JPS631452A - Ion exchange paper and preparation of ion exchange body and ion exchange paper - Google Patents

Abstract

PURPOSE:To improve durability under a severe condition, by adding a flocculant to a slurry containing an inorg. ion exchange powder and pulp before forming the same into paper according to a papermaking process and supporting inorg. ion exchange particles between pulp fibers of the paper formed. CONSTITUTION:A floccuant is added to a slurry containing an inorg. ion exchange powder and pulp before the slurry is formed into paper according to a paper making process. By this method, powder particles 2 are branched or crossed to each other to be held between entangled pulp fibers 3 and further adheres to said pulp fibers 3 by heat fusion at the time of drying and the pulp fibers 3 are entangled mutually and fused to form ion exchange paper 1. Further, rectangular ion exchange papers 5a and ion exchange papers 5a molded into a corrugated shape are stacked alternately and a frame body 6 comprising plastic having chemical resistance such as polypropyrene is assembled around the stacked ones to form a cartridge 4.

Description

[Detailed Description of the Invention] [Field of Industrial Application] This invention can be used to recover valuable materials from natural resources or industrial waste, remove harmful substances from living environment pollutants, and purify various liquids and gases. ion exchange paper and an ion exchanger constructed using the ion exchange paper. It also relates to a method for producing the ion exchange paper. [Prior art] Recovery of valuables from the above-mentioned natural resources or industrial waste, removal of harmful substances from living environment pollutants, and furthermore, various liquids,
As processing materials used for purposes such as gas purification, adsorption/agents made of activated carbon, ion exchange resins, chelate resins, and organic ion exchangers such as active group-bonded organic polymer fibers have been known. Organic ion exchangers made of these materials are relatively easy to mold and process, so they are generally granular. Fibrous.
Membrane-like. It has the advantage that it can be used in various forms such as cloth, and is expected to have a wide range of applications, especially as an ion exchanger.

however. The organic ion exchanger is. For example, as a material for efficiently processing a specific ion species from multiple ion species of the same series, such as capturing only sodium ions from a solution containing multiple types of alkali ions,
It is not yet satisfactory and has the disadvantage of poor heat resistance and radiation resistance. on the other hand. In contrast to the organic ion exchangers mentioned above, inorganic ion exchangers are also known. The inorganic ion exchanger is... It has superior ion selectivity, heat resistance, and radiation resistance compared to the organic ion exchangers mentioned above. In recent years, its use has been progressing for purposes such as removing sodium ions contained in potassium salt solutions and recovering uranium from seawater, but it has not been used on an industrial scale. Most of them are limited to granulated products. [Problems to be solved by the invention] Under certain circumstances, when granulated products of inorganic ion exchangers are used to treat the various solutions mentioned above, severe conditions of use such as high temperatures, alkalinity, and high acidity are required. Below. The binder used for granulation deteriorates significantly over time, which destroys the granulation form and causes problems such as blocking the flow of liquid and increasing pressure loss, making it unsustainable for long-term use. often occurs. In addition, due to their unique properties, ion exchangers can be used for applications other than solution processing, such as solid electrolyte membranes, electrolytic membranes, and gas purification permeable membranes. teeth. Knead with a suitable binder and extrude. It needs to be formed using a roll method, etc. A large amount of binder is required to give the membrane practical strength, but...
Inorganic ion exchangers have a fatal problem in that their original functions are lost or their functions are significantly deteriorated due to the treatment. [Means for solving the problems] This invention provides a window into the current situation. An object of the present invention is to provide an inorganic ion exchange paper that has excellent ion exchange ability and can withstand long-term use under harsh conditions, an ion exchanger formed by forming a cartridge from this ion exchange paper, and a method for producing the ion exchange paper. It is something to do.

That is, the first invention is an ion exchange paper in which particles of an inorganic ion exchanger are supported between pulp fibers.

A second invention is an ion exchanger made using the ion exchange paper of the first invention, in which ion exchange paper made of inorganic ion exchanger particles supported between pulp fibers are maintained at a predetermined interval. This is an ion exchanger that is formed by winding or polymerizing to form a laminate, and then housing and holding the laminate in a frame to form a cartridge.

Furthermore, a third invention relates to a manufacturing method for obtaining the ion exchange paper, by adding a flocculant to a slurry containing an inorganic ion exchange powder and pulp and making paper. The gist is that particles of an inorganic ion exchanger are supported between pulp fibers.

The ion exchange paper in the first invention and the second invention is. It is produced according to the third invention, and specifically obtained by the following method.

First, as a solid content, inorganic ion exchanger powder 20 to 95
% (weight %; the same applies hereinafter). to a slurry containing 80 to 5% pulp. Add 5% or less of each of cationic and anionic flocculants to form aggregates. This aggregate is then made into paper by a known method and dried at a temperature of 100 to 190'C to produce ion exchange paper in which particles of inorganic ion exchange powder are supported on the pulp fibers. The most effective inorganic ion exchanger as the inorganic ion exchanger powder used in this invention is. It is a powder of an inorganic material having an ion-exchangeable OH group, and typical examples of such materials include antimonic acid, hydrous bismuth oxide, and heteropolyacid. Zirconium phosphate, tin phosphate, titanium phosphate. These include hydrated titanium oxide, hydrated zirconium oxide, hydrated iron oxide, apatites, hydrotalcites, etc., and these are used singly or in combination of two or more. In addition, inorganic materials that do not have ion-exchangeable OH groups, such as Huetou cyanide complex, sulfides, alkaline earth metal sulfates, and synthetic zeolites, can also be used. These compounds can be used in either crystalline or amorphous form.

The inorganic ion exchanger powder is mixed with pulp to make a slurry, but the pulp used is wood pulp. Bast fiber, reed pulp, bagasse pulp.
Natural pulp such as straw pulp and bamboo pulp. Alternatively, synthetic pulps such as polypropylene, polyethylene, polyvinyl chloride, and polystyrene may be used.

Also. Inorganic fibers such as alumina fibers, carbon fibers, glass fibers, zirconia fibers, and animina/silica fibers can also be used, but when using such inorganic fibers, the bonding force of the particles is weak, so 100 parts by weight of ion exchange paper is used. On the other hand, it is preferable to use it together with a binder such as NBR latex or SBR latex within 5 parts by weight.

Using natural pulp. Powder particles of an inorganic ion exchanger are sandwiched between finely divided fibers, making it a practical carrier even without the use of a binder, but natural pulp fibers are better suited for chemical resistance than synthetic ones. It is slightly inferior to pulp, so
Depending on the system used, synthetic pulp may be used which can improve this point.

In this case, it is practically difficult to sandwich the powder between the fibers, so some of the fibers are melted during the drying process after paper making to increase the adhesion between the powder and the fibers. It is also possible to mix some of the fibers with other thermoplastic resin fibers.

Using natural pulp produces paper with a good texture and high water absorption and gas permeability, so synthetic pulp and natural pulp should be mixed in an appropriate ratio depending on the purpose of use. It is desirable to adjust the finish of the paper. During production, the preferred blending ratio of the inorganic ion exchanger powder and pulp is in the range of 20 to 95% of the 5 inorganic ion exchanger and 80 to 5% of the pulp. This formulation is made by weighing the inorganic ion exchanger powder and pulp,
This is accomplished by mixing and stirring in water.

In this case, if the content of the inorganic ion exchanger powder is less than 20%, the ion exchange function cannot be fully exhibited. It is particularly preferable that the amount is 50% or more, and the amount used is 95% or more.
If it exceeds %, the amount of pulp as aggregate decreases, and the strength of the resulting ion-exchange paper decreases, making it less practical. Among the flocculants used, aluminum sulfate is a cationic inorganic flocculant. Contains zinc hydroxide, etc.
Examples of anionic organic flocculants include polymeric polymers such as carboxy-methyl-starch (CMS), carboxy-methyl-cellulose (CMC), polyacrylamide cationic heptamer copolymer, sodium polystyrene sulfonate, and maleic acid copolymer. There is. On the other hand, cationic starch is a cationic organic flocculant. Polyacrylamide cationic copolymer. Polyvinylbenzyltrimethyl, ammonium chloride,
Polyvinylpyridine salt. Positive poly7amide as a condensation type polymer aggregate. Water-soluble urea resin, borithiourea salt. Positive polyurea, polyaminotriazole. Amine-epichlorohydrin polycondensate salt. Examples include ammonia epichlorohydrin polycondensate salts. In addition to the above flocculants, nonionic agents such as polyacrylamide agents are also used. Alternatively, amphoteric flocculants can also be used.

What flocculant to use? This is a combination of an anionic flocculant and a cationic flocculant, and by using these together, the inorganic ion exchanger with different charging function and pulp can be flocculated well, and if one of these is lacking, very good a
If no flocculants are added at all, the inorganic ion exchanger powder will remain finely suspended in water during paper making. The powder escapes from the system and does not remain on the paper.

In addition, if the use of each flocculant is more than 5%. If the aggregates become too large, the aggregates will not be of the specified size, and you will not be able to obtain ion-exchange paper in which the powder is uniformly distributed in tlkL, so the amount used should be 5% or less, and generally a small amount is added. It is preferable.

[For production]

In the thus obtained ion exchange paper of the present invention, the mechanism by which particles of inorganic ion exchanger powder are supported in the paper is considered to be as follows.

In other words, many powder particles and pulp fibers are negatively or positively charged in the slurry, so by adding a flocculant with an opposite charge to the charged body in each case,
Charges are neutralized and condensation occurs.

In particular, when a polymer flocculant is used, the polymer creates cross-linked bonds between charged bodies. This causes aggregation and PiI
．． Forms strong aggregates due to disturbances such as stirring.

Due to these coagulation and agglomeration effects, powder particles become powder particles.
Pulp fiber-pulp fiber and powder particle-pulp fiber bonds occur, but these bonds are mainly ionic bonds. It is presumed that this is due to the effects of hydrogen bonds, van der Waals bonds, etc.

The bonding structure of the ion-exchange paper obtained as described above is partially enlarged and conceptually illustrated in Figure 1. That is, the powder particles 2 are sandwiched between the pulp fibers 3 which are divided or intertwined with each other. Furthermore, it adheres to the pulp fibers by heat fusion during drying. The pulp fibers 3 are entangled with each other and fused to form the ion exchange paper 1.

Such ion-exchange paper can be protected from external loads by supporting a single ion-exchange paper with a frame with sufficient mechanical strength. This can be used by flowing the fluid to be treated in a direction approximately perpendicular to the surface of the ion exchange paper so that the fluid penetrates the ion exchange paper, and this method is effective when the fluid is a gas. act.

on the other hand. After forming a laminate by winding or polymerizing the ion-exchange paper of the present invention at a predetermined interval, this is housed in a frame formed according to the external shape to form a cartridge. By using a cartridge cartridge as an ion exchanger. It can fully meet the purposes mentioned above, such as recovering valuables from natural resources or industrial waste, removing harmful substances from living environment pollutants, and purifying various liquids and gases. Cartridges like this. Generally, fluid is introduced into the gaps created by laminating ion-exchange paper. It is made to flow along the surface of the ion exchange paper. In this case, the cartridge frame only needs to be held with a bonding force strong enough to counteract the frictional force caused by the flowing fluid, and the load generated when a large number of ion exchange papers are stacked is exclusively carried by the outer frame. Therefore, compared to the case of granulated products. The load is smaller than that in the case of particles and binder (support), and the load is high. Highly alkaline. It can withstand long-term use and perform ion exchange even under severe conditions such as high acidity.

〔Example〕

The first invention will be explained in more detail below by showing examples. Next cliff ■ 10.5 g of antimonic acid, 4.5 g of natural pulp 3
! water, mixed and stirred, and added polyacrylamide-based Aronfloc C-403H as a cationic flocculant.
(manufactured by Toagosei Chemical Industry) 0.005 g, and polyacrylamide-based Aronfloc A-106 (specially manufactured by Toagosei Chemical Industry) 0. o
osg was added to form aggregates, and then paper was made using a paper machine to obtain ion exchange paper carrying 70% antimonic acid.

This ion exchange paper has a Na ion exchange capacity of 1.3 m
eq/g (paper), and had a sufficient function as an ion exchanger.

Also. Even if this ion exchange paper was soaked in 10% HCj2 for 10 days. The paper quality did not change at all, and there were no problems with durability.

10.5 g of hydrous bismuth oxide and 4.5 g of polyethylene-coated polypropylene synthetic pulp were mixed and stirred in 31 water, and polyacrylamide-based Aronfloc C-403H (Toa (manufactured by Synthetic Kagaku Kogyo ■) 0.005 g, and polyacrylamide-based Aronflotsa as an anionic flocculant.
106 (manufactured by Toagosei Kagaku Kogyo ■) was added to each to form an aggregate, which was then made into paper using a paper machine and dried by heating at a temperature of 140° C. for 5 minutes to obtain ion exchange paper.

This ion exchange paper has an ion exchange capacity of 0 for Cl ions.
, 8 meq/g (Gi), and had sufficient functionality as an ion exchanger.

Further, even when this paper was immersed in 10% NaOH for 10 days, the paper quality did not change at all, and there was no problem with durability.

next. The second invention, which has the ion exchange paper obtained as described above as its main part, will be described in detail.

Figures 2 to 5 show a method of forming a laminate by winding or polymerizing the ion exchange paper obtained according to the first invention at predetermined intervals, and housing and holding the laminate in a frame. It was made into a cartridge. The cartridge 4 shown in FIG. 2 has rectangular ion exchange shields 5a and wavy ion exchange shields 5b stacked alternately. These are surrounded by a frame 6 made of chemically resistant plastic such as polypropylene, polyethylene, ABS resin, or the like.

The cartridge 7 in FIG. A large number of rectangular ion exchange papers 8 are placed on a frame 9 made of the same material as above.
Constant 1 through 10. This maintains the distance. The cartridge 11 in FIG. 1 sheet of ion exchange G12
is wound into a spiral shape, and a number of spacers 13 are used to maintain a predetermined distance between the windings. This is held in a frame 14 made of chemical-resistant plastic.

The cartridge 15 in FIG. Rectangular ion exchanger 1
6a and ion-exchange pads 16b bent in a zigzag pattern are alternately laminated, and the contact portions of the laminations are adhered with adhesive 17 to form a collection of many triangular prisms. This is framed by a frame 18 made of chemical-resistant plastic. These cartridges shown in Figs. 2 to 5 are. As mentioned above, it is used in such a way that the fluid to be treated by ion exchange flows along the surface of the ion exchange paper.

〔Effect of the invention〕

As described in detail above, the first invention involves adding both cationic and anionic flocculants to a mixed slurry of an inorganic ion exchanger and pulp, and performing a flocculation treatment to form paper. It supports particles of inorganic ion exchanger.

therefore. The resulting ion exchange paper is extremely easy to form into a film, which further expands its range of uses, and because there is no need to use any binders like conventional inorganic ion exchangers, it can be used at high temperatures and high temperatures. alkali. It has sufficient durability even under extremely harsh conditions such as high acidity.
It can be used for a long period of time without losing its functionality.

Furthermore, the obtained ion exchange paper can be obtained in large quantities by an extremely simple method, and the inorganic ion exchanger is evenly and firmly supported between the pulp fibers. It can efficiently exchange ions not only in liquids but also in gases. It can also be effectively used for solid electrolyte membranes, electrolytic diaphragms, etc.

The second invention is to form a stack by winding or polymerizing ion exchange papers having the same properties at predetermined intervals. The laminate is housed and held in a frame to form a cartridge, and by introducing a processing fluid into the cartridge and bringing it into contact with ion exchange paper, the contact area with the fluid is increased, and the ion exchange paper is brought into contact with the ion exchange paper. In addition to maximizing the effectiveness of exchange paper. It is simple and easy to replace during use, and its strength is further improved when combined with the frame, making it extremely useful in industry.

The third invention is that ion-exchange paper with inorganic ions supported between pulp fibers can be obtained by an extremely simple and easy method of papermaking, making mass production easy and providing the obtained accessories at low cost. It is something that can be done.

[Brief explanation of the drawing]

Figure 1 is a partially cutaway perspective view of the ion exchange paper of this invention. Fig. 2 to Fig. 5 show an example in which ion exchange paper is made into an effusion. Figure 3 is a longitudinal sectional view of an embodiment in which rectangular ion exchange papers are sequentially stacked to form a cartridge.
Fig. 4 is a longitudinal cross-sectional view of an embodiment in which a sheet of rectangular ion exchange paper is spirally wound to form a cartridge, and Fig. 5 is a longitudinal sectional view of an embodiment in which a rectangular ion exchange paper and a zigzag bent ion exchange paper are alternately assembled. It is a longitudinal cross-sectional view of an example in which the cartridges are combined. 1.5a, 5b, 8.12, 16a, 16b, ...
・Ion exchanger 2...Inorganic ion exchanger particles 3...Pulp fibers 4, 7, 11.15...Cartridges 6.9, 3
．． 18... Frame 10.13... Baseer, 17... Adhesive No. 1
Figure 2 Figure 3 Procedural Amendments July 31, 1986 1. Indication of the incident 1985 Patent Application No. 143768 2. Name of invention: Ion exchange paper. Method for producing ion exchanger and ion exchange paper 3. Relationship with the case of the person making the amendment Patent applicant 5-12-1 Shin-Ia, Minato-ku, Tokyo 5. Column 6 of “Detailed Description of the Invention” of the specification to be amended. Contents of the amendment (1) "Animina silica fiber" on page 7, line 14 of the specification is amended to "alumina silica fiber". (2) rO on page 15, line 3 of the specification Correct .005 gJ to .'0.001 g J. (3) ro.o05 g on page 15, lines 5-6 of the specification.
Correct the word J to '0.010 gJ. that's all

Claims (3)

[Claims] (1) Ion exchange paper characterized by having inorganic ion exchanger particles supported between pulp fibers. (2) Form a laminate by winding or polymerizing ion exchange paper in which particles of an inorganic ion exchanger are supported between pulp fibers while maintaining a predetermined interval, and attach the laminate to a frame. An ion exchanger characterized by being housed and held in a cartridge. (3) An ion exchange paper characterized in that particles of an inorganic ion exchanger are supported between pulp fibers by adding a flocculant to a slurry containing an inorganic ion exchanger powder and pulp and making the paper. Production method.