KR100720035B1 - Water treatment apparatus and method using photocatalyst - Google Patents
Water treatment apparatus and method using photocatalyst Download PDFInfo
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- KR100720035B1 KR100720035B1 KR1020050038237A KR20050038237A KR100720035B1 KR 100720035 B1 KR100720035 B1 KR 100720035B1 KR 1020050038237 A KR1020050038237 A KR 1020050038237A KR 20050038237 A KR20050038237 A KR 20050038237A KR 100720035 B1 KR100720035 B1 KR 100720035B1
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- photocatalyst
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000012528 membrane Substances 0.000 claims abstract description 46
- 238000007539 photo-oxidation reaction Methods 0.000 claims abstract description 34
- 239000002351 wastewater Substances 0.000 claims abstract description 33
- 238000001556 precipitation Methods 0.000 claims abstract description 16
- 238000010979 pH adjustment Methods 0.000 claims abstract description 10
- 230000001376 precipitating effect Effects 0.000 claims abstract description 7
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 1
- 239000012510 hollow fiber Substances 0.000 abstract description 12
- 238000000926 separation method Methods 0.000 abstract description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 17
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- 239000002699 waste material Substances 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000006552 photochemical reaction Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- -1 WO 3 Substances 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910005438 FeTi Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000004457 water analysis Methods 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
- C02F1/325—Irradiation devices or lamp constructions
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/002—Construction details of the apparatus
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- 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
Abstract
본 발명은 광산화 수처리 장치 및 처리방법에 관한 것으로, 폐수 유입관에 의해 외부의 폐수와 광촉매가 유입되며, 광조사램프에 의하여 처리되는 광산화 반응조; 상기 광산화 반응조에서 처리된 처리수를 pH 조절에 의하여 광촉매를 침전시켜 처리수로부터 광촉매를 제거시키는 침전조; 상기 광촉매가 제거된 처리수에 잔존하는 광촉매를 분리하는 진공펌프가 구비된 중공사 분리막 모듈이 설치된 분리막 탱크; 로 구성되는 것을 특징으로 한다. 본 발명에 따른 광산화 수처리 장치는 간단한 pH 조절에 의하여 광촉매를 침전시켜 처리수로부터 광촉매를 제거시키는 방법을 채용함으로서 효율적으로 광촉매를 폐수로부터 분리 및 회수할 수 있는 장점이 있다.The present invention relates to a photo-oxidation water treatment apparatus and a treatment method, the external waste water and the photocatalyst is introduced by the waste water inlet pipe, the photo-acidification tank treated by a light irradiation lamp; A precipitation tank for removing the photocatalyst from the treated water by precipitating the photocatalyst by pH adjustment of the treated water treated in the photoacidification reactor; A membrane tank in which a hollow fiber membrane module having a vacuum pump for separating the photocatalyst remaining in the treated water from which the photocatalyst has been removed is installed; Characterized in that consists of. The photo-oxidation water treatment apparatus according to the present invention has the advantage of efficiently separating and recovering the photocatalyst from the wastewater by employing a method of removing the photocatalyst from the treated water by precipitating the photocatalyst by simple pH adjustment.
광촉매, 침전, pH, 수처리, 분리막, 중공사막 Photocatalyst, precipitation, pH, water treatment, separation membrane, hollow fiber membrane
Description
도 1은 본 발명에 다른 광산화 수처리 장치의 구성도이다. 1 is a block diagram of a photo-oxidation water treatment apparatus according to the present invention.
* 도면의 주요부분에 대한 부호의 설명* Explanation of symbols for main parts of the drawings
1 : 폐수 저장조 2 : 폐수 유입펌프1: wastewater storage tank 2: wastewater inflow pump
3 : 오존발생기 4 : 순환펌프3: ozone generator 4: circulation pump
5 : 광산화 반응조 6 : 오존스크러버5: photo-oxidation reaction tank 6: ozone scrubber
7 : 자외선 램프 8 : 침전조7: ultraviolet lamp 8: settling tank
9 : 분리막 탱크 10 : 압력게이지9: separator tank 10: pressure gauge
11 : 진공펌프 12 : 중공사 분리막11: vacuum pump 12: hollow fiber membrane
본 발명은 광산화 수처리 장치 및 처리방법에 관한 것으로, 상세하게는 유기 물을 함유한 폐액 등 난분해성 오염물질을 처리함에 있어서 광산화 반응에 의하여 오염물질의 분해를 효과적으로 함에 있어서 투입된 광촉매를 간단한 pH 조절에 의하여 침전시킴으로서 효과적으로 분리할 수 있는 광산화 수처리 장치 및 이를 이용한 수처리 방법에 관한 것이다.The present invention relates to a photo-oxidation water treatment apparatus and a treatment method, and more particularly, in the treatment of hardly degradable contaminants such as waste liquid containing organic water, the photocatalyst introduced in the effective decomposition of contaminants by photo-oxidation reaction is used for simple pH adjustment. It relates to a photo-oxidation water treatment apparatus and a water treatment method using the same that can be effectively separated by precipitation.
TiO2, WO3, ZnO, SiC, CdS 등의 광촉매를 처리 대상 폐수에 부유 상으로 투여하고 광산화 반응조 내에 침지된 고압 수은램프와 같은 광원으로 자외선을 대상 원수에 조사시키면 광촉매 활성에 의하여 광화학 반응에 의해 생성된 수산기와 초과산화물이 폐수 중에 함유된 유기물질, 독성물질, 그리고 색도함유 물질을 산화시키는 방법은 한국공개특허공보 1998-50359호 등에 공지되어 있으며, 특히 상기 투입된 광촉매를 회수함에 있어서, 분리막을 사용하는 광촉매-분리막 혼성 수처리 장치들이 한국공개특허공보 2001-26409호와 한국공개특허공보 2004-15928호에 공지되어 있다.When photocatalysts such as TiO 2 , WO 3 , ZnO, SiC, and CdS are suspended in the wastewater to be treated and irradiated with the source water with a light source such as a high-pressure mercury lamp immersed in the photochemical reaction tank, photocatalytic activity is used to The method of oxidizing the hydroxyl group and the superoxide produced by the organic material, the toxic substance, and the chromatic substance contained in the waste water is known from Korea Patent Publication No. 1998-50359 and the like, and particularly, in recovering the introduced photocatalyst, Photocatalyst-membrane hybrid water treatment devices using the same are known from Korean Patent Laid-Open Publication No. 2001-26409 and Korean Patent Publication No. 2004-15928.
그러나 처리대상 폐액에서의 오염물질 함유량이 높아짐에 따라 투입되는 광촉매의 양이 증가함으로 인해 투입되는 광촉매를 광산화 반응 후 분리막을 통하여 효율적으로 분리할 수 없어서, 고농도의 폐액을 광산화 반응에 의한 처리를 하는데 한계가 있는 상황이며, 또한 처리장치 밖으로 유출되는 광촉매의 손실로 인한 처리비용의 증가로 인한 문제가 대두되고 있다.However, due to the increase in the amount of photocatalyst introduced into the waste liquid to be treated, the input photocatalyst could not be efficiently separated through the membrane after the photooxidation reaction. There is a limiting situation, and a problem arises due to an increase in processing costs due to the loss of the photocatalyst flowing out of the processing apparatus.
본 발명은 상기의 문제점을 극복하기 위하여 안출된 것으로서, 본 발명의 목적은 광촉매의 회수가 용이하여 고농도의 폐액을 처리할 수 있는 광산화 수처리 장치와 수처리 방법을 제공하는 것이며, 본 발명의 또 다른 목적은 광촉매의 회수 효율이 좋은 경제적인 광산화 수처리 장치와 수처리 방법을 제공하는 것이다.The present invention has been made to overcome the above problems, and an object of the present invention is to provide a photo-oxidation water treatment apparatus and a water treatment method that can easily recover the photocatalyst to treat a high concentration of waste liquid, another object of the present invention The present invention provides an economical photo-oxidation water treatment apparatus and a water treatment method with good recovery efficiency of a photocatalyst.
본 발명은 광산화 수처리 장치 및 처리방법에 관한 것으로, 본 발명에 따른 광산화 수처리 장치는 폐수 유입관에 의해 외부의 폐수와 광촉매가 유입되며, 광조사램프에 의하여 처리되는 광산화 반응조; 상기 광산화 반응조에서 처리된 처리수를 pH 조절에 의하여 광촉매를 침전시켜 처리수로부터 광촉매를 제거시키는 침전조; 상기 광촉매가 제거된 처리수에 잔존하는 광촉매를 분리하는 진공펌프가 구비된 중공사 분리막 모듈이 설치된 분리막 탱크; 로 구성되는 것을 특징으로 하며, 또한 본 발명에 따른 광산화 수처리 방법은 외부의 폐수와 광촉매를 광조사램프가 구비된 광산화 반응조에 유입되는 단계; 상기 광산화 반응조에서 광산화 램프에 의하여 폐수를 처리하는 단계; 상기 광산화 반응조에서 처리된 처리수를 침전조에 유입시켜 5.5 내지 6.5 범위의 pH로 조절하여 광촉매를 침전시키는 단계; 상기 침전수의 상등액을 진공펌프가 구비된 중공사 분리막 모듈이 설치된 분리막 탱크에 유입시켜 상기 중공사 분리막에 의하여 잔존 광촉매를 분리하는 단계; 로 구성되는 것을 특징으로 한다.The present invention relates to a photo-oxidation water treatment device and a treatment method, the photo-oxidation water treatment device according to the present invention is a waste water inlet pipe and the external waste water and photocatalyst is introduced, the photo-oxidation tank treated by a light irradiation lamp; A precipitation tank for removing the photocatalyst from the treated water by precipitating the photocatalyst by pH adjustment of the treated water treated in the photoacidification reactor; A membrane tank in which a hollow fiber membrane module having a vacuum pump for separating the photocatalyst remaining in the treated water from which the photocatalyst has been removed is installed; Characterized in that consisting of, and further, the photo-oxidation water treatment method according to the present invention comprises the steps of introducing the external wastewater and photocatalyst into a photo-oxidation tank equipped with a light irradiation lamp; Treating the wastewater by a photooxidation lamp in the photoacidification tank; Precipitating a photocatalyst by introducing the treated water treated in the photoacidification tank into a precipitation tank and adjusting the pH to a pH in the range of 5.5 to 6.5; Separating the remaining photocatalyst by the hollow fiber membrane by introducing the supernatant of the precipitated water into a membrane tank having a hollow fiber membrane module equipped with a vacuum pump; Characterized in that consists of.
이하 본 발명에 따른 수처리 장치와 방법을 도면을 참고로 해서 설명한다. Hereinafter, a water treatment apparatus and a method according to the present invention will be described with reference to the drawings.
도 1은 본 발명에 따른 광산화 수처리 장치의 구성도를 도시한 것이다.1 is a block diagram of a photo-oxidation water treatment apparatus according to the present invention.
폐수 유입관에 의해 외부의 폐수가 유입되어 저장되는 폐수저장조(1)로부터 폐수가 도관을 통하여 광산화 반응기(5)에 유입되도록 도관에 폐수 유입펌프(2)가 구비된다. 이때 부유 상으로 광촉매가 유입되도록 도관의 일부에 광촉매를 투입되도록 하는 장치를 도관에 구비하거나 폐수저장탱크 또는 광산화 반응기에 직접 광촉매를 투입하는 장치를 구비될 수 있다. 광산화 반응조(5)는 자외선이 방사되는 고압수은램프 등으로 예시되는 광조사 램프가 구비되며, 상기 광조사 램프에 의하여 조사되는 자외선의 에너지가 부유 상으로 존재하는 광촉매를 활성화 시켜서 폐수 속에 존재하는 유기물 등의 오염물질을 산화시킨다. 본 발명에서는 광촉매로서 TiO2을 사용하였으나, 이외에도 산화물 광촉매인 WO3, ZnO, SiC, CdS 등이 모두 가능하다. 슬러리 상에 분산된 광촉매 입자 집합체(aggregate)의 크기는 이후 채용하는 분리막의 크기보다 커야 하며, 본 발명에서는 평균 입자 크기가 25nm의 것을 사용하였으나, 본 발명이 이에 한정되는 것은 아니며, 분말형 광촉매을 사용하는 것도 가능하며, 최근 들어 개발되고 있는 가시광 활성 광촉매를 채용할 수 있으며, 이때에는 자외선 램프 이외에 가시광 램프를 사용할 수도 있다. The
광산화 반응조에 투입되는 광촉매의 충진 비율은 처리조 폐수의 1000 중량에 대해 1 내지 10 중량%의 비율이 바람직하며, 광촉매의 양이 적으면 광촉매의 효과가 적고, 많으면 폐수중의 광의 투과율이 떨어져 처리효율이 떨어진다.The filling ratio of the photocatalyst introduced into the photochemical reaction tank is preferably in the range of 1 to 10% by weight based on 1000 weight of the wastewater in the treatment tank, and the smaller the amount of the photocatalyst is, the less the effect of the photocatalyst is, the higher the light transmittance in the wastewater is treated. Inefficient
상기와 같이 광촉매로 충진된 반응조 내에 순환펌프(4)를 작동시켜 반응조내의 폐수를 순환 및 교반시킴으로써 광촉매를 폐수중에 균일하게 분산, 현탁시키는 것이 바람직하다. 광촉매를 활성시키기 위한 광조사 램프는 고압·중압·저압수은등, 블랙램프 등이 사용될 수 있으며, 광조사램프의 외표면과 반응조 내벽과의 거리는 강한 광조사강도를 얻을 수 있는 측면에서 가능한 한 짧은 거리, 즉 5 내지 20㎜의 범위로 유지하는 것이 좋다. It is preferable to uniformly disperse and suspend the photocatalyst in the wastewater by circulating and stirring the wastewater in the reaction tank by operating the
본 발명에서는 광촉매를 활성시키기 위한 광조사 램프로서 파장이 200 내지 400nm의 범위에 속하는 자외선을 조사할 수 있는 UV 램프(7)를 사용하였으며, 폐수의 농도 및 유입량에 따라 광조사 램프의 개별 램프의 전력소비 및 전체 램프의 개수를 조절하였다.In the present invention, as a light irradiation lamp for activating the photocatalyst, a
상기의 광산화 반응과 함께 폐액의 처리 효율을 높이기 위하여 광산화 반응조 내에서 원폐수를 폭기하여 산소의 농도를 높여주거나 전처리로서 오존처리, 과산화수소 또는 산소의 주입할 수 있는 장치가 추가로 구비될 수 있으며, 특히 광산화 반응조와 도관으로 연결되는 오존발생장치(3)를 구비하여 오존에 의한 유기폐액의 산화반응을 광산화반응과 결합하여 진행하는 것이 바람직하며, 이때, 광산화 반응기에는 외기로 나가는 오존을 제거하기 위하여 오존스크러버가 구비될 수 있으며, 또한 오존산화 반응의 효율을 높이기 위하여 산화 반응조의 폐액이 오존 발생기와 광산화 반응조를 연결하는 도관을 통하여 순환되도록 하는 순환펌프가 도관에 구비되거나 산기관이 광산화 반응조 내에 구비될 수 있다.In addition to the above-mentioned photooxidation reaction, in order to increase the treatment efficiency of the waste liquid, a waste gas is aerated in the photochemical reaction tank to increase the concentration of oxygen, or as a pretreatment, an apparatus capable of injecting ozone treatment, hydrogen peroxide or oxygen may be further provided. In particular, it is preferable to proceed with the oxidation reaction of the organic waste liquid by ozone combined with the photo-oxidation reaction, and equipped with an ozone generator (3) connected to the photo-oxidation tank and the conduit, in this case, in order to remove the ozone to the outside An ozone scrubber may be provided, and in order to increase the efficiency of the ozone oxidation reaction, a circulating pump is provided in the conduit or an acid pipe is provided in the photooxidation tank so that the waste liquid of the oxidation reaction tank is circulated through the conduit connecting the ozone generator and the photooxidation reaction tank. Can be.
상기 광산화 반응조에서 처리된 처리수는 광촉매를 제거시키는 침전조(8)로 유입된다. 상기 침전조에서는 간단한 pH 조절에 의하여 광촉매를 응집시켜 침전시키게 되며, 이때 광촉매의 응집과 침전에 적절한 pH 범위는 5.5 내지 6.5 범위이며, 광산화 처리된 폐액의 pH는 수산화나트륨 등의 알칼리와 염산 등의 무기산을 이용하여 pH를 조절하게 된다. 상기의 pH 범위를 벗어나는 경우 광촉매의 적절한 응집 및 침전이 이루어지지 않는다. The treated water treated in the photoacidification reactor flows into the
또한, pH 조절공정에 의해 TiO2가 침전 제거된 처리수를 분리막 공정에 도입시 소량의 응집제를 사용하여 침전 제거되는 TiO2의 양을 향상 시키고, 최종 처리의 수질을 향상시키기 위해, 분리막 공정에 도입되는 처리수의 잔류 TiO2를 응집제로서 FeCl3 등을 0.01 내지 0.2 g/L을 첨가하여 재응집시킴으로서 분리막 공정의 처리수질을 보다 향상시킬 수 있다. 상기 응집단계는 침전조에서 pH 조절에 의한 침전 후 진행되거나, 침전조의 상등액이 유입되는 별도의 응집조에서 수행될 수 있으며, 또한 다량의 광촉매가 침전된 침전조의 처리수를 분리막 탱크로 이송시킨 후 상기 응집제를 투여한 후 분리막에 의한 분리공정을 수행하는 것도 가능하나, 침전조에서 침전되는 광촉매를 효율적으로 재활용하기 위해서는 분리막 내에서 응집처리하는 것이 바람직하며, 이때 적절한 pH 범위는 6.5 내지 7.0 이며, 본 발명에서는 pH를 6.8로 조정하여 수행하였다.In addition, in order to improve the amount of TiO 2 precipitated and removed by using a small amount of flocculant when introducing the treated water in which TiO 2 is precipitated and removed by the pH adjustment process, and to improve the quality of the final treatment, The treated water quality of the separation membrane process can be further improved by reaggregating FeTi 3 or the like by adding residual TiO 2 of the treated water to be introduced as a flocculant. The coagulation step may be performed after the precipitation by adjusting the pH in the precipitation tank, or may be performed in a separate coagulation tank into which the supernatant of the precipitation tank is introduced, and also after transferring the treated water of the precipitation tank in which a large amount of the photocatalyst is precipitated to the separation tank. It is also possible to perform a separation process by a membrane after administering a flocculant, but in order to efficiently recycle the photocatalyst precipitated in the sedimentation tank, it is preferable to perform the flocculation process in the membrane, in which the appropriate pH range is 6.5 to 7.0, and the present invention. In the pH was adjusted to 6.8.
상기의 침전조에서 pH의 조절 만으로 산화처리된 폐액 내에 부유 중인 광촉매의 90% 이상이 침전되게 되며, 광촉매의 대부분이 제거된 산화처리된 유기폐액의 상등액은 진공펌프가 구비되고 중공사 분리막 모듈이 설치된 분리막 탱크(9)로 유입되어 상기 광촉매가 제거된 처리수에 잔존하는 광촉매를 분리하게 된다. In the above settling tank, more than 90% of the suspended photocatalyst is precipitated in the oxidized waste liquid only by adjusting the pH, and the supernatant of the oxidized organic waste liquid from which most of the photocatalyst is removed is provided with a vacuum pump and a hollow fiber membrane module is installed. The photocatalyst introduced into the
본 발명에 있어 분리막 모듈은 사용되는 광촉매의 입자크기보다 작은 사이즈를 선정함이 원칙이나 크기가 클 경우 처리되지 않은 폐수가 유출되어 처리효율이 낮아지고, 분리막이 너무 작을 때에는 막의 흐름이 가로막힐 우려가 있으므로 적절한 크기의 분리막을 선정하는 것이 바람직하다. 상기 중공사 분리막 모듈은 침지형 분리막으로 광촉매의 입자 크기와 폐액의 상태 등을 고려하여 적절한 세공크기의 것을 선택하며, 상기의 선택은 당업자에게는 용이한 것이다.In the present invention, the membrane module selects a size smaller than the particle size of the photocatalyst used, but when the size is large, untreated wastewater flows out and treatment efficiency is low, and when the membrane is too small, the flow of membrane may be blocked. Therefore, it is preferable to select a separator having an appropriate size. The hollow fiber membrane module is an immersion type membrane and selects an appropriate pore size in consideration of the particle size of the photocatalyst and the state of the waste liquid, and the above selection is easy for those skilled in the art.
상기 침지형 분리막의 형태는 중공사 막 이외에 관형, 평판형, 회전원통형 중 어느 하나를 적용하거나 혼합하여 적용할 수 있다. 앞서 언급한 바와 같이 침전조에서 광촉매의 90% 이상을 분리하였기 때문에 분리막 모듈에서의 광촉매 분리량은 많지 않으며, 따라서 분리막에서의 부하가 적게 되므로 분리막 모듈의 크기가 종래의 광촉매 회수용 분리막에 비하여 그 크기가 감소할 수 있다.The immersion type separation membrane may be applied by mixing or mixing any one of tubular, flat, and rotary cylindrical in addition to the hollow fiber membrane. As mentioned above, since 90% or more of the photocatalysts are separated from the settling tank, the amount of photocatalyst separation in the membrane module is not large, and thus the load on the membrane is reduced, so the size of the membrane module is larger than that of the conventional photocatalyst recovery membrane. May decrease.
본 발명에 다른 광촉매 수처리 장치는 유입펌프, 광조사램프, pH 조절, 분리막 모듈 등의 운전조건을 프로그램된 논리 제어기(미도시)에 의하여 자동적으로 제어될 수 있다.The photocatalytic water treatment device according to the present invention can be automatically controlled by a programmed logic controller (not shown) for operating conditions such as an inflow pump, a light irradiation lamp, a pH control, a membrane module, and the like.
상술한 바와 같이 본 발명의 기술적 특징은 후술되는 실시예로부터 보다 명백하게 될 것이나, 하기 실시예는 본 발명을 한정하는 것은 아니다.As described above, the technical features of the present invention will become more apparent from the following examples, but the following examples do not limit the present invention.
〈실시예 1〉<Example 1>
폐수 저장조에 저장된 비스페놀-A(BPA) 함유 농도 10ppm로 150L를 폐수유입펌프를 이용하여 광산화 반응조에 유입시켰으며, 이때 첨가되는 광촉매인 TiO2의 양은 1g/L이었다. 사용된 TiO2는 독일의 Degussa 사에서 공급된 P25제품으로서 BET 50m2/g, 공극 부피 0.19cm3/g이고, 평균 공극 크기는 69 Å이며, 평균 입자 크기는 21nm인 것을 사용하였다. 광산화 반응조에서 사용된 자외선램프는 Southern New England Ultra Violet Co, Ltd. PPR 200 제품(파장 2537Å, 35W, intensity 1.65x1016 sec/cm3)의 것을 6개 사용하였다. 폐수처리의 광조사시간은 30 내지 60 분으로 하였다. 광산화반응의 촉진을 위하여 반응기에 순환펌프를 장착하여 처리 폐수를 순환시켰다.At a concentration of 10 ppm of bisphenol-A (BPA) stored in the wastewater storage tank, 150L was introduced into the photochemical reaction tank using a wastewater inflow pump, and the amount of TiO 2 , a photocatalyst added at this time, was 1 g / L. TiO 2 used was P25 from Degussa, Germany, BET 50m 2 / g, pore volume 0.19cm 3 / g, the average pore size is 69 mm 3 , the average particle size is 21nm. Ultraviolet lamps used in photooxidation reactors are Southern New England Ultra Violet Co., Ltd. Six PPR 200 products (wavelength 2537 Hz, 35 W, intensity 1.65 × 10 16 sec / cm 3 ) were used. The light irradiation time of wastewater treatment was 30 to 60 minutes. In order to promote the photooxidation reaction, the treatment wastewater was circulated by installing a circulation pump in the reactor.
광산화 반응산계에서 광촉매 산화반응의 효율을 향상시키기 위해 광산화반응기에 오존 발생기를 결합시켜 0.2 wt% 의 오존을 광산화반응기에 3.8 ml/s로 공급하여 오존을 광촉매 산화반응 동한 병행하여 사용하였다.In order to improve the efficiency of the photocatalytic oxidation reaction in the photoacid reaction system, the ozone generator was coupled to the photooxidation reactor, and 0.2 wt% of ozone was supplied to the photocatalytic reactor at 3.8 ml / s, and ozone was used in parallel with the photocatalytic oxidation reaction.
광산화 처리된 폐수는 침전조에 이송되어 소량의 NaOH 수용액을 이용하여 pH를 6.5로 조정하여 90% 이상의 TiO2를 응집하여 침전시켰다. TiO2를 침전시킨 후 상등액을 분리막 모듈이 장착된 분리막 탱크에 이송시켜 응집제로서 FeCl3를 0.15g/L의 양으로 분리막 탱크에 투입하고, pH를 6.8로 조정함으로서 잔류 TiO2를 응집하여 침전시켰으며, 침지형 중공사 분리막을 이용하여 잔류 TiO2를 최종 분리 제거하였다. 이때의 최종처리 수질은 0.5NTU 이었다.The acidified wastewater was transferred to a settling tank and adjusted to pH 6.5 using a small amount of NaOH aqueous solution to aggregate and precipitate more than 90% of TiO 2 . After precipitation of TiO 2 , the supernatant was transferred to a membrane tank equipped with a membrane module, FeCl 3 was added to the membrane tank in an amount of 0.15 g / L as a flocculant, and the remaining TiO 2 was aggregated and precipitated by adjusting the pH to 6.8. The residual TiO 2 was finally separated and removed using an immersion hollow fiber membrane. The final treated water quality at this time was 0.5NTU.
사용된 분리막은 PVDF 소재의 흡입여과식 중공사 분리막으로서 기공 크기가 0.4 ㎛, 표면적이 0.02 m2, 내경이 1.8 mm, 외경이 2.0 mm인 침지된 중공사 MF 막을 사용하였고, 진공펌프를 사용하였으며, 진공펌프의 작동 압력이 20 cmHg 조건에서 흡입여과 방식으로 수행하였다.The membrane used was a suction filtration hollow fiber membrane made of PVDF material, using an immersed hollow fiber MF membrane with a pore size of 0.4 μm, surface area of 0.02 m 2 , inner diameter of 1.8 mm, and outer diameter of 2.0 mm, and vacuum pump. The vacuum pump was operated by suction filtration at 20 cmHg.
상기의 광산화 처리 과정에서의 처리수의 탁도와 용액속에 잔류하는 TiO2의 입자크기 분석 결과를 표 1에 나타내었다.Table 1 shows the results of turbidity of the treated water and particle size analysis of TiO 2 remaining in the solution during the photooxidation process.
[표1]Table 1
상기 표 1에서 알 수 있는 바와 같이 pH 조절 및 응집 처리에 의한 TiO2 제거 후 탁도가 98% 이상 감소하였음을 알 수 있고, 이는 분리막에서 제거될 TiO2의 양이 매우 적음을 의미하는 것이고, 이는 pH 조절 및 응집 처리에 의하여 TiO2 제거하는 본 발명에 따른 광산화 폐수처리 방법이 TiO2 혼탁액을 직접 분리막에서 제거하는 경우 보다 분리막의 오염도가 감소하고, 장기간 분리막을 유지할 수 있음을 의미한다고 할 수 있다.As can be seen in Table 1, it can be seen that the turbidity was reduced by 98% or more after the TiO 2 removal by pH adjustment and aggregation treatment, which means that the amount of TiO 2 to be removed from the separator is very small. The photooxidation wastewater treatment method according to the present invention, which removes TiO 2 by pH adjustment and flocculation, can reduce the contamination of the membrane and maintain the membrane for a long time than when the TiO 2 turbidity is directly removed from the membrane. have.
본 발명에 따른 광산화 수처리 장치는 간단한 pH 조절에 의하여 광촉매를 침전시켜 처리수로부터 광촉매를 제거시키는 방법을 채용함으로서 효율적으로 광촉매를 폐수로부터 분리 및 회수할 수 있는 장점이 있고, 또한 TiO2 혼탁액을 직접 분리막에서 제거하는 경우 보다 분리막의 오염도가 감소하고, 장기간 분리막을 유지할 수 있는 장점이 있다.The photo-oxidation water treatment device according to the present invention has the advantage of efficiently separating and recovering the photocatalyst from the wastewater by employing a method of removing the photocatalyst from the treated water by precipitating the photocatalyst by simple pH adjustment, and also providing a TiO 2 turbidity liquid. When the membrane is directly removed from the membrane, the contamination of the membrane is reduced, and there is an advantage of maintaining the membrane for a long time.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100696898B1 (en) * | 2004-11-27 | 2007-03-20 | 최명숙 | Process for treating hair of wig and the hair of wig treated by the same |
| KR20160009893A (en) | 2014-07-17 | 2016-01-27 | 한국과학기술연구원 | Flexible nanostructure photocatalyst of TiO2 nanoparticles-immobilized PVDF nanofabric and method for fabricating the same |
| KR20190048686A (en) | 2017-10-31 | 2019-05-09 | 한국과학기술연구원 | Water treatment material with photocatalyst and non-photocatalyst and Method for fabricating the same |
| KR20200010765A (en) * | 2018-07-23 | 2020-01-31 | (주)한경글로벌 | Method for cleaning submerged membrane using photocatalyst and UV-scattering media |
| KR20220067068A (en) | 2020-11-17 | 2022-05-24 | 한국과학기술원 | Catalytic composite for catalytic ozone oxidation process and preparation method thereof |
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| KR100697880B1 (en) * | 2006-02-28 | 2007-03-23 | 순천대학교 산학협력단 | Effective recycling method of photocatalyst used for photocatalytic oxidation in water treatment process |
| CN105060391B (en) * | 2015-08-03 | 2017-07-21 | 河南科技大学 | Outer circulation photocatalysis spinning liquid UF membrane coupled reactor for handling organic wastewater |
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| KR20010026409A (en) * | 1999-09-06 | 2001-04-06 | 김형벽 | Drinking water and refractory wastewater treatment process by coupled membrane photo-oxidation system |
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| JP2000157972A (en) | 1998-11-26 | 2000-06-13 | Nkk Corp | Device for advanced sewage treatment |
| KR20010026409A (en) * | 1999-09-06 | 2001-04-06 | 김형벽 | Drinking water and refractory wastewater treatment process by coupled membrane photo-oxidation system |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100696898B1 (en) * | 2004-11-27 | 2007-03-20 | 최명숙 | Process for treating hair of wig and the hair of wig treated by the same |
| KR20160009893A (en) | 2014-07-17 | 2016-01-27 | 한국과학기술연구원 | Flexible nanostructure photocatalyst of TiO2 nanoparticles-immobilized PVDF nanofabric and method for fabricating the same |
| KR20190048686A (en) | 2017-10-31 | 2019-05-09 | 한국과학기술연구원 | Water treatment material with photocatalyst and non-photocatalyst and Method for fabricating the same |
| KR20200010765A (en) * | 2018-07-23 | 2020-01-31 | (주)한경글로벌 | Method for cleaning submerged membrane using photocatalyst and UV-scattering media |
| KR102109560B1 (en) * | 2018-07-23 | 2020-05-13 | (주)한경글로벌 | Method for cleaning submerged membrane using photocatalyst and UV-scattering media |
| KR20220067068A (en) | 2020-11-17 | 2022-05-24 | 한국과학기술원 | Catalytic composite for catalytic ozone oxidation process and preparation method thereof |
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