KR20160131422A - Non-oxidizing biocide for membrane cleaing, and method for water treatment and membrane cleaning using the same - Google Patents
Non-oxidizing biocide for membrane cleaing, and method for water treatment and membrane cleaning using the same Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000004140 cleaning Methods 0.000 title claims abstract description 21
- 230000003115 biocidal effect Effects 0.000 title claims description 4
- 239000003139 biocide Substances 0.000 title claims description 4
- 230000001590 oxidative effect Effects 0.000 claims abstract description 47
- 239000000417 fungicide Substances 0.000 claims abstract description 23
- 230000000855 fungicidal effect Effects 0.000 claims abstract description 18
- AKUNSPZHHSNFFX-UHFFFAOYSA-M tributyl(tetradecyl)phosphanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC AKUNSPZHHSNFFX-UHFFFAOYSA-M 0.000 claims description 32
- 150000004023 quaternary phosphonium compounds Chemical class 0.000 claims description 28
- 238000001223 reverse osmosis Methods 0.000 claims description 21
- GZDFHIJNHHMENY-UHFFFAOYSA-N Dimethyl dicarbonate Chemical compound COC(=O)OC(=O)OC GZDFHIJNHHMENY-UHFFFAOYSA-N 0.000 claims description 16
- 235000010300 dimethyl dicarbonate Nutrition 0.000 claims description 16
- 229960003333 chlorhexidine gluconate Drugs 0.000 claims description 15
- YZIYKJHYYHPJIB-UUPCJSQJSA-N chlorhexidine gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O.C1=CC(Cl)=CC=C1NC(=N)NC(=N)NCCCCCCNC(=N)NC(=N)NC1=CC=C(Cl)C=C1 YZIYKJHYYHPJIB-UUPCJSQJSA-N 0.000 claims description 15
- 239000004316 dimethyl dicarbonate Substances 0.000 claims description 11
- 239000012527 feed solution Substances 0.000 claims description 9
- 239000003206 sterilizing agent Substances 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 7
- 229920002647 polyamide Polymers 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- 230000002070 germicidal effect Effects 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 230000002147 killing effect Effects 0.000 abstract description 4
- 230000000813 microbial effect Effects 0.000 abstract description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 12
- 239000003899 bactericide agent Substances 0.000 description 12
- 241000191967 Staphylococcus aureus Species 0.000 description 10
- UUIVKBHZENILKB-UHFFFAOYSA-N 2,2-dibromo-2-cyanoacetamide Chemical compound NC(=O)C(Br)(Br)C#N UUIVKBHZENILKB-UHFFFAOYSA-N 0.000 description 9
- 229910019093 NaOCl Inorganic materials 0.000 description 8
- 244000005700 microbiome Species 0.000 description 8
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 8
- 239000001974 tryptic soy broth Substances 0.000 description 8
- 108010050327 trypticase-soy broth Proteins 0.000 description 8
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000010612 desalination reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000004621 scanning probe microscopy Methods 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 230000032770 biofilm formation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
- B01D65/06—Membrane cleaning or sterilisation ; Membrane regeneration with special washing compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/16—Use of chemical agents
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- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
본 발명은 막을 이용한 수처리 공정에 적용시, 높은 미생물 사멸 효과 및 바이오필름 제거 효과를 가지면서도 막 손상을 최소화하여, 막의 수명을 연장시키고 화학적 세정 주기를 줄일 수 있는 새로운 비산화성 살균제 및 이를 이용한 수처리 방법과 막 세정방법에 대한 것이다. The present invention relates to a novel non-oxidizing fungicide capable of minimizing membrane damage, prolonging the lifetime of a membrane and reducing chemical cleaning cycles, while having a high microbial killing effect and a biofilm removal effect when applied to a water treatment process using a membrane, and a water treatment method And a membrane cleaning method.
Description
본 발명은 막을 이용한 수처리 공정에 적용시, 높은 미생물 사멸 효과 및 바이오필름 제거 효과를 가지면서도 막 손상을 최소화하여, 막의 수명을 연장시키고 화학적 세정 주기를 줄일 수 있는 새로운 비산화성 살균제 및 이를 이용한 수처리 방법과 막 세정방법에 대한 것이다.
The present invention relates to a novel non-oxidizing fungicide capable of minimizing membrane damage, prolonging the lifetime of a membrane and reducing chemical cleaning cycles, while having a high microbial killing effect and a biofilm removal effect when applied to a water treatment process using a membrane, and a water treatment method And a membrane cleaning method.
역삼투, 정삼투의 삼투공정 또는 여과공정 등 막을 이용한 수처리 공정은 최근 다양한 수처리 분야에서 주목받고 있는 기술 분야 중 하나이며, 특히, 해수 담수화나 하수재 이용분야에서 막을 이용한 수처리 공정이 확대되고 있는 추세이다.The water treatment process using membrane such as reverse osmosis, osmosis osmosis process or filtration process is one of the technology fields that have recently been attracting attention in various water treatment fields. In particular, water treatment processes using membranes are expanding in the field of seawater desalination and sewage reuse to be.
GWI(Global Water Intelligence)의 "Water Reuse Markets 2005-2015 : A Global Assessment & Forecast"에 따르면 물의 재이용 시장은 세계적으로 볼 때, 현재 200 만톤/일 규모이고, 2015년에는 540 만톤/일 규모로 성장할 것으로 전망하고 있다. 또한, 해수담수화 시장은 현재 300 만톤/일 규모이며 2015년에는 620 만톤/일 규모로 성장할 것으로 전망하고 있다. 이외에도 지표수 및 지하수의 처리, 산업 폐수의 처리 및 무방류 재이용 등의 분야에서 역삼투, 정삼투 방식이나 여과공정은 주목받고 있는 고도한 기술의 수처리 방법이다.According to GWI's "Water Reuse Markets 2005-2015: A Global Assessment & Forecast," the water reuse market is expected to grow to 2 million tons per day globally and 5.4 million tons per day by 2015 . In addition, the seawater desalination market is currently estimated at 3 million tons / day and will grow to 6.2 million tons / day by 2015. In addition, reverse osmosis, reverse osmosis, and filtration processes are highly sophisticated water treatment methods in areas such as surface and groundwater treatment, industrial wastewater treatment and non-flare reuse.
그런데, 역삼투 방식이나 여과공정의 기술을 상용화하는 데에 가장 큰 장애로 작용하는 것이 막오염 문제이며, 상기 막오염의 주요 원인 중 하나는 처리수 내 미생물 및 막 표면에 형성되는 바이오필름 등으로 인하여 발생하는 바이오파울링(biofouling)이다. One of the major causes of the membrane contamination is microorganisms in the treated water and biofilms formed on the surface of the membrane. Is biofouling that occurs because of
상기 바이오파울링 문제를 해결하기 위하여, 종래에는 NaOCl과 같은 강력한 산화성 살균제를 사용하여 막을 세정하였으나, 이를 유기활성층을 가지는 막에 적용할 경우, 막의 산화적 분해로 인하여 막 표면에 손상이 쉽게 발생하는 문제가 있었다. In order to solve the biofouling problem, conventionally, a strong oxidizing bactericide such as NaOCl has been used to clean the membrane. However, when the membrane is applied to a membrane having an organic active layer, damage to the membrane surface occurs easily due to oxidative decomposition of the membrane There was a problem.
이에, DBNPA(dibromocyanoactamide)와 같은 비산화성 살균제를 막 세정에 적용하고자 하는 시도가 이루어지고 있으나, 이러한 종래의 비산화성 살균제들은 pH 8 이상에서는 쉽게 가수분해되어 잔류농도를 유지하지 못하며, 빛에 의해 쉽게 광분해되어 미생물과 충분한 접촉시간을 유지하지 못한다는 한계가 있었다.
Accordingly, attempts have been made to apply non-oxidizing fungicides such as DBNPA (dibromocyanoactamide) to membrane cleaning. However, such conventional non-oxidizing fungicides do not easily maintain hydrolysis at pH 8 or higher, And there was a limit in that it could not maintain sufficient contact time with microorganisms due to photodegradation.
상기와 같은 문제점을 해결하기 위하여, 본 발명은 높은 미생물 사멸 효과 및 바이오필름 제거 효과를 가지면서도 막 손상을 최소화할 수 있는 새로운 비산화성 살균제 및 이를 이용한 수처리 방법과 막 세정방법을 제공하는 것을 목적으로 한다. In order to solve the above problems, it is an object of the present invention to provide a novel non-oxidizing bactericide capable of minimizing membrane damage while having a high microbial killing effect and a biofilm removal effect, and a water treatment method and a membrane cleaning method using the same do.
또한, 본 발명은 pH 또는 빛 조건 등 변화하는 다양한 조건에서도 적용이 가능하며, 수처리용 막에 대한 배제율(rejection rate)이 높아 활용도가 높은 새로운 비산화성 살균제 및 이를 이용한 수처리 방법과 막 세정방법을 제공하는 것을 목적으로 한다.
The present invention also relates to a novel non-oxidizing bactericide which can be applied under various conditions such as pH or light condition and has high utilization rate due to high rejection rate for water treatment film, and a water treatment method and a membrane washing method using the same The purpose is to provide.
상기와 같은 목적을 달성하기 위한 본 발명의 실시예는, 막(membrane)을 이용한 수처리 방법에 있어서, 상기 막의 일측으로 유입되는 피드용액(feed solution) 스트림에 비산화성 살균제(non-oxidizing biocide)를 첨가하는 단계; 및 상기 막의 일측에 유입된 피드용액 스트림이 막을 통과하는 단계;를 포함하는 수처리 방법을 제공한다. According to an embodiment of the present invention, there is provided a water treatment method using a membrane, wherein a non-oxidizing biocide is added to a feed solution stream flowing into one side of the membrane, ; And passing the feed solution stream flowing into one side of the membrane through the membrane.
이때, 상기 비산화성 살균제는 QAPC(Qaternary phosphonium compounds), CHG (Chlorhexidine gluconate) 및 DMDC (Dimethyl dicarbonate)로 이루어진 그룹으로부터 선택되는 어느 하나 또는 이들의 혼합물을 포함하는 것이 바람직하며, 상기 QAPC(Qaternary phosphonium compounds)가 TTPC(Tributyl tetradecyl phosphonium chloride)를 포함하는 것이 바람직하다. The non-oxidizing fungicide preferably includes any one selected from the group consisting of QAPC (quaternary phosphonium compounds), CHG (chlorhexidine gluconate) and DMDC (dimethyl dicarbonate), or a mixture thereof. The QAPC ) Preferably comprises TTPC (Tributyl tetradecyl phosphonium chloride).
또한, 상기 막은 다양한 종류의 수처리용 막이 사용될 수 있으나, 바람직하게는 폴리아미드(polyamide) 계열의 활성층(active layer)을 포함하는 역삼투막(reverse osmosis membrane)이 사용될 수 있으며, 이때 상기 역삼투막의 비산화성 살균제에 대한 배제율(rejection rate)은 95% 이상인 것이 바람직하다. In addition, although various membranes for water treatment can be used as the membrane, a reverse osmosis membrane including a polyamide active layer may be used. In this case, the non-oxidizing sterilizing agent of the reverse osmosis membrane It is preferable that the rejection rate is 95% or more.
한편, 본 발명의 또 다른 실시예는, 수처리용 막(membrane)의 세정방법에 있어서, 상기 수처리용 막과 비산화성 살균제를 포함하는 세정액을 접촉시키는 단계를 포함하는 막 세정방법을 제공한다. According to another embodiment of the present invention, there is provided a film cleaning method comprising a step of contacting a water-treating membrane and a cleaning liquid containing a non-oxidizing sterilizing agent in a cleaning method for a water treatment membrane.
이때, 상기 비산화성 살균제는 QAPC(Qaternary phosphonium compounds), CHG (Chlorhexidine gluconate) 및 DMDC (Dimethyl dicarbonate)로 이루어진 그룹으로부터 선택되는 어느 하나 또는 이들의 혼합물을 포함하는 것이 바람직하며, 상기 QAPC(Qaternary phosphonium compounds)가 TTPC(Tributyl tetradecyl phosphonium chloride)를 포함하는 것이 바람직하다. The non-oxidizing fungicide preferably includes any one selected from the group consisting of QAPC (quaternary phosphonium compounds), CHG (chlorhexidine gluconate) and DMDC (dimethyl dicarbonate), or a mixture thereof. The QAPC ) Preferably comprises TTPC (Tributyl tetradecyl phosphonium chloride).
또한, 상기 막은 다양한 종류의 수처리용 막이 사용될 수 있으나, 바람직하게는 폴리아미드(polyamide) 계열의 활성층(active layer)을 포함하는 역삼투막(reverse osmosis membrane)이 사용될 수 있으며, 이때 상기 역삼투막의 비산화성 살균제에 대한 배제율(rejection rate)은 95% 이상인 것이 바람직하다. In addition, although various membranes for water treatment can be used as the membrane, a reverse osmosis membrane including a polyamide active layer may be used. In this case, the non-oxidizing sterilizing agent of the reverse osmosis membrane It is preferable that the rejection rate is 95% or more.
한편, 본 발명의 또 다른 실시예는, 수처리용 막(membrane)의 바이오파울링(biofouling)을 저감하기 위한 비산화성 살균제로서, QAPC(Qaternary phosphonium compounds), CHG(Chlorhexidine gluconate) 및 DMDC (Dimethyl dicarbonate)로 이루어진 그룹으로부터 선택되는 어느 하나 또는 이들의 혼합물을 포함하는 막 세정용 비산화성 살균제를 제공한다. 상기 QAPC (Qaternary phosphonium compounds)가 TTPC(Tributyl tetradecyl phosphonium chloride)를 포함하는 것이 바람직하다. Yet another embodiment of the present invention is a non-oxidizing fungicide for reducing biofouling of a water treatment membrane, comprising QAPC (quaternary phosphonium compounds), CHG (chlorhexidine gluconate) and DMDC (dimethyl dicarbonate ) Or a mixture thereof. The non-oxidizing fungicide for membrane cleaning according to any one of claims 1 to 3, It is preferable that the QAPC (quaternary phosphonium compounds) include Tributyl tetradecyl phosphonium chloride (TTPC).
상기 막은 다양한 종류의 수처리용 막이 사용될 수 있으나, 바람직하게는 폴리아미드(polyamide) 계열의 활성층(active layer)을 포함하는 역삼투막(reverse osmosis membrane)이 사용될 수 있으며, 이때 상기 역삼투막의 비산화성 살균제에 대한 배제율(rejection rate)은 95% 이상인 것이 바람직하다.
Various membranes for water treatment may be used for the membrane, but preferably a reverse osmosis membrane including a polyamide active layer may be used. The reverse osmosis membrane may be used for the non- The rejection rate is preferably at least 95%.
본 발명의 비산화성 살균제를 막을 이용한 수처리 공정에 적용할 경우, 종래의 산화성 살균제 이상의 바이오파울링 저감 효과를 나타내면서도 막 손상을 최소화하여 막의 수명을 연장시키고 화학적 세정 주기를 줄일 수 있다. When the non-oxidizing bactericide of the present invention is applied to a water treatment process using a membrane, the film damage is minimized while exhibiting biofouling reduction effect over that of the conventional oxidizing bactericide, thereby prolonging the life of the membrane and reducing the chemical washing period.
또한, 본 발명의 비산화성 살균제는 pH 또는 빛 조건 등 변화하는 다양한 조건에서도 적용이 가능하며, 수처리용 막에 대한 배제율(rejection rate)이 높아 다양한 환경 및 조건에서도 활용이 가능하다.
In addition, the non-oxidizing bactericide of the present invention can be applied to various conditions such as pH or light condition, and can be utilized in various environments and conditions due to high rejection rate for the water treatment film.
도 1 - TTPC와 DBNPA의 MIC(Minimum inhibitory concentration), MBC (Minimum bactericide concentration)를 보여주는 그래프 (TBS(Tryptic soy broth) 사용, 온도는 37℃, S.A. 주입농도: 2.0 x 10＾8 CFU/㎖, PA14 주입농도: 5.2x 10＾8 CFU/㎖)
- A. TTPC + S.A.(Staphylococcus Aureus): MIC 10 ppm, MBC 20 ppm
- B. TTPC + PA14 (Pseudomonas aeruginosa stain PA14): MIC 20 ppm, MBC 30 ppm
- C. DBNPA + S.A. : MIC 313 ppm
- D. DBNPA + PA14 : MIC 156 ppm
도 2 - RO 막 표면을 1시간 동안 NaOCl, TTPC 처리(100,000 ppm/hr)한 후, 5,000 x 10,000 x 50,000의 배율로 확대한 SEM 이미지
도 3 - RO 막 표면을 1시간 동안 NaOCl, TTPC 처리(100,000 ppm/hr)한 후, 표면 거칠기(Roughness) 변화를 측정한 AFM (Atomic Force Microscope) 이미지
- A. Control RO 막의 표면
- B. NaOCl 100,000 ppm/hr 처리한 RO 막의 표면
- C. TTPC 100,000 ppm/hr 처리한 RO 막의 표면
도 4 - TTPC의 바이오파울링 저감 효과를 보여주는 위한 CLSM (conforcal laser scanning microscopy) 이미지(Green: Live cell, Red: Dead cell, Blue: Total cell)
- A. TSB(Tryptic soy broth) 배지 주입
- B. TSB + TTPC 20 ppm 처리한 배지 주입FIG. 1 is a graph showing the minimum inhibitory concentration (MIC) and minimum bactericide concentration (TBS) of TTPC and DBNPA using Tryptic soy broth at 37 ° C., 2.0 × 10 8 CFU / PA14 injection concentration: 5.2x10 < 8 > CFU / ml)
- A. TTPC + SA (Staphylococcus aureus):
- B. TTPC + PA14 (Pseudomonas aeruginosa stain PA14):
- C. DBNPA + SA:
- D. DBNPA + PA14:
Figure 2 - SEM image of RO membrane surface treated with NaOCl, TTPC (100,000 ppm / hr) for 1 hour and then magnified at 5,000 x 10,000 x 50,000
Figure 3 - AFM (Atomic Force Microscope) images of surface roughened surface after 1 hour of NaOCl and TTPC treatment (100,000 ppm / hr).
- Surface of Control RO membrane
- B. Surface of RO membrane treated with NaOCl 100,000 ppm / hr
C. Surface of RO membrane treated with 100,000 ppm / hr of TTPC
Figure 4 - Conforcal laser scanning microscopy (CLSM) image (Green: Live cell, Red: Dead cell, Blue: Total cell) for demonstrating the biofouling reduction effect of TTPC.
- A. Tryptic soy broth (TSB) medium injection
- B. Injection of TSB +
이하 본 발명에 따른 바람직한 실시예를 상세히 설명하기로 한다. 이에 앞서, 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니 되며, 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야 한다.Hereinafter, preferred embodiments according to the present invention will be described in detail. Prior to the description, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and should be construed in a sense and concept consistent with the technical idea of the present invention.
본 발명은 수처리용 막(membrane)의 바이오파울링(biofouling)을 저감하기 위하여 비산화성 살균제를 사용하는 것을 특징으로 한다. The present invention is characterized in that a non-oxidizing fungicide is used to reduce the biofouling of a water treatment membrane.
역삼투 방식이나 여과공정과 같이 막을 이용한 수처리 공정은, 처리수 내의 미생물과 유기물들로 인하여 막 표면에 바이오필름이 형성되기 쉽다. 종래에는 NaOCl과 같은 강력한 산화성 살균제를 사용하여 막을 세정하였으나, 이를 유기활성층을 가지는 막에 적용할 경우, 막의 산화적 분해로 인하여 막 표면이 금방 손상된다는 한계가 있었다. In a water treatment process using a membrane such as a reverse osmosis method or a filtration process, a biofilm is likely to be formed on the surface of the membrane due to microorganisms and organic substances in the treated water. Conventionally, a strong oxidizing bactericide such as NaOCl was used to clean the membrane. However, when the membrane was applied to a membrane having an organic active layer, there was a limit in that the membrane surface was immediately damaged due to oxidative decomposition of the membrane.
이에, 비산화성 살균제를 막 세정에 적용하고자 하는 시도가 이루어지고 있으나, 종래의 비산화성 살균제들은 pH 등 처리수의 조건 변화에 대응하지 못하고 쉽게 가수분해되어 잔류농도를 유지하지 못하였다. Accordingly, attempts have been made to apply non-oxidizing sterilizing agents to membrane cleaning. However, conventional non-oxidizing sterilizing agents fail to respond to changes in conditions such as pH and can not be easily hydrolyzed to maintain the residual concentration.
이에, 본 발명에서는 QAPC(Qaternary phosphonium compounds), CHG (Chlorhexidine gluconate) 및 DMDC (Dimethyl dicarbonate)로 이루어진 그룹으로부터 선택되는 어느 하나 또는 이들의 혼합물을 비산화성 살균제로 사용함으로써, 바이오파울링 및 막 손상을 최소화함과 동시에 다양한 조건을 가지는 처리수에도 적용이 가능한 것을 특징으로 한다. Accordingly, in the present invention, by using any one or a mixture thereof selected from the group consisting of QAPC (quaternary phosphonium compounds), CHO (chlorhexidine gluconate) and DMDC (dimethyl dicarbonate) as non-oxidizing fungicides, And can be applied to treatment water having various conditions at the same time.
이때, 상기 QAPC(Qaternary phosphonium compounds), CHG(Chlorhexidine gluconate) 및 DMDC(Dimethyl dicarbonate)는 단독으로 사용될 수 있으나, 일 실시예로 일정한 비율로 혼합되어 사용될 수도 있다. At this time, the QAPC (quaternary phosphonium compounds), CHG (chlorhexidine gluconate) and DMDC (dimethyl dicarbonate) may be used singly, but they may be mixed at a certain ratio in one embodiment.
또한, 상기 QAPC(Qaternary phosphonium compounds)는 다양한 물질이 사용될 수 있으나, 바람직하게는 TTPC(Tributyl tetradecyl phosphonium chloride)가 사용될 수 있다. In addition, QAPC (Quaternary phosphonium compounds) may be various materials, but preferably TTPC (Tributyl tetradecyl phosphonium chloride) may be used.
한편, 상기 비산화성 살균제는 산화성 살균제에 영향을 받는 다양한 종류의 막에 적용될 수 있으나, 바람직하게는 폴리아미드(polyamide)계열의 활성층(active layer)을 포함하는 역삼투막(reverse osmosis membrane)에 사용될 수 있다. On the other hand, the non-oxidizing fungicide may be applied to various kinds of membranes affected by an oxidizing bactericide, but it may preferably be used for a reverse osmosis membrane including a polyamide active layer .
본 발명의 비산화성 살균제는 역삼투막 표면의 활성층을 손상시키지 않을 뿐만 아니라 역삼투막에 대한 배제율(rejection rate)이 높아 역삼투막의 수명을 연장시키고 화학적 세정 주기를 줄일 수 있다. 이때 상기 역삼투막의 비산화성 살균제에 대한 배제율(rejection rate)은 95% 이상인 것이 바람직하다.
The non-oxidizing bactericide of the present invention not only does not damage the active layer on the surface of the reverse osmosis membrane, but also has a high rejection rate for the reverse osmosis membrane, thereby extending the lifetime of the reverse osmosis membrane and reducing the chemical washing period. At this time, the rejection rate of the non-oxidizing fungicide of the reverse osmosis membrane is preferably 95% or more.
한편, 본 발명의 일 실시예는, 막(membrane)을 이용한 수처리 방법에 있어서, 상기 막의 일측으로 유입되는 피드용액(feed solution) 스트림에 비산화성 살균제(non-oxidizing biocide)를 첨가하는 단계, 및 상기 막의 일측에 유입된 피드용액 스트림이 막을 통과하는 단계를 포함하는 수처리 방법을 제공한다. Meanwhile, an embodiment of the present invention provides a water treatment method using a membrane, comprising the steps of adding a non-oxidizing biocide to a feed solution stream flowing into one side of the membrane, and Wherein the feed solution stream introduced into one side of the membrane passes through the membrane.
또한, 본 발명의 또 다른 실시예는, 수처리용 막(membrane)의 세정방법에 있어서, 상기 수처리용 막과 비산화성 살균제를 포함하는 세정액을 접촉시키는 단계를 포함하는 막 세정방법을 제공한다. Still another embodiment of the present invention provides a film cleaning method comprising a step of contacting a cleaning liquid containing a water-treating film and a non-oxidizing bactericide in a method of cleaning a water treatment membrane.
앞서 살펴본 본 발명의 비산화성 살균제는, 막으로 유입되는 피드용액 스트림에 첨가되어 막을 통과하면서 작용할 수 있으며, 또는 별도의 CIP(clean in place) 세정공정에서 세정액의 일 구성성분으로 사용될 수도 있다. The non-oxidizing fungicides of the present invention discussed above can be added to the feed solution stream entering the membrane and act as they pass through the membrane, or they can be used as a component of a rinse solution in a separate clean in place (CIP) rinse process.
피드용액 스트림에 첨가된 비산화성 살균제는 피드용액 내에 존재하는 미생물을 사멸함과 동시에, 막을 통과하면서 자연스럽게 막에 바이오필름이 형성되는 것을 방지하며, 세정액의 일 구성성분으로 사용되는 비산화성 살균제는 CIP(clean in place) 세정공정 중 막 표면과 접촉하여 바이오필름 형성을 방지할 수 있다. The non-oxidizing fungicide added to the feed solution stream kills the microorganisms present in the feed solution while preventing the biofilm from being formed naturally through the membrane, and the non-oxidizing fungicide used as a constituent of the cleaning liquid is CIP it is possible to prevent biofilm formation by contacting the membrane surface during a clean in place cleaning process.
상기 비산화성 살균제 및 비산화성 살균제가 적용되는 수처리용 막의 구체적인 설명은 앞서 살펴본 바와 같다. A detailed description of the water treatment membrane to which the non-oxidizing sterilizing agent and the non-oxidizing sterilizing agent are applied is as described above.
이하에서는, 본 발명의 막 세정용 비산화성 살균제에 대한 실험예들을 살펴본다. 그러나 본 발명의 범주가 이하의 바람직한 실시예에 한정되는 것은 아니며, 당업자라면 본 발명의 권리범위 내에서 본 명세서에 기재된 내용의 여러 가지 변형된 형태를 실시할 수 있다.
Hereinafter, experimental examples of the non-oxidizing fungicide for membrane cleaning of the present invention will be described. However, the scope of the present invention is not limited to the following preferred embodiments. Those skilled in the art can implement various modified embodiments of the present invention within the scope of the present invention.
[실험예 1][Experimental Example 1]
MICMIC , , MBCMBC 측정 실험 Measurement experiment
본 발명의 비산화성 살균제 중 하나인 TTPC(Tributyl tetradecyl phosphonium chloride)에 대한 MIC(Minimum inhibitory concentration), MBC (Minimum bactericide concentration)를 평가하여 도 1에 나타내었다(A,B). 비교를 위하여 또 다른 비산화성 살균제인 DBNPA의 MIC, MBC를 함께 도시하였다(C,D). The minimum inhibitory concentration (MIC) and the minimum bactericide concentration (MBC) of TTPC (Tributyl tetradecyl phosphonium chloride), which is one of the non-oxidizing fungicides of the present invention, are evaluated and shown in FIG. 1 (A, B). For comparison, MIC and MBC of DBNPA, another non-oxidizing fungicide, are also shown (C, D).
도 1에서 A는 TTPC 에 S.A.(Staphylococcus Aureus)를 주입한 결과이며, B는 TTPC 에 PA14 (Pseudomonas aeruginosa stain PA14)를 주입한 결과이고, C는 DBNPA에 S.A.를 주입한 결과이며, D는 DBNPA에 PA14를 주입한 결과이다. In Fig. 1, A is the result of injecting SA (Staphylococcus aureus) into TTPC, B is the result of injecting PA14 (Pseudomonas aeruginosa stain PA14) into TTPC, C is the result of injecting SA into DBNPA, D is the result of DBNPA PA14. ≪ / RTI >
또한, TBS(Tryptic soy broth)를 배지로 사용하였으며, 실험온도는 37℃이고, S.A.(Staphylococcus Aureus) 주입농도는 2.0x10＾8 CFU/㎖, PA14(Pseudomonas aeruginosa stain PA14) 주입농도는 5.2x10＾8 CFU/㎖로 조절하였다. The concentration of SA (Staphylococcus aureus) injection was 2.0 × 10 ^ 8 CFU / ㎖ and the concentration of PA14 (Pseudomonas aeruginosa stain PA14) was 5.2 × 10 ^ 8 CFU / ml.
실험 결과, TTPC는 S.A.에서 MIC 10 ppm, MBC 20 ppm, PA14 에서 MIC 20 ppm, MBC 30 ppm로 측정된 것에 반해, DBNPA는 S.A.에서 MIC 313 ppm, PA14에서 MIC 156 ppm으로 측정되어, TTPC의 미생물 성장을 억제 효과가 DBNPA에 비하여 매우 우수한 것을 알 수 있었다
DBNPA was measured at
[실험예 2][Experimental Example 2]
막 표면 거칠기 실험Film surface roughness experiment
Dow Filmtec에서 제조한 RO 막(SW30HR-380) 표면을 1시간 동안 NaOCl, TTPC 처리(100,000 ppm/hr)한 후, 5,000 x 10,000 x 50,000의 배율로 확대한 SEM 이미지및 AFM (Atomic Force Microscope) 이미지를 도 2, 3에 도시하였다. (A. Control RO 막의 표면, B. NaOCl 100,000 ppm/hr 처리한 RO 막의 표면, C. TTPC 100,000 ppm/hr 처리한 RO 막의 표면)SEM image and AFM (Atomic Force Microscope) image obtained by enlarging the RO membrane (SW30HR-380) manufactured by Dow Filmtec with NaOCl and TTPC treatment (100,000 ppm / hr) for 1 hour at a magnification of 5,000 x 10,000 x 50,000 2 and 3, respectively. (Surface of RO RO membrane treated with A. NaOCl 100,000 ppm / hr, surface of RO RO membrane treated with 100,000 ppm / hr C. TTPC)
산화성 살균제인 NaOCl를 사용한 경우, 완전 산화로 인하여 막 전체 표면이 손상을 입은 것을 확인할 수 있는 반면, TTPC는 막 표면에 전혀 손상이 없는 것을 확인할 수 있었다.
When NaOCl, an oxidizing disinfectant, was used, it was confirmed that the entire surface of the membrane was damaged due to the complete oxidation, whereas TTPC showed no damage to the surface of the membrane.
[실험예 3][Experimental Example 3]
바이오파울링Biofouling 저감Abatement 평가 evaluation
미생물의 사멸 효과 및 바이오파울링에 대한 저감 효과를 확인하기 위하여, Slide Glass 표면에 멸균된 RO 막의 Supporting layer 를 부착시키고 Active layer 에 미생물을 부착시킨 후, Drip-flow cell 장치에 RO 막이 부착된 slide glass를 넣어주고 TSB(Tryptic soy broth)(A) 또는 TSB와 TTPC 20 ppm(B)을 주입한 배지를 RO 막 표면에 흘려 주면서 미생물의 바이오파울링 형성 정도를 CLSM (conforcal laser scanning microscopy) 를 통하여 측정하였다.(Green: Live cell, Red: Dead cell, Blue: Total cell)To confirm the microbial killing effect and biofouling reduction effect, supporting layer of sterilized RO membrane was attached to the surface of slide glass, microorganisms were attached to the active layer, and slide membrane with RO membrane was attached to the Drip-flow cell device glass was added and TSB (Tryptic soy broth) (A) or TSB and 20 ppm (B) of TTPC were injected onto the surface of the RO membrane. The degree of biofouling formation of the microorganisms was measured by CLSM (Conforcal Laser Scanning Microscopy) (Green: Live cell, Red: Dead cell, Blue: Total cell)
도 4에서 화학적 처리가 되지 않은 TSB 의 주입시에는 RO 막의 표면에 바이오파울링이 많이 생성되어 있었고 미생물도 대부분 살아있는 것을 확인할 수 있는 반면, TTPC 20 ppm을 주입한 RO 막 표면은 TBS 배지만을 처리한 RO 막 표면에 비하여 바이오파울링이 현저하게 줄어든 것을 알 수 있었고 미생물도 거의 사멸된 것을 확인할 수 있었다.
In FIG. 4, when the untreated TSB was injected, a large amount of biofouling was generated on the surface of the RO membrane and most of the microorganisms were alive. On the other hand, the RO membrane surface treated with 20 ppm of TTPC was treated with TBS It was found that the biofouling was remarkably reduced and the microorganisms were almost killed as compared with the RO membrane surface.
본 발명은 상술한 특정의 실시예 및 설명에 한정되지 아니하며, 청구범위에서 청구하는 본 발명의 요지를 벗어남이 없이 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자라면 누구든지 다양한 변형 실시가 가능하며, 그와 같은 변형은 본 발명의 보호 범위 내에 있게 된다.The present invention is not limited to the above-described specific embodiment and description, and various changes and modifications may be made by those skilled in the art without departing from the scope of the present invention as claimed in the claims. And such modifications are within the scope of protection of the present invention.
Claims (14)
상기 막의 일측으로 유입되는 피드용액(feed solution) 스트림에 비산화성 살균제(non-oxidizing biocide)를 첨가하는 단계; 및
상기 막의 일측에 유입된 피드용액 스트림이 막을 통과하는 단계;
를 포함하는 수처리 방법. In a water treatment method using a membrane,
Adding a non-oxidizing biocide to a feed solution stream flowing into one side of the membrane; And
Passing a feed solution stream flowing into one side of the membrane through the membrane;
≪ / RTI >
상기 비산화성 살균제가 QAPC(Qaternary phosphonium compounds), CHG (Chlorhexidine gluconate) 및 DMDC (Dimethyl dicarbonate)로 이루어진 그룹으로부터 선택되는 어느 하나 또는 이들의 혼합물을 포함하는 것을 특징으로 하는 수처리 방법. The method according to claim 1,
Wherein the non-oxidizing fungicide comprises any one selected from the group consisting of QAPC (quaternary phosphonium compounds), CHG (chlorhexidine gluconate), and DMDC (dimethyl dicarbonate) or a mixture thereof.
상기 QAPC(Qaternary phosphonium compounds)가 TTPC(Tributyl tetradecyl phosphonium chloride)를 포함하는 것을 특징으로 하는 수처리 방법. The method according to claim 1,
Wherein the QAPC (quaternary phosphonium compounds) comprises TTPC (Tributyl tetradecyl phosphonium chloride).
상기 막이 폴리아미드(polyamide) 계열의 활성층(active layer)을 포함하는 역삼투막(reverse osmosis membrane)인 것을 특징으로 하는 수처리 방법. The method according to claim 1,
Wherein the membrane is a reverse osmosis membrane including a polyamide active layer.
상기 역삼투막의 비산화성 살균제에 대한 배제율(rejection rate)이 95% 이상인 것을 특징으로 하는 수처리 방법. 5. The method of claim 4,
Wherein the rejection rate of the non-oxidizing germicide in the reverse osmosis membrane is 95% or more.
상기 수처리용 막과 비산화성 살균제를 포함하는 세정액을 접촉시키는 단계를 포함하는 막 세정방법. In a method of cleaning a membrane for water treatment,
And contacting the water-treating membrane with a cleaning liquid containing a non-oxidizing sterilizing agent.
상기 비산화성 살균제가 QAPC(Qaternary phosphonium compounds), CHG (Chlorhexidine gluconate) 및 DMDC (Dimethyl dicarbonate)로 이루어진 그룹으로부터 선택되는 어느 하나 또는 이들의 혼합물을 포함하는 것을 특징으로 하는 막 세정방법. The method according to claim 6,
Wherein the non-oxidizing fungicide comprises any one selected from the group consisting of QAPC (quaternary phosphonium compounds), CHG (chlorhexidine gluconate) and DMDC (dimethyl dicarbonate), or a mixture thereof.
상기 QAPC (Qaternary phosphonium compounds)가 TTPC(Tributyl tetradecyl phosphonium chloride)를 포함하는 것을 특징으로 하는 막 세정방법. The method according to claim 6,
Wherein the QAPC (quaternary phosphonium compounds) comprises TTPC (Tributyl tetradecyl phosphonium chloride).
상기 수처리용 막이 폴리아미드(polyamide)계열의 활성층(active layer)을 포함하는 역삼투막(reverse osmosis membrane)인 것을 특징으로 하는 막 세정방법. The method according to claim 6,
Wherein the water treatment membrane is a reverse osmosis membrane including a polyamide active layer.
상기 역삼투막의 비산화성 살균제에 대한 배제율(rejection rate)이 95% 이상인 것을 특징으로 하는 막 세정방법. 10. The method of claim 9,
Wherein the rejection rate for the non-oxidizing germicide in the reverse osmosis membrane is 95% or more.
QAPC(Qaternary phosphonium compounds), CHG(Chlorhexidine gluconate) 및 DMDC (Dimethyl dicarbonate)로 이루어진 그룹으로부터 선택되는 어느 하나 또는 이들의 혼합물을 포함하는 막 세정용 비산화성 살균제. As a non-oxidizing fungicide for reducing the biofouling of a water treatment membrane,
A non-oxidizing fungicide for membrane cleaning comprising any one selected from the group consisting of quaternary phosphonium compounds (QAPC), chlorhexidine gluconate (CHG) and dimethyl dicarbonate (DMDC).
상기 QAPC (Qaternary phosphonium compounds)가 TTPC(Tributyl tetradecyl phosphonium chloride)를 포함하는 것을 특징으로 하는 막 세정용 비산화성 살균제. 12. The method of claim 11,
Wherein the QAPC (quaternary phosphonium compounds) comprises TTPC (Tributyl tetradecyl phosphonium chloride).
상기 수처리용 막이 폴리아미드(polyamide)계열의 활성층(active layer)을 포함하는 역삼투막(reverse osmosis membrane)인 것을 특징으로 하는 막 세정용 비산화성 살균제. 12. The method of claim 11,
Wherein the water treatment membrane is a reverse osmosis membrane containing a polyamide active layer.
상기 역삼투막의 비산화성 살균제에 대한 배제율(rejection rate)이 95% 이상인 것을 특징으로 하는 막 세정용 비산화성 살균제. 14. The method of claim 13,
Wherein the rejection rate of the non-oxidizing fungicide of the reverse osmosis membrane is 95% or more.
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