JP2000225304A - Adsorber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable trace amounts of substance in a fluid to be efficiently removed by packing an adsorbent in a hollow fiber membrane case which stores an aggregation of hollow fiber membranes and has a fluid flow path communicating with the terminal opening parts of the hollow fiber membranes and a fluid flow path communicating with the outer peripheries of the hollow fiber membranes. SOLUTION: Water to be treated is supplied to granular active carbon layers 4 from a supply pipe 21 for water to be treated to remove a hydrophilic substance and an oily substance by adsorption. Next, the water to be treated is made to seep into a hollow part from the outer peripheral faces of the hollow fiber membranes 1 to adsorb the oily substance. Following this step, the treated water penetrating the hollow fiber membranes 1 is delivered to the outside from a treated water delivery pipe 32a. During backward washing, cleaning water is supplied from the treated water delivery pipe 32a to be made to flow into the hollow part from the terminal opening parts I2 of the hollow fiber membranes 1. Further, the cleaning water is made to penetrate the outer peripheral faces of the hollow fiber membranes 1 and the granular active carbon layers 4. Then the cleaning water is made to flow out of the supply pipe 21 for water to be treated and a drain discharge pipe 22 to the outside of a hollow fiber membrane case 2. Thus it is possible to remove a contaminant from the hollow fiber membranes 1 and the granular active carbon layers 4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adsorber, and more particularly to an adsorber capable of efficiently removing trace amounts of oily substances and hydrophilic substances contained in a fluid.

[0002]

2. Description of the Related Art In recent years, tap water has become a problem of contamination with halogenated hydrocarbons such as trihalomethane and trichloroethylene. In addition, unpleasant taste and odor due to dissolved chlorine in tap water also poses a problem.

[0003] As a water purifier for removing dissolved chlorine, halogenated hydrocarbons and the like from tap water, an activated carbon filter filled with activated carbon has been generally used.

[0004] In the activated carbon filtration device, the density of the activated carbon generally varies, so that the tap water selectively flows in a place where the activated carbon density is low. Therefore, in the activated carbon filtration device, there is a problem that the filled activated carbon is not always used with high efficiency, and when the tap water contains a solid, it is difficult to filter the solid. There was a problem.

Further, activated carbon generally adsorbs free chlorine in water, for example, but has a problem that it does not adsorb halogenated compounds such as halogenated hydrocarbons very well.

As another method for separating and removing a solute from an aqueous solution, there is known a separation means using an ion exchange resin. When the solute is either an ionic substance or a polarized or charged substance that is polarized or charged, the solute can be effectively removed by the separation means using the ion exchange resin, but depending on the separation means, Solutes other than the ionic substance and the polarized / charged substance could not be effectively removed.

[0007] A large amount of exhaust gas containing vapors of halogenated hydrocarbons such as trichloroethylene and hydrogen halides generated by decomposition of the halogenated hydrocarbons is generated from painting plants, cleaning plants, semiconductor manufacturing plants and the like. Occurs.

In recent years, regulations on the emission of gaseous halogenated hydrocarbons have become stricter. Therefore, in the factory, the halogenated hydrocarbons and the like contained in the exhaust gas are removed before the exhaust gas is removed. The need to discharge has increased.

Further, in recent years, interest in harmful substances such as formaldehyde released from new building materials has been increasing. Therefore, a means for removing formaldehyde present in a room such as a new house has come to be desired.

Conventionally, an adsorption tower filled with activated carbon has been mainly used for the treatment of the exhaust gas. However, the adsorption tower has the same problems as those described for the activated carbon adsorption apparatus. Was.

[0011]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an adsorber capable of efficiently removing a trace amount of a substance in a fluid.

An object of the present invention is to provide an adsorber capable of efficiently removing trace amounts of oily and hydrophilic solutes in a fluid.

An object of the present invention is to efficiently remove trace solutes present in a liquid or gas, particularly oily substances such as trichloroethylene and trihalomethane, and hydrophilic substances such as chlorine, aldehydes and phenols. It is an object of the present invention to provide an adsorber that can be used.

Another object of the present invention is to make it possible to efficiently adsorb and remove a solute substance from a low-concentration aqueous solution of a solute substance by using a hydrophobic hollow fiber membrane and an adsorbent having a large number of pores.
It is an object of the present invention to provide an adsorber that can be sufficiently practically used as a water purifier.

Another object of the present invention is to provide an adsorber capable of removing solutes, particularly the oily substances, from an aqueous solution containing various solutes.

Another object of the present invention is to provide an adsorber which is suitably used for concentrating and recovering solute substances, particularly oily substances, contained in an aqueous solution containing various solutes.

It is a further object of the present invention to provide an adsorber capable of removing the oily substance and the hydrophilic substance from a gas such as an exhaust gas in which various substances are mixed.

[0018]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention provides an assembly of hollow fiber membranes having at least one open end, and the hollow fiber membrane containing the assembly of hollow fiber membranes. A first communicating with at least one of the terminal openings of the membrane;
An adsorber comprising: a hollow fiber membrane case including a fluid flow path and a second fluid flow path communicating with the outer periphery of the hollow fiber membrane; and an adsorbent present inside the hollow fiber membrane case. It is an invention.

In a preferred embodiment of the adsorber of the present invention, the hollow fiber membrane is a hollow fiber membrane for adsorbing an oily substance in a liquid or a gas, and the oily substance is a halogen-containing organic compound and a carbonaceous material. An adsorber, which is at least one substance selected from the group consisting of hydrogen; an adsorber, wherein the hollow fiber membrane is a hollow fiber membrane formed of a polymer having a contact angle with water of 60 ° or more; An adsorber in which the membrane is a hollow fiber membrane formed of a polymer alloy containing polyarylate and at least one of polysulfone and polyethersulfone as main components, wherein the adsorbent is a hydrophilic substance contained in a liquid or gas And an adsorber that is an adsorbent that adsorbs at least one of an oily substance, the adsorbent is an inorganic adsorbent mainly containing an inorganic substance, and a polymer mainly containing a polymer An adsorber that is at least one of a sorbent, an adsorber in which the adsorbent is an inorganic adsorbent selected from activated carbon and zeolite, and the adsorbent is formed from a polymer having a contact angle to water of 60 ° or more. An adsorber which is a polymer adsorbent thus obtained can be mentioned.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The adsorber of the present invention allows a fluid such as a solution, a suspension, and a gas to flow through the inside thereof.
It has a function of removing or concentrating oily substances and hydrophilic substances contained in the fluid in trace amounts by adsorption.

In the adsorber of the present invention, the hollow fiber and the adsorbent are made to coexist in the hollow fiber membrane case in order to exhibit the above function. 1. Specific examples of the adsorber of the present invention As the adsorber of the present invention, for example, trichloroethylene, dioxin, phenols, chlorine, and removes the harmful substances from liquids such as tap water containing harmful substances such as pesticides. And a gas purifier intended to remove the harmful substance from exhaust gas such as air containing the harmful substance. Hereinafter, specific examples of the liquid purifier and the gas purifier will be described. (1) Example 1 FIG. 1 shows a vertical cross section of the liquid purifier cut along a center line. The liquid purifier shown in FIG. 1 can be called a water purifier in that it is particularly intended for purifying water. Hereinafter, the liquid purifier may be referred to as a “water purifier”.

The water purifier has a substantially cylindrical hollow fiber membrane case 2. An annular projection 2a is formed in the side surface of the hollow fiber case 2, that is, in the vicinity of one end of the outer peripheral surface, in contact with an opening end of a first cap 31, which will be described later, along the circumferential direction of the outer peripheral surface. In the vicinity of the other end of the second cap 32, an annular protrusion 2 that abuts an opening end of a second cap 32, which will be described later, along the circumferential direction of the outer peripheral surface.
b is formed.

The hollow portion of the hollow fiber membrane case 2 is filled with a bundle of hollow fiber membranes 1 having both ends opened in a cylindrical shape.

The hollow fiber membrane 1 is formed of a polymer alloy comprising a polyarylate represented by the following formula (I) and a polyether sulfone represented by the following formula (II). The polymer alloy has a weight ratio of the polyarylate to the polyether sulfone of 1: 1.

[0025]

Embedded image

Embedded image The hollow fiber membrane 1 is a hollow fiber-shaped wet membrane formed by a so-called wet spinning method. The hollow fiber membrane 1 is formed, for example, from an outer annular discharge port of a double-tube spinneret through the polymer alloy n-methylpyrrolidone (N
MP) solution, and an NMP aqueous solution is discharged from an inner discharge port of the double-tube spinneret, and after passing through the air for about several tens of mm, it is guided into a coagulating liquid which is an NMP aqueous solution. And solidify it.

The hollow fiber membrane 1 is potted with a polyurethane resin at both ends of the hollow fiber membrane case 2. Thus, a potting portion 23 is formed at one end of the hollow fiber membrane case 2, and a potting portion 24 is formed at the other end of the hollow fiber membrane case 2.
Each of the potting portions 23 and 24 is cut along both ends of the hollow fiber membrane case 2, thereby forming an end face of the hollow fiber membrane case 2. Therefore, the hollow fiber membrane 1 is also cut at both ends to form a terminal opening 11 and a terminal opening 12.

A substantially cylindrical first cap 31 having an open end is attached to the end of the hollow fiber membrane case 2 where the end opening 11 is formed. End opening 1 of hollow fiber membrane 1 in membrane case 2
A second cap 32, which is also open at one end, is attached to the end on the side where 2 is formed. At the center of the bottom surface of the second cap 32, a treated water take-out pipe 32a for taking out treated water treated by the water purifier of Example 1 is provided upright. An annular projection 2a on the outer peripheral surface of the hollow fiber membrane case 2.
A first O-ring fitting groove 25 and a second O-ring fitting groove 26 are formed in a portion closer to the end and a portion closer to the end than the annular protrusion 2b, respectively. The first O-ring fitting groove 25 is fitted with an O-ring 61 for maintaining the liquid-tightness between the inner peripheral surface of the first cap 31 and the outer peripheral surface of the hollow fiber membrane case 2. Ring fitting groove 26
Is fitted with an O-ring 62 for maintaining the liquid-tightness between the inner peripheral surface of the second cap 32 and the outer peripheral surface of the hollow fiber membrane case 2.

A portion of the side surface of the hollow fiber membrane case 2 between the annular projection 2a and the annular projection 2b is provided with water to be treated by the water purifier to be supplied to the water purifier. A treated water supply pipe 21 and a drain discharge pipe 22 for discharging the treated water as drain as necessary are provided. The treated water supply pipe 21 is located near the annular projection 2a on the side surface, and the drain discharge pipe 22
Are located closer to the annular projection 2b on the side surface. The treated water supply pipe 21 and the drain discharge pipe 22
Both extend outward from the side surface of the hollow fiber membrane case 2 along the radial direction of the hollow fiber case 2. The drain discharge pipe 22 is provided with a drain valve 22a which is a diaphragm valve capable of adjusting a flow rate.

A granular activated carbon having a particle size of about 4 to 250 mesh is filled between the inner wall of the hollow fiber membrane case 2 and the bundle of the hollow fiber membranes 1 and between the hollow fiber membranes 1. A granular activated carbon layer 4 is formed. The drain discharge pipe 22 is provided with a filter 5 for preventing activated carbon fine powder generated by pulverizing granular activated carbon forming the granular activated carbon layer 4 by a water flow to the outside.

In the water purifier shown in FIG. 1, the hollow fiber membrane 1 corresponds to the hollow fiber membrane in the adsorber of the present invention. The hollow fiber membrane case 2, the potting part 23, and the potting 24 correspond to the hollow fiber membrane case in the adsorber of the present invention. The terminal openings 11 and 12 correspond to the first fluid flow path in the adsorber of the present invention,
It corresponds to the second fluid channel in the adsorber of the present invention. Further, the granular activated carbon forming the granular activated carbon layer 4 corresponds to an adsorbent in the adsorber of the present invention.

Hereinafter, a case where the water to be treated containing an oily substance and a hydrophilic substance is purified using the water purifier shown in FIG. 1 will be described as an example.

When the water to be treated is treated in the water purifier (hereinafter referred to as “treatment time”), the treated water supply pipe 21 is provided.
The water to be treated is supplied to the water purifier through. At this time, the drain valve 22a may be fully closed or slightly open. However, if the drain valve 22a is slightly opened, accumulation of dirt on the outer wall surface of the hollow fiber membrane 1 is possible. Is preferred because it decreases.

First, the water to be treated passes through the granular activated carbon layer 4, whereby the hydrophilic substance and the oily substance contained in the water to be treated are adsorbed and removed. The water to be treated that has passed through the granular activated carbon layer 4 then permeates into the hollow from the outer peripheral surface of the hollow fiber membrane 1. The oily substance contained in the water to be treated is adsorbed in the hollow fiber membrane 1. The treated water that has passed through the hollow fiber membrane 1 is taken out of the water purifier through a treated water take-out pipe 32a.

When the water purifier is backwashed (hereinafter referred to as "backwashing"), either the hydrophilic substance or the oily substance is contained in a small amount or substantially not through the treated water discharge pipe 32a. Supply wash water which is not contained. At this time, the drain valve 22a is opened as needed.

The washing water is supplied to the end opening 1 of the hollow fiber membrane 1.
2 flows into the hollow portion and permeates the outer peripheral surface of the hollow fiber membrane 1. Then, it passes through the granular activated carbon layer 4 and flows out of the hollow fiber membrane case 2 from the water to be treated supply pipe 21 and the drain discharge pipe 22. Thereby, the dirt accumulated in the hollow fiber membrane 1 and the granular activated carbon layer 4 during the treatment is removed. On this occasion,
When the adsorber and the washing water are heated, the effect of removing dirt can be improved.

In the water purifier shown in FIG. 1, the granular activated carbon layer 4 is easily formed by supplying a slurry of granular activated carbon from the water supply pipe 21 to the inside of the hollow fiber membrane case 2. be able to. The granular activated carbon layer 4
It is preferable that the drain valve 22a be in the open state.

The water purifier of Example 1 can remove a wide range of harmful substances.

In the water purifier of Example 1, the granular activated carbon layer 4 and the hollow fiber membrane 1 are accommodated in the hollow fiber membrane case 2, so that the granular activated carbon and the hollow fiber membrane are separated from each other. It can be made extremely small as compared with a water purifier having a form accommodated in a water purifier. Further, inside the hollow fiber membrane case 2, the water to be treated flows along the hollow fiber membrane 1,
Even if the granular activated carbon layer 4 has a slight density, it flows almost uniformly inside the granular activated carbon layer 4. Therefore, in the water purifier in FIG. 1, the utilization efficiency of the granular activated carbon in the granular activated carbon layer 4 is high.

Further, in the water purifier of Example 1, as described above, the water to be treated permeates through the hollow fiber membrane 1 after flowing through the granular activated carbon layer 4. Accordingly, the hollow fiber membrane 1 prevents the activated carbon fine powder contained in the granular activated carbon layer 4 from being mixed into the permeated water. (2) Example 2 Another example of the water purifier according to the present invention will be described below.

FIG. 2 shows a longitudinal section of the water purifier according to Example 2 cut along the center line. In FIG. 2, the same reference numerals as those in FIG. 1 indicate the same constituent elements as those indicated in FIG. 1 unless otherwise specified.

Also in the water purifier shown in FIG. 2, the hollow fiber membrane case 2 is substantially cylindrical, and an annular projection 2a is formed in the circumferential direction near one end of the outer peripheral surface of the hollow fiber case 2. In the vicinity of the other end of the outer peripheral surface, an annular projection 2b is formed in the circumferential direction. Further, in the hollow fiber membrane case 2, an O-ring fitting groove 25 is formed at a portion closer to the end than the annular projection 2a, and an O-ring fitting groove 26 is formed at a portion closer to the end than the annular projection 2b. Is formed.

The annular projection 2 in the hollow fiber membrane case 2
A cylindrical first cap 31 having an open end is attached to an end on the side where a is formed, and a cylindrical first cap 31 having an open end is also mounted on an end on the side where the annular projection 2b is formed. The second cap 32 is attached. A treated water supply pipe 31a for supplying treated water to the water purifier is formed in a protruding state at a central portion of a bottom of the first cap. The treated water supply pipe 31a extends in a direction opposite to the direction in which the treated water take-out pipe 32a extends.

In the hollow part of the hollow fiber membrane case 2,
As in the case of the water purifier described above, a bundle in which the hollow fiber membranes 1 are bundled in a cylindrical shape is accommodated. However, unlike the hollow fiber membrane 1 in the water purifier shown in FIG. 1, the hollow fiber membrane 1 is formed in a U-shape, and the end of the hollow fiber membrane 1 on the side bent in a U-shape is The hollow fiber is formed so as to face the bottom surface of the first cap 31 and to face the bottom surface of the second cap 32 so that the end of the hollow fiber membrane 1 opposite to the U-shaped bent end faces the bottom surface of the second cap 32. It is housed in the hollow part of the membrane case 2.

As in the case of the water purifier shown in FIG.
Are potted at both ends of the hollow part of the hollow fiber membrane case 2, whereby a potting part 23 and a potting part 24 are formed at both ends of the hollow fiber membrane case 2. Here, the potting unit 23
Is a potting portion formed at the end of the hollow fiber membrane 1 on the U-shaped bent side, and the potting portion 24 is a potting portion formed at the end opposite to the potting 23. . The potting section 23
And 24 are cut at both ends of the hollow fiber membrane case 2, thereby forming an end face of the hollow fiber membrane case 2. The hollow fiber membrane 1 is cut together with the potting part 24, whereby the hollow fiber membrane 1 has an end opening 12. In a portion of the potting portion 23 outside the hollow fiber membrane 1,
A to-be-processed water distribution channel 13 which is a through hole parallel to the hollow fiber membrane 1 is formed.

In the water purifier shown in FIG. 2, the hollow fiber membrane 1 corresponds to the hollow fiber membrane in the adsorber of the present invention. The hollow fiber membrane case 2, the potting part 23, and the potting 24 correspond to the hollow fiber membrane case in the adsorber of the present invention. The terminal opening 12 corresponds to the first fluid flow path in the adsorber of the present invention, and the water supply pipe 31a and the water flow path 13 correspond to the second fluid flow path in the adsorber of the present invention. I do. Further, the granular activated carbon forming the granular activated carbon layer 4 corresponds to an adsorbent in the adsorber of the present invention.

Hereinafter, a case where the water to be treated containing an oily substance and a hydrophilic substance is purified using the water purifier shown in FIG. 2 will be described as an example.

During the treatment in the water purifier, the water to be treated is supplied to the water purifier through the water supply pipe 31a.

The water to be treated flows into the hollow fiber membrane case 2 through the water passage 13 to be treated. The water to be treated that has flowed into the hollow fiber membrane case 2 passes through the granular activated carbon layer 4 along the hollow fiber membrane 1. Thereby, the hydrophilic substance and the oily substance are adsorbed and removed. The water to be treated that has passed through the granular activated carbon layer 4 permeates into the hollow portion from the outer peripheral surface of the hollow fiber membrane 1, and an oily substance is adsorbed on the hollow fiber membrane 1. The treated water from which the oily substance has been removed in the hollow fiber membrane 1 is taken out of the water purifier through a treated water take-out pipe 32a.

At the time of back washing, washing water containing only a small amount or substantially neither of the above-mentioned hydrophilic substance and the above-mentioned oily substance is supplied from the treated water take-out pipe 32a.

The washing water is supplied to the end opening 1 of the hollow fiber membrane 1.
2 flows into the hollow portion and permeates the outer peripheral surface of the hollow fiber membrane 1. Then, the water passes through the granular activated carbon layer 4, passes through the treated water flow passage 13 and the treated water supply pipe 31 a, and flows out of the hollow fiber membrane case 2. Therefore, the hollow fiber membrane 1 is
In addition, dirt accumulated in the granular activated carbon layer 4 is removed. At this time, when the adsorber and the washing water are heated, the effect of removing dirt can be improved.

The water purifier of Example 2 has, in addition to the features of the water purifier of Example 1, no water supply pipe and a drain discharge pipe on the side surface of the hollow fiber membrane case 2. It has the feature that the structure is simpler than that of the container.

In the water purifier of Example 2, the treated water supply pipe 31a and the treated water take-out pipe 32a are positioned substantially on the axis of the hollow fiber membrane case 2. Therefore, the water purifier of Example 2 also has a feature that the piping can be made more compact in piping than the water purifier of Example 1.

Further, in the water purifier of Example 2, the water to be treated flows in the granular activated carbon layer 4 in a direction substantially parallel to the hollow fiber membrane 1. Therefore, the water purifier of Example 2 also has a feature that the unevenness of the distribution of the water to be treated in the granular activated carbon layer 4 can be further reduced as compared with the water purifier of Example 1.

(3) Example 3 An example of an adsorber (hereinafter, sometimes referred to as a "gas purifier") for removing an oily substance from an exhaust gas containing a hydrophilic substance and an oily substance is shown in FIG. 3 shows a longitudinal section. In FIG. 3, the same reference numerals as those in FIGS.
Unless otherwise specified, the same components as those indicated by the reference numerals in FIGS. 1 and 2 are shown.

The gas purifier shown in FIG.
However, except that it is a dried hollow fiber membrane obtained by drying the hollow fiber membrane 1 in the water purifier of FIG. 1, it has substantially the same structure as the water purifier shown in FIG. The granular activated carbon forming the granular activated carbon layer 4 is the same as the granular activated carbon in the granular activated carbon layer 4 in the water purifier shown in FIG.

The first cap 31 on the side surface of the hollow fiber membrane case 2 provided in the gas purifier shown in FIG.
A gas supply pipe 27 for supplying a gas to be treated, such as the exhaust gas, which is a gas to be treated by the gas purifier of Example 3, is provided at the end on the side where is mounted. The to-be-processed gas supply pipe 27 is a pipe extending outward in the radial direction of the hollow fiber case 2. Then, the second cap 32
A processing gas take-out pipe 32b for taking out the processing gas processed by the gas purifier is provided upright at the center of the bottom surface.

In the gas purifier shown in FIG. 3, the hollow fiber membrane 1 corresponds to the hollow fiber membrane in the adsorber of the present invention. The hollow fiber membrane case 2, the potting part 23, and the potting 24 correspond to the hollow fiber membrane case in the adsorber of the present invention. The terminal openings 11 and 12 correspond to the first fluid flow path in the adsorber of the present invention, and the gas supply pipe 27 corresponds to the second fluid flow path in the adsorber of the present invention. Further, the granular activated carbon forming the granular activated carbon layer 4 corresponds to an adsorbent in the adsorber of the present invention.

At the time of purification, the gas to be treated is supplied through the gas supply pipe 27 into the hollow fiber membrane case 2.

The gas to be treated is firstly supplied to the granular activated carbon layer 4.
Pass through. Thereby, the hydrophilic substance and the oily substance contained in the gas to be treated are adsorbed and removed. The gas to be treated that has passed through the granular activated carbon layer 4 then permeates into the hollow portion from the outer peripheral surface of the hollow fiber membrane 1. The oily substance contained in the gas to be treated is adsorbed in the hollow fiber membrane 1. The processing gas that has passed through the hollow fiber membrane 1 is extracted to the outside of the gas purifier through the processing gas extraction pipe 32b.

When desorbing the hydrophilic substance and the oily substance adsorbed on the gas purifier (hereinafter referred to as “during desorption”), a small amount of both the hydrophilic substance and the oily substance are passed through the processing gas outlet pipe 32b. A clean gas such as nitrogen gas or air containing only or substantially no nitrogen gas is supplied.

The clean gas flows into the hollow from the end opening 12 of the hollow fiber membrane 1 and permeates the outer peripheral surface of the hollow fiber membrane 1. Then, it passes through the granular activated carbon layer 4 and flows out of the hollow fiber membrane case 2 from the gas supply pipe 27 to be treated. As a result, the hydrophilic substance and the oily substance and the like that have been filtered and adsorbed in the hollow fiber membrane 1 and the granular activated carbon layer 4 are desorbed, and the hollow fiber membrane 1 and the granular activated carbon layer 4 are regenerated.
In addition, at the time of the desorption, if the gas purifier is heated or the clean gas is heated as required, the desorption effect of the dirt can be improved.

2. General description of the present invention (1) Fluid that can be treated by the adsorber of the present invention Examples of the fluid that can be treated by the adsorber of the present invention include a liquid to be treated containing an oily substance and / or a hydrophilic substance and The gas to be treated can be mentioned.

Examples of the liquid to be treated include tap water, well water, dialysate, physiological saline, infusion, brine, and alcohol fermentation liquid.

Examples of the gas to be treated include exhaust gas containing the oily substance from a coating factory, a cleaning shop, a cleaning factory, a semiconductor factory, or the like. As the exhaust gas containing the oily substance, besides, the air containing the oily substance and water vapor generated by blowing high-temperature steam or high-temperature air into the aqueous solution in which the oily substance is dissolved may also be mentioned. it can.

The oily substance has a molecular weight of 1,000.
0 or less, and compounds that are hardly soluble or slightly soluble in water. For example, an organic compound having a solubility in water of about 1 g / 100 g of water or less can be said to be slightly soluble or poorly soluble in water, and thus is included in the oily compound.

Specific examples of the oily substance include trihalomethanes such as chloroform, bromodichloromethane, dibromochloromethane, and bromoform; aromatic halogen-containing organic compounds such as DDT, dioxin, and PCB; trichloroethane, tribromoethane; Examples include trihaloethanes such as monochlorodibromoethane, and aliphatic halogen-containing organic compounds such as tetrachloroethylene, tetrachloroethane, trichloroethylene, and carbon tetrachloride.

Other examples of oily substances include hydrocarbons such as benzene, anthracene, and hexane.

On the other hand, the hydrophilic substance has a molecular weight of 1,
000 or less, and compounds having water solubility or hydrophilicity. As the hydrophilic compound, for example, a solubility in water of 1.0 g / water 10
Organic or inorganic compounds weighing about 0 g or more can be mentioned. In addition, the hydrophilic compound includes a compound which has low solubility in water per se, but becomes highly soluble in water when a specific ion, acid, alkali or the like is present in water. Specific examples include halogens and hydrophilic organic compounds having at least one hydrophilic group such as a hydroxyl group, an amino group, a carboxyl group, a sulfoxyl group, a nitroxyl group, and a sulfonic acid group.

Examples of the halogens include fluorine,
Chlorine, bromine and iodine can be mentioned.

Examples of the hydrophilic organic compound include phenols such as phenol and cresol, aldehydes such as formaldehyde, acetaldehyde and propionaldehyde, alcohols such as methanol, ethanol and isopropanol, amines and anionic surfactants. And various agricultural chemicals.

(2) Hollow Fiber Membrane In the adsorber of the present invention, the hollow fiber membrane contains a small amount of the substance to be adsorbed contained in the fluid, specifically, “(1) treatment in the adsorber of the present invention” It has a function of adsorbing one or both of the oily substance and the hydrophilic substance described in the section “Fluid that can be used”. In addition, "a trace amount is contained in the fluid"
Means, for example, that the concentration in the fluid is 1% or less.

The hollow fiber membrane also has a function of making the fluid flow uniform inside the hollow fiber membrane case. That is, as in the conventional adsorber, in an adsorber in which activated carbon powder or particles are simply filled in a container, a densely filled portion and a coarsely filled portion of activated carbon are formed in the container. Therefore, the fluid flowing in the container flows through a portion where the density of the activated carbon is coarse, that is, a portion through which the fluid easily passes, and is distributed throughout the activated carbon filled in the container. However, in the adsorber of the present invention, since the fluid flows along the hollow fiber membrane, the fluid uniformly contacts the adsorbent filled in the adsorber.

(2-1) Form of Hollow Fiber Membrane The hollow fiber membrane of the present invention includes a hollow fiber membrane having either a hollow fiber form or a thin tube form. The outer diameter of the hollow fiber membrane is usually about 3 mm or less, and preferably in the range of about 40 μm to 2 mm. The inside of the hollow fiber membrane is naturally hollow. Hereinafter, the hollow portion of the hollow fiber membrane may be referred to as “hollow space”.

The hollow fiber membrane includes, for example, a hollow fiber membrane having a pore size of a microfiltration membrane for removing particles having a size of sub-μm or more such as cells and bacteria, and viruses, proteins and polysaccharides. And high-molecular organic matter such as colloid particles and emulsion particles
A hollow fiber membrane having a pore size equivalent to that of an ultrafiltration membrane capable of removing particles having the following sizes can be used.

As the hollow fiber membrane, for example, a homogeneous membrane having a homogeneous porous structure, an asymmetric membrane having a dense surface layer and a sponge-like support layer, and pores are formed by tearing a nonporous thin film. Examples of the membrane include a stretched membrane and a fibril structure, that is, a fibril membrane having a network-like structure provided with through holes communicating with each other in the thickness direction of the membrane.

Further, as the hollow fiber membrane, any of an internal pressure type hollow fiber membrane through which fluid permeates from inside to outside and an external pressure type hollow fiber membrane through which fluid permeates from outside to inside can be used.

As the hollow fiber membrane, any of a wet hollow fiber membrane in a wet state containing a liquid such as water and a dry hollow fiber membrane in a dry state containing almost no liquid can be used. The wet hollow fiber membrane is preferably used for the adsorber of the present invention, particularly for the adsorber for treating liquids such as solutions and suspensions, and the dry hollow fiber membrane is preferably used for the adsorber of the present invention, particularly for gas. It is preferably used for an adsorber for treating a mixture.

(2-2) Material of Hollow Fiber Membrane The material of the hollow fiber membrane can be arbitrarily selected depending on whether the substance to be adsorbed is an oily substance or a hydrophilic substance. For example,
When the hollow fiber membrane adsorbs an oily substance such as trichloroethylene, the contact angle with water is 60
A hollow fiber membrane formed from a polymer having a temperature of at least 70 °, preferably at least 70 °, particularly 70 to 110 ° (hereinafter sometimes referred to as “hydrophobic polymer”) is preferable. On the other hand, in the case where a hydrophilic substance such as chlorine is adsorbed on the hollow fiber membrane, a polymer having a contact angle with water of less than 60 ° (hereinafter sometimes referred to as “hydrophilic polymer”).
Is preferred.

The contact angle is determined by contacting distilled water
The angle between the tangent drawn on the liquid at the three-phase contact point of solid, liquid, and gas and the solid surface on the side containing the liquid. The device for measuring the contact angle is not particularly limited, but is usually a contact angle meter (CA-
A type) is preferably used.

In general, the contact angle of the polymer with water is 6
If it is 0 ° or more, the polymer will adsorb oily substances,
And it shows hydrophobicity. Therefore, the hydrophobic polymer adsorbs the oily substance. Examples of the hydrophobic polymer include polysulfone, polyether sulfone, polyarylate, polystyrene, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, 1,2-polybutadiene,
Examples thereof include 1,4-polybutadiene, polystyrene-polybutadiene block polymer, polyisoprene, and polychloroprene. In the present invention, as the hydrophobic polymer, one kind of polymer selected from the above polymers may be used alone, or two or more kinds of polymers selected from the above polymers may be used in combination. In addition, the thing which has thermoplasticity among the said hydrophobic polymers may be hereafter called "thermoplastic hydrophobic polymer".

Preferred examples of the hydrophobic polymer include polysulfone, polyethersulfone, polyarylate, and a polymer alloy of polyarylate and polysulfone and / or polyethersulfone. Particularly preferred are: The said polymer alloy can be mentioned.

The polyarylate is represented by the following formula (I
A polymer having a repeating unit shown in II) can be suitably used.

[0083]

Embedded imageHowever, in the formula (III), R¹And R^TwoHas 1 to 5 carbon atoms
Is a lower alkyl group. R¹And R^TwoAre identical to each other
Or they may be different. R ¹And R^Two
Are, for example, methyl, propyl, butyl,
And an ethyl group. In the present invention,
R¹And R^TwoIs preferably a methyl group.

The molecular weight of this polyarylate is 20,0
A range of about 00 to 50,000 is preferable.

As the polyarylate, a polyarylate appropriately synthesized by polycondensation of a dihydric phenol and an aromatic dicarboxylic acid may be used, or a commercially available product may be used. Commercially available products include a product sold under the trade name "U-Polymer" by Unitika, a product sold under the trade name "APE" by Bayer, and a product sold under the trade name "DUREL" by Celanese Corporation. And products sold by DuPont under the trade name "Arylon".

As the polysulfone, a polymer having a repeating unit represented by the following formula (IV) can be suitably used.

[0087]

Embedded image However, in the formula (IV), R ³ and R ⁴ are lower alkyl groups having 1 to 5 carbon atoms. R ³ and R ⁴ may be the same or different. Examples of R ³ and R ⁴ include a methyl group, a propyl group, a butyl group, a pentyl group and the like. In the present invention, R
Preferably, ³ and R ⁴ are methyl groups.

The polysulfone having a repeating unit represented by the formula (IV) preferably has a molecular weight of about 20,000.
~ 40,000.

As the polysulfone, an appropriately synthesized polysulfone may be used, or a commercially available product may be used. As a commercially available product, a product manufactured by Union Carbide Co., Ltd., which is sold as a product name “P-3500” can be mentioned.

As the polyether sulfone, the following formula (I)
Polymers having a repeating unit represented by I) can be mentioned.

[0091]

Embedded image The molecular weight of the polyether sulfone is preferably about 2
It ranges from 000 to about 40,000.

As the polyether sulfone, an appropriately synthesized polyether sulfone may be used, or a commercially available product may be used. Examples of commercially available products include Sumitomo Chemical Industries, Ltd. products sold under the trade name "Sumika Excel PES".

When a polymer alloy of polyarylate and polysulfone and / or polyethersulfone is used as the hydrophobic polymer, a mixture of polyarylate (A) and polysulfone and / or polyethersulfone (B) in the polymer alloy is used. Weight ratio (A / B)
Is usually in the range of 0.1 to 10, preferably in the range of 0.3 to 4.

(2-3) Manufacturing Method of Hollow Fiber Membrane Among the hollow fiber membranes, a wet hollow fiber membrane is prepared, for example, by using a spinning stock solution obtained by dissolving the hydrophobic polymer in an appropriate solvent from a double-tube spinneret. It can be manufactured by a wet spinning method in which the material is extruded into a coagulation bath, which is a bath of coagulation liquid, and coagulated.

The solvent used for dissolving the hydrophobic polymer in the preparation of the spinning solution is, for example, n
-Methylpyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMA), tetrahydrofuran (THF), dioxane, morpholine and the like.

The concentration of the hydrophobic polymer in preparing the spinning solution is usually from 10 to 25% by weight. Particularly as hydrophobic polymers, polyarylate and polysulfone and / or
Alternatively, when a polymer alloy with polyethersulfone is used, the hydrophobic polymer concentration is preferably in the above range.
When a polymer alloy is used as the hydrophobic polymer, the “concentration of the hydrophobic polymer” means the sum of the concentrations of the components of the polymer alloy, that is, the concentration of the entire polymer alloy.

As the coagulating liquid, a solvent which is a poor solvent for the hydrophobic polymer and which is miscible with the good solvent used for preparing the spinning dope can be used. Specific examples of such a solvent include water, lower alcohols and lower ketones, and a mixed solvent thereof.

[0098] Various additives such as potassium chlorate can be blended into the spinning solution as long as the object of the present invention is not hindered.

When spinning a wet hollow fiber membrane using the double tube spinneret, it is preferable to discharge either air or core liquid from the inner tube of the double tube spinneret. As the core liquid, for example, a mixture of a good solvent and the poor solvent of the hydrophobic polymer can be used,
Specifically, a mixed liquid having the same composition as that of the coagulating liquid can be used.

Among the above hollow fiber membranes, the dry hollow fiber membrane is prepared by, for example, immersing a wet hollow fiber membrane immediately after spinning in a lower alcohol such as ethanol, methanol, or isopropanol to form the water contained in the wet hollow fiber membrane. Is substituted by the lower alcohol, and then dried.

As another method for producing a dry hollow fiber membrane, water contained in a wet hollow fiber membrane immediately after spinning is mixed with a polyhydric alcohol such as ethylene glycol, propylene glycol or glycerin which is liquid at normal temperature. , Followed by drying, and a method of drying the wet hollow fiber membrane as it is.

(3) Adsorbent In the adsorber of the present invention, the adsorbent exists at any position inside the hollow fiber membrane case. The adsorbent has a function of removing a substance to be adsorbed that is difficult to be adsorbed / removed by the hollow fiber membrane or is not adsorbed / removed among substances to be adsorbed such as an oily substance and a hydrophilic substance in the fluid. Adsorbents can be mentioned.

Examples of the adsorbent include an inorganic adsorbent mainly composed of an inorganic material such as activated carbon and zeolite, and a polymer adsorbent mainly composed of a polymer. The inorganic adsorbent and the polymer adsorbent will be described in detail below.

(3-1) Inorganic adsorbent Examples of the inorganic adsorbent include activated carbon, zeolite, and packing for chromatography. The inorganic adsorbent mainly adsorbs a hydrophilic substance in a fluid, but when the hollow fiber membrane is formed of a hydrophobic polymer and is a hollow fiber membrane that adsorbs an oily substance, the inorganic fiber adsorbent removes the hollow fiber membrane. It also has the function of adsorbing permeating oily substances.

(3-1-1) Activated carbon Examples of the activated carbon include powdered activated carbon, granular activated carbon, molded carbon obtained by molding activated carbon into a specific shape, fibrous activated carbon, and activated carbon fibers in which activated carbon is supported on arbitrary fibers. Can be mentioned.

Examples of the powdered activated carbon include activated carbon particles having a particle size smaller than 250 mesh.

Examples of the granular activated carbon include activated carbon particles having a particle size of about 4 to 250 mesh.

As the shaped carbon, for example, any of a lump of activated carbon, powdered activated carbon, and particulate activated carbon may be used as a cube,
Activated carbon formed into a predetermined shape such as a rectangular parallelepiped, a cylinder, and a sphere can be given. The size of the coal is 1
Preferably, it is about 0 mesh or larger. When the shaped coal is cubic, the size of the shaped coal is usually about 1 to 20 mm square, preferably 2 to 8 mm
It is about the corner. When the coal is a rectangular parallelepiped,
The size of the coal is usually from 1 to the diagonal length of the bottom.
The length is about 20 mm, the height is about 1 to 20 mm, and preferably, the length of the diagonal line of the bottom surface is about 2 to 8 mm, and the height is about 2 to 8 mm. When the formed coal is columnar, the size of the formed coal usually has a diameter of 1 to
The diameter is about 20 mm, the height is about 1 to 20 mm, preferably the bottom diameter is about 2 to 8 mm, and the height is 2 to 8 mm.
mm. When the shaped coal is spherical, the dimension of the shaped coal is usually about 1 to 20 mm in diameter, preferably about 2 to 8 mm.

As the activated carbon, an activated carbon sintered body obtained by sintering any of powdered activated carbon, granular activated carbon, and fibrous activated carbon into a predetermined shape can be used. Examples of the shape of the activated carbon sintered body include a cylindrical shape and a cylindrical shape.

(3-1-2) Zeolite Examples of the zeolite used as the adsorbent in the adsorber of the present invention include natural zeolites and synthetic zeolites.

Examples of the natural zeolite include mordenite, chabazite, clinoptilolite and the like.

Examples of the synthetic zeolite include zeolite A, zeolite X, zeolite Y, hydrated sodalite,
Examples include zeolite B, zeolite ZK-5, zeolite Ω, zeolite S, zeolite R, zeolite D, zeolite G, zeolite T, zeolite L, hydrated cancrinite, zeolite W, zeolone, zeolite C, and zeolite NA. be able to. The form of the zeolite is not particularly limited, and examples of the form include a pellet, a bead, and a powder.

(3-1-3) Packing Material for Chromatography Examples of packing material for chromatography include packing material for gas chromatography, packing material for gel permeation chromatography (GPC), packing material for adsorption chromatography, packing material for reversed phase chromatography. And a filler for ion exchange chromatography.

As the packing material for chromatography,
Specific examples include silica gel, porous glass, porous alumina, magnesia, and hydroxyapatite.

(3-2) Polymer adsorbent Examples of the polymer adsorbent include a hydrophobic polymer adsorbent formed from the hydrophobic polymer and a hydrophilic polymer adsorbent formed from the hydrophilic polymer. . The hydrophobic polymer adsorbent has a function of mainly adsorbing an oily substance in a fluid, and the hydrophilic polymer adsorbent has a function of mainly adsorbing a hydrophilic substance in a fluid.

The form of the polymer adsorbent includes, for example,
Various forms such as a long form such as a sheet form, a string form, a strip form and the like, a granular form such as a granular form, a granular form, a powder form, and a fibrous form can be exemplified. In other words, the polymer adsorbent has various forms such as a tube, a sponge, a block, and a spiral.

Further, the polymer adsorbent has the form
The shape may be any of a flat film shape, a granular shape, a rod shape, a Raschig ring shape, and a flake shape, and may be a shape obtained by cutting a hollow fiber membrane. In any case, a polymer adsorbent having a form having a large specific surface area and a polymer adsorbent having a form having a large surface true volume ratio are preferable.

Examples of the polymer forming the polymer adsorbent include a polymer alloy of polyarylate and polysulfone and / or polyethersulfone. Examples of the polymer alloy include, for example, the same as the solid polymer alloy described in “(2-2) Material of hollow fiber membrane” in the section of “(2) Hollow fiber membrane”.
Polymer alloys composed of polyarylate and polysulfone and / or polyethersulfone can be mentioned.

Examples of the polymer adsorbent formed from the polymer alloy include, for example, a string formed by extruding a polymer stock solution obtained by dissolving the polymer alloy in an organic solvent from a spinneret or an extrusion die and introducing into a coagulation solution. Can be mentioned. Here, when the diameter of the string is small, it can be said that the string has a thread-like or fibrous form. The string-shaped body may be cut into a predetermined length to be used as a granulated, pellet-shaped, or shaft-shaped adsorbent, that is, an adsorbent. Without cutting, the string-shaped, thread-shaped, or fibrous adsorbent may be used. That is, it may be used as an adsorbent.

It is desirable that the cross-section of the cord obtained by extrusion from a spinneret or an extrusion die is a hollow, star-shaped or other irregular shape having a large surface area, rather than an apparently simple circular shape.

In preparing the polymer stock solution used for forming the string, for example, THF, dioxane, DMF, DMA, NMP, etc. can be used as the organic polar solvent.

The above-mentioned polymer stock solution and the above-mentioned polymer alloy include, as long as the object of the present invention is not impaired,
Various additives may be blended.

As the polymer adsorbent, the hollow fiber membrane described in “(2) Hollow fiber membrane” may be used in addition to the polymer adsorbent.
A cut example of a hollow fiber membrane cut to a length of about 30 mm can be given.

Examples of the cut hollow fiber membranes include cut wet hollow fiber membranes obtained by cutting a wet hollow fiber membrane formed from the polymer alloy and dry hollow fiber membranes prepared from the wet hollow fiber membranes. And dried hollow fiber cut material. The cut wet hollow fiber membrane is preferably used to adsorb oily substances in a liquid, and the cut dry hollow fiber membrane is preferably used to adsorb oily substances in a gas.

Other examples of the polymer adsorbent include a porous cylindrical body and a porous cylindrical body formed of any of the hydrophobic polymer and the hydrophilic polymer.

[0126]

EXAMPLES (Reference Example 1) Preparation of a water purifier A polyarylate resin in which R ¹ and R ² are both methyl groups in the above formula (I) (trade name, manufactured by Unitika Ltd .;
U polymer “U-100”, contact angle to water: 74.
Once abbreviated as “PA”. ) And a polyether sulfone resin represented by the formula (III) (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumika Excel PES, contact angle with water: 66.4 degrees, hereinafter abbreviated as “PES”). To N
In addition to MP, the mixture was dissolved while heating at 60 ° C. to prepare a spinning stock solution. The total polymer concentration of PA and PES in the spinning dope was 17% by weight, and the mixing weight ratio of PA and PES was 1: 1. The contact angle of the polymer with water was 70.6 °.

From the inside of the double tube spinneret, as the core liquid,
Discharging a mixture of 50% by volume of NMP and 50% by volume of water,
Discharging the spinning solution from outside the double-tube spinneret,
After passing through the air for 20-50mm, NMP 60% by volume
And a coagulation solution, which is a mixture of 40% by volume of water, and coagulated to obtain a hollow fiber membrane. Double tube spinneret temperature is 7-8
Set to ° C.

Using the obtained hollow fiber membrane, a water purifier having an effective membrane area of 1.2 m ² and having the structure shown in FIG. 1 was produced.

<Oil Substance Removal Performance Test> (1) Raw water (water to be treated) containing DDT as an oil substance at a concentration of 0.0023 mg / liter was supplied to the water purifier at a rate of 1 liter / minute for 10 minutes. After passing water, the permeate was collected. No DDT was detected in the permeate. However,
The detection limit of DDT was 0.0002 mg / liter.

(2) Benzene is used as an oily substance in an amount of 0.01
Raw water contained at a concentration of 0 mg / liter (water to be treated)
Was passed through the water purifier at a rate of 1 liter / min for 10 minutes, and a permeate was collected. Benzene in the permeate is 0.00
It was detected at a concentration of 2 mg / liter. The benzene removal rate was 80%.

(3) Raw water (water to be treated) containing tetrachloroethylene at a concentration of 0.0068 mg / liter as an oily substance was passed through the water purifier at a rate of 1 liter / minute for 10 minutes, and a permeate was collected. did. No tetrachlorethylene was detected in the permeate. However, the detection limit of tetrachloroethylene is 0.0002 mg / liter.

(4) Raw water (water to be treated) containing 1,1,2-trichloroethylene at a concentration of 0.0066 mg / liter as an anionic surfactant, which is an example of a hydrophilic substance, is added to the water purifier in the amount of 1%. 10 at the rate of liter / minute
After passing water for a minute, the permeate was collected. 1, 1, 2
-Trichloroethylene was detected at a concentration of 0.0019 mg / l. The removal rate of 1,1,2-trichloroethylene was 71.2%.

(5) Raw water (water to be treated) containing 0.24 mg / liter of sodium dodecylbenzenesulfonate as an oily substance was passed through the water purifier at a rate of 1 liter / minute for 10 minutes. The permeate was collected. No sodium dodecylbenzenesulfonate was detected in the permeate. However, the detection limit of sodium dodecylbenzenesulfonate is 0.02 mg / liter.

(6) 6.6 mg of humic acid as an oily substance
/ Liter of raw water (water to be treated) was passed through the water purifier at a rate of 1 liter / minute for 10 minutes, and a permeate was collected. Humic acid was detected in the permeate at a concentration of 2.4 mg / liter. Humic acid removal rate is 63.6.
%Met.

Reference Example 2 (1) Preparation of Raw Water Chloroform, bromodichloromethane, dibromochloromethane and bromoform were used as trihalomethanes.
A methanol mixed solution containing the species was prepared. The methanol mixed solution was added to activated carbon treated water flowing at a rate of 10 liters / minute by a metering pump at a flow rate of 0.5 ml / minute, and further a 0.3% sodium hypochlorite solution was added. Raw water was prepared specifically. The contents of the four types of trihalomethanes and chlorine in the raw water were as shown in Table 1 below.

(2) Trihalomethane and chlorine removal performance test The raw water was passed through the filtration device at a water temperature of 16 ° C and a flow rate of 0.2.
It was distributed under the condition of liter / min. The flow direction was a direction from the inside to the outside of the hollow fiber membrane. 50 of the raw water
After passing the water for 1 minute, the permeated water filtered through the hollow fiber membrane is collected, and the concentrations of the four types of trihalomethanes are measured using a gas chromatograph. Was measured by Table 1 shows the results.

[0137]

[Table 1]

From the results of Reference Examples 1 and 2, it was found that the hollow fiber membrane adsorbs oily substances but hardly adsorbs free chlorine.

Example 1 In the same manner as in Reference Example 1, a water purifier having an effective membrane area of 1.2 m ² and having the structure shown in FIG. 1 was produced. The space between the hollow fiber membrane bundle and the hollow fiber membrane case was filled with 25 g of granular activated carbon having a particle size of 10 mesh.

<Oil-based substance removal performance test> (1) Raw water (water to be treated) containing DDT as an oil-based substance at a concentration of 0.0023 mg / liter was supplied to the water purifier at a rate of 1 liter / minute for 10 minutes. After passing water, the permeate was collected. No DDT was detected in the permeate. However,
The detection limit of DDT was 0.0002 mg / liter.

(2) Benzene as an oily substance in 0.01
Raw water contained at a concentration of 0 mg / liter (water to be treated)
Was passed through the water purifier at a rate of 1 liter / min for 10 minutes, and a permeate was collected. Benzene in the permeate is 0.00
It was detected at a concentration of 1 mg / liter. The benzene removal rate was 90%.

(3) Raw water (treatment water) containing tetrachloroethylene at a concentration of 0.0068 mg / liter as an oily substance was passed through the water purifier at a rate of 1 liter / minute for 10 minutes, and the permeate was collected. did. No tetrachlorethylene was detected in the permeate. However, the detection limit of tetrachloroethylene was 0.0002 mg / liter.

(4) Raw water (water to be treated) containing 1,1,2-trichloroethylene at a concentration of 0.0066 mg / liter as an oily substance was added to the water purifier at a rate of 1 liter / liter.
After passing water for 10 minutes at a rate of 10 minutes, a permeate was collected. 0.0006m of 1,1,2-trichloroethylene in the permeate
g / litre. The removal rate of 1,1,2-trichloroethylene was 90.9%.

(5) Raw water (water to be treated) containing sodium dodecylbenzenesulfonate at a concentration of 0.24 mg / liter as an anionic surfactant, which is an example of a hydrophilic substance, is added to the water purifier at a rate of 1 liter / liter. After passing water for 10 minutes at a rate of 10 minutes, a permeate was collected. No sodium dodecylbenzenesulfonate was detected in the permeate. However, the detection limit of sodium dodecylbenzenesulfonate is 0.02 mg
/ Liter.

(6) 6.6 mg of humic acid as an oily substance
/ Liter of raw water (water to be treated) was passed through the water purifier at a rate of 1 liter / minute for 10 minutes, and a permeate was collected. Humic acid was detected in the permeate at a concentration of 1.2 mg / liter. The removal rate of humic acid is 81.8.
%Met.

Example 2 (1) Preparation of Raw Water Chloroform, bromodichloromethane, dibromochloromethane and bromoform were used as trihalomethanes.
A methanol mixed solution containing the species was prepared. The methanol mixed solution was added to activated carbon treated water flowing at 10 liter / minute by a metering pump at a flow rate of 0.5 ml / minute, and further, a 0.3% sodium hypochlorite solution was added. Raw water was prepared specifically. The contents of the four types of trihalomethanes and chlorine in the raw water were as shown in Table 2 below.

(2) Trihalomethane and chlorine removal performance test The raw water was passed through the filtration device at a water temperature of 16 ° C and a flow rate of 0.2.
It was distributed under the condition of liter / min. The flow direction was a direction from the inside to the outside of the hollow fiber membrane. 50 of the raw water
After passing the water for one minute, the permeated water filtered through the hollow fiber membrane was collected, and the concentrations of the four types of trihalomethanes (oil-based substances) and chlorine (hydrophilic substances) were measured using a gas chromatograph. Table 2 shows the results.

[0148]

[Table 2]

(Example 3) <Preparation of gas purifier> The same P as described in Example 1 was used.
A and PES similar to PES described in Example 1 were dissolved in NMP at a mixing weight ratio of 1: 1 to obtain a spinning dope.

This spinning stock solution was wet-spun in the same manner as in Example 1 to obtain a hollow fiber membrane. The obtained hollow fiber membrane was washed with water and dried to prepare a gas purifier having a structure shown in FIG. The effective membrane area in the gas purifier is 1.2 m ²
Met. In the gas purifier, 25 g of granular activated carbon having a particle size of 60 mesh was filled between the hollow fiber membrane bundle and the hollow fiber membrane case.

<Trichlorethylene Removal Test> a) Configuration of Test Apparatus The gas purifier was connected to a test apparatus having a configuration shown in FIG. 4 to examine the trichlorethylene removal performance.

In the test apparatus, as shown in FIG. 4, a nitrogen gas cylinder and a flow controller (both not shown) are connected to the inlet side of the flow meter A.

The outlet side of the flow meter A is connected to a first Erlenmeyer flask B containing trichlorethylene therein.

The first Erlenmeyer flask B has a function of preparing a supply gas by adding a predetermined concentration of trichloroethylene to the nitrogen gas from the nitrogen cylinder. A silicon rubber stopper is attached to the opening of the first Erlenmeyer flask B, and the silicon rubber stopper is connected to an outlet side of the flow meter side, and an inlet-side glass tube B1 through which nitrogen gas is introduced, and An outlet glass tube B2 through which the supply gas, which is a nitrogen gas containing a predetermined concentration of trichlorethylene, flows out through the inside of the first Erlenmeyer flask B is attached. In addition, the vicinity of the bottom surface of the Erlenmeyer flask B is immersed in a thermostat J maintained at a predetermined temperature.

The outlet side glass tube B2 of the first Erlenmeyer flask B is connected to a second Erlenmeyer flask C which is an empty Erlenmeyer flask having the same size and shape as the first Erlenmeyer flask B. The second Erlenmeyer flask C prevents the trichloroethylene from splashing into the gas purifier D described later when the Nitrogen gas from the inflow glass tube B1 in the first Erlenmeyer flask B produces droplets of trichlorethylene. Has a function to prevent.

Like the first Erlenmeyer flask B, the second Erlenmeyer flask C also has a silicone rubber stopper attached to the opening, and the silicon rubber stopper has a predetermined shape from the first Erlenmeyer flask B. An inlet-side glass tube C1 into which a nitrogen gas containing a concentration of trichlorethylene is introduced, and an outlet-side glass tube C2 through which a nitrogen gas containing a predetermined concentration of trichlorethylene flows out are mounted. still,
The tip of the inlet side glass tube C1 extends to near the bottom of the second Erlenmeyer flask C.

The outlet glass tube C2 of the second Erlenmeyer flask C is connected to the gas supply pipe 27 to be treated in the gas purifier D having the structure shown in FIG.

The processing gas that has passed through the hollow fiber membrane 1 of the gas purifier D flows out of the processing gas outlet pipe 32b.

A branch line F branches from a line E connecting the outlet side glass tube C2 and the gas supply pipe 27 to be processed. A three-way valve H for communicating the second Erlenmeyer flask C with one of the branch line F and the gas purifier D is provided at a portion of the line E where the branch line F branches. An on-off valve G is interposed between the valve H and the gas supply pipe 27 to be processed.

B) Test conditions The test for removing trichloroethylene was performed under the following conditions. -Trichlorethylene concentration: shown in Table 3. Carrier gas: nitrogen Carrier gas flow rate: 2.5 liters / minute Temperature: room temperature (25 ° C.) Trichlorethylene concentration in the supply gas: the three-way valve H is switched to connect the second Erlenmeyer flask C and the branch line F. The supply gas flowing through the conduit E is collected from the branch conduit F,
The trichlorethylene concentration was determined by gas chromatography. Trichlorethylene concentration in the processing gas: the three-way valve H is switched to communicate the second Erlenmeyer flask C with the gas purifier D, and the processing gas is collected from the processing gas outlet pipe 32b.
The trichlorethylene concentration was determined by gas chromatography.

C) Results The results of the above trichlorethylene removal test are shown in Table 3.

[0162]

[Table 3]

As is clear from the results shown in Table 3,
In the gas purifier having an effective membrane area of 1.2 m ² , 15
About 440 mg of trichlorethylene was removed in 0 minutes.

At 105 minutes after the start of the supply gas flow, the adsorbed amount of trichlorethylene was 393.2 mg. The adsorption amount corresponds to 89.3% of the total trichlorethylene adsorption amount for 150 minutes.

[0165] On the other hand, 10 seconds after the start of supply gas distribution,
By the time after 5 minutes, the amount of trichlorethylene brought into the gas purifier by the supply gas is approximately [(1.65 + 1.90) / 2] (mg / liter) × 2.5.
(Liter / min) × 105 (min) = 465.9 (mg).

[0166] Therefore, the amount of trichlorethylene introduced into the gas purifier by the supply gas by the gas purifier up to 105 minutes after the start of the flow of the supply gas was 393.2 (mg) / 465. It turns out that 9 (mg) = 84.4% was removed.

[0167]

The adsorber provided by the present invention comprises (1)
By the hollow fiber membrane, the flow of the fluid flowing inside the adsorbent layer is made uniform, so that the adsorption efficiency of the substance to be adsorbed by the adsorbent is greatly improved. Since the hollow fiber membrane and the adsorbent are used in combination, the adsorption efficiency of the substance to be adsorbed per volume is high,
(3) By using an adsorbent that adsorbs a substance different from the substance adsorbed by the hollow fiber membrane, an adsorber capable of adsorbing a wide range of substances can be obtained, and (4) It is steep and has various features such as requiring almost no startup time.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view showing an example of a water purifier according to the present invention.

FIG. 2 is a longitudinal sectional view showing another example of the water purifier according to the present invention.

FIG. 3 is a longitudinal sectional view showing an example of a gas purifier according to the present invention.

FIG. 4 is a schematic diagram showing an outline of a configuration of a test apparatus used when performing a trichloroethylene removal test on the gas purifier shown in FIG. 3;

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Hollow fiber membrane, 11, 12 ... Terminal opening part; 2 ... Hollow fiber membrane case, 21 ... Water supply pipe to be treated, 22 ... Drain discharge pipe
23, 24: potting portion, 25, 26: O-ring fitting groove, 27: gas supply pipe to be processed; 31: first cap,
32 ... second cap, 31a ... treated water supply pipe, 32a
... treated water outlet pipe, 32b ... treated gas outlet pipe; 4
... Granular activated carbon layer; 5 ... Filter; 61, 62 ... O-ring; A ... Flow meter, B ... First Erlenmeyer flask, B1 ... Inlet side glass tube, B2 ... Outlet side glass tube, C ... Second Erlenmeyer flask, C1 ... Inlet side glass tube, C2 ... Outlet side glass tube, D
... gas purifier, E ... pipeline, F ... branch pipeline, G ... open / close valve,
H: three-way valve, J: constant temperature bath.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] January 7, 2000 (2000.1.7)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

(4) Raw water (treatment water) containing 1,1,2-trichloroethylene as an oily substance at a concentration of 0.0066 mg / liter was added to the water purifier at 1 liter / liter.
After passing water for 10 minutes at a rate of 10 minutes, a permeate was collected. 0.0019m of 1,1,2-trichloroethylene in the permeate
g / litre. The removal rate of 1,1,2-trichloroethylene was 71.2%.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

(5) An anionic system which is an example of a hydrophilic substance
Raw water (water to be treated) containing sodium dodecylbenzenesulfonate at a concentration of 0.24 mg / liter as a surfactant was passed through the water purifier at a rate of 1 liter / minute for 10 minutes, and a permeate was collected. . No sodium dodecylbenzenesulfonate was detected in the permeate. However, the detection limit of sodium dodecylbenzenesulfonate is 0.02 mg
/ Liter.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C02F 1/28 C02F 1/28 F 1/44 1/44 B

Claims (9)

[Claims] 1. An assembly of hollow fiber membranes having at least one open end, a first fluid flow path containing the assembly of hollow fiber membranes and communicating with at least one of the terminal openings of the hollow fiber membranes; An adsorber comprising: a hollow fiber membrane case having a second fluid flow path communicating with the outer periphery of the hollow fiber membrane; and an adsorbent present in the hollow fiber membrane case. 2. The adsorber according to claim 1, wherein the hollow fiber membrane in the first aspect is a hollow fiber membrane that adsorbs an oily substance in a liquid or a gas. 3. The adsorber according to claim 2, wherein the oily substance according to claim 2 is at least one substance selected from the group consisting of a halogen-containing organic compound and a hydrocarbon. 4. The adsorber according to claim 3, wherein the hollow fiber membrane according to claim 1 is a hollow fiber membrane formed of a polymer having a contact angle with water of 60 ° or more. 5. The adsorption according to claim 4, wherein the hollow fiber membrane according to claim 1 is a hollow fiber membrane formed of a polymer alloy containing polyarylate and at least one of polysulfone and polyethersulfone. vessel. 6. The adsorbent according to claim 1, wherein the adsorbent according to claim 1 is an adsorbent that adsorbs at least one of a hydrophilic substance and an oily substance contained in a liquid or a gas. vessel. 7. The adsorbent according to claim 1, wherein the adsorbent is at least one of an inorganic adsorbent mainly formed of an inorganic substance and a polymer adsorbent mainly formed of a polymer. Adsorber. 8. The adsorber according to claim 7, wherein the adsorbent according to claim 1 is an inorganic adsorbent selected from activated carbon and zeolite. 9. The adsorber according to claim 7, wherein the adsorbent according to claim 1 is a polymer adsorbent formed from a polymer having a contact angle with water of 60 ° or more.