JP5130967B2 - Manufacturing method of composite semipermeable membrane - Google Patents

Description

  The present invention relates to a composite semipermeable membrane useful for selective separation of a liquid mixture and a method for producing the same. For example, the present invention relates to a method for producing a composite semipermeable membrane in which a polyamide separation functional layer is formed on a microporous support membrane having both high water permeability and high removal rate in desalination of seawater and brine.

  Regarding the separation of a mixture, there are various techniques for removing substances (for example, salts) dissolved in a solvent (for example, water). In recent years, a membrane separation method has been used as a process for saving energy and resources. Yes. Examples of membranes used in the membrane separation method include microfiltration membranes, ultrafiltration membranes, nanofiltration membranes (also referred to as loose RO membranes), and reverse osmosis membranes. These membranes have been used, for example, in the case of obtaining drinking water from seawater, canned water, and water containing harmful substances, in the production of industrial ultrapure water, in wastewater treatment, and in recovery of valuable materials.

  Most of the reverse osmosis membranes and nanofiltration membranes currently on the market are composite semipermeable membranes, a type having a gel layer and an active layer obtained by crosslinking a polymer on a porous support membrane, and a porous support membrane. There are two types: a type having an active layer obtained by polycondensation of monomers. Among them, a composite semipermeable membrane obtained by coating a porous support membrane with a separation functional layer made of a crosslinked polyamide obtained by a polycondensation reaction between a polyfunctional amine and a polyfunctional acid halide is widely used. It is important for these composite semipermeable membranes to achieve both high solute removal properties and water permeability in order to improve the water quality obtained when used and to reduce operating costs.

As a means for improving the solute removability and water permeability of the membrane, a method of modifying the separation functional layer after forming a polyamide separation functional layer by interfacial polycondensation is effective from the viewpoint of versatility. As such a modification method, for example, in Patent Document 1, a semipermeable membrane having a separation functional layer containing a primary amino group is used as a reagent that reacts with a primary amino group to produce a diazonium salt or a derivative thereof. A method of contacting for 1 second or more and 60 minutes or less is disclosed. However, both higher solute removability and water permeability are desired.
JP 2005-177741 A

  An object of this invention is to provide the manufacturing method of a composite semipermeable membrane which has high solute removal property and high water permeability.

In order to achieve the above object, the present invention has the following configuration (1) .

(1) forming a semipermeable membrane having a separation functional layer containing a primary amino group, and reacting the semipermeable membrane having the separation functional layer with a primary amino group to produce a diazonium salt or a derivative thereof. Contacting with the resulting compound (I) to form a diazonium salt , and having reactivity with at least one compound (I) selected from the group consisting of sulfamic acid, ammonia, its acid salt, and amino acid A method for producing a composite semipermeable membrane, comprising a step of contacting with a water-soluble compound (II).

  According to the method of the present invention, a composite semipermeable membrane having both high water permeability and high solute removability can be obtained. Moreover, the burden on waste liquid treatment can be reduced by using an inorganic compound for the modification treatment.

  The present invention is a method for improving the properties of a semipermeable membrane having a separation functional layer containing a primary amino group. Here, the separation functional layer containing a primary amino group means that a compound having at least one primary amino group and / or a salt thereof is present in the separation functional layer. The type of the compound is not particularly limited, and examples thereof include aromatic amines, polyvinyl amines, and polyamides having terminal amino groups. For ease of handling, the primary amino group is preferably an aromatic amine. These may be constituent components of the separation functional layer, or may not be accompanied by a chemical bond with the separation functional layer.

  In the present invention, the composite semipermeable membrane is preferably formed by coating a separation functional layer having substantially separation performance on a porous support membrane having substantially no separation performance. It consists of a crosslinked polyamide obtained by the reaction of a functional amine and a polyfunctional acid halide. Here, the polyfunctional amine comprises at least one component of an aliphatic polyfunctional amine and an aromatic polyfunctional amine.

  The aliphatic polyfunctional amine is an aliphatic amine having two or more amino groups in one molecule, and is preferably a piperazine-based amine and a derivative thereof. For example, piperazine, 2,5-dimethylpiperazine, 2-methylpiperazine, 2,6-dimethylpiperazine, 2,3,5-trimethylpiperazine, 2,5-diethylpiperazine, 2,3,5-triethylpiperazine, 2- Examples thereof include n-propylpiperazine and 2,5-di-n-butylpiperazine, and piperazine and 2,5-dimethylpiperazine are particularly preferable from the viewpoint of stability of performance.

  The aromatic polyfunctional amine is an aromatic amine having two or more amino groups in one molecule, and is not particularly limited, but includes metaphenylene diamine, paraphenylene diamine, 1, 3, 5 -Triaminobenzene and the like, and N-alkylated products thereof include N, N-dimethylmetaphenylenediamine, N, N-diethylmetaphenylenediamine, N, N-dimethylparaphenylenediamine, N, N-diethylparaphenylenediamine, etc. In view of the stability of performance, metaphenylenediamine and 1,3,5-triaminobenzene are particularly preferable.

  The polyfunctional acid halide is an acid halide having two or more carbonyl halide groups in one molecule, and is not particularly limited as long as it gives a polyamide by reaction with the amine. Examples of the polyfunctional acid halide include oxalic acid, malonic acid, maleic acid, fumaric acid, glutaric acid, 1,3,5-cyclohexanetricarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid. 1,3,5-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3-benzenedicarboxylic acid, and acid halides of 1,4-benzenedicarboxylic acid can be used. Among acid halides, acid chlorides are preferred, and are acid halides of 1,3,5-benzenetricarboxylic acid, particularly in terms of economy, availability, ease of handling, and ease of reactivity. Trimesic acid chloride is preferred. Although the said polyfunctional acid halide can also be used independently, you may use it as a mixture.

  The organic solvent that dissolves the polyfunctional acid halide is not miscible with water, and preferably does not destroy the porous support membrane, and may be any as long as it does not inhibit the formation reaction of the crosslinked polyamide. . Typical examples include halogenated hydrocarbons such as liquid hydrocarbons and trichlorotrifluoroethane, but they are substances that do not destroy the ozone layer, are easily available, are easy to handle, and are safe for handling. In consideration of the properties, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, heptadecane, hexadecane, etc., and simple substances such as cyclooctane, ethylcyclohexane, 1-octene, 1-decene or mixtures thereof are preferably used.

  Next, the preferable manufacturing method of a semipermeable membrane is demonstrated. The separation functional layer having substantially separation performance in the semipermeable membrane is, for example, an aqueous solution containing the above-mentioned polyfunctional amine and an organic solvent immiscible with water containing the above-mentioned polyfunctional acid halide. It forms by making it react on the below-mentioned porous support membrane using a solution.

  Here, the concentration of the aqueous solution containing the polyfunctional amine is preferably 0.1 to 20% by weight, more preferably 0.5 to 15% by weight.

  In the case of an aqueous solution containing a polyfunctional amine or an organic solvent solution containing a polyfunctional acid halide, an acylation catalyst, a polar solvent, an acid scavenger may be used as long as it does not interfere with the reaction between the two components. In addition, compounds such as surfactants and antioxidants may be contained.

  In the present invention, the porous support membrane is used to support a separation functional layer such as a crosslinked polyamide. Although the structure of a porous support membrane is not specifically limited, As a preferable porous support membrane, the polysulfone support membrane reinforced with the cloth etc. can be illustrated. The pore diameter and the number of pores of the porous support membrane are not particularly limited, but it has uniform fine pores or gradually large pores from one side to the other side, and the size of the fine pores is the size of one side. A support film having a structure in which the surface of the film is 100 nm or less is preferable.

  The porous support membrane used in the present invention can be selected from various commercially available materials such as “Millipore Filter VSWP” (trade name) manufactured by Millipore and “Ultra Filter UK10” (trade name) manufactured by Toyo Roshi Kaisha. “Office of Saleen Water Research and Development Progress Report” No. 359 (1968).

  The material used for the porous support membrane is not particularly limited. For example, polysulfone, cellulose acetate, cellulose nitrate, polyvinyl chloride, or other homopolymers or blended materials can be used, but chemically, mechanically, and thermally. It is preferable to use polysulfone having high stability. Specifically, a solution of polysulfone in dimethylformamide (hereinafter referred to as DMF) is applied on a densely woven polyester cloth or non-woven fabric to a substantially constant thickness, and sodium dodecyl sulfate 0.5 wt% DMF 2 wt% By wet coagulation in an aqueous solution containing, a suitable porous support membrane having most of the surface with fine pores having a diameter of several tens of nm or less can be obtained.

  The surface of the porous support membrane may be coated with an aqueous solution containing a polyfunctional amine as long as the aqueous solution is uniformly and continuously coated on the surface. For example, the coating may be carried out by a method of coating a porous support membrane in the aqueous solution. Next, the excessively applied aqueous solution is removed by a liquid draining step. As a method for draining liquid, for example, there is a method in which the film surface is allowed to flow naturally while being held in a vertical direction. After draining, the membrane surface may be dried to remove all or part of the water in the aqueous solution. Then, the organic solvent solution containing the above-mentioned polyfunctional acid halide is applied to the porous support membrane coated with the aqueous solution containing the polyfunctional amine, and a separation functional layer of crosslinked polyamide is formed by reaction.

  The concentration of the polyfunctional acid halide is not particularly limited, but is preferably about 0.01 to 1.0% by weight in the organic solvent solution in order to sufficiently form the separation functional layer as the active layer.

  In the present invention, the semipermeable membrane produced by the above-described method is contacted with a compound (I) (hereinafter abbreviated as a diazonium chloride compound) that reacts with a primary amino group to produce a diazonium salt or a derivative thereof. After forming a diazonium salt, the composite semipermeable membrane is modified by contacting with a water-soluble compound (II) having reactivity with the diazonium chloride compound (hereinafter abbreviated as the second treatment compound). Do. The method of bringing the diazonium chloride compound into contact with the composite semipermeable membrane and the method of bringing the second treatment compound into contact are not particularly limited. For example, a method of immersing the entire semipermeable membrane in a liquid containing these compounds may be used. A method of spraying a liquid containing a compound may be used, and the method is not limited as long as the separation functional layer and the compound come into contact with each other.

Examples of the liquid containing the diazonium chloride compound used in the method of the present invention include an aqueous solution containing nitrous acid and a salt thereof, a nitrosyl compound and the like. Since an aqueous solution of nitrous acid or a nitrosyl compound easily generates gas and decomposes, it is preferable to sequentially generate nitrous acid by, for example, a reaction between nitrite and an acidic solution. In general, nitrite reacts with hydrogen ions to produce nitrous acid (HNO ₂ ), but is efficiently produced at 20 ° C. when the pH of the aqueous solution is 4 or less. Among these, an aqueous solution of sodium nitrite reacted with hydrochloric acid or sulfuric acid in an aqueous solution is particularly preferable because of easy handling.

  In the present invention, the concentration of nitrous acid or nitrite in the liquid containing the diazonium chloride compound brought into contact with the membrane is preferably in the range of 0.01 to 1% by weight at 20 ° C. Within this range, a sufficient effect can be obtained to react with the primary amino group in the film to produce a diazonium salt or a derivative thereof.

In performing such treatment, in the semipermeable membrane, the amount of unreacted primary amine having a molecular weight of 300 or less remaining during the polyamide formation reaction, or the amount of primary amine having a molecular weight of 300 or less added separately, It is preferably 500 mg or less per 1 m ^{2 of} membrane area. Within this range, a sufficient effect can be obtained to react with the primary amino group in the film to produce a diazonium salt or a derivative thereof. In addition, the amount of primary amine can be determined by cutting a semipermeable membrane 10 × 10 cm, immersing it in 50 g of ethanol for 8 hours, and analyzing the components extracted into ethanol by ultraviolet absorption visible spectrum, chromatography, mass spectrometry and the like.

  The amino group present in the functional layer is diazonium salified with a diazonium chloride compound and then partially converted to a phenolic hydroxyl group. This can be understood as a reaction of the produced diazonium salt with water. The phenolic hydroxyl group can be identified by NMR method. For example, a liquid separation membrane having a separation functional layer on a support in which a porous support membrane made of polysulfone is formed on a substrate is identified as follows when identifying a compound by the NMR method. First, a substrate (taffeta or nonwoven fabric made of polyester fiber) which is a part of the support is peeled off to obtain a mixture of a microporous support membrane made of polysulfone and a separation functional layer of crosslinked polyamide. This is dissolved in methylene chloride and then filtered to obtain a separation functional layer. The separation functional layer is dried and collected in a sealed container. A 6N aqueous sodium hydroxide solution is added, and the mixture is heated to 120 ° C. for dissolution, followed by filtering insoluble matters. The obtained filtrate is put in an NMR tube and analyzed by an FT-NMR analyzer, and the compound is identified from the δ value of the obtained proton.

  Examples of the liquid containing the second treatment compound used in the method of the present invention include sulfamic acid, ammonia, an acid salt thereof, and an aqueous solution containing one or more of amino acids. Among these, a sulfamic acid aqueous solution is particularly preferable because of its high reactivity.

  Here, the concentration of the aqueous sulfamic acid solution brought into contact with the membrane is preferably in the range of 0.01 to 1% by weight at 20 ° C. If it is within this range, it is possible to obtain a sufficient effect for quickly reacting with and removing the excess diazonium chloride compound in the film.

  The time for contacting the membrane with the liquid containing the second treatment compound is preferably 10 seconds or longer and within 24 hours, preferably within 1 hour, because it reacts quickly with the excess diazonium chloride compound in the membrane. More preferably.

When the performance of the semipermeable membrane having the separation functional layer of the present invention is 25 ° C., pH 6.5, and an aqueous solution having a sodium chloride concentration of 0.2% by weight is permeated at an operating pressure of 0.5 MPa, the salt removal rate Is 60% or more, and the amount of permeated water is preferably 0.4 m ³ / m ² · day or more.

  According to the present invention, when the semipermeable membrane once manufactured is modified and salt water having a pH of 6.5 and a sodium chloride concentration of 0.2% by weight is permeated at an operating pressure of 0.5 MPa. In addition, it is possible to easily obtain a semipermeable membrane having higher performance than that before the modification, both in terms of salt removal rate and permeated water amount.

  In the present invention, the form of the semipermeable membrane is not limited and may be a hollow fiber membrane or a flat membrane. In addition, the composite semipermeable membrane obtained by modification by the method of the present invention is used by forming an element or a module when used for liquid separation, but its form is also particularly limited to a module type, a spiral type, etc. is not.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

<Characteristic evaluation 1>
The characteristics of the membranes in Reference Example 1, Comparative Example 1, Comparative Example 2, and Example 1 are as follows. Seawater (TDS concentration: about 3.5%, boron concentration: about 3.5%) adjusted to a composite semipermeable membrane at a temperature of 25 ° C. and a pH of 6.5. 5.0 ppm) was supplied at an operating pressure of 5.5 MPa, membrane filtration was performed, and the quality of the permeated water and the feed water was measured, and the following formula was obtained.

(TDS removal rate)
TDS removal rate (%) = 100 × {1− (TDS concentration in permeated water / TDS concentration in feed water)}
(Membrane permeation flux)
Membrane permeation flux (m ³ / m ² / day) was expressed in terms of the permeation amount of the feed water (seawater) per square meter of the membrane surface with the permeation amount per day (cubic meter).

(Reference Example 1)
A fabric-reinforced polysulfone support membrane (ultrafiltration membrane), which is a porous support membrane, was produced by the following method. That is, a wet nonwoven fabric having a permeability of 0.7 cm ³ / cm ² · second and an average pore diameter of 7 μm or less, comprising a mixed yarn of polyester fiber having a single yarn fineness of 0.5 dtex and 1.5 dtex polyester fiber. An object having a size of 30 cm in length and 20 cm in width was fixed on a glass plate, and a solution of dimethylformamide (DMF) solvent having a polysulfone concentration of 15% by weight (2.5 poise: 20 ° C.) was added to the glass plate. The film was cast to a thickness of 210 to 215 μm and immediately immersed in water to produce a polysulfone porous support membrane. The obtained porous support membrane is referred to as a PS support membrane.

The PS support film thus obtained was immersed in a 3.4% by weight aqueous solution of metaphenylenediamine (hereinafter referred to as mPDA) for 2 minutes, the support film was slowly pulled up in the vertical direction, and nitrogen was blown from an air nozzle. After removing the excess aqueous solution from the surface of the support membrane, an n-decane solution containing 0.175% by weight of trimesic acid chloride (hereinafter referred to as TMC) was completely wetted at a rate of 160 cm ³ / m ^2. It was applied and allowed to stand for 1 minute. Next, in order to remove excess solution from the membrane, the membrane was held vertically for 1 minute to drain the solution. Then, it washed with 90 degreeC hot water for 2 minutes, and obtained the composite reverse osmosis membrane. The composite semipermeable membrane thus obtained was evaluated. The membrane permeation flux and the TDS removal rate were the values shown in Table 1, respectively.

(Comparative Example 1)
The membrane obtained in Reference Example 1 was immersed in a 0.05 wt% sodium nitrite aqueous solution adjusted to pH 3.0 with concentrated sulfuric acid at 35 ° C. for 30 seconds, and then immediately immersed in a water bath. When the obtained composite semipermeable membrane was evaluated, the membrane permeation flux and the TDS removal rate were the values shown in Table 1, respectively.

(Comparative Example 2)
The film obtained in Reference Example 1 was immersed in a 0.1% aqueous sulfamic acid solution at 20 ° C. for 3 hours. When the obtained composite semipermeable membrane was evaluated, the membrane permeation flux and the TDS removal rate were the values shown in Table 1, respectively.

Example 1
The film obtained in Comparative Example 1 was immersed in a 0.1% aqueous sulfamic acid solution at 20 ° C. for 3 hours. When the obtained composite semipermeable membrane was evaluated, the membrane permeation flux and the TDS removal rate were the values shown in Table 1, respectively.

  From the results of Example 1 and Comparative Examples 1 and 2, it can be seen that in order to improve both the membrane water permeability and the desalination rate, it is necessary to use nitrous acid treatment and sulfamic acid treatment in combination.

<Characteristic evaluation 2>
The characteristics of the membranes in Reference Example 2, Reference Example 3, Reference Example 4, Comparative Example 3, Comparative Example 4, Example 2, and Example 3 were as follows: composite semipermeable membrane, temperature 25 ° C., pH 6.5 sodium chloride concentration 0 . The salt water adjusted to 2% by weight was supplied at an operating pressure of 0.5 MPa, membrane filtration treatment was performed, and the quality of the permeated water and the feed water was measured, and the following formula was obtained.

(Salt removal rate)
Salt removal rate (%) = 100 × {1− (salt concentration in permeated water / salt concentration in feed water)}
(Membrane permeation flux)
Membrane permeation flux (m ³ / m ² / day) was expressed in terms of the permeation amount of the feed water (salt water) per square meter of the membrane surface with the permeation amount per day (cubic meter).

(Reference Example 2)
When the membrane obtained in Reference Example 1 of <Characteristic Evaluation 1> was evaluated under the conditions shown in <Characteristic Evaluation 2>, the membrane permeation flux and the salt removal rate were the values shown in Table 2, respectively.

(Reference Example 3)
The PS support membrane was immersed in a 3.1 wt% aqueous solution of mPDA for 2 minutes, the support membrane was slowly pulled up vertically, and nitrogen was blown from an air nozzle to remove excess aqueous solution from the surface of the support membrane. An n-decane solution containing% by weight was applied at a rate of 160 cm ³ / m ² so that the surface of the support membrane was completely wetted and allowed to stand for 1 minute. Next, in order to remove excess solution from the membrane, the membrane was held vertically for 1 minute to drain the solution. Then, it washed with 90 degreeC hot water for 2 minutes, and obtained the composite reverse osmosis membrane. When the composite semipermeable membrane thus obtained was evaluated, the membrane permeation flux and the salt removal rate were the values shown in Table 2, respectively.

(Reference Example 4)
After immersing the PS support membrane in a 2.0% by weight aqueous solution of mPDA for 2 minutes, the support membrane was slowly pulled up in the vertical direction, and nitrogen was blown from the air nozzle to remove excess aqueous solution from the surface of the support membrane. An n-decane solution containing% by weight was applied at a rate of 160 cm ³ / m ² so that the surface of the support membrane was completely wetted and allowed to stand for 1 minute. Next, in order to remove excess solution from the membrane, the membrane was held vertically for 1 minute to drain the solution. Then, it washed with 90 degreeC hot water for 2 minutes, and obtained the composite reverse osmosis membrane. When the composite semipermeable membrane thus obtained was evaluated, the membrane permeation flux and the salt removal rate were the values shown in Table 2, respectively.

(Comparative Example 3)
The membrane obtained in Reference Example 3 was immersed in a 0.35 wt% sodium nitrite aqueous solution adjusted to pH 3.0 with concentrated sulfuric acid at 35 ° C. for 2 minutes, and then immediately immersed in a water bath. When the obtained composite semipermeable membrane was evaluated, the membrane permeation flux and the salt removal rate were the values shown in Table 2, respectively.

(Comparative Example 4)
The membrane obtained in Reference Example 4 was immersed in a 0.35 wt% sodium nitrite aqueous solution adjusted to pH 3.0 with concentrated sulfuric acid at 35 ° C. for 2 minutes, and then immediately immersed in a water bath. When the obtained composite semipermeable membrane was evaluated, the membrane permeation flux and the salt removal rate were the values shown in Table 2, respectively.

(Example 2)
The film obtained in Comparative Example 3 was immersed in a 0.1% aqueous sulfamic acid solution at 30 ° C. for 5 minutes. When the obtained composite semipermeable membrane was evaluated, the membrane permeation flux and the salt removal rate were the values shown in Table 2, respectively.

(Example 3)
The film obtained in Comparative Example 4 was immersed in a 0.1% aqueous sulfamic acid solution at 30 ° C. for 5 minutes. When the obtained composite semipermeable membrane was evaluated, the membrane permeation flux and the salt removal rate were the values shown in Table 2, respectively.

  From the results of Examples 2 and 3 and Comparative Examples 3 and 4, it can be seen that it is necessary to use nitrous acid treatment and sulfamic acid treatment together in order to improve the membrane water permeability and the desalination rate most.

Claims (1)

A method for producing a composite semipermeable membrane, comprising a separation functional layer containing a primary amino group by reacting a polyfunctional amine containing metaphenylenediamine with a polyfunctional acid halide on a porous support membrane. Forming a semipermeable membrane;
Contacting the semipermeable membrane having the separation functional layer with a compound (I) that reacts with a primary amino group to produce a diazonium salt or a derivative thereof to form a diazonium salt;
And a step of contacting a water-soluble compound (II) having reactivity with at least one compound (I) selected from the group consisting of sulfamic acid, ammonia, an acid salt thereof, and an amino acid. A method for producing a composite semipermeable membrane.