CN111565825B - Method for cleaning membrane separation device - Google Patents
Method for cleaning membrane separation device Download PDFInfo
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- CN111565825B CN111565825B CN201980007462.7A CN201980007462A CN111565825B CN 111565825 B CN111565825 B CN 111565825B CN 201980007462 A CN201980007462 A CN 201980007462A CN 111565825 B CN111565825 B CN 111565825B
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- amphoteric surfactant
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- 239000012528 membrane Substances 0.000 title claims abstract description 147
- 238000004140 cleaning Methods 0.000 title claims abstract description 124
- 238000000926 separation method Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000002280 amphoteric surfactant Substances 0.000 claims abstract description 40
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 239000012466 permeate Substances 0.000 claims abstract description 8
- 239000012510 hollow fiber Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 9
- 229960003237 betaine Drugs 0.000 claims description 5
- 239000004973 liquid crystal related substance Substances 0.000 claims description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims 1
- 239000000243 solution Substances 0.000 description 38
- 239000000126 substance Substances 0.000 description 22
- 230000000694 effects Effects 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000004094 surface-active agent Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 238000011109 contamination Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000035699 permeability Effects 0.000 description 8
- 239000002736 nonionic surfactant Substances 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000000693 micelle Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 239000000356 contaminant Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- -1 alkyl aminopropionate Chemical compound 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000004382 potting Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GMXGPYJHZDLPKI-UHFFFAOYSA-N N-(2-hydroxysulfonothioylethyl)pentadecan-1-amine Chemical compound CCCCCCCCCCCCCCCNCCS(=O)(=S)O GMXGPYJHZDLPKI-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003657 drainage water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 238000001471 micro-filtration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- FLHWLBNLXDWNJC-UHFFFAOYSA-N 4,5-dihydroimidazole-1-sulfonic acid Chemical compound OS(=O)(=O)N1CCN=C1 FLHWLBNLXDWNJC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- UDIICMPTKUDXJR-UHFFFAOYSA-L [Na+].S(=O)(=O)([O-])[O-].OCCN1C=NCC1.[Na+] Chemical class [Na+].S(=O)(=O)([O-])[O-].OCCN1C=NCC1.[Na+] UDIICMPTKUDXJR-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000011086 high cleaning Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QEALYLRSRQDCRA-UHFFFAOYSA-N myristamide Chemical compound CCCCCCCCCCCCCC(N)=O QEALYLRSRQDCRA-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- HLERILKGMXJNBU-UHFFFAOYSA-N norvaline betaine Chemical compound CCCC(C([O-])=O)[N+](C)(C)C HLERILKGMXJNBU-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/02—Hollow fibre modules
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention provides a method for cleaning a membrane separation apparatus including a membrane module having an interior partitioned into a raw water chamber and a permeate water chamber by a separation membrane, the method including a cleaning step of bringing a cleaning solution containing an amphoteric surfactant into contact with a raw water chamber side membrane surface of the separation membrane. The cleaning solution contains 0.01 wt% to 5 wt% of an amphoteric surfactant but no phosphorus and no oxidizing agent. Preferably, the raw water chamber of the membrane module is brought into contact with air before the cleaning step to dry the surface of the raw water chamber-side membrane.
Description
Technical Field
The invention relates to a cleaning method of a membrane separation device for water treatment. The present invention relates to a method for efficiently cleaning a membrane separation apparatus (a turbidity removal membrane apparatus) which separates and removes suspended substances, organic/inorganic colloids, and organic/inorganic dissolved substances in water using, for example, an UF (ultrafiltration) membrane or an MF (microfiltration) membrane.
Background
In a membrane separation apparatus (a turbidity removal membrane apparatus) using a UF membrane (ultrafiltration membrane) or an MF membrane (microfiltration membrane) for the purpose of removing turbidity, since dirt adheres to a separation membrane during filtration, a cleaning fluid (water and/or gas) is usually supplied intermittently at intervals of 30 seconds to 60 minutes to a raw water chamber or a permeate water chamber of a membrane module for physical cleaning of the membrane.
If contamination that cannot be removed is deposited on the membrane surface or inside the membrane during physical cleaning, the filtration capacity of the membrane gradually decreases. When the raw water contains turbid materials or when the apparatus is operated at a high water recovery rate, solid components such as turbid materials accumulate in the form of a cake (cake) between membranes or between a membrane and a housing (housing), and the effective filtration area of the membrane decreases. Therefore, the turbidity removing membrane apparatus needs to be cleaned with chemicals periodically or aperiodically or cleaned with intensive physical cleaning for the purpose of removing turbidity.
In general, an acid agent (sulfuric acid, hydrochloric acid, nitric acid, citric acid, oxalic acid), an alkali agent (sodium hydroxide), an oxidizing agent (sodium hypochlorite), or the like is used for chemical cleaning (non-patent document 1). Which agent is used depends on the raw material of the membrane or the fouling (fouling) component of the membrane. In the intensified physical cleaning, a cleaning fluid (water and/or gas) is vigorously blown to the raw water chamber side of the membrane module for the purpose of vibrating the membrane, and a method of subjecting the membrane module to ultrasonic waves is also known (non-patent document 2).
The chemical cleaning and the enhanced physical cleaning are rarely used alone, and are usually performed over a combination of half a day to several days. In particular, when turbid contaminants such as turbid substances are deposited on the membrane surface or inside the module, the cleaning effect is insufficient if only chemical cleaning is performed, and therefore, a combination with intensive physical cleaning is required.
In a turbidity removing membrane device in which the membrane end is fixed to the module case, there are cases where: even if the intensive physical cleaning is performed, the membrane does not vibrate sufficiently, and a sufficient effect of removing the turbidity cannot be obtained. In particular, in a turbidity removing membrane apparatus using an internal pressure type hollow fiber membrane module, since the raw water chamber is located in the hollow fiber membrane module having a diameter of about 1mm, it is difficult to discharge the turbid matter in the raw water chamber to the outside of the membrane module, and a physical cleaning method in which the membrane is oscillated by blowing air into the raw water chamber cannot be used.
The internal pressure type hollow fiber membrane module has a structure that easily causes turbid contamination and is difficult to clean turbid contamination, and improvement of a cleaning method thereof is desired.
The surfactant is used as a solvent, a dispersant, or a pore former for a raw material resin in a process of producing a separation membrane of a membrane separation apparatus (patent document 1).
In the course of operation, a surfactant is rarely used for the purpose of cleaning the membrane separation apparatus, but in patent document 2, a surfactant is used for cleaning the ultrapure water production apparatus. Patent document 3 describes the use of an amphoteric surfactant for modification to impart antimicrobial properties to a separation membrane.
Neither patent document 2 nor patent document 3 is a technique for cleaning a turbidity removing membrane device.
Patent document 1: japanese patent laid-open No. 2005-146230
Patent document 2: japanese patent laid-open No. 2004-122020
Patent document 3: japanese patent laid-open No. 2009-112927
Patent document 4: japanese patent laid-open No. 2012-106160
Non-patent document 1: zetian's Provisions of Membrane filtration technology useful in the field (2006) p 120-121.
Non-patent document 2: zetian's Provisions of Membrane filtration technology useful in the field (2006) p 94-95.
Disclosure of Invention
The invention aims to provide a cleaning method which uses a cleaning solution without phosphorus and oxidant and is effective for turbid matter pollution even in a turbidity removal membrane device with an internal pressure type hollow fiber membrane component.
The present inventors have found that turbid contaminants on a separation membrane of a turbidity removing membrane apparatus can be efficiently cleaned and removed by a cleaning solution containing an amphoteric surfactant but not containing phosphorus and an oxidizing agent.
That is, the present invention is summarized as follows.
[1] A method for cleaning a membrane separation device having a membrane module whose interior is partitioned into a raw water chamber and a permeate water chamber by a separation membrane, the method comprising a cleaning step of bringing a cleaning solution containing an amphoteric surfactant into contact with the raw water chamber side membrane surface of the separation membrane.
[2] The method for cleaning a membrane separation device according to [1], wherein the cleaning solution contains 0.01 to 5 wt% of the amphoteric surfactant and does not contain phosphorus or an oxidizing agent.
[3] The method for cleaning a membrane separation device according to [1] or [2], which comprises a drying step of drying the membrane surface on the raw water chamber side by bringing the raw water chamber into contact with air, and wherein the cleaning step is performed after the drying step.
[4] The method for cleaning a membrane separation device according to any one of [1] to [3], wherein the cleaning step includes: either or both of a step of introducing the cleaning solution from the permeate water chamber side of the membrane module to the raw water chamber side and a step of circulating the cleaning solution on the raw water chamber side of the membrane module.
[5] The method for cleaning a membrane separation device according to any one of [1] to [4], wherein the membrane module is an internal pressure type hollow fiber membrane module.
[ Effect of the invention ]
According to the present invention, a cleaning solution containing an amphoteric surfactant is brought into contact with the raw water chamber-side membrane surface to effectively float and discharge turbid contaminants on the membrane surface to the outside of the system, and thereby a high cleaning effect can be obtained even for a turbidity removal membrane apparatus having an internal pressure type hollow fiber membrane module.
Further, the cleaning solution used in the present invention does not contain phosphorus and an oxidizing agent, and does not have the problems of biofouling caused by phosphorus and excessive rinsing operation for discharging the oxidizing agent.
In the present invention, a higher turbidity removing effect can be obtained by performing a pretreatment of exposing the raw water chamber to air to dry the raw water chamber side membrane surface before performing the cleaning step with the cleaning solution.
Drawings
Fig. 1 is a graph showing the results of example 1, example 2, and comparative examples 1 to 4.
Fig. 2a and 2b are diagrams showing the structure of the internal pressure type small module (minimodule) testing apparatus manufactured in example 3.
Detailed Description
Hereinafter, an embodiment of the method for cleaning a membrane separation device according to the present invention will be described in detail.
< mechanism >
The cleaning action of the cleaning solution containing an amphoteric surfactant in the cleaning method of a membrane separation apparatus according to the present invention and the action and effect of the drying operation before cleaning can be considered as follows.
The surfactant has an effect of infiltrating into the turbid substance contamination by its permeation action, and then floating and removing the turbid substance contamination from the membrane surface by emulsification/dispersion action. The amphoteric surfactant has both anionic and cationic groups in the hydrophilic part of the molecule, and therefore, the adjoining amphoteric surfactant molecules are firmly and tightly bonded to each other. Therefore, compared to a micelle (micelle) formed of a cationic, anionic or nonionic surfactant, a micelle formed of an amphoteric surfactant can easily discharge turbid materials to the outside of the system without disintegrating the micelle in a state in which the turbid materials are enclosed in the micelle.
By drying the membrane surface on the raw water side, the cake-like turbid matter adhering to the membrane surface can be dried/shrunk, and a gap can be formed between the turbid matter contamination and the membrane surface, or cracks can be formed between the turbid matter contamination. This increases the contact area between the turbid substance and the cleaning solution, and thus provides an effect of facilitating the suspension of the turbid substance from the membrane surface.
< cleaning solution >
In the present invention, the amphoteric surfactant used as an active ingredient of the cleaning solution includes the following surfactants and the like.
Amino acid type amphoteric surfactant: sodium higher alkyl aminopropionate having 12 to 18 carbon atoms in the alkyl group, and the like
Betaine amphoteric surfactant: alkyl dimethyl betaine having 12 to 18 carbon atoms in the alkyl group, alkyl dihydroxyethyl betaine having 12 to 18 carbon atoms in the alkyl group, and the like
Sulfate salt type amphoteric surfactant: sodium sulfate salts of higher alkylamines having 8 to 18 carbon atoms in the alkyl group, sodium hydroxyethyl imidazoline sulfate salts, and the like
Sulfonate type amphoteric surfactant: pentadecylthiotaurine (pentadecylthiotaurine), imidazolinesulfonic acid, and the like
The amphoteric surfactant may be used alone or in combination of two or more. Among them, betaine-type amphoteric surfactants are preferable.
The content of the amphoteric surfactant in the cleaning solution is 0.01 wt% or more, and particularly preferably 0.5 wt% or more. If the content of the amphoteric surfactant is too small, a sufficient cleaning effect may not be obtained. The upper limit of the content of the amphoteric surfactant in the washing solution is determined by the micelle concentration of the amphoteric surfactant, and is not particularly limited, but if too much, there is a problem that foaming occurs and the load on the drain equipment increases, or there is a possibility that washing water and time after washing increase, and therefore, it is preferably 5% by weight or less.
It is important that the cleaning solution used in the present invention is substantially free of other components, particularly phosphorus and oxidizing agents, as an aqueous solution of the amphoteric surfactant.
The cleaning solution used in the present invention preferably has a strong alkaline pH of 11 or more, particularly about 12 to 13, in terms of the effect of removing and removing turbid materials. In order to adjust the pH, the cleaning solution may contain an alkaline agent such as sodium hydroxide or potassium hydroxide.
The cleaning solution used in the present invention is preferably a cleaning solution containing an amphoteric surfactant at a concentration of 1 to 5% by weight under a strong alkaline condition of pH13 or more.
< cleaning Process >
In the present invention, a cleaning solution containing an amphoteric surfactant is brought into contact with the surface of a raw water chamber-side membrane of a membrane module, the interior of which is partitioned into a raw water chamber and a permeate water chamber by a separation membrane, to thereby clean the separation membrane. Specifically, the cleaning step is preferably performed by the following step (1) and/or step (2).
(1) And introducing a cleaning solution from the side of the permeation water chamber of the membrane module to the side of the raw water chamber.
(2) And circulating a cleaning solution on the raw water chamber side of the membrane module.
When the step (1) and the step (2) are performed, either step may be performed first, but the step (1) is preferably performed first. By performing the step (1) and then the step (2), the raw water chamber side membrane surface can be hydrophilized after removing the contamination of the membrane surface with turbid substances, and the hydrophilization treatment can be performed in a short time because the contact efficiency between the cleaning liquid and the raw water side membrane surface is improved. The steps (1) and (2) may be alternately repeated.
The cleaning conditions such as the cleaning time and the flow rate of the cleaning solution may be appropriately set so that a desired cleaning effect can be obtained, depending on the concentration or pH of the amphoteric surfactant in the cleaning solution to be used and the degree of contamination of the separation membrane to be cleaned.
After the washing, the washing is preferably performed according to a conventional method.
< drying Process >
In the present invention, it is preferable that a drying step of drying the membrane surface on the raw water chamber side by bringing the raw water chamber of the membrane module into contact with air is performed before the cleaning step. By performing the drying step, a higher turbid substance removing effect can be obtained.
The drying step is not particularly limited, and may be performed by blowing compressed air into the raw water chamber side of the membrane module, or by leaving the membrane module in contact with the outside air.
< Membrane Module >
The membrane separation apparatus to be cleaned according to the cleaning method of the membrane separation apparatus of the present invention is not particularly limited, and the cleaning method of the present invention is excellent in removing turbid materials in particular, and therefore is effective for cleaning the UF membrane or the MF membrane of the turbidity removing membrane apparatus used for separating and removing suspended materials, organic/inorganic colloids, organic/inorganic dissolved materials, and the like in water. The invention is especially suitable for removing turbid substances in the internal pressure type hollow fiber membrane module which is difficult to discharge turbid substances in a raw water chamber to the outside of the module and is difficult to apply a physical cleaning method.
[ examples ]
The present invention will be described in more detail with reference to examples.
The surfactants used in the following examples and comparative examples are as follows.
< amphoteric surfactant >
Amphoteric surfactant a: "Lebang (LEBON) CIB" (Alkylcarboxymethylhydroxyethylimidazolium betaine represented by the following structural formula) manufactured by Sanyo chemical industries, Ltd
[ chemical formula 1]
Amphoteric surfactant B: "Lebang (LEBON) MY-30" (myristic acid amide propyl betaine represented by the following structural formula) manufactured by Sanyo chemical industry Co., Ltd
[ chemical formula 2]
< nonionic surfactant >
Nonionic surfactant a: nalodi (Naroasty) ID-40 (polyoxyethylene alkyl ether) manufactured by Sanyo chemical industries Co., Ltd
Nonionic surfactant B: nalodi (Naroasty) ID-60 (polyoxyethylene alkyl ether) manufactured by Sanyo chemical industries Co., Ltd
< negative type surfactant >
Negative surfactant a: sanded EN manufactured by Sanyo chemical industries Ltd
Example 1, example 2, and comparative examples 1 to 4
The following cleaning test examined the cleaning effect on turbid materials derived from the liquid crystal plant drainage.
(1) And introducing the drainage water of the liquid crystal factory into an MF film with the aperture of 0.45 mu m to prepare the MF pollution film.
(2) 10mL of pure water was fed to the MF-contaminated membrane, and the time T0 required for the water to be fed was determined.
(3) The MF-contaminated membrane was immersed in the cleaning solution for 3 minutes, and then 10mL of pure water was introduced, to obtain a time T1 required for water passage.
As the cleaning solutions, those shown in Table 1 were used, respectively. The blank of comparative example 1 was water adjusted to pH12 with NaOH, and the other cleaning solutions were prepared by dissolving each surfactant at a concentration of 1 wt% and adjusting to pH12 with NaOH.
(4) The above (1) to (3) were carried out on 3 test specimens of the MF-contaminated membrane having a deviation in T0, while changing the amount of water discharged into the MF membrane.
(5) The horizontal axis represents T0, and the vertical axis represents T1, and the cleaning effect was evaluated from the inclination T1/T0 derived from the test results at 3 points.
The larger T1/T0, the lower the cleaning effect, and the smaller T1/T0, the higher the cleaning effect.
The results are shown in table 1 and fig. 1.
[ Table 1]
| Cleaning solution | T1/T0 value | |
| Example 1 | 1% amphoteric surfactant A (pH12) | 0.20 |
| Example 2 | 1% amphoteric surfactant B (pH12) | 0.11 |
| Comparative example 1 | Blank group (pH12) | 0.78 |
| Comparative example 2 | 1% nonionic surfactant A (pH12) | 0.44 |
| Comparative example 3 | 1% nonionic surfactant B (pH12) | 0.35 |
| Comparative example 4 | 1% female surfactant A (pH12) | 0.38 |
As can be seen from table 1 and fig. 1, the cleaning effect is amphoteric surfactant > negative surfactant ≈ nonionic surfactant > blank group, and the amphoteric surfactant shows the most excellent cleaning effect.
[ example 3]
The hollow fiber membrane was taken out from the contaminated internal pressure type hollow fiber membrane module (hollow fiber UF membrane, pore diameter 0.03 μm, membrane inner diameter 0.9mm, polyethersulfone as a membrane raw material) in the liquid crystal plant drain recovery apparatus, and a cleaning test was carried out in the following order.
As the cleaning solution, a solution prepared by dissolving the amphoteric surfactant a in water at a concentration of 1 wt% and adjusting to pH13 with NaOH was used.
(1) An internal pressure type small module test device (membrane length 7.5cm, area 10.6 cm) shown in FIGS. 2a and 2b was fabricated using contaminated membranes (5 membranes)2)。
In fig. 2a, 1 is a contaminated hollow fiber membrane, 2 is a Potting agent (Potting agent), 3 is a permeated water outlet, 4 is a module case, and 5 hollow fiber membranes 1 are packed therein.
Raw water is introduced into the hollow fiber membrane 1 from both ends thereof, and permeate water having permeated through the membrane is taken out from the take-out port 3.
As shown in fig. 2b, a pipe is connected to the internal pressure type small module 10 to produce an internal pressure type small module testing apparatus. In this test device, the valve V is opened1Valve V4And closing the valve V2Valve V3Air can be introduced into the hollow fiber membrane 1 through the pipe 11, the pipe 12, and the pipe 13. The pump P is operated and the valve V is opened3Closing valve V1Valve V2Valve V4This enables the cleaning solution in the cleaning solution tank 5 to circulate through the pipe 14, the pipe 12, and the pipe 13. The reference numeral 6 denotes a through water tank.
(2) Compressed air of 0.15MPa was blown to the raw water chamber side for 1 hour to dry the membrane.
(3) Then, the cleaning solution was circulated on the raw water chamber side for 6 hours, and then the cleaning solution in the cleaning solution tank 5 was changed to pure water, the pump P was operated, and the valve V was opened4Closing valve V1Valve V2Valve V3Thereby, the inside of the hollow fiber membrane 1 is sufficiently washed with pure water, and the cleaning liquid is removed.
(4) The pump P was operated and the valve V was opened against the water permeability of the new membrane before the test, the contaminated membrane before the cleaning and the membrane after the cleaning2Closing valve V1Valve V3Valve V4Thus, the flow rate (Flux) (permeation amount) 2m is obtained3/m2The pure water/d is fed into the hollow fiber membrane 1 so as to be filtered in total, and the pressure at that time is measured by a pressure gauge PI, and the water permeability (permeation amount in terms of operating pressure 1 bar, unit l mh) of each of the new membrane, the contaminated membrane before cleaning, and the membrane after cleaning is calculated. Further, the water permeability recovery rate was calculated by the following equation.
Water permeability recovery (%)
Water permeability after washing [ lmh ]/water permeability of new membrane [ lmh ] × 100
The results are shown in Table 2.
[ example 4]
A cleaning test was performed in the same manner as in example 3 except that the step (2) was omitted, and the results are shown in table 2.
[ Table 2]
As is clear from table 2, the water permeability recovery rate of example 4 in which the washing was performed without drying was about 30%, whereas the water permeability recovery rate of example 3 in which the drying was performed before the washing was 99%, and the washing effect was remarkably improved by the drying.
This is considered to be because the drying causes drying/shrinkage of turbid contaminants fixed or adhering to the membrane surface, and the contaminants are easily peeled off from the membrane, thereby increasing the cleaning effect of the amphoteric surfactant.
While the present invention has been described in detail with reference to the specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the purpose and scope of the invention.
The present disclosure is based on japanese patent application 2018-038748 filed on 3/5 of 2018, and the entire contents of which are incorporated herein by reference.
Description of reference numerals
1: a hollow fiber membrane;
2: a potting agent;
3: a permeated water outlet;
4: a component housing;
5: a cleaning solution tank;
6: passing through a water tank;
10: internal pressure type small-sized component.
Claims (4)
1. A method for cleaning a membrane separation device having a membrane module whose inside is partitioned into a raw water chamber and a permeate water chamber by a separation membrane, the method comprising: a cleaning step in which an alkaline cleaning solution containing an amphoteric surfactant and having a pH of 11 to 13 is brought into contact with the membrane surface of the separation membrane on the raw water chamber side; and a drying step of drying the surface of the raw water chamber side membrane by bringing the raw water chamber into contact with air, and the cleaning step is performed after the drying step.
2. The method for cleaning a membrane separation device according to claim 1, wherein the cleaning solution contains 0.01 to 5 wt% of the amphoteric surfactant, and the amphoteric surfactant is alkylcarboxymethylhydroxyethylimidazolium betaine and/or myristoylamidopropylbetaine, but the cleaning solution contains no phosphorus and no oxidizing agent.
3. The method for cleaning a membrane separation device according to claim 1 or 2, wherein the cleaning step includes: either or both of a step of introducing the cleaning solution from the permeate water chamber side of the membrane module to the raw water chamber side and a step of circulating the cleaning solution on the raw water chamber side of the membrane module.
4. The method for cleaning a membrane separation device according to any one of claims 1 to 3, wherein the membrane module is an internal pressure type hollow fiber membrane module into which a fouling membrane of liquid crystal plant drainage is introduced.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018-038748 | 2018-03-05 | ||
| JP2018038748A JP6642606B2 (en) | 2018-03-05 | 2018-03-05 | Cleaning method for membrane separation equipment |
| PCT/JP2019/006320 WO2019171956A1 (en) | 2018-03-05 | 2019-02-20 | Method for cleaning membrane separation apparatus |
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| Publication Number | Publication Date |
|---|---|
| CN111565825A CN111565825A (en) | 2020-08-21 |
| CN111565825B true CN111565825B (en) | 2021-09-10 |
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| CN201980007462.7A Active CN111565825B (en) | 2018-03-05 | 2019-02-20 | Method for cleaning membrane separation device |
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| Country | Link |
|---|---|
| JP (1) | JP6642606B2 (en) |
| CN (1) | CN111565825B (en) |
| TW (1) | TWI774933B (en) |
| WO (1) | WO2019171956A1 (en) |
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| WO2014208599A1 (en) * | 2013-06-28 | 2014-12-31 | 三菱レイヨン株式会社 | Method for cleaning filtration membrane |
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- 2019-02-20 CN CN201980007462.7A patent/CN111565825B/en active Active
- 2019-02-20 WO PCT/JP2019/006320 patent/WO2019171956A1/en active Application Filing
- 2019-03-04 TW TW108107101A patent/TWI774933B/en active
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| JPH08126824A (en) * | 1994-10-28 | 1996-05-21 | Ebara Corp | Washing of filter membrane |
| JP2001300530A (en) * | 2001-04-02 | 2001-10-30 | Daicel Chem Ind Ltd | Method of purifying natural water with membrane |
| JP2007181773A (en) * | 2006-01-06 | 2007-07-19 | Daicen Membrane Systems Ltd | Filtration film performance recovering method |
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| TWI774933B (en) | 2022-08-21 |
| TW201938257A (en) | 2019-10-01 |
| CN111565825A (en) | 2020-08-21 |
| WO2019171956A1 (en) | 2019-09-12 |
| JP6642606B2 (en) | 2020-02-05 |
| JP2019150789A (en) | 2019-09-12 |
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