TWI769425B - Method for cleaning membrane - Google Patents

Method for cleaning membrane Download PDF

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Publication number
TWI769425B
TWI769425B TW108148578A TW108148578A TWI769425B TW I769425 B TWI769425 B TW I769425B TW 108148578 A TW108148578 A TW 108148578A TW 108148578 A TW108148578 A TW 108148578A TW I769425 B TWI769425 B TW I769425B
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cleaning
ionic liquid
temperature
thin film
membrane
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TW108148578A
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Chinese (zh)
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TW202126380A (en
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許皓翔
劉柏逸
張敏超
邵信
洪仁陽
梁德明
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財團法人工業技術研究院
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Priority to CN202010157639.6A priority patent/CN113117529B/en
Priority to JP2020178615A priority patent/JP7053759B2/en
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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
    • 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
    • B01D2321/168—Use of other chemical agents

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Abstract

A method for cleaning membrane is provided. The method includes, for example, providing a membrane, introducing a thermo-sensitive ionic liquid to contact the membrane and perform a cleaning procedure to collect a cleaning solution, and layering the cleaning solution to form an aqueous layer and an ionic liquid layer at a specific temperature.

Description

薄膜的清洗方法How to clean the film

本發明係有關於一種薄膜的清洗方法，特別是有關於一種藉由導入溫敏性離子液體(thermo-sensitive ionic liquid)所進行的薄膜清洗方法。The present invention relates to a method for cleaning a thin film, and more particularly, to a method for cleaning a thin film by introducing a thermo-sensitive ionic liquid.

薄膜分離技術常被應用於水處理程序，在長期操作下，薄膜表面會因水中汙染物的沉積而降低薄膜對水處理的效能，現有技術係藉由對薄膜表面進行親水化改質的方式來延長薄膜的操作時間，但仍無法完全克服薄膜結垢的問題，因此，薄膜清洗劑的導入是恢復薄膜初始效能的最終手段。Membrane separation technology is often used in water treatment procedures. Under long-term operation, the deposition of pollutants on the membrane surface will reduce the efficiency of the membrane for water treatment. The existing technology is to hydrophilize the membrane surface. Extending the operating time of the membrane still cannot completely overcome the problem of membrane fouling. Therefore, the introduction of membrane cleaning agents is the ultimate means to restore the initial performance of the membrane.

然而，目前常見的薄膜清洗劑為酸、鹼、界面活性劑、或螯合劑等一次性藥劑，在清洗程序結束後直接排放，造成環境的危害。另一方面，上述藥劑的使用常伴隨著極高或極低的pH值環境，縱使對薄膜上結垢物的移除有效，但在長期極端pH值環境下操作，反覆清洗極易造成薄膜損壞及易降低薄膜效能。However, currently common film cleaning agents are disposable agents such as acids, alkalis, surfactants, or chelating agents, which are directly discharged after the cleaning process, causing environmental hazards. On the other hand, the use of the above chemicals is often accompanied by extremely high or low pH environment. Even if the removal of scale on the membrane is effective, it is easy to damage the membrane if it is operated in an extreme pH environment for a long time. And it is easy to reduce the film performance.

因此，業界需要一種新穎的薄膜清洗方式，用以解決習知技術所遭遇到的問題。Therefore, the industry needs a novel thin-film cleaning method to solve the problems encountered in the prior art.

為清除薄膜結垢物，本揭露提供一種新穎的薄膜清洗方法，藉由導入溫敏性離子液體並搭配溫度調控，以達到清潔薄膜並能有效回收清洗劑的目的。In order to remove the foulants from the film, the present disclosure provides a novel method for cleaning the film. The temperature-sensitive ionic liquid is introduced and the temperature is controlled to achieve the purpose of cleaning the film and effectively recovering the cleaning agent.

根據本揭露的一實施例，提供一種薄膜的清洗方法，包括：提供一薄膜；導入一溫敏性離子液體，使該溫敏性離子液體與該薄膜接觸，進行一清洗程序，並收集一清洗液；以及於一特定溫度下，使該清洗液分層形成一水層與一離子液體層。According to an embodiment of the present disclosure, a method for cleaning a thin film is provided, including: providing a thin film; introducing a temperature-sensitive ionic liquid, making the temperature-sensitive ionic liquid contact the thin film, performing a cleaning procedure, and collecting a cleaning liquid; and at a specific temperature, the cleaning liquid is layered to form a water layer and an ionic liquid layer.

在一實施例中，該薄膜包含結垢物。在一實施例中，該結垢物包括有機物、無機物、或其組合。在一實施例中，該薄膜包括超過濾(ultrafiltration，UF)薄膜、奈米過濾(nanofiltration，NF)薄膜、或逆滲透(reverse osmosis，RO)薄膜。In one embodiment, the membrane contains foulants. In one embodiment, the foulant includes organic matter, inorganic matter, or a combination thereof. In one embodiment, the membrane comprises an ultrafiltration (UF) membrane, a nanofiltration (NF) membrane, or a reverse osmosis (RO) membrane.

在一實施例中，該溫敏性離子液體的濃度介於1wt%至30wt%之間，例如5wt%至15wt%、5wt%至20wt%。若溫敏性離子液體的濃度過低，雖仍具清洗能力，但需高能耗或花費更多程序回收離子液體(即濃度太低不易回收離子液體)，若溫敏性離子液體的濃度過高，則在清洗程序中因掃流速度不足，而無法突顯其清洗效果。在一實施例中，該溫敏性離子液體的陽離子包括磷鹽(phosphonium)或銨鹽(ammonium)。在一實施例中，該溫敏性離子液體的陽離子包括

Figure 02_image001
、
Figure 02_image002
或
Figure 02_image004
。In one embodiment, the concentration of the temperature-sensitive ionic liquid is between 1 wt % and 30 wt %, for example, 5 wt % to 15 wt %, 5 wt % to 20 wt %. If the concentration of the temperature-sensitive ionic liquid is too low, although it still has the cleaning ability, it requires high energy consumption or more procedures to recover the ionic liquid (that is, if the concentration is too low, it is difficult to recover the ionic liquid). If the concentration of the temperature-sensitive ionic liquid is too high , the cleaning effect cannot be highlighted due to insufficient sweep flow speed in the cleaning process. In one embodiment, the cation of the temperature-sensitive ionic liquid includes phosphonium or ammonium. In one embodiment, the cations of the temperature-sensitive ionic liquid include
Figure 02_image001
,
Figure 02_image002
or
Figure 02_image004
.

在一實施例中，該溫敏性離子液體的陰離子包括羧酸鹽(carboxylate)或磺酸鹽(sulfonate)。在一實施例中，該溫敏性離子液體的陰離子包括

Figure 02_image006
、
Figure 02_image007
、
Figure 02_image008
、
Figure 02_image009
、
Figure 02_image011
或
Figure 02_image013
。In one embodiment, the anion of the temperature-sensitive ionic liquid includes carboxylate or sulfonate. In one embodiment, the anions of the temperature-sensitive ionic liquid include
Figure 02_image006
,
Figure 02_image007
,
Figure 02_image008
,
Figure 02_image009
,
Figure 02_image011
or
Figure 02_image013
.

在一實施例中，該溫敏性離子液體包括

Figure 02_image015
、
Figure 02_image016
、
Figure 02_image017
、
Figure 02_image018
、
Figure 02_image020
、
Figure 02_image022
或
Figure 02_image024
。In one embodiment, the temperature-sensitive ionic liquid includes
Figure 02_image015
,
Figure 02_image016
,
Figure 02_image017
,
Figure 02_image018
,
Figure 02_image020
,
Figure 02_image022
or
Figure 02_image024
.

在一實施例中，該清洗程序的溫度介於20°C至30°C之間，若清洗程序的溫度過低，會降低清洗劑(離子液體)擴散至結垢物之速率而影響其清洗效果，若清洗程序的溫度過高，則易造成薄膜損壞。在一實施例中，該清洗程序包括浸泡步驟與沖洗步驟。在一實施例中，該浸泡步驟的時間介於1分鐘至30分鐘之間，若浸泡步驟的時間太少，清洗劑(離子液體)不具足夠時間溶解結垢物而降低清洗效果，若浸泡步驟的時間過長，則可能導致清洗劑(離子液體)過度滲透至膜孔內，造成不可逆之膜孔阻塞。在一實施例中，該沖洗步驟的時間介於1分鐘至30分鐘之間。在一實施例中，該清洗液包括該溫敏性離子液體與該結垢物。在一實施例中，使該清洗液分層形成該水層與該離子液體層的特定溫度介於25°C至90°C之間。在一實施例中，該離子液體層包含該溫敏性離子液體，以及該水層包含該結垢物。In one embodiment, the temperature of the cleaning process is between 20°C and 30°C. If the temperature of the cleaning process is too low, the rate at which the cleaning agent (ionic liquid) diffuses to the foulant will be reduced and the cleaning will be affected. As a result, if the temperature of the cleaning process is too high, it is easy to cause damage to the film. In one embodiment, the cleaning procedure includes a soaking step and a rinsing step. In one embodiment, the time of the soaking step is between 1 minute and 30 minutes. If the time of the soaking step is too short, the cleaning agent (ionic liquid) does not have enough time to dissolve the scale and reduce the cleaning effect. If the time is too long, it may lead to excessive penetration of the cleaning agent (ionic liquid) into the membrane pores, resulting in irreversible membrane pore blockage. In one embodiment, the time of the rinsing step is between 1 minute and 30 minutes. In one embodiment, the cleaning solution includes the temperature-sensitive ionic liquid and the foulant. In one embodiment, the specific temperature for layering the cleaning solution to form the water layer and the ionic liquid layer is between 25°C and 90°C. In one embodiment, the ionic liquid layer includes the temperature-sensitive ionic liquid, and the water layer includes the scale.

在一實施例中，本揭露薄膜的清洗方法更包括於導入該溫敏性離子液體(thermo-sensitive ionic liquid)的步驟之前，進行第一水洗步驟。在一實施例中，該第一水洗步驟的溫度介於20°C至30°C之間。在一實施例中，該第一水洗步驟的時間介於1分鐘至30分鐘之間。在一實施例中，本揭露薄膜的清洗方法更包括於該清洗程序之後，進行第二水洗步驟。在一實施例中，該第二水洗步驟的溫度介於20°C至30°C之間。在一實施例中，該第二水洗步驟的時間介於1分鐘至30分鐘之間。In one embodiment, the method for cleaning the film of the present disclosure further includes a first water washing step before the step of introducing the thermo-sensitive ionic liquid. In one embodiment, the temperature of the first water washing step is between 20°C and 30°C. In one embodiment, the time of the first water washing step is between 1 minute and 30 minutes. In one embodiment, the method for cleaning the film of the present disclosure further includes performing a second water washing step after the cleaning process. In one embodiment, the temperature of the second water washing step is between 20°C and 30°C. In one embodiment, the time of the second water washing step is between 1 minute and 30 minutes.

本揭露將溫敏性離子液體(thermo-sensitive ionic liquid)作為薄膜清洗劑，其優勢在於可藉由調整溫敏性離子液體的結構(組合)或陰、陽離子的修飾，改變溫敏性離子液體的親、疏水性。此外，離子液體可藉由對陰離子的選擇，調控其酸鹼度，使離子液體表現出不同酸鹼性，而不需額外再添加酸或鹼。再者，由於離子液體本身具有獨特的形狀、結構、類溶劑及界面活性劑等特性，使其對結垢物例如蛋白質或金屬離子具有極佳的萃取能力，亦即具備優異的薄膜清洗能力，且因具有溫敏相分離特性，在特定溫度下，清洗液會自發性地分成水層及離子液體層，而使離子液體回收容易且可重複使用。The present disclosure uses a thermo-sensitive ionic liquid as a thin-film cleaning agent, which has the advantage that the thermo-sensitive ionic liquid can be changed by adjusting the structure (combination) of the thermo-sensitive ionic liquid or modification of anions and cations. hydrophilicity and hydrophobicity. In addition, the pH of the ionic liquid can be adjusted by the selection of the anion, so that the ionic liquid exhibits different acidity and alkalinity without adding additional acid or base. Furthermore, due to its unique shape, structure, solvent-like and surfactant-like properties, ionic liquids have excellent extraction ability for scale substances such as proteins or metal ions, that is, excellent film cleaning ability. And because of its temperature-sensitive phase separation characteristics, at a specific temperature, the cleaning solution will spontaneously be divided into a water layer and an ionic liquid layer, so that the ionic liquid can be easily recovered and reused.

根據本揭露的一實施例，提供一種薄膜的清洗方法，包括：提供一薄膜；導入一溫敏性離子液體，使溫敏性離子液體與上述薄膜接觸，進行一清洗程序，並收集清洗液；以及於特定溫度下，上述清洗液可分層形成一水層與一離子液體層。According to an embodiment of the present disclosure, a method for cleaning a thin film is provided, including: providing a thin film; introducing a temperature-sensitive ionic liquid, making the temperature-sensitive ionic liquid contact the thin film, performing a cleaning procedure, and collecting the cleaning liquid; And at a specific temperature, the cleaning solution can be layered to form a water layer and an ionic liquid layer.

在一實施例中，上述薄膜包含結垢物，例如，有機物、無機物、或其組合。在一實施例中，上述薄膜可包括超過濾(ultrafiltration，UF)薄膜、奈米過濾(nanofiltration，NF)薄膜、或逆滲透(reverse osmosis，RO)薄膜。In one embodiment, the membranes described above comprise foulants, eg, organic, inorganic, or a combination thereof. In one embodiment, the above-mentioned membrane may comprise an ultrafiltration (UF) membrane, a nanofiltration (NF) membrane, or a reverse osmosis (RO) membrane.

在一實施例中，上述溫敏性離子液體的濃度大約介於1wt%至30wt%之間。在一實施例中，上述溫敏性離子液體的陽離子可包括磷鹽(phosphonium)或銨鹽(ammonium)。在一實施例中，上述溫敏性離子液體的陽離子可包括

Figure 02_image001
、
Figure 02_image002
或
Figure 02_image004
。In one embodiment, the concentration of the temperature-sensitive ionic liquid is approximately between 1 wt % and 30 wt %. In one embodiment, the cation of the temperature-sensitive ionic liquid may include phosphonium or ammonium. In one embodiment, the cations of the temperature-sensitive ionic liquid may include
Figure 02_image001
,
Figure 02_image002
or
Figure 02_image004
.

在一實施例中，上述溫敏性離子液體的陰離子可包括羧酸鹽(carboxylate)或磺酸鹽(sulfonate)。在一實施例中，上述溫敏性離子液體的陰離子可包括

Figure 02_image006
、
Figure 02_image007
、
Figure 02_image008
、
Figure 02_image028
、
Figure 02_image030
或
Figure 02_image013
。In one embodiment, the anion of the temperature-sensitive ionic liquid may include carboxylate or sulfonate. In one embodiment, the anions of the temperature-sensitive ionic liquid may include
Figure 02_image006
,
Figure 02_image007
,
Figure 02_image008
,
Figure 02_image028
,
Figure 02_image030
or
Figure 02_image013
.

在一實施例中，上述溫敏性離子液體可包括

Figure 02_image015
、
Figure 02_image016
、
Figure 02_image017
、
Figure 02_image018
、
Figure 02_image020
、
Figure 02_image022
或
Figure 02_image024
。In one embodiment, the above-mentioned temperature-sensitive ionic liquid may include
Figure 02_image015
,
Figure 02_image016
,
Figure 02_image017
,
Figure 02_image018
,
Figure 02_image020
,
Figure 02_image022
or
Figure 02_image024
.

在一實施例中，上述清洗程序的溫度大約介於20°C至30°C之間。在一實施例中，上述清洗程序可包括浸泡步驟與沖洗步驟。在一實施例中，上述浸泡步驟的時間大約介於1分鐘至30分鐘之間。在一實施例中，上述沖洗步驟的時間大約介於1分鐘至30分鐘之間。在一實施例中，上述清洗液可包括上述溫敏性離子液體與上述結垢物。在一實施例中，使上述清洗液分層形成上述水層與上述離子液體層的上述特定溫度大約介於25°C至90°C之間。在一實施例中，上述離子液體層可包含上述溫敏性離子液體，以及上述水層可包含上述結垢物。In one embodiment, the temperature of the above cleaning process is approximately between 20°C and 30°C. In one embodiment, the above cleaning procedure may include a soaking step and a rinsing step. In one embodiment, the time of the soaking step is about 1 minute to 30 minutes. In one embodiment, the time of the above-mentioned rinsing step is about 1 minute to 30 minutes. In one embodiment, the cleaning solution may include the temperature-sensitive ionic liquid and the scaling substance. In one embodiment, the specific temperature for layering the cleaning solution to form the water layer and the ionic liquid layer is approximately between 25°C and 90°C. In one embodiment, the ionic liquid layer may include the temperature-sensitive ionic liquid, and the water layer may include the scaling substance.

本揭露利用溫敏性離子液體結構可調性、萃取能力以及溫敏相變特性，可讓薄膜在較溫和之環境下進行清洗，在清洗後利用相分離特性回收，改善傳統清洗劑損壞薄膜之風險及對環境危害。The present disclosure utilizes the structure tunability, extraction ability and temperature-sensitive phase transition properties of the temperature-sensitive ionic liquid, which allows the film to be cleaned in a milder environment, and can be recovered by the phase separation property after cleaning, thereby improving the damage of the film by traditional cleaning agents. risks and hazards to the environment.

實施例1Example 1

溫敏性temperature sensitivity 離子液體的相變特性Phase transition properties of ionic liquids

首先，將陰離子(

Figure 02_image006
(代稱Mal)、
Figure 02_image007
(代稱TFA)、以及
Figure 02_image008
(代稱TsO))分別與陽離子(
Figure 02_image001
(代稱P4444 ))以莫耳比1:1的方式混合，並於常溫下攪拌24小時。接著，將上述各混合物置入70°C的烘箱移除溶液中水份，即可獲得由上述陰、陽離子所組成的離子液體(代稱[P4444 ][Mal]、[P4444 ][TFA]、以及[P4444 ][TsO])。各取不同重量的離子液體與水混合，觀察不同濃度離子液體的相變溫度，如第1圖所示。由第1圖相變溫度曲線的結果顯示本揭露離子液體水溶液皆具備低溫臨界溶解溫度(lower critical solution temperature，LCST)的相變特性。First, the anion (
Figure 02_image006
(referred to as Mal),
Figure 02_image007
(codenamed TFA), and
Figure 02_image008
(referred to as TsO)) and cation (
Figure 02_image001
(designated as P 4444 )) in a molar ratio of 1:1, and stirred at room temperature for 24 hours. Next, put the above mixtures into an oven at 70°C to remove the water in the solution, and then the ionic liquids (referred to as [P 4444 ][Mal], [P 4444 ][TFA] composed of the above-mentioned anions and cations can be obtained. , and [P 4444 ][TsO]). Different weights of ionic liquids were mixed with water, and the phase transition temperatures of ionic liquids with different concentrations were observed, as shown in Figure 1. The results of the phase transition temperature curve in Fig. 1 show that the ionic liquid aqueous solutions of the present disclosure all have phase transition characteristics of lower critical solution temperature (LCST).

實施例2Example 2

溫敏性temperature sensitivity 離子液體的黏度特性Viscosity properties of ionic liquids

首先，將陰離子(

Figure 02_image006
(代稱Mal)、
Figure 02_image007
(代稱TFA)、以及
Figure 02_image008
(代稱TsO))分別與陽離子(
Figure 02_image001
(代稱P4444 ))以莫耳比1:1的方式混合，並於常溫下攪拌24小時。接著，將上述各混合物置入70°C的烘箱移除溶液中水份，即可獲得由上述陰、陽離子所組成的離子液體(代稱[P4444 ][Mal]、[P4444 ][TFA]、以及[P4444 ][TsO])。各取不同重量的離子液體與水混合，觀察不同濃度離子液體的黏度變化，如第2圖所示。由第2圖所測得的黏度結果顯示當離子液體的濃度高於50wt%時，其黏度已大於10cps，過高的黏度會導致幫浦需消耗更大功率來維持高掃流速度，亦或是流速大幅下降造成能耗成本增加，或無法有效帶離薄膜上的結垢物。因此，對於奈米過濾(nanofiltration，NF)薄膜來說，清洗時離子液體的濃度大約小於30wt%。First, the anion (
Figure 02_image006
(referred to as Mal),
Figure 02_image007
(codenamed TFA), and
Figure 02_image008
(referred to as TsO)) and cation (
Figure 02_image001
(designated as P 4444 )) in a molar ratio of 1:1, and stirred at room temperature for 24 hours. Next, put the above mixtures into an oven at 70°C to remove the water in the solution, and then the ionic liquids (referred to as [P 4444 ][Mal], [P 4444 ][TFA] composed of the above-mentioned anions and cations can be obtained. , and [P 4444 ][TsO]). Different weights of ionic liquids were mixed with water, and the viscosity changes of ionic liquids with different concentrations were observed, as shown in Figure 2. The viscosity results measured in Figure 2 show that when the concentration of the ionic liquid is higher than 50wt%, its viscosity is greater than 10cps. Too high viscosity will cause the pump to consume more power to maintain a high sweep flow rate, or It is because the flow rate is greatly reduced that the energy consumption cost is increased, or the scale cannot be effectively removed from the membrane. Therefore, for nanofiltration (NF) membranes, the concentration of ionic liquid during cleaning is about less than 30 wt%.

實施例3Example 3

評估不同薄膜清洗劑對薄膜的清洗效果Evaluate the cleaning effect of different film cleaners on films (( 使用平板膜Use flat film ))

首先，將已充分濕潤的平板膜(50cm2 )置入系統中，以2,000ppm的MgSO4 為進料進行新膜的初始效能測試，量測初始通量J0 。之後，將進料變更為2,000ppm的MgSO4 以及1,000ppm的牛血清白蛋白(BSA)結垢物進行結垢實驗，隨時間量測結垢後通量JF ，待通量下降率(FDR)達20%時開始進行清洗程序。之後，以RO水對結垢的平板膜進行沖洗10分鐘，沖洗後，以2,000ppm的MgSO4 進行結垢後效能測試，量測RO水沖洗後通量JC1 ，並確定膜上結垢無法藉由水移除。之後，將配製完成的薄膜清洗劑(HCl (pH=1)、NaOH (pH=12)、0.2wt% EDTA-Na4 /NaOH (pH=12)、0.4wt% EDTA-Na4 /NaOH (pH=12)、0.6wt% EDTA-Na4 /NaOH (pH=12)、0.025wt% SDS-Na/NaOH (pH=12)、0.03wt% SDS-Na/NaOH (pH=12)、20wt% [P4444 ][Mal]、20wt% [P4444 ][TFA]、以及20wt% [P4444 ][TsO])分別導入系統中，以浸泡攪拌30分鐘(清洗溫度: 25°C)的清洗程序進行膜垢去除。洗後將清洗劑排出，再通入RO水移除殘留於系統中的清洗劑溶液。清洗結束後，以2,000ppm的MgSO4 進行薄膜效能測試，量測清洗劑清洗後通量JC2 。計算在不同清洗劑作用下平板膜的通量回復率，結果如第3圖所示。First, a fully wetted flat membrane (50 cm 2 ) was placed in the system, and the initial performance test of the new membrane was carried out with 2,000 ppm of MgSO 4 as the feed to measure the initial flux J 0 . After that, the feed was changed to 2,000 ppm of MgSO 4 and 1,000 ppm of bovine serum albumin (BSA) foulants to conduct fouling experiments. The flux J F after fouling was measured over time, and the flux reduction rate (FDR) was measured over time. ) reaches 20% to start the cleaning program. After that, the scaled flat membrane was rinsed with RO water for 10 minutes. After rinsing, the post-scaling efficiency test was carried out with 2,000ppm MgSO 4 to measure the flux J C1 after RO water rinsing, and it was determined that the fouling on the membrane could not be carried out. Remove with water. After that, the prepared membrane cleaning agent (HCl (pH=1), NaOH (pH=12), 0.2wt% EDTA-Na 4 /NaOH (pH=12), 0.4wt% EDTA-Na 4 /NaOH (pH=12) =12), 0.6wt% EDTA-Na 4 /NaOH (pH=12), 0.025wt% SDS-Na/NaOH (pH=12), 0.03wt% SDS-Na/NaOH (pH=12), 20wt% [ P 4444 ][Mal], 20wt% [P 4444 ][TFA], and 20wt% [P 4444 ][TsO]) were introduced into the system respectively, and the cleaning procedure was carried out by soaking and stirring for 30 minutes (cleaning temperature: 25°C). Membrane scale removal. After washing, the cleaning agent is discharged, and then RO water is introduced to remove the cleaning agent solution remaining in the system. After cleaning, the membrane efficiency test was performed with 2,000ppm MgSO 4 to measure the flux J C2 after cleaning by the cleaning agent. The flux recovery rate of the flat membrane under the action of different cleaning agents was calculated, and the results are shown in Figure 3.

J0 : 初始通量JF : 結垢後通量JC1 : RO水沖洗後通量JC2 : 清洗劑清洗後通量 FDR: Flux Decline Ratio (通量下降率) 通量下降率(%): (1-(JF /J0 ))

Figure 02_image037
100% 通量回復率(%):JC2 /J0
Figure 02_image039
100% J 0 : Initial flux J F : Flux after scaling J C1 : Flux after RO water flushing J C2 : Flux after cleaning with detergent FDR: Flux Decline Ratio (Flux Decline Ratio) Flux Decline Ratio (%) : (1-( J F / J 0 ))
Figure 02_image037
100% Flux Recovery Rate (%): J C2 / J 0
Figure 02_image039
100%

由第3圖的結果顯示對於BSA結垢的薄膜，傳統清洗劑常伴隨pH=1或12之酸鹼濃度，對膜材本身極易造成損壞。本揭露離子液體可藉由陰、陽離子之調控而可達到pH=5-8，降低膜材損壞之機率。從離子液體([P4444 ][Mal]、[P4444 ][TFA]、以及[P4444 ][TsO])實驗結果發現，離子液體的清洗效果皆大於66%，優於傳統清洗劑例如酸、鹼、螯合劑(EDTA)(當EDTA使用濃度越高伴隨的pH值越低)、界面活性劑(SDS)等。The results in Figure 3 show that for BSA fouled membranes, traditional cleaning agents are often accompanied by pH=1 or 12 acid-base concentration, which can easily cause damage to the membrane itself. The ionic liquid of the present disclosure can reach pH=5-8 through the regulation of anions and cations, thereby reducing the probability of membrane damage. From the experimental results of ionic liquids ([P 4444 ][Mal], [P 4444 ][TFA], and [P 4444 ][TsO]), it is found that the cleaning effect of ionic liquids is greater than 66%, which is better than that of traditional cleaning agents such as acid , alkali, chelating agent (EDTA) (the higher the concentration of EDTA is, the lower the pH value is), surfactant (SDS), etc.

實施例4Example 4

評估不同濃度的離子液體薄膜清洗劑對薄膜的清洗效果Evaluating the cleaning effect of different concentrations of ionic liquid membrane cleaners on membranes (( 使用平板膜Use flat film ))

首先，將已充分濕潤的平板膜(50cm2 )置入系統中，以2,000ppm的MgSO4 為進料進行新膜的初始效能測試，量測初始通量J0 。之後，將進料變更為2,000ppm的MgSO4 以及1,000ppm的牛血清白蛋白(BSA)結垢物進行結垢實驗，隨時間量測結垢後通量JF ，待通量下降率(FDR)達20%時開始進行清洗程序。之後，以RO水對結垢的平板膜進行沖洗10分鐘，沖洗後，以2,000ppm的MgSO4 進行結垢後效能測試，量測RO水沖洗後通量JC1 ，並確定膜上結垢無法藉由水移除。之後，將配製完成具有不同濃度的離子液體薄膜清洗劑(20wt% [P4444 ][Mal]、10wt% [P4444 ][Mal]、以及5wt% [P4444 ][Mal])分別導入系統中，以浸泡25分鐘、沖洗5分鐘(清洗溫度: 25°C)的清洗程序進行膜垢去除。洗後將離子液體清洗劑排出收集，再通入RO水移除殘留於系統中的離子液體溶液。清洗結束後，以2,000ppm的MgSO4 進行薄膜效能測試，量測離子液體清洗後通量JC2 。利用實施例3所揭示通量回復率的公式(JC2 /J0

Figure 02_image039
100%)計算在不同濃度離子液體清洗劑作用下平板膜的通量回復率，結果如第4圖所示。First, a fully wetted flat membrane (50 cm 2 ) was placed in the system, and the initial performance test of the new membrane was carried out with 2,000 ppm of MgSO 4 as the feed to measure the initial flux J 0 . After that, the feed was changed to 2,000 ppm of MgSO 4 and 1,000 ppm of bovine serum albumin (BSA) foulants to conduct fouling experiments. The flux J F after fouling was measured over time, and the flux reduction rate (FDR) was measured over time. ) reaches 20% to start the cleaning program. After that, the scaled flat membrane was rinsed with RO water for 10 minutes. After rinsing, the post-scaling efficiency test was carried out with 2,000ppm MgSO 4 to measure the flux J C1 after RO water rinsing, and it was determined that the fouling on the membrane could not be carried out. Remove with water. After that, the ionic liquid membrane cleaning agents with different concentrations (20wt% [P 4444 ][Mal], 10wt% [P 4444 ][Mal], and 5wt% [P 4444 ][Mal]) were respectively introduced into the system , remove the membrane scale with a cleaning procedure of soaking for 25 minutes and rinsing for 5 minutes (cleaning temperature: 25°C). After washing, the ionic liquid cleaning agent is discharged and collected, and then RO water is introduced to remove the ionic liquid solution remaining in the system. After the cleaning, the membrane efficiency test was performed with 2,000ppm MgSO 4 to measure the flux J C2 after cleaning with the ionic liquid. Using the formula for the flux recovery rate disclosed in Example 3 ( J C2 / J 0
Figure 02_image039
100%) to calculate the flux recovery rate of the flat membrane under the action of different concentrations of ionic liquid cleaning agents, and the results are shown in Figure 4.

由第4圖的結果顯示本揭露3種不同濃度的離子液體清洗劑對薄膜皆具備清洗效果，且通量回復率會隨著離子液體濃度的下降而上升，其中5 wt% [P4444 ][Mal]的清洗效果，薄膜的通量回復率可達90%。The results in Figure 4 show that the three different concentrations of ionic liquid cleaning agents of the present disclosure have cleaning effects on the thin film, and the flux recovery rate will increase with the decrease of the ionic liquid concentration, of which 5 wt% [P 4444 ][ Mal] cleaning effect, the flux recovery rate of the film can reach 90%.

實施例5Example 5

評估不同清洗程序對薄膜的清洗效果Evaluate the cleaning effect of different cleaning procedures on thin films (( 使用平板膜Use flat film ))

首先，將已充分濕潤的平板膜(50cm2 )置入系統中，以2,000ppm的MgSO4 為進料進行新膜的初始效能測試，量測初始通量J0 。之後，將進料變更為2,000ppm的MgSO4 以及1,000ppm的牛血清白蛋白(BSA)結垢物進行結垢實驗，隨時間量測結垢後通量JF ，待通量下降率(FDR)達20%時開始進行清洗程序。之後，以RO水對結垢的平板膜進行沖洗10分鐘，沖洗後，以2,000ppm的MgSO4 進行結垢後效能測試，量測RO水沖洗後通量JC1 ，並確定膜上結垢無法藉由水移除。之後，將配製完成具有特定濃度的離子液體薄膜清洗劑(5wt% [P4444 ][Mal])導入系統中，在清洗溫度25°C下，分別以(1) 沖洗1分鐘、(2) 浸泡1分鐘、沖洗1分鐘、(3) 浸泡5分鐘、沖洗5分鐘、以及(4) 浸泡25分鐘、沖洗5分鐘等清洗程序進行膜垢去除。洗後將離子液體清洗劑排出收集，再通入RO水移除殘留於系統中的離子液體溶液。清洗結束後，以2,000ppm的MgSO4 進行薄膜效能測試，量測離子液體清洗後通量JC2 。利用實施例3所揭示通量回復率的公式(JC2 /J0

Figure 02_image039
100%)計算在不同清洗程序下平板膜的通量回復率，結果如第5圖所示。First, a fully wetted flat membrane (50 cm 2 ) was placed in the system, and the initial performance test of the new membrane was carried out with 2,000 ppm of MgSO 4 as the feed to measure the initial flux J 0 . After that, the feed was changed to 2,000 ppm of MgSO 4 and 1,000 ppm of bovine serum albumin (BSA) foulants to conduct fouling experiments. The flux J F after fouling was measured over time, and the flux reduction rate (FDR) was measured over time. ) reaches 20% to start the cleaning program. After that, the scaled flat membrane was rinsed with RO water for 10 minutes. After rinsing, the post-scaling efficiency test was carried out with 2,000ppm MgSO 4 to measure the flux J C1 after RO water rinsing, and it was determined that the fouling on the membrane could not be carried out. Remove with water. After that, the ionic liquid membrane cleaning agent (5wt% [P 4444 ][Mal]) prepared with a specific concentration was introduced into the system. 1 minute, rinse 1 minute, (3) soak for 5 minutes, rinse for 5 minutes, and (4) soak for 25 minutes, rinse for 5 minutes and other cleaning procedures for membrane scale removal. After washing, the ionic liquid cleaning agent is discharged and collected, and then RO water is introduced to remove the ionic liquid solution remaining in the system. After the cleaning, the membrane efficiency test was performed with 2,000ppm MgSO 4 to measure the flux J C2 after cleaning with the ionic liquid. Using the formula for the flux recovery rate disclosed in Example 3 ( J C2 / J 0
Figure 02_image039
100%) to calculate the flux recovery rate of the flat membrane under different cleaning procedures, and the results are shown in Figure 5.

由第5圖的結果顯示當本揭露離子液體清洗劑進一步搭配適當的清洗條件(例如浸泡5分鐘、沖洗5分鐘)時，平板膜的通量回復率可達93%。The results in Figure 5 show that when the ionic liquid cleaning agent of the present disclosure is further matched with appropriate cleaning conditions (eg soaking for 5 minutes, rinsing for 5 minutes), the flux recovery rate of the flat membrane can reach 93%.

實施例6Example 6

評估不同薄膜清洗劑對薄膜的清洗效果Evaluate the cleaning effect of different film cleaners on films (( 使用膜管Use a membrane tube ))

首先，將已充分濕潤的膜管(0.4m2 )置入系統中，以2,000ppm的MgSO4 為進料進行新膜的初始效能測試，量測初始通量J0 。之後，將進料變更為2,000ppm的MgSO4 以及1,000ppm的牛血清白蛋白(BSA)結垢物進行結垢實驗，隨時間量測結垢後通量JF ，待通量下降率(FDR)達20%時開始進行清洗程序。之後，以RO水對結垢的膜管進行沖洗10分鐘，沖洗後，以2,000ppm的MgSO4 進行結垢後效能測試，量測RO水沖洗後通量JC1 ，並確定膜上結垢無法藉由水移除。之後，將配製完成的薄膜清洗劑(5wt% [P4444 ][Mal]、5wt% [P4444 ][TFA]、5wt% [P4444 ][TsO]、以及0.03wt% SDS-Na/NaOH (pH=12))分別導入系統中。本實施例中，不同種類的薄膜清洗劑搭配不同的清洗條件進行膜垢去除。洗後將清洗劑排出，再通入RO水移除殘留於系統中的清洗劑溶液。清洗結束後，以2,000ppm的MgSO4 進行薄膜效能測試，量測清洗劑清洗後通量JC2 。利用實施例3所揭示通量回復率的公式(JC2 /J0

Figure 02_image039
100%)計算在不同清洗劑作用下膜管的通量回復率，結果如第6圖所示。First, a fully wetted membrane tube (0.4 m 2 ) was put into the system, and 2,000 ppm of MgSO 4 was used as the feed for the initial performance test of the new membrane, and the initial flux J 0 was measured. After that, the feed was changed to 2,000 ppm of MgSO 4 and 1,000 ppm of bovine serum albumin (BSA) foulants to conduct fouling experiments. The flux J F after fouling was measured over time, and the flux reduction rate (FDR) was measured over time. ) reaches 20% to start the cleaning program. After that, the fouled membrane tube was rinsed with RO water for 10 minutes. After rinsing, the post-scaling efficiency test was performed with 2,000ppm MgSO 4 to measure the flux J C1 after RO water rinse, and it was determined that the fouling on the membrane could not be Remove with water. After that, the prepared film cleaning agent (5wt% [P 4444 ][Mal], 5wt% [P 4444 ][TFA], 5wt% [P 4444 ][TsO], and 0.03wt% SDS-Na/NaOH ( pH=12)) were introduced into the system respectively. In this embodiment, different types of membrane cleaning agents are used with different cleaning conditions to remove membrane scale. After washing, the cleaning agent is discharged, and then RO water is introduced to remove the cleaning agent solution remaining in the system. After cleaning, the membrane efficiency test was performed with 2,000ppm MgSO 4 to measure the flux J C2 after cleaning by the cleaning agent. Using the formula for the flux recovery rate disclosed in Example 3 ( J C2 / J 0
Figure 02_image039
100%) to calculate the flux recovery rate of the membrane tube under the action of different cleaning agents, and the results are shown in Figure 6.

第6圖的結果，其步驟流程於前述實施例4-6相同故不再此贅述。由第6圖的結果顯示在傳統清洗劑SDS-Na/NaOH作用下(清洗溫度: 30°C、浸泡25分鐘、沖洗5分鐘)，膜管的通量回復率約為93%，在5wt% [P4444 ][TsO]作用下(清洗溫度: 25°C、浸泡5分鐘、沖洗5分鐘)，膜管的通量回復率約為93%，在5wt% [P4444 ][TFA]作用下(清洗溫度: 25°C、浸泡10分鐘、沖洗5分鐘)，膜管的通量回復率可達95%，而在5wt% [P4444 ][Mal]作用下(清洗溫度: 25°C、浸泡5分鐘、沖洗5分鐘)，膜管的通量回復率可高達98%。The result shown in FIG. 6 is the same as that of the above-mentioned Embodiments 4-6, so it will not be repeated here. The results in Figure 6 show that under the action of the traditional cleaning agent SDS-Na/NaOH (cleaning temperature: 30°C, immersion for 25 minutes, rinse for 5 minutes), the flux recovery rate of the membrane tube is about 93%, and at 5wt% Under the action of [P 4444 ][TsO] (cleaning temperature: 25°C, soaking for 5 minutes, rinsing for 5 minutes), the flux recovery rate of the membrane tube was about 93%, and under the action of 5wt% [P 4444 ][TFA] (cleaning temperature: 25°C, soaking for 10 minutes, rinsing for 5 minutes), the flux recovery rate of the membrane tube can reach 95%, and under the action of 5wt% [P 4444 ][Mal] (cleaning temperature: 25°C, Soak for 5 minutes, rinse for 5 minutes), the flux recovery rate of the membrane tube can be as high as 98%.

實施例7Example 7

評估離子液體薄膜清洗劑的回收再利用效果Evaluating the recycling and reuse effects of ionic liquid membrane cleaners (( 使用膜管Use a membrane tube ))

首先，將已充分濕潤的膜管(0.4m2 )置入系統中，以2,000ppm的MgSO4 為進料進行新膜的初始效能測試，量測初始通量J0 。之後，將進料變更為2,000ppm的MgSO4 以及1,000ppm的牛血清白蛋白(BSA)結垢物進行結垢實驗，隨時間量測結垢後通量JF ，待通量下降率(FDR)達20%時開始進行清洗程序。之後，以RO水對結垢的膜管進行沖洗10分鐘，沖洗後，以2,000ppm的MgSO4 進行結垢後效能測試，量測RO水沖洗後通量JC1 ，並確定膜上結垢無法藉由水移除。之後，將配製完成具有特定濃度的離子液體薄膜清洗劑(5wt% [P4444 ][Mal])導入系統中，在清洗溫度25°C下，以浸泡5分鐘、沖洗5分鐘的清洗程序進行膜垢去除。洗後將離子液體清洗劑排出收集，再通入RO水移除殘留於系統中的離子液體溶液。清洗結束後，以2,000ppm的MgSO4 進行薄膜效能測試，量測離子液體清洗後通量JC2 。利用實施例3所揭示通量回復率的公式(JC2 /J0

Figure 02_image039
100%)計算膜管的通量回復率。之後，以相同膜管重複進行牛血清白蛋白(BSA)結垢實驗，並利用上述回收後的離子液體([P4444 ][Mal])再次進行膜管的清洗程序，清洗結束後，同樣計算膜管的通量回復率，結果如第7圖所示。First, a fully wetted membrane tube (0.4 m 2 ) was put into the system, and 2,000 ppm of MgSO 4 was used as the feed for the initial performance test of the new membrane, and the initial flux J 0 was measured. After that, the feed was changed to 2,000 ppm of MgSO 4 and 1,000 ppm of bovine serum albumin (BSA) foulants to conduct fouling experiments. The flux J F after fouling was measured over time, and the flux reduction rate (FDR) was measured over time. ) reaches 20% to start the cleaning program. After that, the fouled membrane tube was rinsed with RO water for 10 minutes. After rinsing, the post-scaling efficiency test was performed with 2,000ppm MgSO 4 to measure the flux J C1 after RO water rinse, and it was determined that the fouling on the membrane could not be Remove with water. After that, the ionic liquid membrane cleaning agent (5wt% [P 4444 ][Mal]) prepared with a specific concentration was introduced into the system, and the membrane was soaked for 5 minutes and rinsed for 5 minutes at a cleaning temperature of 25°C. Scale removal. After washing, the ionic liquid cleaning agent is discharged and collected, and then RO water is introduced to remove the ionic liquid solution remaining in the system. After the cleaning, the membrane efficiency test was performed with 2,000ppm MgSO 4 to measure the flux J C2 after cleaning with the ionic liquid. Using the formula for the flux recovery rate disclosed in Example 3 ( J C2 / J 0
Figure 02_image039
100%) to calculate the flux recovery rate of the membrane tube. After that, the bovine serum albumin (BSA) fouling experiment was repeated with the same membrane tube, and the cleaning procedure of the membrane tube was performed again with the recovered ionic liquid ([P 4444 ][Mal]). The flux recovery rate of the membrane tube, the results are shown in Figure 7.

由第7圖的結果顯示利用回收後的離子液體再次進行清洗後，膜管的通量回復率仍可達97%，說明本揭露離子液體作為薄膜清洗劑確實具有可回收再利用的效果。The results in Figure 7 show that the flux recovery rate of the membrane tube can still reach 97% after using the recovered ionic liquid for cleaning again, indicating that the ionic liquid of the present disclosure can indeed be recycled as a membrane cleaning agent.

上述實施例之特徵有利於本技術領域中具有通常知識者理解本發明。本技術領域中具有通常知識者應理解可採用本發明作基礎，設計並變化其他製程與結構以完成上述實施例之相同目的及/或相同優點。本技術領域中具有通常知識者亦應理解，這些等效置換並未脫離本發明精神與範疇，並可在未脫離本發明之精神與範疇的前提下進行改變、替換、或更動。The features of the above-described embodiments are helpful for those skilled in the art to understand the present invention. Those skilled in the art should understand that the present invention can be used as a basis to design and change other processes and structures to achieve the same purpose and/or the same advantages of the above embodiments. Those skilled in the art should also understand that these equivalent replacements do not depart from the spirit and scope of the present invention, and can be changed, replaced, or modified without departing from the spirit and scope of the present invention.

無none

第1圖係根據本揭露的一實施例，顯示溫敏性離子液體的相變溫度曲線圖； 第2圖係根據本揭露的一實施例，顯示不同溫敏性離子液體濃度對黏度關係圖； 第3圖係根據本揭露的一實施例，顯示不同薄膜清洗劑對薄膜的清洗效果(使用平板膜)； 第4圖係根據本揭露的一實施例，顯示不同濃度的薄膜清洗劑對薄膜的清洗效果(使用平板膜)； 第5圖係根據本揭露的一實施例，顯示不同清洗程序對薄膜的清洗效果(使用平板膜)； 第6圖係根據本揭露的一實施例，顯示不同薄膜清洗劑對薄膜的清洗效果(使用膜管)；以及 第7圖係根據本揭露的一實施例，顯示薄膜清洗劑的回收再利用效果(使用膜管)。FIG. 1 is a graph showing a phase transition temperature curve of a temperature-sensitive ionic liquid according to an embodiment of the present disclosure; FIG. 2 is a graph showing the relationship between the concentration of different temperature-sensitive ionic liquids and the viscosity according to an embodiment of the present disclosure; FIG. 3 shows the cleaning effect of different film cleaning agents on films (using a flat film) according to an embodiment of the present disclosure; FIG. 4 shows the cleaning effects of different concentrations of thin-film cleaning agents on thin-film (using a flat film) according to an embodiment of the present disclosure; FIG. 5 shows the cleaning effect of different cleaning procedures on the film (using a flat film) according to an embodiment of the present disclosure; FIG. 6 shows the cleaning effect of different film cleaning agents on the film (using a film tube) according to an embodiment of the present disclosure; and FIG. 7 shows the recycling effect of the film cleaning agent (using a film tube) according to an embodiment of the present disclosure.

Claims (16)

一種薄膜的清洗方法，包括：提供一薄膜；導入一溫敏性離子液體，使該溫敏性離子液體與該薄膜接觸，進行一清洗程序，並收集一清洗液，其中該溫敏性離子液體的濃度介於1wt%至30wt%之間，該溫敏性離子液體的陽離子包括
Figure 108148578-A0305-02-0020-1
、
Figure 108148578-A0305-02-0020-3
或
Figure 108148578-A0305-02-0020-4
，該溫敏 性離子液體的陰離子包括
Figure 108148578-A0305-02-0020-5
、
Figure 108148578-A0305-02-0020-6
、
Figure 108148578-A0305-02-0020-7
、
Figure 108148578-A0305-02-0020-8
、
Figure 108148578-A0305-02-0020-9
或
Figure 108148578-A0305-02-0020-13
，以及該清洗 程序的溫度介於20℃至30℃之間；以及於一特定溫度下，該清洗液分層形成一水層與一離子液體層，其中該特定溫度介於25℃至90℃之間。 A method for cleaning a thin film, comprising: providing a thin film; introducing a temperature-sensitive ionic liquid, making the temperature-sensitive ionic liquid contact the thin film, performing a cleaning procedure, and collecting a cleaning solution, wherein the temperature-sensitive ionic liquid The concentration of the temperature-sensitive ionic liquid is between 1wt% and 30wt%, and the cations of the temperature-sensitive ionic liquid include
Figure 108148578-A0305-02-0020-1
,
Figure 108148578-A0305-02-0020-3
or
Figure 108148578-A0305-02-0020-4
, the anions of the temperature-sensitive ionic liquid include
Figure 108148578-A0305-02-0020-5
,
Figure 108148578-A0305-02-0020-6
,
Figure 108148578-A0305-02-0020-7
,
Figure 108148578-A0305-02-0020-8
,
Figure 108148578-A0305-02-0020-9
or
Figure 108148578-A0305-02-0020-13
, and the temperature of the cleaning process is between 20°C and 30°C; and at a specific temperature, the cleaning solution is layered to form a water layer and an ionic liquid layer, wherein the specific temperature is between 25°C and 90°C between. 如申請專利範圍第1項所述的薄膜的清洗方法，其中該薄膜包含結垢物。 The method for cleaning a thin film as described in claim 1, wherein the thin film contains foulants. 如申請專利範圍第2項所述的薄膜的清洗方法，其中該結垢物包括有機物、無機物、或其組合。 The method for cleaning a thin film as described in item 2 of the claimed scope, wherein the fouling substance includes organic matter, inorganic matter, or a combination thereof. 如申請專利範圍第1項所述的薄膜的清洗方法，其中該薄膜包括超過濾(ultrafiltration，UF)薄膜、奈米過濾(nanofiltration，NF)薄膜、或逆滲透(reverse osmosis，RO)薄膜。 The method for cleaning membranes as described in claim 1, wherein the membranes include ultrafiltration (UF) membranes, nanofiltration (NF) membranes, or reverse osmosis (RO) membranes. 如申請專利範圍第1項所述的薄膜的清洗方法，其中 該溫敏性離子液體包括
Figure 108148578-A0305-02-0021-12
、
Figure 108148578-A0305-02-0021-10
 The method for cleaning a thin film as described in claim 1, wherein the temperature-sensitive ionic liquid comprises
Figure 108148578-A0305-02-0021-12
,
Figure 108148578-A0305-02-0021-10
 如申請專利範圍第1項所述的薄膜的清洗方法，其中該清洗程序包括浸泡步驟與沖洗步驟。 The method for cleaning a thin film as claimed in claim 1, wherein the cleaning procedure includes a soaking step and a rinsing step. 如申請專利範圍第6項所述的薄膜的清洗方法，其中該浸泡步驟的時間介於1分鐘至30分鐘之間。 The method for cleaning a thin film as claimed in item 6 of the claimed scope, wherein the time of the soaking step is between 1 minute and 30 minutes. 如申請專利範圍第6項所述的薄膜的清洗方法，其中該沖洗步驟的時間介於1分鐘至30分鐘之間。 The method for cleaning a thin film according to claim 6, wherein the time of the rinsing step is between 1 minute and 30 minutes. 如申請專利範圍第2項所述的薄膜的清洗方法，其中該清洗液包括該溫敏性離子液體與該結垢物。 The method for cleaning a thin film as claimed in claim 2, wherein the cleaning solution includes the temperature-sensitive ionic liquid and the scaling substance. 如申請專利範圍第1項所述的薄膜的清洗方法，其中該離子液體層包含該溫敏性離子液體，以及該水層包含該結垢物。 The method for cleaning a thin film as claimed in claim 1, wherein the ionic liquid layer contains the temperature-sensitive ionic liquid, and the water layer contains the foulant. 如申請專利範圍第1項所述的薄膜的清洗方法，更包括於導入該溫敏性離子液體的步驟之前，進行第一水洗步驟。 The method for cleaning the thin film as described in the first item of the claimed scope further includes performing a first water washing step before the step of introducing the temperature-sensitive ionic liquid. 如申請專利範圍第11項所述的薄膜的清洗方法，其中該第一水洗步驟的溫度介於20℃至30℃之間。 The method for cleaning a thin film as claimed in claim 11, wherein the temperature of the first water washing step is between 20°C and 30°C. 如申請專利範圍第11項所述的薄膜的清洗方法，其中該第一水洗步驟的時間介於1分鐘至30分鐘之間。 The method for cleaning a thin film as claimed in claim 11, wherein the time of the first water washing step is between 1 minute and 30 minutes. 如申請專利範圍第1項所述的薄膜的清洗方法，更包括於該清洗程序之後，進行第二水洗步驟。 The method for cleaning a thin film as described in item 1 of the claimed scope further includes performing a second water washing step after the cleaning procedure. 如申請專利範圍第14項所述的薄膜的清洗方法，其中該第二水洗步驟的溫度介於20℃至30℃之間。 The method for cleaning a thin film as claimed in claim 14, wherein the temperature of the second water washing step is between 20°C and 30°C. 如申請專利範圍第14項所述的薄膜的清洗方法，其中該第二水洗步驟的時間介於1分鐘至30分鐘之間。 The method for cleaning a thin film as claimed in claim 14, wherein the time of the second water washing step is between 1 minute and 30 minutes.
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