JP3193792B2 - Hollow fiber membrane module - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hollow fiber membrane module having excellent solvent resistance.

[0002]

2. Description of the Related Art With the recent development of synthetic polymer chemistry,
Semipermeable membranes having various separation characteristics such as reverse osmosis type, ion exchange type, pervaporation type, ultrafiltration type and the like have been developed, and are manufactured in the form of a flat membrane, a spiral, a hollow fiber or the like.

[0003] Hollow fiber membrane modules can increase the membrane surface area per unit volume of the device, and can reduce the size and cost of the device. Therefore, they are widely used in medical applications, precision electronic industry applications, food industry applications, and physicochemical applications. It's being used.

To form a hollow fiber membrane into a module, the bundled hollow fiber membranes are filled in a module case, and the gap between the hollow fiber membranes and the gap between the hollow fiber bundle and the module case are fixed at the end of the module case or the like. Therefore, epoxy-based and urethane-based adhesives have conventionally been used. In particular, epoxy adhesives that cure with a polyamine-based curing agent
It is widely used because of its low curing temperature and practical heat resistance.

[0005] However, modules manufactured using these adhesives include butyl ether, ethyl acetate,
During high temperature chemical treatment such as filtration of organic solvents such as acetone, acetic acid, aniline, acetic anhydride, toluene, hexane, and trichlene, swelling and cracking of the adhesive occur, and the use is restricted in terms of solvent resistance. Have been.

In order to solve this problem, Japanese Patent Application Laid-Open No.
Japanese Patent No. 29006 discloses a technique of vulcanizing rubber having excellent chemical resistance to fix the end of the hollow fiber bundle.
A high temperature treatment of 160 ° C. or more is required for vulcanization, only hollow fibers made of a specific material can be used, and the manufacturing process is complicated.

[0007] JP-A-2-268815 discloses a resin comprising a reaction product of an epoxy resin having a polysulfide bond and an alicyclic amine, which fixes the ends of a large number of porous membranes to a membrane module case. Although a technique is disclosed, since an amine bond is present in the reaction product, it reacts with an organic acid such as acetic acid particularly in an organic solvent, swelling is remarkable, cracks and the like are generated, so use is limited. .

JP-A-3-221128 discloses a technique for fixing an end of a hollow fiber bundle with an adhesive resin containing at least one component of a polyolefin obtained by copolymerizing an unsaturated carboxylic acid. However, a polyolefin copolymerized with an unsaturated carboxylic acid alone has a problem in heat resistance, and when mixed with another polyolefin, the compatibility is poor and a long-term stability is a problem.

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above problems and to provide a hollow fiber module having excellent solvent resistance.

[0010]

Means for Solving the Problems As a result of intensive studies, the present inventors have solved the above-mentioned problems by curing an epoxy resin with a specific curing agent and fixing an end of a bundle of hollow fiber membranes. The present inventors have found that the present invention can be solved and completed the present invention.

That is, according to the present invention, an epoxy resin having neither an amine bond nor an ester bond in a resin as a base material is used as an adhesive for fixing an end of a bundle of hollow fiber membranes as a curing agent.
Aniline - it using a cationic polymerization type curing agent consisting of boron trifluoride complexes, the 80 wt% aqueous acetic acid solution 80 ° C.
Abnormality in the adhesive seal when contacted for at least 35 hours
The present invention relates to a hollow fiber membrane module having characteristics that do not occur .

As the epoxy resin , those cured with a cationic polymerization type curing agent and having no amine bond or ester bond in the resin are preferable, and novolak type epoxy resins and aromatic glycidyl ether type epoxy resins are particularly preferable. In order to improve heat resistance and solvent resistance, it is preferable to increase the crosslink density by blending a polyfunctional epoxy resin having three or more functional groups.

Examples of the cationic polymerization type curing agent include diazonium salts, iodonium salts, sulfonium salts, ferrocene salts, aluminum complex-silanol catalysts, boron trifluoride complexes, and the like, among which boron trifluoride complexes. An aniline-boron trifluoride complex is preferred in terms of solubility in an epoxy resin and a reaction initiation temperature. When the epoxy resin is cured with this hardener, the epoxy group is opened and linked by an ether bond, and a cured product particularly resistant to organic acids such as acetic acid is obtained. . Since the cationic polymerization type curing agent also polymerizes the epoxy group in a chain, the curing generally starts rapidly and the curing temperature becomes high. Therefore, the hollow fiber membrane should not melt or deteriorate.
Nodea the selection and amount of optimization Do curing agent is important
You .

It is preferable to add an inorganic filler to the adhesive in order to reduce the curing shrinkage and the exothermic temperature of the curing, to improve the mechanical strength such as the tensile strength, the heat resistance and the solvent resistance.

Examples of the inorganic filler include alumina, kaolin clay, carbon black, glass, graphite, calcium silicate, diatomaceous earth, magnesium oxide, titanium oxide, aluminum hydroxide, silica gel, talc, mica and the like. The selection and the amount of the filler are determined according to the purpose, the epoxy resin to be used, and the curing agent.

As the material of the hollow fiber membrane, various polymers can be used, for example, polyacrylonitrile resin, polymethyl methacrylate resin, polyethylene, polypropylene, cellulose acetate resin, polysulfone resin, polyethersulfone resin, polyimide Resin, silicon resin, Teflon resin, polyamide resin and the like.

By selecting a hollow fiber membrane, water, alcohols such as methanol, ethanol and isopropyl alcohol, ethers such as diethyl ether and dipropyl ether, esters such as ethyl acetate and ethyl propionate, acetone and methyl ethyl ketone Ketones, etc.
Organic acids such as acetic acid and propionic acid, amines such as diethylamine and aniline, aliphatic hydrocarbons such as hexane and octane, aromatic hydrocarbons such as benzene and toluene,
A mixture of at least two or more of organic compounds such as halogenated hydrocarbons such as chloroform and trichlene can be treated as a liquid to be separated.

The shape, material and the like of the module case are selected depending on the application. Usually, the shape of the module case is cylindrical, and a side surface of the module case has a nozzle used for supplying a processing liquid. As the material, conventionally known materials such as polyvinyl chloride, polycarbonate, polymethyl acrylate, polymethyl methacrylate, polysulfone, polyether sulfone, and stainless steel can be used.
Polyether sulfone and stainless steel are particularly preferred.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in more detail with reference to embodiments.

Example 1 A polyacrylonitrile copolymer hollow fiber membrane having an inner diameter of 500 μm and an outer diameter of 800 μm was treated with
After hydrolyzing at 0 ° C. for 55 minutes to convert a part of the nitrile group into a carboxyl group, polyion complex was formed with an ionene-type polycation. The hollow fiber membrane was uniformly bundled, the tip was sealed, and housed in a cylindrical polyethersulfone case. A phenol novolak type epoxy resin (Epicoat 152, manufactured by Yuka Shell Epoxy), which had been heated to 50 ° C. in advance, and an aniline-boron trifluoride complex were mixed at a weight ratio of 100: 2.5 and defoamed. The end of the case was filled by centrifugation and reacted at 60 ° C. for 2 hours to fix the hollow fiber bundle and the case. Further, post-curing was performed at 80 ° C. for 5 hours. The module was completed by cutting both ends to open the hollow fiber, and its performance was evaluated using a 99 wt% aqueous ethanol solution at 60 ° C., and the separation coefficient α = 2,34
0, a transmission coefficient Q of 48 g / m ² · h, indicating a sufficient performance. The evaluation was performed for 7 consecutive days, and no abnormality was found in the sealed portion.

Example 2 Acrylonitrile having an inner diameter of 500 μm and an outer diameter of 800 μm
A hollow fiber membrane composed of a methyl methacrylate copolymer (molar ratio = 95/5) was used. As an epoxy resin, a bifunctional epoxy resin (HELOXY69, RHONE-POUL)
ENC), 4-functional epoxy resin (Epicoat 1031)
S, made of oily shell epoxy), aniline-boron trifluoride complex as a cationic polymerization type curing agent, Si as a filler
licagel60 (manufactured by MERCK) in a weight ratio of 80:
The mixture was mixed and defoamed at 20: 5: 20. Using these, a module was produced in the same manner as in Example 1. 8 at 80 ° C
When the performance was evaluated with a 0 wt% acetic acid aqueous solution, the separation coefficient α
= 1,550, and transmission speed Q = 300 g / m ² · h, indicating sufficient performance. The evaluation was performed for 7 consecutive days, and no abnormality was found in the sealed portion.

Example 3 Using the module prepared in Example 2, the temperature of 98.degree.
When the performance was evaluated using a wt% aqueous toluene solution, the separation coefficient α = 1,400 and the permeability coefficient Q = 230 g / m ² · h, indicating sufficient performance. The evaluation was performed continuously for 7 days, and no abnormality was found in the sealed portion.

Comparative Example 1 As an epoxy-based adhesive, Epicoat 828 (made of oil-based shell epoxy) was used as a base material, and an amine-based curing agent Epicure U (made of oil-based shell epoxy) was used as a hardening agent. The mixture was mixed at a weight ratio of 25. The same hollow fiber membrane as in Example 2 was used, and the bundle was uniformly focused and the tip was sealed. The hollow fiber bundle was housed in a cylindrical polyethersulfone case, and both ends were fixed in the same manner as in Example 1 using the above adhesive. In order to open the hollow fiber membrane, both ends were cut, and the performance was evaluated using an 80 wt% acetic acid aqueous solution at 80 ° C., where a separation coefficient α = 1,730 and a transmission coefficient Q = 300 g /
m was ² · h. However, 24 hours later, the adhesive layer was cracked and could not be evaluated.

Comparative Example 2 Coronate 4403 was used as a main agent as a urethane-based adhesive.
(Manufactured by Nippon Polyurethane), Nipporan 4235 as a curing agent
(Manufactured by Nippon Polyurethane) and mixed at a weight ratio of 60:40. The same hollow fiber membrane as in Example 2 was used, and thereafter, a module was manufactured in the same manner as in Example 1. 80
When the performance was evaluated using an 80 wt% acetic acid aqueous solution at 80 ° C., a separation coefficient α = 1,650 and a permeability coefficient Q = 270 g / m ² · h
Met. However, after 35 hours, the adhesive layer was cracked and could not be evaluated.

[0025]

According to the present invention, an epoxy resin is used as a main component as an adhesive and a cationic polymerization type or an anion type curing agent is used as a curing agent. By fixing the hollow fiber membrane module to the case, a hollow fiber membrane module having excellent solvent resistance can be obtained.

Continuation of the front page (56) References JP-A-2-218714 (JP, A) JP-A-1-14437 (JP, A) JP-A-2-26623 (JP, A) JP-A-60-110390 (JP) JP-A-59-149924 (JP, A) JP-A-47-4975 (JP, A) JP-A-2-31821 (JP, A) JP-A-2-293024 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) B01D 63/02 B01D 63/00 500

Claims (2)

(57) [Claims] 1. An epoxy resin having neither an amine bond nor an ester bond in a resin as a base material and an aniline-trifluoride as a curing agent as an adhesive for fixing an end portion of a bundle of hollow fiber membranes .
Using consisting boron complex cationic polymerization type curing agent
For at least 35 hours
Characteristics that do not cause abnormalities in the adhesive seal when contacted
A hollow fiber membrane module. 2. An adhesive according to claim 1, wherein an inorganic filler is compounded.
The hollow fiber membrane module according to the above.