JPS59166245A - Method for ion exchange or ion adsorption - Google Patents

Abstract

PURPOSE:To subject useless and useful substances in a liquid to be treated to ion exchange and ion adsorption for a short time and to enlarge remarkably the treating capacity, by treating said liquid with an ion exchange resin and further with an ion exchange fiber. CONSTITUTION:In order to subject useless and useful substances in a liquid to be treated to ion exchange and ion adsorption with an ion exchange material, the liquid to be treated is worked up with the ion exchange resin and further with the ion exchange fiber. The ratio of said fiber to said resin by the exchanging capacity to be used is usually 0.01-50%, however, 0.1-20% ratio is especially preferable. This method is applied in fields where conventional ion exchange resins are used such as softening of water, desalting of sea water, purified water manufacturing, removal of harmful metals such as copper, mercury, cadmium at the condensing system and the water purification system in a nuclear power station and a thermal power station, separation and recovery of useful heavy metals such as uranium and rare earth metals in sea water, and purification and separation of antibiotics and several drugs.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an ion exchange or adsorption method and a method for producing pure water. More specifically, the present invention relates to a method for ion exchange or adsorption of unnecessary substances and useful substances in a liquid to be treated.

BACKGROUND ART Conventionally, methods of treating a liquid to be treated with an ion exchange resin have been widely used in fields requiring ion exchange or adsorption. However, this method suffers from the fact that the exchange groups of the ion exchange resin are much more present inside the network structure than on the surface of the resin particles.9 The reaction rate is slow, the processing time is long, and the The disadvantage is that it is difficult to perform ion exchange and adsorption. On the other hand, if the ion exchange resin is turned into powder or fine particles, it becomes difficult to handle.

Another disadvantage is that the resistance to liquid passage becomes extremely large. In recent years, a method of processing using ion exchange fibers with a large surface area has been proposed because the reaction rate is high and the degree of freedom in usage is increased. However, this method has a fatal drawback in that the processing capacity is small because the fibers are bulky.

The inventors of the present invention have arrived at the present invention as a result of intensive studies aimed at improving these drawbacks.

That is, the present invention.

(1) A method of ion-exchanging or adsorbing unnecessary or useful substances in a liquid to be treated with an ion exchanger, which is characterized in that the liquid to be treated is treated with an ion-exchange resin and then treated with an ion-exchange fiber. Replacement still concerns the adsorption method.

In the present invention, the liquid to be treated is treated with an ion exchange resin and then treated with an ion exchange fiber.

Surprisingly, we discovered that unnecessary and useful substances in the liquid to be treated can be highly ion-exchanged and adsorbed in a short time, and that the processing capacity is extremely large. This method provides an ion exchange and adsorption method that is far superior to conventional methods. Another object of the present invention is to provide a method for producing pure water that can perform ion exchange and adsorption of waste materials from raw water in a short time to obtain a large amount of highly purified water.

The ion exchange resin constituting the present invention usually has a diameter of 100 mm.
~i oooμ is meant to refer to known and commercially available ion exchange resins. Specific examples include gel type and MR type ion exchange resins in which ion exchange groups are introduced into a styrene-divinylbenzene copolymer that has excellent chemical resistance and heat resistance. Types of ion exchange resins include cation exchange resins having cation exchange groups such as sulfonic acid groups, phosphonic acid groups, and carboxylic acid groups, and 1- to 6-class amine groups.

Anion exchange resins having anion exchange groups such as quaternary ammonium groups and aminocarboxylic acid groups.

Amidoxime group, amine phosphate group, polyamine group.

Examples include chelate resins having chelate groups such as pyridine groups and dithiocarnocumic acid groups.

The ion exchange fibers constituting the present invention usually have a diameter of 0.
It means a known ion-exchange fiber having a diameter of 1 to 100 microns, preferably 1 to 100 microns. Specifically, flJ is an insoluble synthetic organic ion in which an ion exchange group is introduced into a synthetic organic polymer (ion exchange polymer) such as polystyrene, polyphenol, polyvinyl alcohol, polyacrylic, or polyamide. Mention may be made of exchange fibers. The base material is a fiber consisting of an ion exchange polymer and a reinforcing polymer, preferably a multifilamentary mixed or composite fiber with an ion exchange polymer as the main component of the sheath component and a reinforcing polymer as the core component. The ion-exchange fiber is good because it has sufficient mechanical strength and shape retention for operation. The ratio of reinforcing row f lima is usually 10 to 90 cracks, but if it is too low, the mechanical strength will be weakened, and if it is too high, the amount of ion exchange and adsorption will decrease, so the ratio is 20 to 90. A range of 80% is preferred. As ion exchange polymers, poly(monovinyl aromatic compounds), especially poly-1-nostyrene compounds, have excellent chemical resistance and heat resistance9. This is preferable because the operation can be repeated many times over a long period of time. Furthermore, as the reinforcing polymer, poly-α-olefin is preferable because it has excellent chemical resistance.

The moisture content of the fibers in the present invention is usually 05 to 10, but if the thickness is too small, it will be difficult to perform ion exchange or adsorption to a high degree, and if the thickness is too large, the resistance to liquid will increase. The range of 5 to 5 is preferable. Here, water-containing dust refers to Na-type (Cl-type) cation (anion) exchange fibers that are soaked in distilled water and then centrifuged for 5 minutes in a household centrifugal dehydrator.
B. Dehydrate to remove surface moisture, immediately determine the weight (W), dry thoroughly, and measure the weight! 1) (WO)
, is the value obtained from the following formula.

W　-W.

Water-containing dust - WO Examples of the ion exchange fibers include the aforementioned cation exchange fibers, anion exchange fibers, and chelate fibers having cation exchange groups, anion exchange groups, and chelate groups. As for the form of fiber.

Examples include short fibers, filament yarns, felt, woven fabrics, non-woven fabrics (1) knitted fabrics) fiber bundles, strings (2) paper, any known forms, aggregates, or cut products thereof. Among them, dishes 01-6 in particular.

Desirably, short fibers of 0.5 to 2 m are easy to fill.

In addition, it is preferable to use it because it is easy to mix different types of fibers together.

Although the present invention can be carried out by a batch method, a fixed bed method in which the liquid to be treated passes through a layer of ion exchange resin and then ion exchange and adsorption through a layer of ion exchange fibers is easy to operate and has a high degree of ionization. This is preferable because it can be replaced and adsorbed. The method of the present invention is usually carried out after treatment with at least one ion exchange agent.

By treating with the same type of ion-exchange fiber, it is possible to highly ion-exchange and adsorb waste and useful substances in the liquid to be treated in a short time and in large quantities.

In the present invention, the exchange capacity ratio of the ion exchange fiber to the ion exchange resin is usually 0.01 to 50, but it is difficult to perform ion exchange or adsorption to a high degree in a short time using a too small colander. On the other hand, if it is too large, the processing capacity per fixed bed capacity will decrease, so it is preferably 0.05 to 60.

Particularly preferred is 01 to 20 inches. Further, the type and combination (composite, mixed) of ion exchange resins to be used are appropriately selected depending on the types of waste materials and useful materials in the liquid to be treated.

The method of the present invention is applicable to water softening, desalination of water, nonaqueous solutions (organic solvents), seawater, etc., production of pure water, condensate systems and pure water systems in nuclear power plants and thermal power plants, copper, mercury, cadmium, etc. Removal of harmful metals such as.

Separation and recovery of useful heavy metals such as uranium and rare earths in seawater,
Removal of chromic acid 2 Decolorization and desalting of various sugar solutions.

Purification and separation of antibiotics and various pharmaceuticals such as streptomycin and penicillin, purification and separation of amino acids such as lysine and glutamic acid, separation of isomerized forms and optically active forms of glucose and fructose, adsorption of various organic acids and organic bases, and surface activity. It can be applied to fields that are performed using ordinary ion exchange resins, such as adsorption of agents, purification of iodine, purification of formalin, adsorption of pigment substances such as dyes, and removal of water.

Additionally, proteins, peptides, enzymes, and nucleic acids.

Hormones, nucleotides, alkaloids, lipids.

For adsorption and removal of cells such as steroids, viruses, and bacteria, colloidal substances, acidic gases such as hydrogen sulfide, hydrogen sulfide, and sulfur dioxide gas, and basic gases such as ammonia and amines, and purification of blood and plasma. can also be applied.

The method of the present invention is particularly preferably used in the field of purifying a liquid to be treated by ion exchange or adsorption of waste materials. Among these, it is most preferably used in a method of producing pure water by treating raw water with a cation exchanger and an anion exchanger.

The method for producing pure water will be described in detail below.

Usually, a cation exchanger having a cation exchange group, preferably a sulfonic acid group, is activated with an acid, and an anion exchanger having an anion exchange group, preferably a quaternary ammonium group, is activated with an alkali.

As the raw water, 7 normal industrial water, city water, well water, tap water, ground water, RO membrane permeated water, distilled water, condensate from a nuclear power plant or a thermal power plant, etc. are preferably used. Usually, it is preferable to include a step of treating with at least one kind of ion exchange resin and then treating with the same kind of ion exchange fiber.

A specific example of the processing order is KR-+ K, →AR
2KR-+AR-+KF, KR-+ a→A□→A,,
K.

→AR-+ KF-+ Aa, KR→AR→NiaAF
I KRA, -) K, AF, KR-+AR-+KR
AR-+KFA1. Examples include, but are not limited to, the following.

Here, KR2AR is a cation exchange resin.

Anion exchange resin, KF, AF means cation exchange fiber, anion exchange fiber, KRAR means a mixture of cation and anion exchange resin, KFA means a mixture of cation and anion exchange fiber.

A mixture of cation exchange fibers and powdered anion exchange fibers or a mixture of anion exchange fibers and powdered cation exchange resin may be used to replace the mixture of cation and anion exchange fibers.

To produce high purity water, after treatment with ion exchange resin,
It is preferable to treat with a mixture of at least cation and anion exchange fibers, and a specific example of the treatment order is KR'+ AR-+ K, A, as described above.

KRAR-+ I(, A, , KR-+ AR-+
K, A, →, Aa, etc. can be mentioned. Here, the mixing (equivalent) ratio of cation exchanger and anion exchanger, especially fiber, is usually 5:1 to 1:5, but preferably 6:1 to 1:6.

Furthermore, pretreatment - RO membrane → ion exchange → ultraviolet sterilization - M
By applying the present invention to ion exchange of known ultrapure water systems consisting of F, UF or RO membranes, electrical resistivity can be improved compared to conventional methods.

Ultrapure water that is far superior in terms of T Oc- (organic matter), number of fine particles, and number of viable bacteria can be easily and economically produced.

As mentioned above, the method of the present invention has the following advantages: first, ion exchange and adsorption can be performed in a short time; second, ion exchange and adsorption can be performed to a high degree; and sixth, the processing capacity for ion exchange and adsorption is large. Fourthly, high purity water can be produced in large quantities in a short period of time.

It has the following characteristics.

Examples are shown below, but the invention is not limited thereto.

Implementation/Example 1 Commercially available cation exchange resin Amberlite IR-120B
40m, / (76 meq) column (1,7aTIφ
x 18 am) and activated with acid (column K
R). A column (17 mm φ
17 am,) and activated with acid (column KF
). Commercially available anion exchange resin Diaion S A 20
A P 80 mJ (108 meq.) was packed into a column (1.7 cmφ x 36 c!m) and activated with alkali (column AR). 3. Tap water. A liquid was passed in the order of Column KR, Column KF, and Column AR at a flow rate of J/hr, and the electrical resistivity of the effluent was measured to examine the ability to remove cationic components and simultaneously produce pure water. Table 1 shows the relationship between the amount of liquid passed and the electrical resistivity.

Comparative Example 1 According to Example 1, from column KR to column AR,
- The electrical resistivity of the effluent was measured for the force ram AR.

Table 1 shows the relationship between the amount of liquid passed and the electrical resistivity.

Tables 1 to 2 With the present invention, even at a flow rate of 73/hr, 78 tons of treated water with a resistance of 1 MΩ・(3) or more can be produced! In the comparative example, even if they are 42z and 9i, the total is 51t.
! 2, it can be seen that the method of the present invention has a very large processing capacity. However, in the present invention, the electrical resistivity is high, and the cationic components in the liquid to be treated are highly ion-exchanged and adsorbed.
It can be seen that a large amount of highly purified water can be obtained.

Example 2 Commercially available mixed resin Amberly) MB-1 0ml (cation weight: 29 millimeters, anion weight: 21 millimeters) was used as the lower layer, and MB-290 mJ (cation: 57 milliequivalents, anion: 81 milliequivalents) was used as the upper layer. Column (1,7c
fnφx 54 am) (column KRAR
). 120 m of fiber mixture cut into one dish
7 (15 milliequivalents of cation.

10 meq. of anions) to a column (1,71! mφX5
4aT+) (column, A, ). Column KRAR → Column KFA at a flow rate of tap water Ig/hr
, to produce pure water. Table 1 shows the relationship between the amount of liquid passed and the electrical resistivity.

Comparative Example 2 Purified water was produced separately according to Example 2 using the column KRAR and the column KFAF. Table 2 shows the relationship between the amount of liquid passed and the electrical resistivity.

From Table 2, 1 In the present invention, even at a flow rate of 3 J/hr,
'D MΩ・- or higher treated water is 47z, and in the comparative example, each is 25.7? , 7J and the sum of both is 321
! 2, it can be seen that the method of the present invention has a very large processing capacity. It can be seen that in the present invention, the electrical resistivity is still high, impurities in the liquid to be treated are highly ion-exchanged and adsorbed, and a large amount of high-purity water can be obtained.

Example 50 mJ (3.8 meq. of cations, 2.5 meq. of anions) of a fiber mixture in the form of 1 mm cut fibers was added to the lower layer, and a commercially available mixed resin (Amberly) MB-29.0 was added to the lower layer.
Column (1,7-φx 54 mm
(column KRAR9' OmJ)
-+ KPAF30 ml). 31 for tap water! /h
Pure water was produced by passing the liquid through the column from the top at a flow rate of r.

Table 6 shows the relationship between the amount of liquid passed and the electrical resistivity.

Example 4 10 mJ of 1 m cut fiber mixture (1.3 meq. of cation, 0.85 meq. of anion) was added to the lower layer of commercially available mixed resin Amberlite MB-2110m.
Column (1,7C!mφ×
54(2)) (column KRAR 110ml
-+ K, A, 10 ml'). Table 6 shows the relationship between the amount of liquid passed and the electrical resistivity when pure water was produced according to Example B.
Shown below.

Comparative Example 6 Commercially available mixed resin Amberlite'MB-2120ml!
(Cation 76 milliequivalents, anion 108 milliequivalents)
(K
RAR120ml). Table 6 shows the relationship between the amount of liquid passed and the electrical resistivity when pure water was produced according to Example B.

From Table 6, 2 In the present invention, even at a flow rate of 3 J/hr, 10
Treated water with MΩ・(2) or more is 5 each! ! .

It's 4sz, and the comparative example is 60I! It can be seen that the method of the present invention has a large processing capacity per fixed bed capacity. It has also been found that in the present invention, the electrical resistivity is high, impurities in the liquid to be treated are highly ion-exchanged and adsorbed, and a large amount of high-purity water can be obtained.

It can be seen that when the usage capacity of the fibers increases, the purity of the treatment liquid increases, but the treatment capacity decreases, and conversely, when it is too small, the treatment capacity increases, but the purity of the treatment liquid decreases.

The cation and anion exchange fibers used in the Examples and Comparative Examples were manufactured by the following method.

Multicore sea-island composite fiber (undrawn yarn) [sea component (polystyrene/polypropylene)/island component (polypropylene), =
(47//'4)/49 (High school 16. Fiber diameter 64
μ)] was cut to a length of 1 mm to obtain a cut fiber. 1 part by weight of the cut fibers was added to a crosslinking/sulfonation solution consisting of 5 parts by volume of commercially available primary sulfuric acid Z and 0.15 parts by weight of paraformaldehyde, reacted at 80° C. for 4 hours, and then washed with water. Next, a cation exchange fiber having a sulfonic acid group was obtained by treating with alkali) and washing with water (exchange capacity: 2.8 milliequivalents/g=Na+ hydrous carbon: 1.5).

1 part by weight of the above cut fiber was added to a crosslinking solution consisting of 5 parts by volume of commercially available primary sulfuric acid, 05 parts by volume of water, 02 parts by weight of paraform and aldehyde, and a crosslinking reaction was carried out at 80° C. for 4 hours. Next, the crosslinking system was added to a solution consisting of 85 parts by volume of chloromethyl ether and 1.5 parts by volume of stannic chloride, and the mixture was reacted at 60° C. for 1 hour.

After the reaction was completed, it was washed with 10-dihydrochloric acid, distilled water, and acetone. Add chloromethylated system to 30% trimethylamine aqueous solution 1
0 parts by volume, aminated at 60° C. for 1 hour, and washed with water. Further, by treating with hydrochloric acid and washing with water, anion exchange fibers having trimethylammonium methyl groups were obtained (exchange capacity: 2:4 milliequivalents/g-at:, water content: 1.8).

The fiber mixture was prepared by activating cation exchange fibers and anion exchange fibers with acid and 'flukali, respectively.

A stirred mixture of both at a predetermined ratio was used.

Claims (1)

[Claims] (1) A method of ion-exchanging or adsorbing unnecessary or useful substances in a liquid to be treated with an ion exchanger, which is characterized in that the liquid to be treated is treated with an ion-exchange resin and then treated with an ion-exchange fiber. Exchange method or adsorption method.