AGENT, LIQUID, AND METHOD FOR CLEANING REVERSE OSMOSIS MEMBRANE

Abstract

An agent for cleaning an RO membrane, which includes an aldonic acid and/or a salt of an aldonic acid, removes effectively foulants that cannot be sufficiently removed with conventional cleaning agents when an RO membrane used for water treatment. In a method for cleaning an RO membrane with the cleaning agent or the cleaning liquid, while the detachment and hydrolysis effects are achieved by performing cleaning under alkaline conditions, chelation of heavy metals is caused by the aldonic acid and/or the salt of an aldonic acid. When an anionic surfactant is used in combination with the aldonic acid and/or the salt of an aldonic acid, the anionic surfactant causes the detachment of foulants. When a polyol having a molecular weight of 1000 or less is used in combination with the aldonic acid and/or the salt of an aldonic acid, the polyol causes wetting and swelling of foulants.

Claims

1. An agent for cleaning a reverse osmosis membrane, the agent comprising an aldonic acid and/or a salt thereof.

2. The agent for cleaning a reverse osmosis membrane according to claim 1, wherein the aldonic acid and/or the salt thereof is selected from gluconic acid, glucoheptonic acid, a salt of gluconic acid, and a salt of glucoheptonic acid.

3. The agent for cleaning a reverse osmosis membrane according to claim 1, the agent being used under an alkaline condition.

4. The agent for cleaning a reverse osmosis membrane according to claim 1, the agent further comprising an anionic surfactant.

5. The agent for cleaning a reverse osmosis membrane according to claim 1, the agent further comprising a polyol having a molecular weight of 1000 or less.

6. A liquid for cleaning a reverse osmosis membrane, the liquid comprising the agent for cleaning a reverse osmosis membrane according to claim 1.

7. The liquid for cleaning a reverse osmosis membrane according to claim 6, the liquid being an alkaline liquid having a pH of 8 or more.

8. The liquid for cleaning a reverse osmosis membrane according to claim 6, wherein the concentration of the aldonic acid and/or the salt thereof is 0.3% by weight or more.

9. A method for cleaning a reverse osmosis membrane, the method comprising using the agent for cleaning a reverse osmosis membrane according to claim 1.

10. The method for cleaning a reverse osmosis membrane according to claim 9, wherein the reverse osmosis membrane is an aromatic polyamide reverse osmosis membrane.

11. The method for cleaning a reverse osmosis membrane according to claim 9, wherein the reverse osmosis membrane is a reverse osmosis membrane that has been used for desalination of seawater.

12. A method for cleaning a reverse osmosis membrane, the method comprising using the liquid for cleaning a reverse osmosis membrane according to claim 6.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0040] FIG. 1 is a schematic diagram illustrating a flat-membrane testing apparatus used in Examples.

[0041] FIG. 2 is a cross-sectional view of a closed container included in the flat-membrane testing apparatus illustrated in FIG. 1, illustrating the structure of the closed container.

[0042] FIGS. 3a and 3b are graphs illustrating the results of analysis of the types of fouling of RO membranes used in a seawater desalination system site A and a salt-water desalination system site B. FIG. 3a illustrates the amount of TOC adhered on the surface of each of the membranes. FIG. 3b illustrates the amounts of Ca, Mg, Al, and Fe adhered on the surface of each of the membranes.

DESCRIPTION OF EMBODIMENTS

[0043] An embodiment of the present invention is described below in detail.

[0044] [Mechanism of Action]

[0045] The mechanism of the action according to the present invention is not clear in detail but presumably as follows.

[0046] While the detachment and hydrolysis effects are achieved by performing cleaning under alkaline conditions, chelation of heavy metals is caused by an aldonic acid and/or a salt of an aldonic acid (hereinafter, may be referred to as aldonic acid (salt)). When an anionic surfactant is used in combination with the aldonic acid (salt), the anionic surfactant makes the foulants hydrophilic and causes the detachment of the foulants. When a polyol having a molecular weight of 1000 or less is used in combination with the aldonic acid and/or the salt thereof, the polyol causes replacement and detachment of the foulants. The above components synergistically increase the alkali cleaning effect.

[0047] [RO Membrane]

[0048] The RO membrane that is to be cleaned in the present invention may be either a polyamide RO membrane, such as an aromatic polyamide RO membrane, or a cellulose acetate RO membrane. The present invention is particularly effective for cleaning an aromatic polyamide RO membrane. In particular, the present invention is effective on an RO membrane used for desalination of seawater which has become fouled with organic substances and inorganic substances in a combined manner, which can not be sufficiently cleaned with cleaning agents known in the related art.

[0049] [Agent for Cleaning RO Membrane]

[0050] The agent for cleaning an RO membrane according to the present invention includes an aldonic acid (salt). The agent for cleaning an RO membrane according to the present invention is commonly prepared by dissolving the aldonic acid (salt) and optional components, such as an alkaline agent and other chemicals, in water.

[0051] The term cleaning agent used herein refers to an agent that is prepared for the distribution and storage of the products and contains the aldonic acid (salt) and the other chemicals at concentrations higher than those required when the chemicals are used for cleaning an RO membrane. The term cleaning liquid used herein refers to a liquid prepared by diluting the cleaning agent with water to the concentrations at which the chemicals are used for cleaning an RO membrane.

[0052] <Aldonic Acid (Salt)>

[0053] The term aldonic acid is a general term for hydroxy monocarboxylic acids obtained by oxidation of only an aldehyde group of an aldose. Examples of an aldonic acid include gluconic acid, glucoheptonic acid, mannonic acid, mannoheptonic acid, galactonic acid, and galactoheptonic acid. Examples of an aldonic acid salt include alkali metal salts of the above aldonic acids, such as a sodium salt and a potassium salt; amine salts of the above aldonic acids; and the ammonium salts of the above aldonic acids.

[0054] The aldonic acid (salt) used in the present invention is desirably, but not limited to, gluconic acid, a salt of gluconic acid, glucoheptonic acid, or a salt of glucoheptonic acid in consideration of ease of availability and safety.

[0055] The above aldonic acids (salts) may be used alone or in a mixture of two or more.

[0056] <Other Components>

[0057] The agent for cleaning an RO membrane according to the present invention may include, in addition to the aldonic acid (salt), an alkaline agent, a detergent, and a solvent other than water that are necessary for cleaning an RO membrane.

[0058] Examples of the alkaline agent included in the agent for cleaning an RO membrane according to the present invention include hydroxides of alkali metals, such as sodium hydroxide and potassium hydroxide.

[0059] Examples of another cleaning component that can be used in combination with the aldonic acid (salt) include an anionic surfactant and a polyol having a molecular weight of 1000 or less. Using an anionic surfactant in combination with the aldonic acid (salt) promotes the detachment of foulants adhered on the surface of the membrane and thereby further increases the cleaning effect. Using a polyol having a molecular weight of 1000 or less in combination with the aldonic acid (salt) enhances the wettability of the cleaning component and thereby further increases the cleaning effect.

[0060] Examples of the anionic surfactant include alkylbenzenesulfonates, such as sodium dodecylbenzenesulfonate, and alkyl sulfates, such as sodium dodecyl sulfate.

[0061] A polyol is a compound having a plurality of OH groups. Examples of polyols include alkylene glycols, such as ethylene glycol, propylene glycol, and trimethylene glycol; glycerin; polyglycols, such as diethylene glycol and other polyalkylene glycols; and sugar alcohols, such as erythritol and mannitol. Among the above polyols, alkylene glycols, such as ethylene glycol, propylene glycol, and trimethylene glycol, are preferable in terms of ease of availability and economy. A polyol having a high molecular weight exceeding 1000 may act as a substance that causes fouling of the membrane. Accordingly, the molecular weight of the polyol used in the present invention is 1000 or less and is preferably 400 or less.

[0062] The cleaning agent according to the present invention may further include a solvent. Examples of the solvent include alcohols, such as ethanol; amines, such as monoethanolamine, diethanolamine, and triethanolamine; ketones, such as acetone; and ethers, such as dimethyl ether, diethyl ether, and diethylene glycol monomethyl ether.

[0063] The above solvents may be used alone or in combination with two or more.

[0064] The agent for cleaning an RO membrane according to the present invention may be a one-part cleaning agent prepared by mixing the aldonic acid (salt) with the alkaline agent, the other detergents, and the like. The cleaning agent may also be a two-part cleaning agent, that is, some of the above components may be separately provided in the form of a second part of the agent. Alternatively, the cleaning agent may be constituted by three or more parts.

[0065] The liquid for cleaning an RO membrane according to the present invention, which is prepared by diluting the agent for cleaning an RO membrane according to the present invention with water, may also be constituted by one part, two parts, or three or more parts. In the case where the cleaning liquid is constituted by two parts or three or more parts, for example, an RO membrane is cleaned with a cleaning liquid including the aldonic acid (salt) and subsequently with another cleaning liquid including the other detergents.

[0066] The concentration of each chemical in the agent for cleaning an RO membrane according to the present invention is adjusted to be about 5 to 100 times by weight the concentration of the chemical in the liquid for cleaning an RO membrane according to the present invention, which is described below, so that the preferable concentration of the chemical in the liquid for cleaning an RO membrane is achieved when the cleaning agent is diluted with water, which is preferably pure water, about 5 to 100 times by weight.

[0067] The agent for cleaning an RO membrane according to the present invention may be prepared in the form of an aqueous solution. Alternatively, the entirety or a part of the cleaning agent may be prepared in the form of a powder or a solid.

[0068] [Cleaning Liquid]

[0069] The liquid for cleaning an RO membrane according to the present invention is an aqueous solution prepared by diluting the agent for cleaning an RO membrane according to the present invention with water. The liquid for cleaning an RO membrane according to the present invention may also be prepared by diluting the agent for cleaning an RO membrane according to the present invention with water and optionally adding the alkaline agent, the detergents, the solvents, and the like to the diluted cleaning agent at the predetermined concentrations.

[0070] The liquid for cleaning an RO membrane according to the present invention is not necessarily prepared from the agent for cleaning an RO membrane according to the present invention and may be directly prepared such that the predetermined chemical concentrations are achieved.

[0071] The preferable concentration of the aldonic acid (salt) in the liquid for cleaning an RO membrane according to the present invention varies with the type of the aldonic acid (salt) used, the pH of the cleaning liquid, the presence of the other detergents used in combination with the aldonic acid (salt), the types and concentrations of the other detergents, and the like. The concentration of the aldonic acid (salt) in the cleaning liquid is preferably 0.1% by weight or more and is particularly preferably 0.3% by weight or more. If the concentration of the aldonic acid (salt) is lower than the above lower limit, it is not possible to sufficiently clean an RO membrane by using the aldonic acid (salt). On the other hand, setting the concentration of the aldonic acid (salt) to be excessively high does not increase the above advantageous effects in accordance with the concentration of the aldonic acid (salt) and just disadvantageously increases the TOC concentration in the cleaning liquid that is to be disposed of. Accordingly, the concentration of the aldonic acid (salt) in the liquid for cleaning an RO membrane according to the present invention is preferably 2% by weight or less.

[0072] The pH of the liquid for cleaning an RO membrane according to the present invention is preferably 8 or more and is particularly preferably 10 to 14 in consideration of the cleaning effect.

[0073] If the pH of the cleaning liquid is less than 8, the permeability of the membrane may fail to be sufficiently recovered by cleaning. The higher the pH of the cleaning liquid, the larger the cleaning effect. However, setting the pH of the cleaning liquid to be excessively high reduces ease of handling of the cleaning liquid and increases the risk of the degradation of the RO membrane. The pH of the cleaning liquid is preferably 14 or less and is more preferably 11 or more and 13 or less.

[0074] The pH of the liquid for cleaning an RO membrane according to the present invention is adjusted to be the above preferable pH value by the addition of the alkaline agent.

[0075] In the case where the liquid for cleaning an RO membrane according to the present invention is used for cleaning a cellulose acetate membrane, the pH of the cleaning liquid is preferably set to be less than 8, and a surfactant may be added to the cleaning liquid.

[0076] In the case where the liquid for cleaning an RO membrane according to the present invention includes the anionic surfactant, the concentration of the anionic surfactant in the liquid for cleaning an RO membrane according to the present invention is preferably 100 to 10000 mg/L and is particularly preferably 300 to 5000 mg/L. If the concentration of the anionic surfactant is excessively low, a sufficient dispersion effect of the anionic surfactant may fail to be achieved. In addition, the cleaning effect may fail to be sufficiently enhanced by using the anionic surfactant. If the concentration of the anionic surfactant is excessively high, the degree of association of anionic surfactant molecules is increased. This may reduce the cleaning effect.

[0077] In the case where the liquid for cleaning an RO membrane according to the present invention includes the polyol having a molecular weight of 1000 or less, the concentration of the polyol having a molecular weight of 1000 or less in the liquid for cleaning an RO membrane according to the present invention is preferably 0.1% to 10% by weight and is particularly preferably 0.5% to 5% by weight. If the concentration of the polyol having a molecular weight of 1000 or less is excessively low, the replacement and detachment effects of the cleaning component may fail to be sufficiently enhanced by using the polyol. Setting the concentration of the polyol having a molecular weight of 1000 or less to be excessively high disadvantageously increases the TOC concentration in the cleaning liquid that is to be disposed of.

[0078] <Method for Producing Agent and Liquid for Cleaning RO Membrane>

[0079] The agent for cleaning an RO membrane according to the present invention is prepared by mixing the aldonic acid (salt), the optional alkaline agent, and the other optional cleaning components with water. The entirety or a part of the agent for cleaning an RO membrane according to the present invention may be prepared in the form of a powder or a solid.

[0080] The liquid for cleaning an RO membrane according to the present invention is produced by diluting the agent for cleaning an RO membrane according to the present invention, which is produced by the above-described method, with water, which is preferably pure water, and optionally adding the alkaline agent, the detergents, the other solvents, and the like to the diluted cleaning agent. The liquid for cleaning an RO membrane according to the present invention is not necessarily produced from the agent for cleaning an RO membrane according to the present invention and may be directly produced by the above-described method.

[0081] <Cleaning Method>

[0082] For cleaning an RO membrane with the liquid for cleaning an RO membrane according to the present invention, any method in which the cleaning liquid is brought into contact with the RO membrane may be employed. One of the common methods is immersion cleaning, in which the cleaning liquid is introduced into a raw-water-side portion of an RO-membrane module and the RO-membrane module is subsequently left to stand. Optionally, circulation cleaning, in which the cleaning liquid is used in a circulatory manner, may be performed prior or subsequent to the immersion cleaning.

[0083] In the case where the agent and the liquid for cleaning an RO membrane according to the present invention are constituted by two parts or three or more parts, the parts may be mixed together before used for cleaning. Alternatively, the parts may be each separately used and cleaning may be performed in multiple stages with the respective parts. For example, after cleaning has been performed with a cleaning liquid including the aldonic acid (salt), another cleaning is performed with a cleaning liquid including the other chemicals.

[0084] The immersion cleaning described above or a combination of the immersion cleaning and the circulation cleaning described above is commonly used even in the case where another cleaning, such as cleaning using an aqueous alkaline solution or an aqueous acidic solution, is performed prior or subsequent to the cleaning using the liquid for cleaning an RO membrane according to the present invention.

[0085] An example of cleaning using a cleaning liquid other than the liquid for cleaning an RO membrane according to the present invention is cleaning using an aqueous alkaline solution that does not contain the aldonic acid (salt) subsequent to the cleaning using the liquid for cleaning an RO membrane according to the present invention. Examples of an alkaline agent included in the aqueous alkaline solution are the same as the above-described examples of the alkaline agent included in the liquid for cleaning an RO membrane according to the present invention. The pH of the aqueous alkaline solution is preferably 10 or more and is particularly preferably 11 to 13 in consideration of the cleaning effect and ease of handling.

[0086] Another example of cleaning using a cleaning liquid other than the liquid for cleaning an RO membrane according to the present invention is cleaning using an aqueous acidic solution, which is effective for the removal of scale and metal colloid particles. For performing cleaning using an aqueous acidic solution, an aqueous solution that includes one or more acids selected from hydrochloric acid, nitric acid, citric acid, oxalic acid, and the like may be used. The pH of the aqueous acidic solution is preferably 4 or less and is particularly preferably 1 to 3 in consideration of the cleaning effect and ease of handling.

[0087] The amount of time during which immersion cleaning using the liquid for cleaning an RO membrane according to the present invention or the other cleaning liquid is performed is not limited and may be set such that the properties of the membrane are recovered at desired recovery rate. The immersion cleaning is commonly performed for about 2 to 24 hours. In the case where the circulation cleaning is performed prior or subsequent to the immersion cleaning, the amount of time during which the circulation cleaning is performed is not limited and may be set such that the properties of the membrane are recovered at desired recovery rate. The circulation cleaning is commonly performed for about 0.5 to 3 hours.

[0088] In the case where the cleaning using the liquid for cleaning an RO membrane according to the present invention and the cleaning using the aqueous alkaline solution and/or the aqueous acidic solution are performed in a combined manner, the order in which the two cleanings are conducted is not limited. Performing cleaning using the aqueous acidic solution prior or subsequent to the cleaning using the liquid for cleaning an RO membrane according to the present invention enables removal of scale and advantageously increases the cleaning effect.

[0089] Subsequent to the cleaning using the above cleaning liquids, commonly, high-purity water, such as pure water, is passed through the membrane in order to perform finish-cleaning. Subsequently, the operation of the RO membrane system is restarted.

EXAMPLES

[0090] The present invention is described below further specifically with reference to Examples and Comparative examples.

[0091] In Examples and Comparative examples below, the RO-membrane cleaning effect was determined using the flat-membrane testing apparatus illustrated in FIGS. 1 and 2.

[0092] In the flat-membrane testing apparatus, RO-membrane feed is fed to a raw-water chamber 1A included in a closed container 1 with a high-pressure pump 4 through a pipe 11. The raw-water chamber 1A is located below a flat-membrane cell 2 including an RO membrane. As illustrated in FIG. 2, the closed container 1 is constituted by a lower casing 1a and an upper casing 1b, which are located on the raw-water-chamber-1A side and the permeate-chamber-1B side, respectively. The flat-membrane cell 2 is fixed in position by being interposed between the lower casing 1a and the upper casing 1b with an O-ring 8. The flat-membrane cell 2 is constituted by an RO membrane 2A and a porous supporting plate 2B that supports the permeate-side surface of the RO membrane 2A. The inside of the raw-water chamber 1A, which is located below the flat-membrane cell 2, is stirred by a stirrer 3 rotating a stirring bar 5. The permeate of the RO membrane is passed into a permeate chamber 1B located above the flat-membrane cell 2 and subsequently drawn through a pipe 12. The concentrate is drawn through a pipe 13. The pressure inside the closed container 1 is adjusted with a pressure gage 6 disposed in the feed pipe 11 and a pressure control valve 7 disposed in the concentrate-drawing pipe 13.

[0093] Cleaning tests were all conducted at 25 C.

[0094] The permeation flux and salt rejection rate of the RO membrane were calculated using the following formulae.

Permeation Flux [m.sup.3/(m.sup.2.Math.day)]=Flow Rate of Permeate [m.sup.3/day]/Area of Membrane [m.sup.2]Temperature Conversion Coefficient[]

Salt Rejection Rate [%]=(1Electric Conductivity of Permeate [mS/m]/Electric Conductivity of Concentrate [mS/m])100

Examples 1 to 4 and Comparative Examples 1 to 4

[0095] The cleaning tests described below were conducted using the following cleaning liquids.

[0096] <Cleaning Liquids>

Example 1

[0097] Aqueous sodium hydroxide solution containing 0.1-weight % sodium gluconate and having a pH of 12

Example 2

[0098] Aqueous sodium hydroxide solution containing 0.5-weight % sodium gluconate and having a pH of 12

Example 3

[0099] Aqueous sodium hydroxide solution containing 0.3-weight % sodium gluconate and having a pH of 12

Example 4

[0100] Aqueous sodium hydroxide solution containing 0.5-weight % sodium gluconate, 1500-mg/L sodium dodecyl sulfate, and 2-weight % propylene glycol and having a pH of 12

Comparative Example 1

[0101] Aqueous sodium hydroxide solution having a pH of 12

Comparative Example 2

[0102] Aqueous sodium hydroxide solution containing 0.5-weight % EDTA (ethylenediaminetetraacetic acid) and having a pH of 12

Comparative Example 3

[0103] Aqueous sodium hydroxide solution containing 0.5-weight % hexametaphosphoric acid and having a pH of 12

Comparative Example 4

[0104] Aqueous sodium hydroxide solution containing 0.5-weight % EDTA, 1500-mg/L sodium dodecyl sulfate, and 2-weight % propylene glycol and having a pH of 12

[0105] <Test Method>

[0106] An aromatic polyamide RO membrane TM-820A (fresh membrane, permeation flux: 0.6 [m.sup.3/(m.sup.2.Math.day)]) produced by Toray Industries, Inc. was attached to an RO apparatus included in a seawater desalination RO system. The RO system was subsequently operated for three years. After the operation of the RO system had been terminated, the membrane was removed from the RO apparatus and dismantled to prepare a flat membrane sample of a fouled membrane. The flat membrane sample was cut into a circular shape and placed on the flat-membrane testing apparatus illustrated in FIGS. 1 and 2 to which a membrane having the same size as the flat membrane sample can be attached. Subsequently, a test was conducted in the following manner.

[0107] (1) Pure water was passed, at 1.55 MPa, through the fouled membrane that had not yet been cleaned in order to measure the pure-water permeation flux of the fouled membrane before cleaning. Subsequently, a 2000-mg/L aqueous sodium chloride solution was passed through the fouled membrane under the same conditions as above in order to measure the salt rejection rate of the membrane.

[0108] (2) A specific one of the above cleaning liquids was fed to the membrane in order to clean the membrane. For each case, the cleaning was performed in the order of 2-hour circulation cleaning, 15-hour immersion cleaning, and 2-hour circulation cleaning. The operating pressure during the circulation cleaning was set to 0.2 MPa.

[0109] (3) The pure-water permeation flux and salt rejection rate of the cleaned membrane were measured as in (1) above.

[0110] (4) The recovery rate was calculated using the following formula.

Recovery Rate[]=(Permeation Flux of Cleaned Membrane)/(Permeation Flux of Fresh Membrane)

[0111] Table 1 shows the results. In Table 1, GANa refers to sodium gluconate, SDS refers to sodium dodecyl sulfate, and PG refers to propylene glycol.

TABLE-US-00001 TABLE 1 Permeation flux [m.sup.3/(m.sup.2 .Math. day)] Recovery Cleaning liquid Before After rate pH Cleaning component cleaning cleaning [] Example 1 12 0.1% GANa + NaOH 0.28 0.42 0.70 Example 2 12 0.5% GANa + NaOH 0.30 0.47 0.78 Example 3 12 0.3% GANa + NaOH 0.27 0.47 0.78 Example 4 12 0.3% GANa + NaOH + 0.29 0.49 0.82 SDS + PG Comparative 12 NaOH 0.29 0.41 0.68 example 1 Comparative 12 0.5% EDTA + NaOH 0.27 0.40 0.67 example 2 Comparative 12 0.5% 0.27 0.42 0.70 example 3 Hexametaphosphoric acid + NaOH Comparative 12 0.5% EDTA + NaOH + 0.33 0.43 0.72 example 4 SDS + PG

[0112] As is clear from the results shown in Table 1, sodium gluconate exhibited a cleaning effect comparable to the cleaning effects of the other chelating agents even when used at a low concentration. A cleaning liquid including sodium gluconate at a concentration of 0.3% by weight or more had a markedly higher cleaning effect than the other chelating agents.

[0113] The results obtained in Example 4 confirm that using sodium gluconate in combination with an anionic surfactant and a polyol having a molecular weight of 1000 or less promoted detachment of foulants and markedly increased the permeation flux ratio.

[0114] In all of Examples 1 to 4 and Comparative examples 1 to 4, the salt rejection rate of the cleaned RO membrane was substantially equal to that of the RO membrane before cleaning, that is, about 98% to 99%.

[0115] Although the present invention has been described in detail with reference to particular embodiments, it is apparent to a person skilled in the art that various modifications can be made therein without departing from the spirit and scope of the present invention.

[0116] The present application is based on Japanese Patent Application No. 2015-147780 filed on Jul. 27, 2015, which is incorporated herein by reference in its entirety.

REFERENCE SIGNS LIST

[0117] 1 CONTAINER [0118] 2 FLAT-MEMBRANE CELL [0119] 2A RO MEMBRANE [0120] 2B POROUS SUPPORTING PLATE [0121] 3 STIRRER [0122] 4 HIGH-PRESSURE PUMP [0123] 5 STIR BAR [0124] 6 PRESSURE GAGE [0125] 7 PRESSURE CONTROL VALVE [0126] 8 O-RING