JPH0910565A - Semipermeable composite membrane - Google Patents

Abstract

PURPOSE: To provide a nano-filtration composite membrane and a reverse osmosis composite membrane in which water permeation performance is excellent even in the conditions of ultra-low pressure and resistance to an oxidizing agent is equipped by specifying an amino compound and membrane performance respectively in the case of forming a separation active layer of polyamide obtained by polycondensation of a polyfunctional reactive amino compound and a polyfunctional reactive acid halide. CONSTITUTION: A semipermeable composite membrane is composed of a thin separation active layer and a microporous supporting membrane for supporting the layer. The separation active layer comprises polyamide obtained by polycondensation of a polyfunctional reactive amino compound and a polyfunctional acid halide having at least two halogenated carbonyl groups of in a molecule. The polyfunctional reactive amino compound is shown by the formula (wherein R1 to R3 denote the same or different linear organic group, and R4 to R6 denote hydrogen or the same or different at most 5 C aliphatic organic group) and an amino group in the molecule is directly bonded to secondary or tertiary carbon. In the semipermeable composite membrane obtained by such a method, the removing rate for magnesium sulfate of 500mg/l concentration of supply liquid is >=10% at 1-10kg/cm<2> of operation pressure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a semipermeable separation membrane used for selectively permeating a solid or a solute from a liquid mixture, and further to a reverse osmosis membrane and a reverse osmosis membrane. The present invention relates to a nanofiltration membrane having selective separation characteristics intermediate between those of ultrafiltration membranes.

[0002]

2. Description of the Related Art Separation and concentration of a liquid mixture by a membrane method are performed by:
Compared to separation technology such as distillation, it is an energy-saving method and it does not change the state of the substance, so it concentrates fruit juice, food fields such as separation of beer enzymes, drinking water by desalination of seawater and brackish water, production of industrial water, etc. It is widely used in various fields such as water purification field such as ultrapure water production in electronic industry, aseptic water production in pharmaceutical industry and medical field, and recovery of valuable materials from industrial wastewater. The expansion of such applications has promoted the development of new separation membranes and new separation techniques using separation membranes, and in particular, has seen rapid development in recent years. What has spurred this development is the need in the ultrapure water field, where the demand for higher-quality semiconductors has increased with the high integration of semiconductors, and progress has been made in response to this demand. This is probably the establishment of a composite membrane technology by the interfacial polymerization method.

Generally, a separation active layer and a supporting layer made of the same material is called an asymmetric membrane, and a material made of different materials is called a composite membrane. Asymmetric membranes can generally be obtained by the phase inversion method, while composite membranes are produced by the same procedure as for asymmetric membranes, after forming a supporting membrane to serve as a supporting layer, and then coating, interfacial polymerization or plasma polymerization methods on the surface of this. Etc. to form a thin separation active layer. Among these, the interfacial polymerization method involves dissolving two or more kinds of reactive monomers that react with each other in water and an organic solvent immiscible with water, bringing the solutions into contact with each other, and reacting at the interface to produce a polymer. In this method, an interfacial polymerization reaction is carried out on the surface of a microporous support membrane made of polysulfone to obtain a composite membrane. The present invention relates to a composite membrane obtained by this interfacial polymerization method.

Studies on reverse osmosis composite membranes by the interfacial polymerization method
Mainly in the US North Star Research and Development
The NS-100 (1972
Year), NS-200 (1973), NS-300 (1977) and FT-30
(1978) etc. Among these, NS-100 is a polysulfone ultrafiltration membrane coated with an aqueous solution of polyethyleneimine, which is a water-soluble amine, and then contacted with a hexane solution containing tolylene diisocyanate, a bifunctional monomer that reacts with amino groups. To form a water-insoluble polymer having a urea bond (JP-A-49-1).
33282). In addition, NS-200 uses furfuryl alcohol instead of the polyethyleneimine, and an aqueous solution containing this and sulfuric acid or the like as an acid catalyst is applied to the surface of the polysulfone microporous support membrane and heat treated at about 150 ° C to increase the crosslinking. The active layer composed of a water-insoluble polymer is formed by simultaneously performing molecularization and sulfonation (JECadotte).
et.al., OSW PB-Rep., No.982 (1974)). Furthermore NS-300
Is piperazine instead of polyethyleneimine, and an aqueous solution containing this and a basic compound as an acid scavenger is applied to the surface of the polysulfone microporous support membrane to prepare a hexane solution containing bifunctional and trifunctional carboxylic acid chlorides. A water-insoluble polymer having an amide bond is formed by contacting with (JP-B1-38522, USP-4,259,183, JECa).
dotte et. al., OSW PB-Rep., 80-127574), FT-30 uses meta-phenylenediamine instead of piperazine.
A water-insoluble polymer having an amide bond is formed by the same method as NS-300 (USP-4,277,344, JP-A-55-1).
47106).

The above reverse osmosis composite membrane was developed with the goal of desalination of seawater from the historical background of its development, and has high desalination performance and water permeation performance. In particular, FT-30 is still in practical use today. Have been used for. However, when NS-100 is subjected to reverse osmosis treatment under low pressure when desalting canned water, water permeability is often low and satisfactory membrane performance is not obtained, and NS-100 It also has the drawback of not being sufficiently chlorinated, while NS-200 and NS-300 have a very thin coating of the active layer, so defects can easily occur due to scratches or foreign matter on the microporous support membrane, and stable reproduction is possible. It was difficult to obtain a reverse osmosis membrane with good performance and high performance. Despite these drawbacks NS
Regarding -300, since this reverse osmosis composite membrane uses piperazine consisting of a secondary amino group, it has characteristics such as excellent resistance to oxidizing agents, which is important when actually using the reverse osmosis membrane. Things were also found.

In order to respond to diversified uses and higher quality of required water quality, various water-soluble polymers and monomers or combinations of monomers and monomers utilizing this interfacial polymerization reaction have been studied, and various inverses have been investigated. Infiltration composite membranes have been put to practical use. In particular, the progress of low-pressure reverse osmosis composite membranes used when the solute concentration in the liquid to be treated is low and the osmotic pressure is low, is currently i) low pressure and high inhibition with high reverse osmosis performance at lower operating pressure. Reverse osmosis membrane, i
i) It is roughly classified into a low pressure low blocking reverse osmosis membrane having a blocking performance intermediate between the ultrafiltration membrane and the reverse osmosis membrane at a low operating pressure. The low pressure low blocking reverse osmosis membrane is also called a nanofiltration membrane.

The low-pressure high-blocking reverse osmosis membrane has a very high sodium chloride rejection rate of 98-99.5% even at an operating pressure of 15-20 kg / cm ² , and is also excellent in water permeation performance. 147
106, JP-A-55-137005, JP-A-57-27102 or JP-A-63-218208, the main component of which is an aromatic cross-linked polyamide formed by an interfacial polymerization reaction in the active layer of a composite film. Many things are known.

On the other hand, a reverse osmosis membrane having a sodium chloride rejection rate of less than 90% is defined as a nanofiltration membrane, and this membrane is also characterized by having a high rejection rate for organic substances having a molecular weight of several hundreds. It is used for softening water with high hardness, desalting water-soluble organic substances with a molecular weight of 100 or more such as sugar and organic acids, desalting and concentrating amino acids, and concentrating and recovering low-molecular-weight organic valuables in the food industry. Recently, attention has been paid to the use of purified water treatment for the purpose of removing soluble organic substances in a simple water supply facility, wastewater treatment for the purpose of recovering industrial wastewater, and the like. Currently published nanofiltration membranes are composite membranes similar to low-pressure high-inhibition reverse osmosis membranes, and some have been reported to consist of inorganic compounds, but the active layer contains sulfonated polysulfone and fat formed by interfacial polymerization reaction. Many are known to have a cross-linked polyamide containing a group component as a main component.

As a composite film having a crosslinked polyamide containing an aliphatic component as an active layer, an active layer made of polyamide produced by interfacial polymerization of a polyfunctional aromatic amine and a polyfunctional aliphatic acid halide has been used so far. It is known that it is formed on a hydrophilic support film (see, for example, JP-A-62-25870).
No. 5, JP-A-63-218208, etc.). It is also known that an active layer made of polyamide produced by interfacial polymerization of a polyfunctional aliphatic amine and a polyfunctional aromatic acid halide is formed on a microporous support film as in the case of NS-100 described above. (For example, EP-A1-0313354, Japanese Patent Publication No. 2-53089, Japanese Patent Publication
2-39299, Japanese Patent Publication No. 5-65213, etc.).

However, these composite membranes have, for example, 5k
The water permeation performance is insufficient under ultra low pressure operation conditions of g / cm ² or less, and there is a demand for nanofiltration membranes and reverse osmosis membranes having excellent water permeation performance even under such ultra low pressure conditions.

[0011]

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide a nanofiltration composite membrane and a reverse osmosis composite membrane which are excellent in water permeation performance even under ultra-low pressure conditions and are also excellent in resistance to oxidizing agents such as chlorine. And

[0012]

Means for Solving the Problems That is, the present invention provides a semipermeable composite membrane comprising a thin separation active layer and a microporous support membrane supporting the thin separation active layer, wherein the separation active layer comprises:

[0013]

Embedded image (Wherein R 1, R 2 and R 3 independently represent a linear aliphatic organic group which may be the same or different;
1, the total number of carbon atoms of all the organic groups constituting R2 and R3 is 3 or more and 15 or less, and R4, R5 and R6 may independently be the same or different from each other, or hydrogen or a carbon number of 5 or less. Represents an aliphatic organic group, l and n represent 0 or a positive integer, m represents an integer of 1 or more, and also l +
m = n ≧ 2), at least one of the amino groups present in the molecule represented by the formula is a polyfunctional reactive amino compound directly bonded to a secondary or tertiary carbon as a main amine component unit, It comprises a polyamide obtained by polycondensing the amine component and a polyfunctional reactive acid halide having two or more carbonyl halide groups in one molecule, and has an operating pressure of 1-10.
Disclosed is a semipermeable composite membrane having a removal rate of 10% or more for magnesium sulfate having a feed solution concentration of 500 mg / l at Kg / cm ² .

The separation active layer in the present invention is a thin film layer having substantially separation performance and made of polyamide which can be obtained by a polycondensation reaction of a polyfunctional reactive amino compound and a polyfunctional reactive acid halide. . The thickness of the thin film layer is preferably as thin as there are no pinholes, but in order to maintain mechanical strength or chemical resistance, it must have an appropriate thickness. Considering film forming stability, permeation performance, etc. It is preferably 1.0 μm or less, more preferably 0.5 μm or less. A protective layer made of, for example, polyvinyl alcohol, polyacrylic acid, or polyvinylpyrrolidone may be formed on the surface of the separation active layer, if necessary.

The polyfunctional reactive amino compound referred to in the present invention is essentially a monomer compound having two or more primary amino groups or secondary amino groups in the molecule, and At least one of the groups represents an essentially linear aliphatic amino compound directly bonded to the secondary or tertiary carbon.

Specifically, for example, 1,2-diaminopropane, 1,2-diamino-2-methylpropane, N-
Isopropyl-1,2-diamino-2-methylpropane, N, N'-dimethyl-1,2-diaminopropane,
N '-(2-hydroxyethyl) -1,2-diamino-
2-methylpropane, 1,3-diaminobutane, 2,3
-Diaminobutane, 1,3-diaminopentane, 2,4
-Diaminopentane, 2,4-diamino-2-methylpentane, N, N'-diethyl-1,4-diaminopentane, 2,5-diamino-2,5-dimethylhexane and the like can be mentioned. A single type or a mixture can be used. In the present invention, 1,2-diaminopropane, 1,2-diamino-2-methylpropane and 1,3-diaminobutane are particularly preferably used.

The polyfunctional reactive acid halide used in the present invention is essentially a monomer and is an aromatic or aliphatic acid halide having two or more carbonyl halide groups in one molecule. As the aromatic acid halide, trimesic acid halide, trimellitic acid halide, isophthalic acid halide, terephthalic acid halide, pyromellitic acid halide, benzophenonetetracarboxylic acid halide, biphenyldicarboxylic acid halide, naphthalenedicarboxylic acid halide, pyridinedicarboxylic acid Examples thereof include acid halides, and these can be used alone or as a mixture. In the present invention, trimesic acid chloride alone, or a mixture of trimesic acid chloride and isophthalic acid chloride, or a mixture of trimesic acid chloride and terephthalic acid chloride is preferably used.

As the aliphatic acid halide, polyfunctional compounds such as cyclobutanedicarboxylic acid halide, cyclopentanedicarboxylic acid halide, cyclopentanetricarboxylic acid halide, cyclopentanetetracarboxylic acid halide, cyclohexanedicarboxylic acid halide and cyclohexanetricarboxylic acid halide Alicyclic acid halides, or propane tricarboxylic acid halides, butane tricarboxylic acid halides, pentane tricarboxylic acid halides, succinic acid halides, glutaric acid halides, and the like, and these can be used alone or in a mixture. Further, a mixture with the above-mentioned polyfunctional aromatic acid halide can also be used.

Further, the microporous support membrane in the present invention is a membrane that does not exhibit substantially no separation performance for an object to be separated and supports the separation active layer, and is a conventionally known microporous support membrane. Any structure may be used as long as it has fine pores of preferably 0.1 μm or less, more preferably 0.05 μm or less on its outer surface, and the structure up to the back surface other than the outer surface has fluid permeation resistance more than necessary. In order not to increase the size, it is preferable that the pores are larger than the fine pores on the outer surface, and the mesh-like shape,
It may be either a finger void or a mixed structure thereof.
Also, these microporous support membranes may be reinforced by being lined with a woven or non-woven fabric. Its transmission performance is 0.2-10
m ³ / (m ²・ day ・ (kg / cm ² )), preferably 0.5 to ⁵ m ³ / (m ²・
(Kg / cm ² ) / day, and if the amount of water permeation is too small, the permeation performance of the resulting composite membrane will also be small, and if it is too large, the strength as a supporting membrane will be small, so depending on the operating pressure, it may become The sexual support membrane may be destroyed.

As a material for the microporous support film, any material can be used as long as it can be formed into the microporous support film. However, it is necessary that the microporous support membrane is not chemically damaged by the solvent used in the production of the composite membrane, and polysulfone and polyethersulfone are preferably used in view of chemical resistance, film-forming property, durability and the like. It is preferable that at least one selected from polyacrylonitrile, polyethylene, polypropylene, and polyamide is contained as a main component, more preferably at least one selected from polysulfone and polyether sulfone is contained as a main component.

When the microporous support membrane is of a hollow fiber type, the size of the microporous hollow fiber support membrane is not particularly limited, but it is outside considering the operability during membrane formation, the membrane area of the module, and the pressure resistance. Diameter 100 (μm) to 2000 (μm), inner diameter 30
(Μm) to 1800 (μm) is preferable, outer diameter is 150 (μm) to 500 (μm), inner diameter is 50 (μm) to 30
0 (μm) is more preferable. Furthermore, it is necessary to withstand at least a pressure higher than the operation pressure of the composite hollow fiber membrane. Such a microporous hollow fiber supporting membrane can also be selected from the above materials, and can be usually produced by a known dry-wet film forming method or melt film forming method. Further, if necessary, a well-known wet heat treatment for the microporous hollow fiber support membrane after membrane formation (PB Report 76-248666, JP-A-58-199007).
It is also possible to perform hot water treatment (Japanese Patent Laid-Open No. 60-190204).

In the semipermeable composite membrane of the present invention, for example, a first solution comprising an aqueous solution containing the polyfunctional reactive amino compound is uniformly applied on the surface of the microporous support membrane by a coating method or a dipping method. And continuously coated, and then the excessively applied first solution is drained by a natural flow-down method, a pressing method, a drying method or the like, and then the water-immiscible organic solvent containing the polyfunctional reactive acid halide. Second consisting of solution
The solution can be obtained by forming a separation active layer made of polyamide on the surface of the microporous support membrane by an interfacial polymerization reaction that progresses by applying the solution using the above means, but these are not always required. The method is not limited to.

The semipermeable composite membrane thus obtained is subsequently subjected to a heat treatment at about 20 to 150 ° C., preferably 50 to 130 ° C. for about 1 to 10 minutes, preferably 2 to 8 minutes. It is more preferable as the method for producing the semipermeable composite membrane in.

The concentrations of the polyfunctional reactive amino compound and the polyfunctional reactive acid halide contained in the first solution and the second solution differ depending on the kind of the polyfunctional reactive compound and the partition coefficient to the solvent, and are not particularly limited. However, the polyfunctional reactive amino compound is generally about 0.1 to 10% by weight, preferably about 0.5 to 5% by weight, and the polyfunctional reactive acid halide is about 0.01 to 10% by weight. It is preferably about 0.1 to 5% by weight. If the concentration of these is low, the formation of the interfacial polymerized film is incomplete and defects are likely to occur, leading to a decrease in separation performance.On the contrary, if the concentration is too high, the interfacial polymerized film becomes too thick and the permeation performance deteriorates. The amount of residual unreacted substances of (3) increases, which may adversely affect the membrane performance.

Further, as the solvent of the first solution and the solvent of the second solution, the polyfunctional reactive amino compound and the polyfunctional reactive acid halide are respectively dissolved, and when the solutions come into contact with each other, the liquid-liquid interface is formed. There is no particular limitation as long as it is formed and does not damage the microporous support film. As such a solvent, for example, the solvent of the first solution is water, alcohol alone or a mixture, and the solvent of the second solution is n-.
Examples thereof include hydrocarbon solvents such as hexane, cyclohexane, n-heptane, n-octane, n-nonane, and n-decane, alone or in a mixture.

Further, in order to promote the above-mentioned interfacial polymerization reaction, alkali is used as an acid scavenger capable of removing hydrogen halide generated by the reaction, and wettability with a microporous support film is improved. Therefore, a surfactant can be used, or a catalyst for accelerating the reaction can be used as necessary. Examples of acid scavengers include:
Examples thereof include caustic alkali such as sodium hydroxide, sodium phosphate such as trisodium phosphate, sodium carbonate such as sodium carbonate, and tertiary amines such as trimethylamine, triethylamine and triethylenediamine. Examples thereof include sodium lauryl sulfonate, sodium lauryl benzene sulfonate, sodium dodecyl benzene sulfonate, and the like, and examples of the catalyst include dimethylformamide and the like. These can be included in the first solution or the second solution in advance.

The semipermeable composite membrane thus obtained is
This alone expresses sufficiently good membrane performance, but as disclosed in Japanese Patent Publication No. Sho 63-36803, the semipermeable composite membrane is further subjected to chlorine treatment with hypochlorous acid or the like to improve salt removal performance. It is also possible to improve.

[0028]

EFFECT OF THE INVENTION The semipermeable composite membrane according to the present invention has 1 to 10 because the separation active layer contains specific components as its constituent components.
Nanofiltration, which has the characteristics of excellent water permeation performance even under operating conditions of ultra-low pressure of Kg / cm ² and also excellent resistance to oxidants such as chlorine, and practical performance under operating conditions of ultra-low pressure. It provides a semipermeable composite membrane that enables the softening of water with high hardness and a molecular weight of 100, such as sugar and organic acids.
Water purification treatment for the purpose of desalting the above water-soluble organic substances, desalting and concentrating amino acids, concentrating and recovering low-molecular weight organic valuables in the food industry, and removing soluble substances in simple water facilities
It can be suitably used in fields of use such as wastewater treatment for the purpose of recovering industrial wastewater.

[0029]

The present invention will be described below with reference to examples and comparative examples, but the examples given here do not limit the present invention.

Example 1 2.0% by weight of 1,2-diamino-2-methylpropane, 0.1% by weight of sodium lauryl sulfate, 0.2% of sodium carbonate
A commercially available polysulfone microporous support membrane (Toyo Roshi Kaisha, Ltd., UK-50) was dipped in an aqueous solution containing 50% by weight at 25 ° C for several minutes, and then the excess aqueous solution was removed by a squeezing method to form an aqueous solution on the support membrane. The liquid film layer of was formed.

Then, a hexane solution containing 0.4% by weight of trimesic acid chloride was contacted with the supporting membrane at 25 ° C. for several seconds, left in the air for several minutes, and then kept in a hot air dryer at 50 ° C. for 4 minutes. Then, a separation active layer was formed on the supporting membrane to obtain a target semipermeable composite membrane.

The obtained semipermeable composite membrane was thoroughly washed with water and then mounted in a membrane performance evaluation cell, and the concentration of magnesium sulfate in the feed solution was 0.05%, the feed solution pH was 6.5, and the feed solution temperature was 25.
° C., the operating pressure: 5Kg / cm ^2, the recovery rate: was evaluated at 5% for the salt removal rate in electric conductivity measurement of the permeate 96.2
%, And the amount of permeated water was 2.5 m ³ / m ² · day. The salt removal rate in the conductivity measurement means the salt removal rate (%) = [1−
(Conductivity of permeated liquid) / (conductivity of supply liquid)] × 100.

Example 2 The semipermeable composite membrane obtained in Example 1 was further immersed in an aqueous solution of 500 mg / l sodium hypochlorite for 15 hours at 25 ° C., and then under the same conditions as in Example 1. When the membrane performance was evaluated, the salt removal rate in the conductivity measurement of the permeated liquid was 98.0%, and the permeated water amount was 1.7 m ³ / m ² · day. The membrane was further immersed in 300 mg / l sodium hydrogen sulfite aqueous solution at 25 ° C.
After soaking for 60 minutes, the membrane performance was evaluated again under the same conditions as in Example 1. As a result, the salt removal rate in the conductivity measurement of the permeate was 96.5%, and the permeated water amount was 2.4 m ³ / m ² · day. The performance and the performance recovery after chlorine exposure were also good.

Examples 3 to 6 In Example 1, as the polyfunctional reactive amino compound, 1,2-diaminopropane, N, N'-dimethyl-1,
2-diaminopropane, 1,3-diaminobutane, 1,
A semipermeable composite membrane was prepared in the same manner as in Example 1 except that 3-diaminopentane was used. Table 1 also shows these membrane performances.

Example 7 A semipermeable composite membrane was prepared in the same manner as in Example 1 except that 1,3,5-cyclohexanetricarboxylic acid chloride was used as the polyfunctional reactive acid halide. . Table 1 also shows these membrane performances.

Example 8 A semipermeable composite membrane was prepared in the same manner as in Example 1 except that a mixture of trimesic acid chloride and isophthalic acid chloride was used as the polyfunctional reactive acid halide. Table 1 also shows these membrane performances.

Comparative Examples 1 to 4 In Example 1, as the polyfunctional reactive amino compound, metaphenylenediamine, 1,3-propanediamine,
A semipermeable composite membrane was prepared in the same manner as in Example 1 except that 1,5-pentanediamine and N, N′-diethylethylenediamine were used. Table 1 also shows these membrane performances.

Reference Example 1 25 parts by weight of aromatic polysulfone (UDEL P-3500, manufactured by Amoco), 0.5 parts by weight of sodium laurylbenzenesulfonate, polyethylene glycol (molecular weight: 400)
A membrane-forming solution consisting of 5 parts by weight and DMAC 69.5 parts by weight was discharged from the tube-in-orifice nozzle into the coagulation bath through the running part in the air to obtain a microporous hollow fiber supporting membrane.

The obtained hollow fiber membrane was thoroughly washed with water and then washed with 85
Heat treatment was performed for 30 minutes at ℃, to create a mini module. Attaching such a mini module to the ultrafiltration membrane performance evaluation cell,
Dextran (molecular weight: 185,000) concentration in the feed solution: 500m
When the ultrafiltration membrane performance was confirmed under the conditions of g / l, feed liquid temperature: 25 ° C, operating pressure: 2 Kg / cm ² , the dextran removal rate was
87.1%, the amount of permeated water was 7.0 m ³ / m ² · day. The dextran concentration in the feed water and the permeate was measured by the anthrone-sulfuric acid method.

Example 9 2.0% by weight of 1,2-diamino-2-methylpropane, 0.1% by weight of sodium lauryl sulfate, sodium hydroxide
The polysulfone microporous hollow fiber support membrane obtained in Reference Example 1 was immersed in an aqueous solution containing 2% by weight at 25 ° C. for several minutes, and then the excess aqueous solution was removed by a hot air method to form an aqueous solution on the support membrane. The liquid film layer of was formed.

Then, a hexane solution containing 1.0% by weight of trimesic acid chloride was brought into contact with the supporting film at 25 ° C. for several seconds, and then passed through a hot air drying tower at 50 ° C. for several seconds to form a film on the supporting film. A separation active layer was formed to obtain a desired semipermeable hollow fiber composite membrane.

The obtained semipermeable hollow fiber composite membrane was thoroughly washed with water and then mounted on a membrane performance evaluation cell, and the concentration of magnesium sulfate in the feed solution was 0.05%, the pH of the feed solution was 6.5, and the temperature of the feed solution was 25. When evaluated under the conditions of ℃ and operating pressure: 5 kg / cm ² , the salt removal rate in the conductivity measurement of the permeated liquid was 93.4%, and the permeated water amount was 1.8 m ³ / m ² · day.

Example 10 Using the semipermeable hollow fiber composite membrane obtained in Example 9, magnesium sulfate concentration in the feed solution: 0.05%, feed solution pH: 6.5.
, Feed liquid temperature: 25 ℃, operating pressure: 2Kg / cm ² , recovery rate:
When evaluated under the condition of 1%, the salt removal rate in the conductivity measurement of the permeated liquid was 85.0%, and the amount of permeated water was 0.7 m ³ / m ² ·
It was a day.

Example 11 Using the semipermeable hollow fiber composite membrane obtained in Example 9, magnesium sulfate concentration in the feed solution: 0.05%, feed solution pH: 6.5.
When the feed liquid temperature: 25 ° C and the operating pressure: 10 kg / cm ² were evaluated, the salt removal rate in the conductivity measurement of the permeate was
It was 98.1%, and the amount of permeated water was 3.5 m ³ / m ² · day.

Comparative Example 5 A semipermeable composite membrane was prepared in the same manner as in Example 11 except that metaphenylenediamine was used as the polyfunctional reactive amino compound in Example 12, and the same conditions as in Example 1 were used. When the membrane performance was evaluated, the salt removal rate in the conductivity measurement of the permeated liquid was 98.2%, and the permeated water amount was 0.2 m ³ / m ² · day.

The semipermeable composite membrane was further immersed in an aqueous solution of 500 mg / l of sodium hypochlorite for 15 hours at 25 ° C., and then the membrane performance was evaluated under the same conditions as in Example 1.
The salt removal rate in the conductivity measurement of the permeated liquid was 57.1%, the permeated water amount was 0.5 m ³ / m ² · day, and the separation active layer was decomposed by chlorine exposure and the performance deteriorated.

[0047]

[Table 1]

Claims (6)

[Claims] 1. A semipermeable composite membrane comprising a thin separation active layer and a microporous support membrane supporting the thin separation active layer, wherein the separation active layer comprises: (Wherein R 1, R 2 and R 3 independently represent a linear aliphatic organic group which may be the same or different;
1, the total number of carbon atoms of all organic groups constituting R2 and R3 is 3 or more and 15 or less, and R4, R5 and R6 may independently be the same or different from each other, or hydrogen or a carbon number of 5 or less. Represents an aliphatic organic group, l and n represent 0 or a positive integer, m represents an integer of 1 or more, and also l +
m = n ≧ 2), at least one of the amino groups present in the molecule represented by the formula is a polyfunctional reactive amino compound directly bonded to a secondary or tertiary carbon as a main amine component unit, It comprises a polyamide obtained by polycondensing the amine component and a polyfunctional reactive acid halide having two or more carbonyl halide groups in one molecule, and has an operating pressure of 1 to 10
A semipermeable composite membrane having a removal rate of 10% or more for magnesium sulfate having a feed solution concentration of 500 mg / l at Kg / cm ² . ## STR2 ## (Wherein R 1, R 2 and R 3 independently represent a linear aliphatic organic group which may be the same or different;
1, the total number of carbon atoms of all the organic groups constituting R2 and R3 is 3 or more and 15 or less, o and q represent 0 or a positive integer, p represents an integer of 1 or more, and in addition, o + p + q ≧
2. The semipermeable composite membrane according to claim 1, wherein the semipermeable composite membrane comprises a polyamide containing a polyfunctional reactive amino compound represented by (2) as a main amine component unit. (3) (Wherein R 7, R 8 and R 9 independently represent a linear aliphatic organic group which may be the same or different;
7. The semipermeable membrane according to claim 1, wherein the main amine component unit is a bifunctional reactive amino compound represented by the total carbon number of all the organic groups constituting 7, R8 and R9 is from 4 to 10). Composite membrane. 4. A polyfunctional reactive amino compound is 1,2-
The semipermeable composite membrane according to claim 1, which is diamino-2-methylpropane. 5. The semipermeable composite film according to any one of claims 1 to 4, wherein the acid halide is an aromatic polyfunctional acid chloride. 6. The semipermeable composite membrane according to claim 1, wherein the semipermeable composite membrane is a hollow fiber type semipermeable composite membrane.