 유지시키면서 반응시켜 폐수중의 질소성분의 주물질인 암모니아성 질소를 제거하는 것으로 이루어진다.The method of the present invention for achieving the above object is a method for treating wastewater by using UV / TiO 2 photocatalytic oxidation method, by blowing air into the ammonia wastewater to dissolve dissolved oxygen 4-10 mg / l and pH 8 ~ The reaction is carried out while maintaining the temperature of 10 to remove ammonia nitrogen, which is the main substance of nitrogen in the wastewater.
도 1은 본 발명의 실시예 1에 따라 2차 생물학적 처리후의 침출수를 대상으로 운전조건을 달리하며 광촉매산화 실험을 실시하여 암모니아성 질소의 제거효율을 나타낸 그래프이다.1 is a graph showing the removal efficiency of ammonia nitrogen by performing photocatalytic oxidation experiments with different operating conditions for leachate after the second biological treatment according to Example 1 of the present invention.
도 2는 본 발명의 실시예 1에 따라 2차 생물학적 처리후의 침출수를 대상으로 운전조건을 달리하며 광촉매산화 실험을 실시하여 암모니아성 질소의 NO2-N로의 산화를 농도로 나타낸 그래프이다.FIG. 2 is a graph showing the oxidation of ammonia nitrogen to NO 2 -N as a concentration by performing a photocatalytic oxidation experiment with different operating conditions for leachate after the second biological treatment according to Example 1 of the present invention.
도 3은 본 발명의 실시예 1에 따라 2차 생물학적 처리후의 침출수를 대상으로 운전조건을 달리하며 광촉매산화 실험을 실시하여 암모니아성 질소의 NO3-N로의 산화를 농도로 나타낸 그래프이다.3 is a graph showing the oxidation of ammonia nitrogen to NO 3 -N as a concentration by performing photocatalytic oxidation experiments with different operating conditions for leachate after the second biological treatment according to Example 1 of the present invention.
도 4는 본 발명의 실시예 2에 따라 pH를 조정하지 않은 침출수(약 pH 8.5)와 NaOH를 가하여 pH를 10.2와 12까지 각각 상승시킨 침출수를 광촉매반응없이 단순 폭기하여 암모니아가 탈기되는 양을 측정한 그래프이다.Figure 4 is a measure of the amount of ammonia is degassed by simply aeration without photocatalytic reaction to the leachate without adjusting the pH according to Example 2 of the present invention (about pH 8.5) and NaOH added to raise the pH to 10.2 and 12, respectively, without photocatalytic reaction One graph.
도 5는 본 발명의 실시예 3에 따라 암모니아수를 증류수에 가하여 농도가 약 1,130mg/ℓ NH3-N로 제조하여 광촉매 산화반응 유무에 따라 암모니아성 질소의 탈기효율를 나타낸 그래프이다.FIG. 5 is a graph showing the degassing efficiency of ammonia nitrogen with or without photocatalytic oxidation by adding ammonia water to distilled water and preparing a concentration of about 1,130 mg / L NH 3 -N according to Example 3 of the present invention.
이하 본 발명을 좀 더 구체적으로 살펴보면 다음과 같다.Looking at the present invention in more detail as follows.
본 발명에서는 광촉매인 TiO2(Degussa P-25: BET 표면적 50㎡/g, 평균 1차입자크기 21 nm)를 대상폐수에 혼합하여 촉매를 현탁액 상태로 하여 촉매의 이용효율을 높일 수 있는 현탁식 반응장치(slurry reactor)를 광촉매 반응기로 채택하였다. 이때 광촉매량은 0.1∼0.5wt% 정도이며, 바람직하게는 0.3wt%이다. 이러한 사용량은 통상의 사용량이다.In the present invention, a suspension catalyst which can increase the efficiency of the catalyst by mixing the catalyst TiO 2 (Degussa P-25: BET surface area 50㎡ / g, average primary particle size 21 nm) in the target wastewater to make the catalyst as a suspension A slurry reactor was adopted as the photocatalytic reactor. At this time, the amount of photocatalyst is about 0.1 to 0.5 wt%, preferably 0.3 wt%. Such usage is normal usage.
폐수와 촉매가 혼합되어 UV 조사에 의한 광산화 반응을 일으키는 부분은 외부가 스테인레스 스틸(stainless steel, O.D: 48.6 mm, ID: 43.2 mm)로 되어있고, 내부는 석영관(Quartz tube, O.D: 38 mm, I.D: 35 mm) 내에 길이 1.5m, 파장 254nm 의 UV 램프(Fisher & Porter LTD, Hg lamp)가 장착 되어있으며 전체 반응기의 반응조 체적은 약 10.7ℓ이다.The part where the waste water and the catalyst are mixed to cause the photooxidation reaction by UV irradiation is made of stainless steel (OD: 48.6 mm, ID: 43.2 mm) on the outside, and the inside is a quartz tube (OD: 38 mm). , ID: 35 mm) is equipped with UV lamp (Fisher & Porter LTD, Hg lamp) of 1.5m length and wavelength of 254nm and the reactor volume of the entire reactor is about 10.7ℓ.
일반적으로, 광촉매 산화는 OH 라디칼(radical)을 생성시키는 반응이다. 광촉매에서 발생된 전자는 수중의 산소와 반응하여 여러과정을 거친 후 OH 라디칼을 생성하는데, 이때에 산소가 고갈되게 되면 반응속도는 전체적으로 저하되기 시작한다. 따라서, 종래에는 과산화수소와 같은 산화보조제를 사용하였으나, 상기 과산화수소가 고가인 단점이 있다.In general, photocatalytic oxidation is a reaction that produces OH radicals. The electrons generated in the photocatalyst react with oxygen in the water to generate OH radicals after various processes. At this time, when oxygen is depleted, the reaction rate starts to decrease as a whole. Therefore, in the past, an oxidizing aid such as hydrogen peroxide was used, but there is a disadvantage in that the hydrogen peroxide is expensive.
한편, 본 발명에서는 상기 과산화수소 대신에 순산소를 공급하거나 공기를 불어 넣었다. 이 경우, 폐수내의 용존산소(DO)를 4∼10㎎/ℓ으로 유지하여야만 암모니아성 질소의 직접 산화 및 제거 효과를 얻을 수 있다. 선택적으로, 과산화수소와 같은 산화보조제를 공급할 경우 더욱 향상된 효율을 얻을 수 있다. 그러나, 경제적인 측면 및 대상 폐수의 성상을 고려하여, 본 발명의 방법에 상기 과산화수소를 선택적으로 사용할 수 있다. 상기 과산화수소는 산소보다 더 우수한전자 수용체이므로 산소를 공급할 때 보다 더 나은 산화효과를 기대할 수 있다. 그 외의 산화보조제로는 오존이 사용 가능하다.Meanwhile, in the present invention, instead of the hydrogen peroxide, pure oxygen is supplied or air is blown. In this case, the dissolved oxygen (DO) in the waste water must be maintained at 4 to 10 mg / l to directly oxidize and remove the ammonia nitrogen. Optionally, improved efficiency can be obtained by supplying an oxidizing aid, such as hydrogen peroxide. However, considering the economic aspect and the properties of the target wastewater, the hydrogen peroxide can be selectively used in the method of the present invention. Since hydrogen peroxide is a better electron acceptor than oxygen, a better oxidation effect can be expected than when oxygen is supplied. As other oxidizing aids, ozone can be used.
아울러, 상기와 같이 용존산소를 적정 수준으로 유지하면서 폐수의 pH를 알카리성, 즉 pH 8∼10으로 유지시키는 것이 암모니아성 질소의 제거면에서 바람직하다. 이때, pH가 8 미만이면 암모니아성 질소가 염을 형성하고, 10을 초과하면 경제적으로 불리한 단점이 있다. 상기 pH의 조절은 NaOH, CaCO3, 또는 KOH 등을 이용하는 것이 바람직하나, 이에 한정되는 것은 아니다. 이러한 조건하에서, 폐수중의 암모니아성 질소는 NO2 -1, NO3 -1로 전환되는 것을 최대한 억제시키고, 직접 N2로 산화시키는 것이다.In addition, maintaining the dissolved oxygen at an appropriate level as described above, it is preferable to maintain the pH of the waste water to be alkaline, that is, pH 8 to 10 in terms of removal of ammonia nitrogen. At this time, if the pH is less than 8, ammonia nitrogen forms a salt, and if it exceeds 10, there is an economic disadvantage. The pH is preferably adjusted using NaOH, CaCO 3 , or KOH, but is not limited thereto. Under these conditions, the ammonia nitrogen in the waste water is maximally inhibited from converting to NO 2 -1 , NO 3 -1 , and directly oxidized to N 2 .
전술한 바와 같이, 암모니아성 질소를 처리하지 않은 상태로 배출할 경우 매우 유해한 환경 조건이 발생되며, 특히 pH 8.2 이상의 수용액 내에서 유리 암모니아를 형성하여 독성을 띄게 됨으로 반드시 처리해야 할 대상이다. 광촉매 산화는 폐수중의 유기물을 완전히 산화시켜 이산화탄소와 물, 및 일부 무기화합물 만을 남기게되므로, 하기 반응식 1과 같이 암모니아성 질소를 아질산성 질소와 질산성 질소로 산화시키거나, 질소가스로 또는 하기 반응식 2와 같이 기체상의 암모니아로 전환 탈기시키기도 한다.As described above, when the ammonia nitrogen is discharged without treatment, very harmful environmental conditions are generated, and in particular, the free ammonia is formed in an aqueous solution having a pH of 8.2 or higher to be toxic. Since photocatalytic oxidation completely oxidizes organic matter in the wastewater, leaving only carbon dioxide, water, and some inorganic compounds, the ammonia nitrogen is oxidized to nitrite nitrogen and nitrate nitrogen as shown in Scheme 1, or to nitrogen gas or As shown in Fig. 2, conversion to gaseous ammonia is also carried out.
따라서 상기 광촉매법을 이용하여 pH 및 DO를 조업조건 변경으로 우수한 효율로 암모니아성 질소를 처리할 수 있어 경제적인 효과가 있어 다양한 폐수 및 공정에 적용할 수 있다.Therefore, it is possible to treat ammonia nitrogen with excellent efficiency by changing the operating conditions of pH and DO using the photocatalyst method, and thus it is economically effective and can be applied to various wastewater and processes.
이하 실시예를 통하여 본 발명을 좀 더 구체적으로 살펴보지만, 하기 예에 본 발명의 범주가 한정된 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the following examples.
실시예 1Example 1
2차 생물학적 처리후의 침출수를 대상으로 운전조건을 달리하며 광촉매산화 실험을 실시하여 암모니아성 질소의 변화를 측정하였다. 우선 교반 이외에 알카리조건에서의 pH조건을 조사하기 위하여 다른 물리적 화학적 첨가없이 오직 UV/TiO2에 의한 산화 실험(이하 '(가)실험'이라 함)을 실시하였다. 이때 광촉매량은 0.3wt%이며, UV는 253.7nm(20W) 파장, 유량은 2.9liter/min로 하였다. 이하, 실험에서 광촉매량, UV 및 유량은 동일한 조건에서 실시하였다.Changes in ammonia nitrogen were measured by photocatalytic oxidation experiments with different operating conditions for leachate after the second biological treatment. First of all, in order to investigate pH conditions under alkaline conditions in addition to stirring, oxidation experiments using only UV / TiO 2 (hereinafter referred to as '(a) experiment') were performed without any other physical chemical addition. At this time, the amount of photocatalyst was 0.3wt%, UV was 253.7nm (20W) wavelength, and flow rate was 2.9liter / min. Hereinafter, in the experiment, the photocatalyst amount, UV, and flow rate were performed under the same conditions.
두 번째로는 광촉매 산화실험에 산소를 공급하기 위해 산기기를 이용하여 공기를 불어넣으며 실험(이하 '(나)실험'이라 함)을 실시하였다.Second, the experiment was performed by blowing air using an acid machine to supply oxygen to the photocatalytic oxidation experiment (hereinafter referred to as '(b) experiment').
세 번째 실험은 침출수 내 고농도의 알카리도(Alkalinity)을 제거하기 위해 침출수를 초기에 pH 4이하로 조정한 후 공기를 불어넣으며 실험(이하 '(다) 실험'이라 함)을 실시하였다. 알카리도는 OH 라디칼과의 반응속도가 유기물의 반응속도보다 훨씬 커서 고농도의 알카리도를 함유할 경우 그 외의 물질의 산화가 어렵게 되므로 알카리성을 제거하기 위한 것과 pH 범위를 산(acid)조건으로 하기 위하여 실시하였다.In the third experiment, the leachate was initially adjusted to pH 4 or less in order to remove the high concentration of alkalinity in the leachate, and the experiment was carried out by blowing air (hereinafter referred to as '(c) experiment'). Alkaline is used to remove the alkalinity and to make the pH range into acid condition because the reaction rate with OH radical is much higher than the reaction rate of organic matter, which makes it difficult to oxidize other substances when containing alkalinity of high concentration. .
네 번째 실험은 산화 효율을 증가시키기 위해 500mg/ℓ에 해당하는 과산화수소를 초기에 일시 투여한 후 실험(이하 '(라) 실험'이라 함)을 실시하였다. 실시에 사용된 2차 생물학적 처리를 거친 쓰레기 침출수의 물리화학적 특성을 하기 표 1에 기재하였다.In the fourth experiment, an initial temporary administration of 500 mg / l of hydrogen peroxide was performed to increase the oxidation efficiency (hereinafter referred to as '(d) experiment'). The physicochemical characteristics of the waste leachate subjected to the second biological treatment used in the examples are shown in Table 1 below.
실험 결과는 도 1, 도 2, 및 도 3과 같다. 도 1은 조업조건에 따른 NH3-N의 농도변화이며, 도 2는 NO2-N, 도 3은 NO3-N의 농도 변화이다. 도 1에서 (가)실험, (나)실험에서의 암모니성 질소는 시간에 따라 감소함을 볼 수 있으나, pH를 4 이하로 조절한 실험((다) 실험 및 (라) 실험)은 오히려 증가하는 것을 알 수 있다. 이는 암모니아가 산성 조건에서는 NH4+형태로 전환되고 반대로 알칼리성 조건에서는 NH3(g) 형태로 탈기되거나 산화되어 NO2-N과 NO3-N 또는 질소가스로 산화되기 때문이다. 알칼리 조건에서 제거가 우수한 이유는 광촉매의 표면 전하와 관련된 것으로 대개 pH 6 이하에서 광촉매 TiO2의 표면 전하는 (+)를 pH 6 이상에서는 (-)를 띄므로 수중의 NH4+가 알칼리 조건에서 광촉매에 쉽게 흡착되어 반응이 유리하게 진행되며, 반대로 산성 조건(pH 6이하)에서는 NH4+가 광촉매 표면에의 흡착이 어려워 반응이 진행되기 어려워진다. 산성조건에서 암모니아성 질소가 증가하는 것은 침출수중의 유기물질과 결합된 질소가 산화되어 암모나아성 질소로 변하기 때문이다. 유기성분은 산성조건에서 산화가 잘 일어난다. 이에 대한 결과는 도 2와 도 3에 도시된 바와 같다. NO2-N과 NO3-N이 산성조건에서는 거의 변화가 없으나 알칼리성 조건에서는 암모니아성 질소가 산화되는 것을 보여 주고있다. 암모니아성 질소의 탈기에 제거와 산화에 의한 제거의 효율은 (나) 실험에서 가장 우수하였다. 즉, 가장 단순한 형태의 폭기에 의하여 DO를 조절할 수 있는 산소를 공급하여 주면 탈질효율이 높아진다는 것을 보여주고 있다. (나)실험의 결과는 하기 표 2에 기재하였다.Experimental results are the same as in FIGS. 1, 2, and 3. 1 is a change in the concentration of NH 3 -N according to the operating conditions, Figure 2 is a NO 2 -N, Figure 3 is a change in the concentration of NO 3 -N. In Figure 1 (a) experiment, (b) the ammonia nitrogen in the experiment can be seen to decrease with time, but the experiment to adjust the pH to 4 or less ((c) experiment and (d) experiment) rather increased I can see that. This is because ammonia is converted to NH 4+ form under acidic conditions and conversely degassed or oxidized to NH 3 (g) form under alkaline conditions and oxidized to NO 2 -N and NO 3 -N or nitrogen gas. The reason why the removal is excellent under alkaline conditions is related to the surface charge of the photocatalyst. Since the surface charge of the photocatalyst TiO 2 is generally negative (+) at pH 6 and below, the NH 4+ in water is photocatalyst under alkaline conditions. The reaction proceeds favorably due to the adsorption on the other hand, and on the contrary, in the acidic condition (pH 6 or less), the adsorption of NH 4+ on the surface of the photocatalyst becomes difficult and the reaction does not proceed easily. The increase in ammonia nitrogen under acidic conditions is due to the oxidation of the nitrogen associated with organic matter in the leachate to ammonia nitrogen. Organic components oxidize well under acidic conditions. The results are as shown in FIGS. 2 and 3. NO 2 -N and NO 3 -N show little change under acidic conditions, but ammonia nitrogen is oxidized under alkaline conditions. The efficiency of removal of ammonia nitrogen by degassing and removal by oxidation was the best in (B) experiment. That is, the denitrification efficiency is improved by supplying oxygen to control DO by the simplest type of aeration. (B) The results of the experiment are shown in Table 2 below.
상기 표 2와 같이 NH3-N은 약 1,300mg/ℓ이 제거되어 90%의 제거가 가능하였으며, NO2-N는 약 60mg/ℓ, NO3-N은 약 34mg/ℓ 정도 증가하였다. NO2-N와 NO3-N의 증가량은 NH3-N의 제거량에 비해 상대적으로 적다. 따라서 암모니아성 질소의 일부는 아질산성 질소나 질산성 질소로 산화되고 대부분이 암모나아와 질소가스로 탈기된다고 판단할 수 있다. 이상의 결과로부터 암모니아성 질소의 제거가 알칼리성 조건에서 유리하다고 할 수 있다. (나) 실험에 H2O2를 첨가하거나 pH를 더욱 상승시키면 효율이 증가할 것으로 판단되나 비용이 발생하여 경제적으로 단점이 발생한다.As shown in Table 2, the NH 3 -N was removed about 1,300mg / ℓ 90%, NO 2 -N was about 60mg / ℓ, NO 3 -N was increased about 34mg / ℓ. The increase of NO 2 -N and NO 3 -N is relatively small compared to the removal of NH 3 -N. Therefore, it can be judged that some of the ammonia nitrogen is oxidized to nitrite nitrogen or nitrate nitrogen, and most of it is degassed by ammonia and nitrogen gas. From the above result, it can be said that removal of ammonia nitrogen is advantageous in alkaline conditions. (B) If H 2 O 2 is added to the experiment or the pH is increased further, the efficiency will be increased, but the cost will be incurred.
실시예 2Example 2
도 4는 pH를 조정하지 않은 침출수 (약 pH 8.5 정도)와 NaOH를 가하여 pH를 10.2와 12까지 각각 상승시킨 침출수를 산기기로 폭기하여 암모니아가 탈기되는 양을 측정한 것이다. 이것은 암모니아성 질소가 광촉매 산화에 의하여 질소가스로 간화되어 탈기되는 것을 확인하기 위하여 실시하였다. 도 4에서와 같이 탈기되는 양은 매우 적으며 pH를 10.2로 조정한 것은 약 10% 정도 감소되는 양상을 보였다. 그러나 pH 조정직후 약 4%의 감소를 보여 강알칼리성 조건에서 암모니아성 질소 탈기가 일어남을 알 수 있었다. 초기 pH를 12로 상승시킨 후 동일한 실험을 했을 때도 20%에 못 미치는 저조한 탈기 효과를 나타내었으며 5시간 후의 pH는 약 11.1정도였다. 따라서, 폐수속의 암모니아성 질소가 폭기에 의하여 일부 암모니아 가스로 탈기되고 일부는 NO2-N과 NO3-N 전환되고, 나머지는 직접 질소로 산화되는 것을 보여주는 결과이다.Figure 4 is a measure of the amount of ammonia is degassed by aeration of the leaching water (no pH adjusted about pH 8.5) and NaOH added to raise the pH up to 10.2 and 12, respectively, by an acid machine. This was done to confirm that ammonia nitrogen was degassed and degassed with nitrogen gas by photocatalytic oxidation. As shown in Figure 4, the amount of degassing is very small, and adjusting the pH to 10.2 showed a decrease of about 10%. However, a decrease of about 4% was observed immediately after pH adjustment, indicating that ammonia nitrogen degassing occurred under strong alkaline conditions. After increasing the initial pH to 12, the same experiment showed a less than 20% degassing effect, and the pH after 5 hours was about 11.1. Therefore, ammonia nitrogen in the wastewater is degassed into some ammonia gas by aeration, some are converted to NO 2 -N and NO 3 -N, and the rest are directly oxidized to nitrogen.
실시예 3Example 3
도 5는 28% 암모니아수를 증류수에 가하여 약 1000mg/ℓ NH3-N으로 제조한 후 이 인공폐수를 동일한 조건에서 광촉매 반응시킨 것이다. 초기 제조 농도가 약 1,130mg/ℓ NH3-N이며, 본 실시예의 경우 산기기를 통하여 산소를 비롯한 공기가 공급되기 때문에 인공폐수 속의 암모니아성 질소가 탈기되어 제거되기도 한다. 따라서 폭기에 의한 탈기가 어느 정도 영향을 미치는지를 파악하기 위하여 본 실시예의 실험에서 자외선을 조사하지 아니하고 실험을 실시하였다. 도 5은 자외선을 조사한 경우와 자외선을 조사하지 않은 경우 암모니아성 질소의 제거율을 비교하여 도시한 도면이다. 접촉시간으로 약 6시간이 지난 후 자외선을 조사한 실험은 상기와 같이 약 80% 이상의 제거율을 보인 반면, 자외선을 조사하지 않은 경우는 약 40%에 미치지 못하는 제거율을 나타내었다. 실시예 2와 비교해 볼 때 폭기에 의한 암모니아성 질소의 제거율이 다소 높이 나타난다. 실시예 2의 경우 침출수 속의 다른 성분들의 방해작용으로 인하여 이러한 결과가 도출되었으리라 추측된다.FIG. 5 shows that 28% ammonia water is added to distilled water to prepare about 1000 mg / L NH 3 -N, and the artificial wastewater is photocatalytically reacted under the same conditions. The initial production concentration is about 1,130mg / ℓ NH 3 -N, in the case of the present embodiment, since the air, including oxygen is supplied through the acid machine, ammonia nitrogen in the artificial waste water is degassed and removed. Therefore, the experiment was performed without irradiating ultraviolet rays in the experiment of the present embodiment in order to determine how much aeration caused by aeration. 5 is a view illustrating a comparison of removal rates of ammonia nitrogen when irradiated with ultraviolet rays and when not irradiated with ultraviolet rays. After about 6 hours as the contact time, the experiment irradiated with ultraviolet rays showed a removal rate of about 80% or more as described above, whereas the UV irradiation did not reach about 40%. Compared with Example 2, the removal rate of ammonia nitrogen by aeration appears somewhat higher. In the case of Example 2, it is speculated that this result was obtained due to the disturbing action of other components in the leachate.
따라서, 본 발명은 TiO2를 광촉매로 사용하고, 253.7nm의 자외선을 광원으로 사용하는 광촉매 산화법을 이용하여 폐수속의 암모니아성 질소를 알카리성 용액에서 단순한 폭기에 의하여 경제적이며 효과적으로 제거할 수 있다.Therefore, the present invention can economically and effectively remove ammonia nitrogen in the wastewater by simple aeration from the alkaline solution by using a photocatalytic oxidation method using TiO 2 as a photocatalyst and using 253.7 nm ultraviolet light as a light source.
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| KR101508954B1 (en) | 2014-04-30 | 2015-04-08 | 주식회사 에스비이앤이 | Water treatment system and method for treating water using the same |
| CN111533348A (en) * | 2020-05-22 | 2020-08-14 | 云南云铜锌业股份有限公司 | Method and device for removing ammonia nitrogen in zinc smelting wastewater |
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