JPH0689093B2 - Separation functional jelly - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a separation-functional jelly and a method for treating an aqueous liquid, wherein the separation-functional jelly according to the present invention separates and concentrates a solute in an aqueous liquid, That is, solute separation and concentration in water treatment of tap water / industrial water, solute separation / concentration in wastewater treatment of industrial wastewater, sewage, night soil, etc. Separation / concentration of solute of production process liquid in agriculture / mining / industry It is used for the separation and concentration of solutes from seawater, especially the removal of chromaticity in water treatment, the reduction of BOD and COD, the removal of silica, the removal of phosphoric acid, and the humic compounds widely used in the fermentation industry. Removal of coloring components such as lignin-based substances, decolorization of saccharified liquid (starch sugar),
It is used for decoloring sucrose liquid (sweet potato sugar, beet sugar).

[Summary of the Invention] Recently, remarkable progress has been made in the technology for separating and concentrating dissolved substances in liquids due to the progress in the synthesis and utilization techniques of polymer substances.
It utilizes the pores and separation function of a solid (gel body) of a polymer (colloidal particle) substance.

Their functions depend on the size, ionicity, adsorptivity, etc. of the dissolved substances. (1) Various ion exchange resins, adsorbents, etc. by the method of bringing a solid substance (powder, fiber, cloth, etc.) into contact with the solution. There is a method of using a chelate resin or the like and (2) a method of permeating a solution through a membrane of a solid substance. Various types of membrane permeation methods are known, which are called microfiltration membranes, ultrafiltration membranes, and semipermeable membranes from large ones depending on the size of pores of continuous bubbles (continuous pores). They are used under pressure of liquid and are called microfiltration, ultrafiltration and reverse osmosis. Further, there is an electrodialysis method that operates by applying a voltage.

In the case of the membrane method, a pressure of 1 kg / cm ² or more is generally required to permeate the solution through the membrane (gel body) having fine pores, and the power cost is high. The electrodialysis method is mainly applied to sodium chloride as a solute, and the electric power cost is high.

The present invention, unlike conventional ion exchange resins, chelate resins, etc., is a solid (jelly) produced by a remarkably low concentration of an ion exchange / adsorption active resin having a reticulated structure, and humic acid, ligninsulfonic acid and other polymer electrolytes. It is based on the fact that it has been found to be particularly effective for separation / concentration applying the ion exchange / adsorptivity of the above.

With current technology, separation of humic acid and lignin sulfonic acid from solution must rely on membrane methods or activated carbon. The membrane method involves ultrafiltration and reverse osmosis, but high pressure is necessary and membrane fouling is a problem. With the method using MR resin or activated carbon, the ion exchange / adsorption properties of these anionic polymer substances are not good.

Among ordinary ion exchange resins, there are MR resins with a high degree of crosslinking, but the size of the pores is relatively small. Further, although their swelling properties are expected, the conventional ion exchange resin has a maximum water content of about 80% (concentration of about 20%). In the 10% concentration swelling gel and the 1% concentration jelly of the same structure, the pore size has a difference of 10 times in three dimensions and about 4 to 7 times in two dimensions, and the linear shape. The permeability of macromolecules, graft polymers and cross-linked polymers and the molecular weight of permeable molecules are significantly high.

On the other hand, a recently developed swellable resin is a water absorbent resin.
Data has been obtained that absorbs about 1,000 times as much water as a water-absorbent resin, but about 50 to 100 times the limit for salt solutions such as seawater. In addition, these water-absorbed resins (swelling resins) have a small degree of cross-linking, and are generally unstable and sticky, for example, alkali polyacrylate or poly (acrylamide-alkali acrylate) copolymer, and are The strength is extremely weak, and each has an anionic group.

Regarding the manufacturing method of water-containing cured resin (jelly), various technologies are used in the development of chemical grout used for soil stabilization method, development of bioreactor and biosensor applying immobilized enzyme and immobilized microorganism, and development of carrier for liquid chromatography. Are known.

The present invention was invented from a method for producing a stable, ion-exchange / adsorptive jelly (an elastic body made of a hydrophilic gel of a network resin) having a remarkably low concentration and a study of their separating function.

The present invention firstly synthesizes a water-soluble polyamine compound having a large number of amine groups (amino group, imino group) in a molecule by reacting an aliphatic polyvalent amine with epihalohydrin, and then further diluting them with an aqueous solution of dilute concentration. Remarkably high water content (remarkably low concentration) by adding aldehydes
It was found that the jelly with high water content was obtained, and the obtained jelly (elastic solid composed of water-containing resin) has a remarkable effect on the separation and concentration of humic acid, ligninsulfonic acid and other anionic substances. It is based on the facts found.

[Prior Art] Water solutes (inorganic substances, organic substances, etc.) in water treatment such as tap water or industrial water, industrial wastewater treatment, sewage treatment, wastewater treatment such as human waste treatment, industrial process liquid treatment, etc.
For the purpose of separating and concentrating, the precipitation method, the ion exchange method using an ion exchanger, the adsorption method using an adsorbent or a chelating resin, and the membrane method (ultrafiltration method using an ultrafiltration membrane, semipermeable membrane) The reverse osmosis method using, the electrodialysis method using an ion exchange membrane, and the extraction method are used.

The styrene-divinylbenzene copolymer, which is a conventional ion exchange resin, is a micropore, and its size is said to be around 1 mm. A material having a small mixing ratio of divinylbenzene as a cross-linking agent is called a macropore, but the size of the pore is small and, for example, the ion exchange / adsorption ability of a polymer anion such as humic acid is small.

[Problems to be Solved by the Invention] Conventionally, as a resin or a membrane used for separating solutes, a xerogel body of a polymer substance is used, and xerogel (dry glue) or a swollen form thereof has a concentration of 20%. %
Above (water content is about 80% or less), the pores of the gel are small.
Therefore, conventional ion-exchange resins, MR resins, and chelate resins are xerogels, so they are used to separate small cations and anions such as metal ions, metal complex ions, non-metal ions, and low-molecular ions. It has little effect on the separation of and the ion exchange rate is low.

Also, conventional adsorbents such as activated carbon have small pores,
Even when applied to the separation of water-soluble molecular substances, the adsorption amount is small and the adsorption rate is low.

[Means for Solving the Problem] The separation-functional jelly according to the present invention is further reacted by adding an aldehyde to an aqueous solution of a water-soluble polycondensate obtained by reacting an aliphatic polyvalent amine with epihalohydrin. A method for producing a separation-functional jelly having a high water content characterized by that, and a method for bringing powders of those jellies, a membrane or a plate-like composition into contact with an aqueous liquid, or an aqueous liquid at a normal pressure using a jelly membrane. The method for treating an aqueous liquid is characterized by separating and concentrating not only small anions but also dissolved substances such as polymer anions by a method of permeating under reduced pressure or pressure.

The jelly according to the present invention contains a water-soluble polycondensate as a raw material at a concentration of about
A 30% or less aqueous solution that reacts with aldehydes to form macromolecules with a three-dimensional, network structure by a cross-linking reaction. It is a water-insoluble resin and has a high water content jelly (water-curing resin of elastic body). Is. The high water content means a water content of about 80% or more (concentration of about 20% or less), preferably a water content of about 95% or more (concentration of about 5% or less). Since it contains 95% or more of water, it has a great feature that it has huge pores.
It has a high permeability to liquids and solutes, and therefore is capable of ion exchange / adsorption of fairly large molecules (polymeric substances), and is capable of separating solutes by permeation, and has a high separation rate.

The aliphatic polyamine according to the present invention has two or more amino groups or imino groups in the molecule, and ethylenediamine,
Alkylenediamine such as hexamethylenediamine, polyethylenepolyimine, polyalkylenepolyimine such as polyhexamethylenepolyimine, polyvinylimizoline,
Polyacrylic acid aminoethyl ester, polymethacrylic acid aminoethyl ester, natural product chitosan, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxapyro [5,5] undecane, xylyl Diamine, 4-aminomethyl-1,8-octadiamine, 1,6,11-undecanetriamine, etc. are used. As epihalohydrin according to the present invention, epichlorohydrin, epibromohydrin, epiiodohydrin and the like are used.

As the aldehydes according to the present invention, formaldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, adipaldehyde and the like are used alone or in combination.

The reaction temperature is below the boiling point. The concentration is about 20% or less, and can be arbitrarily changed within the range of producing jelly. The present invention is greatly characterized in that the size of pores can be arbitrarily changed by a method of changing the concentration under the synthesis conditions. When the jelly-forming resin according to the present invention has active hydrogen, it can be alkylated and quaternized with a sodium hydroxide solution and a dialkyl sulfate.

The addition amount (molar ratio) of the aldehydes to the water-soluble polyvalent amine is not jelly when it is too small and often precipitates when it is too large, and the proper addition amount is experimentally determined.

The compressive strength of jelly is about 0.1 to 1 kg / cm ² , but powder
When mixed with 20 to 50%, it can be ¹ to 5 kg / cm ² . Further, the strength can be increased by attaching it to paper, cloth or the like.

The permeability of jelly is about 10 ^-5 .

The porosity of jelly is about 80% or more in terms of water content.

Jelly can be used as a powder by crushing and crushing.

The jelly can be used in a spherical shape depending on the method of emulsion polymerization.

The jelly can be used in the form of a plate that is attached to paper or cloth.

The contact between the powder and the aqueous liquid is by mixing them, a fixed bed, a moving bed, a fluidized bed, countercurrent contact or the like. The permeation of the membrane is reduced pressure,
Performed by gravity and pressure.

Next, examples of the present invention will be described.

Example 1 An experiment was conducted on a method for producing a high water content functional jelly according to the present invention.

Hexamethylenediamine (hereinafter, HMD
20 g) (shown as A), 40 g of water are added, and 15.9 g of epichlorohydrin (hereinafter referred to as ECH) in an equimolar amount to HMDA is gradually added, and the mixture is stirred at 45 ° C for 50 minutes, and then 2 times with water. It was diluted twice and stirred at 45 ° C. for 20 minutes. The pH of the obtained polycondensate was adjusted to 4 with hydrochloric acid, and the concentration was diluted to 10%.
The 1% concentration solution of this polycondensate had a relative viscosity to water at 20 ° C. of 4.8.

An aqueous solution of this HMDA-ECH polycondensate hydrochloride was diluted with water to prepare 10%, 5% and 2.5% solutions, and 100 ml of each solution was prepared.
After adding 5 ml of a 50% aqueous solution of glutaraldehyde (hereinafter referred to as GA) with stirring, the mixture was allowed to stand,
Both were made into jelly (solidified).

Each of these was ground to about 1 mm ³ , heated at 80 ° C. for 1 hour, washed with water, and dehydrated by centrifugal filtration. These jellies are referred to below as jelly (1), jelly (2), and jelly (3), respectively. Their ion exchange capacities were all about 7-8 meq / g.

When aldehydes were similarly treated with formalin, glyoxal, etc., all produced low-concentration jelly.

Comparative Example In the aqueous reaction of HMDA and ECH, it was difficult to form jelly having a water content of 95% or more even if the molar ratio of both was changed.

Example 2 An experiment was conducted on the production of a low-concentration functional jelly according to the present invention.

4-aminomethyl-1,8-octanediamine (hereinafter referred to as TA) (10 g) is placed in a 200 ml flask, water (61.4 g) is added thereto, and an equimolar amount of ECH (5.35 g) is gradually added with stirring. It was stirred for 140 minutes. The obtained polycondensate was adjusted to pH 4 by adding water and hydrochloric acid and diluted to a concentration of 5%. The relative viscosity of the 1% strength solution was 4.1.

When a small amount of a 15% GA aqueous solution was added to this TA-ECH polycondensate aqueous solution, jelly was formed at a polycondensate concentration of 4%. Jelly was formed at pH 7 at 3.3% and at pH 10 at 1.7%. These were crushed to about 1 mm ³ , heated at 80 ° C. for 1 hour, washed with water, and dehydrated by centrifugal filtration. These jellies are jelly (a), jelly (b), and jelly (c), respectively.
Indicate. Their ion exchange capacity is about 7-8 meq
It was / g.

Comparative Example In the aqueous reaction of TA and ECH, even if the molar ratio of both is changed,
It was difficult to form jelly with a water content of 95% or more.

<Example 3> 50 ml of a solution having a concentration of 500 to 2000 mg / 1 of sodium ligninsulfonate as a COD component and a coloring component was taken, and 0.3 to 1 g of the jelly produced in each of Example 1 and Example 2 was added, and 20
After agitating in a thermostat bath at ℃, the absorbance at a wavelength of 420 nm was measured to obtain the concentration, and the adsorption amount was calculated. Equilibrium concentration 10
The amount of ion exchange / adsorption at 00 mg / 1 was as shown in Table 1.

Comparative example Commercially available ion exchange resin (Dowex WGR) and activated carbon C
The same experiment as described above was performed for AL. The obtained results are shown in Table 1 as a comparative example.

<Example 4> For each of the jellies produced in Example 1 and Example 2, an experiment was carried out in the same manner as in Example 3 using a solution of ammonium humate as a coloring component and a COD component. The amount of adsorption at the equilibrium concentration of 50 mg / 1 was as shown in Table 2.

Comparative example Commercially available ion exchange resin (Dowex WGR) and activated carbon C
Similar experiments were performed for AL. The obtained results are shown in Table 2 as a comparative example.

<Example 5> The jelly (c) according to the present invention of Example 4 was added to each aqueous solution of sodium chloroplatinate, sodium chloroaurate, and sodium chromate (concentrations were about 50 mg / 1, pH 8.1). After adding and stirring for 24 hours, the ion exchange / adsorption amount was calculated to be 7.05 mg / g, 6.42 mg / g, 4.85 mg, respectively.
It was / g.

From these results, the high water content jelly of the (amine-epihalohydrin) -aldehyde polycondensate according to the present invention has a loose network structure and has an anion exchange adsorption action due to having large pores and amine groups. I think.

[Effect of the Invention] The separation-functional jelly according to the present invention relates to a method for producing a jelly having a remarkably high water content, in other words, a low concentration. Since it has a functional group, it has a large ion exchange / adsorption property. The size of the pores can be arbitrarily changed by changing the concentration of the raw material.

The remarkably ion-exchange / adsorption ability of the separation-functional jelly of the present invention, especially for water-soluble polymer electrolytes, is that the pores are large, and the water-soluble polymer electrolytes have colloidal characteristics, and are partially ion-exchanged / adsorbed. It is thought that this is due to the fact that separation is possible, and the technology of the present invention is a new separation technology developed, and its industrial value is great.

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area C08G 73/02 NTC 9285-4J

Claims (2)

[Claims] 1. An aqueous solution of a water-soluble polycondensate obtained by reacting a water-soluble aliphatic polyamine with epihalohydrin,
A method for producing a separation-functional jelly having a high water content, which further comprises adding aldehydes to react. 2. An aqueous solution of a water-soluble polycondensate obtained by reacting a water-soluble aliphatic polyvalent amine with epihalohydrin,
Further, by adding aldehydes and reacting to produce a high water content jelly, the powder, a method of contacting the membrane or plate-like structure with an aqueous liquid, or an aqueous liquid at normal pressure using a jelly membrane, A method for treating an aqueous liquid, which comprises separating and concentrating dissolved substances such as anions and anionic polymer substances by a method of permeation under reduced pressure or pressure.