JPS621299B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides an adsorbent that has excellent mechanical strength and adsorption performance, and is inexpensive to manufacture. In recent years, the phenomenon of eutrophication in closed water bodies such as the Seto Inland Sea and Lake Biwa has progressed one step further and is now becoming a major social problem. In particular, the removal of phosphate ions, which is one of the causative substances, is an important issue that must be solved immediately. By the way, the current phosphate ion removal technology involves adding chemicals containing metal ions such as calcium and aluminum to wastewater containing phosphate ions, and removing the phosphate ions as poorly soluble phosphates. The coagulation-sedimentation method is considered to be the only method. However, this method generates a large amount of sludge, which may cause secondary pollution, and is not necessarily a satisfactory method, and there is a strong need for the development of a new phosphate ion removal technology. On the other hand, titanium oxide, zirconium oxide, and tin oxide hydrates have properties as ion exchangers, and for example, in acidic solutions, they fix H ⁺ and become anion exchangers, and phosphate ions and elementary ions, sulfate ions, chloride ions, arsenate ions,
Adsorbs arsenite ions, chromate ions, molybdate ions, etc. Additionally, in alkaline solutions, these hydrates fix OH ^- and use UO ₂ ⁺ as a cation exchanger.
It is known to adsorb things such as The present inventors have conducted research and development of adsorbents focusing on the ion exchange properties of these metal oxide hydrates, but when manufacturing adsorbents using only metal oxide hydrates, the main raw material Both zirconium and titanium are relatively expensive metals, which inevitably increases the cost of the adsorbent. In addition, when producing an adsorbent using the precipitate of these metal oxide hydrates, there are many problems in production, such as the precipitate being gel-like and requiring time for overtreatment;
It has been found that the adsorbent produced in this manner has a fatal drawback of being unable to withstand industrial conditions of use due to its low mechanical strength. As a result of further research, the inventors found that titanium,
At least one of hydrated ferrites of zirconium and tin, or a mixture thereof with at least one of hydrated oxides of titanium, zirconium, tin, and iron, is mixed with an unsaturated polyester resin or a polyurethane resin, and the mixture is cured. The inventors found that the resulting adsorbent has excellent mechanical strength and adsorption performance, and is inexpensive to manufacture.Based on these findings, the present invention was completed. That is, the present invention provides at least one of the hydrated ferrites of titanium, zirconium, and tin, or a mixture thereof with at least one of the hydrated oxides of titanium, zirconium, tin, and iron.
It relates to an adsorbent formed by mixing with 1/10 to 3 times the amount (weight) of unsaturated polyester resin or polyurethane resin and curing. At least one of the hydrated ferrites of titanium, zirconium, and tin, or a mixture thereof with at least one of the hydrated oxides of titanium, zirconium, tin, and iron used to produce the adsorbent of the present invention is, for example, It is manufactured by the following method. A ferrous salt is added to a solution containing metal ions prepared by dissolving at least one metal salt of titanium, zirconium, and tin in an amount equivalent to about 0.2 to 11 times the mole of the metal ions contained in the solution. After adding, an alkali is added to maintain the pH of the liquid at about 6 or more, preferably about 7 to 12. After this, if necessary, after bringing the temperature of the solution to about 30-100°C, blowing in an oxidizing gas such as air, oxygen gas or ozone, or adding an oxidizing agent such as hydrogen peroxide, Forms an acid salt precipitate. The resulting precipitate is separated, washed with water, and then dried.
Drying is performed by air drying or at a temperature below about 100°C, preferably below about 50°C, for about 1 to 20 hours. As mentioned above, the moisture content after drying is preferably within the range of about 6 to 30% by weight. In this way, at least one of the hydrated ferrites of titanium, zirconium and tin or a mixture thereof with at least one of the hydrated oxides of titanium, zirconium, tin and iron is obtained. More specifically, at least one of the hydrated ferrites of titanium, zirconium and tin, or a mixture thereof with a hydrated oxide of iron, is a metal salt of at least one of titanium, zirconium and tin in the aforementioned method. It is produced in the same manner as the above method, except that a ferrous salt corresponding to about 2 to 11 times the mole of metal ions contained in this solution is added to a solution containing dissolved and prepared metal ions. Ru. Here, hydrated oxides of iron include, for example, FeO,
Represents hydrates (monohydrate, dihydrate, trihydrate, tetrahydrate, etc.) of iron oxides such as Fe ₂ O ₃ and Fe ₃ O ₄ . The ratio of hydrated ferrite to hydrated oxide of iron is such that the hydrated ferrite content is about 24-100% by weight. The mixture of at least one hydrated ferrite of titanium, zirconium and tin and at least one hydrated oxide of titanium, zirconium and tin dissolves the metal salt of at least one of titanium, zirconium and tin in the aforementioned method. Add about 0.2 times the mole or more of the metal ions contained in the solution to the solution containing metal ions prepared by
It is produced in the same manner as the above method except that the ferrous salt is added in an amount less than about 2 times the molar amount. in this case,
The hydrated ferrite content ranges from about 20% to less than 100% by weight. Here, the hydrated oxide of titanium has the general formula
It is represented by TiO ₂ ·nH ₂ O (in the formula, n is a positive number from 0.5 to 2.0). Specifically, for example, TiO ₂ .H ₂ O (TiO(OH) ₂ ), TiO ₂ .2H ₂ O
(Ti(OH) ₄ ), TiO ₂ .nH ₂ O (n≈1.5 to 2.0), and the like. The hydrated oxide of zirconium is represented by the general formula ZrO ₂ .nH ₂ O (in the formula, n is a positive number from 0.5 to 2.0). Specifically, for example, ZrO ₂・H ₂ O (ZrO(OH) ₂ ), ZrO ₂・2H ₂ O
(Zr(OH) ₄ ), ZrO ₂ .nH ₂ O (n≒1.5 to 2.0), and the like. The hydrated oxide of tin has the general formula
It is represented by SnO ₂ ·nH ₂ O (in the formula, n is a positive number from 0.5 to 2.0). Specifically, for example, SnO ₂・H ₂ O (SnO(OH) ₂ ), SnO ₂・2H ₂ O
(Sn(OH) ₄ ), SnO ₂ .nH ₂ O (n≒1.5 to 2.0), and the like. The metal salts of titanium, zirconium or tin used in the above production method include, for example, titanium tetrachloride (TiCl ₄ ), titanium sulfate (Ti
(SO ₄ ) ₂ ), zirconium oxychloride (ZrOCl ₂
8H ₂ O), zirconium tetrachloride (ZrCl ₄ ), zirconium nitrate (Zr(NO ₃ )・4H ₂ O), zirconium sulfate (Zr(SO ₄ ) ₂・4H ₂ O), zirconium acetate (Zr
(CH ₃ COO) ₄ ), tin tetrachloride (SnCl ₄ ), tin nitrate (Sn(NO ₃ ) ₄ ), and tin sulfate (Sn(SO ₄ ) ₂ ). These metal salts are typically about 0.05 to 2.0
Used in molar solution form. Examples of ferrous salts include ferrous sulfate ( _FeSO4.7H2O ) and ferrous nitrate (Fe( _{NO3 ) 2} .
6H ₂ O), ferrous chloride (FeCl ₂ ), etc. These ferrous salts are usually added in solid form, but may also be added in solution form. Examples of the alkali include sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, and sodium carbonate. These are usually used in an aqueous solution of about 5 to 20% by weight. When blowing oxidizing gas, the time varies depending on the type of oxidizing gas, but usually about 1~
It takes about 3 hours. As the oxidizing agent, for example, hydrogen peroxide, sodium hypochlorite, potassium hypochlorite, etc. are used. The shape of the hydrated ferrite or the mixture of it and the hydrated oxide may be any shape, but those having a particle size of about 250 μm or less are particularly preferable from the viewpoint of mixing operation with the resin and adsorption performance, which will be described later. In the present invention, the thus obtained hydrated ferrite or a mixture of it and a hydrated oxide is
It is mixed with 1/10 to 3 times the amount, preferably about 1/5 to 1 times the amount (by weight) of unsaturated polyester resin or polyurethane resin. When the amount of the resin exceeds about 3 times the amount, the mechanical strength of the adsorbent increases, but the adsorption performance decreases. On the other hand, the proportion of resin is small, about 1/1/2 of the above.
If the amount is less than 10 times, the adsorption performance is excellent, but the mechanical strength is reduced and may not be suitable for industrial use. The unsaturated polyester resin used to produce the adsorbent of the present invention may be any known unsaturated polyester resin, but specifically,
For example, a compound obtained by condensing a dicarboxylic acid having a double bond in the molecule, such as maleic acid or its anhydride, or fumaric acid, with a dihydric alcohol, such as ethylene glycol or propylene glycol, by a known method. For example, saturated cotton-like polyesters dissolved in vinyl type monomers such as styrene, chlorostyrene, methyl methacrylate, diallyl phthalate, etc. can be mentioned. The dicarboxylic acids mentioned above may be modified with unsaturated or saturated dicarboxylic acids, such as fumaric acid, itaconic acid, phthalic anhydride, adipic acid, hettic acid, sebacic acid, isophthalic acid, terephthalic acid. Dihydric alcohols may also be modified with glycols such as bisphenol A, hydrogenated bisphenol A, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, trimethylene glycol, hexanediol, and pentanediol. good. Any known polyurethane resin can be used as the polyurethane resin, but specifically, polyurethane resins having two or more hydroxyl groups in the molecule, such as polyether polyols, polyester polyols,
Polymer polyols, butadiene polyols,
Polyols such as polycarbonate diol and castor oil have two or more isocyanate groups in the molecule, such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (Piure MDI), naphthalene diisocyanate (NPI), and dimethyl diphenyl diisocyanate (TODI). , polymethylene polyphenyl polyisocyanate (crude MDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), and other polyisocyanates are reacted by a known method. can give. This polyurethane resin is usually produced by reacting isocyanate groups contained in the resin with each other by heat or a crosslinking agent, or by reacting with isocyanate groups such as ethylene glycol, propylene glycol, butanediol, glycerin, hexanetriol, and trimethylolpropane. , reacts with water etc. to become a thermosetting resin. If the aforementioned unsaturated polyester resin or polyurethane resin is liquid at room temperature, it can be used as is, but if it is solid,
For example, hydrocarbons such as butane, hexane, cyclohexane, benzene, toluene, halogenated hydrocarbons such as methylene chloride, chloroform, trichloroethane, chlorobenzene, methanol,
Alcohols such as ethanol and propanol; ketones such as acetone and methyl ethyl ketone; esters such as methyl acetate and ethyl acetate; Boil until liquid. A specific method for mixing with an unsaturated polyester resin or polyurethane resin is, for example, mixing hydrated ferrite or a mixture of it with a hydrated oxide and the resin by stirring at high speed in a container equipped with a stirrer. Examples include a method of batchwise or continuous mixing using a kneader, and a method of batchwise or continuous mixing using a device used for mixing solids and liquids. For unsaturated polyester resins, for example benzoyl peroxide (BPO), lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide,
Appropriate amounts of catalysts such as t-butyl peroxide isobutyrate and curing accelerators such as cobalt naphthenate, manganese naphthenate, dimethylaniline, phenylmorpholine, diethanolaniline, panadyl acetylacetonate, phenylphosphinic acid, etc. May be added. After mixing with resin, harden. The curing operation is usually carried out at room temperature, but if the curing time is long, it may be heated to about 30 to 90°C. If necessary, the cured product may be crushed using a hammer mill, a roll crusher, etc., and then granulated. In that case, the particle size is preferably about 3 to 120 mesh, preferably about 24 to 80 mesh.
Alternatively, the mixture may be continuously extruded in a cylindrical manner onto equipment such as a steel belt conveyor,
After holding the mixture on the steel belt conveyor for a residence time to cure, the cured cylindrical adsorbent may be cut into appropriate lengths. In addition, using a dish-type rolling granulator or centrifugal flow coating granulator using small particles of the mixture as cores, coating granulation is performed by simultaneously supplying water-containing ferrite, etc., and liquid resin to produce spherical adsorbents. You may create one. The adsorbent of the present invention obtained in this manner can be used as an adsorbent for various anions and cations, but in particular, with regard to anion adsorption, it selectively adsorbs phosphate ions from acidic solutions. Therefore, it can be used as an adsorbent for phosphate ions. Furthermore, the adsorbent of the present invention has the property of selectively adsorbing a larger amount of phosphate ions in the pH range of about 1 to 5, but hardly adsorbing them on the alkaline side. Therefore, after performing an adsorption operation in an acidic solution with a pH of about 1 to 5, it can be desorbed with an alkaline solution, and it can be used repeatedly. In addition, the adsorbent of the present invention has excellent mechanical strength, so it can withstand industrial usage conditions, and can be applied not only to fixed bed adsorption equipment, but also to moving bed and fluidized bed adsorption equipment, especially when performing adsorption operations. I can't help it. Furthermore,
It also has excellent resistance to chemicals such as acids and alkalis, so it does not deteriorate even after repeated desorption and adsorption, and can be used repeatedly for a long time. In particular, hydrated ferrite forms a crystal lattice of a stable compound, and titanium, titanium,
Since it is presumed that zirconium or tin atoms are incorporated and form a solid solution, these metals have the advantage of being stable and difficult to elute. Furthermore, the adsorbent of the present invention can be magnetically separated, and solid-liquid separation of the adsorbent is easy. Furthermore, the adsorbent of the present invention can be produced by a simple operation of simply mixing hydrated ferrite or a mixture thereof with a hydrated oxide and an unsaturated polyester resin or polyurethane resin and curing the mixture. , has the advantage of low manufacturing cost. EXAMPLES The present invention will be described in more detail with reference to Examples below. Example 1 A 0.15 mol aqueous solution of titanium tetrachloride was prepared. This solution contains 7gr of metal ions as Ti. 84g of ferrous sulfate crystals (FeSO ₄ .7H ₂ O) are added to this aqueous solution and dissolved with stirring. This amount corresponds to 0.3 mol as ferrous ion. Next, a 15% by weight sodium hydroxide solution is added dropwise to this aqueous solution while stirring.
This produces a blue-green precipitate. Continue dropping until the pH of the aqueous solution reaches 10. Next, air is blown into the aqueous solution at a flow rate of 10/hour while heating it to 60 to 70°C.
Continuing to blow air will lower the pH of the aqueous solution, so in this case, add 15% by weight sodium hydroxide solution to maintain the pH at 10. Air is blown for about 2 hours to form a black titanium hydrated ferrite precipitate. Next, this black precipitate was suctioned off, washed with deionized water until the solution became neutral, and then washed for 70 minutes.
Dry below ℃. This is ground in a mortar to a particle size of 120 microns or less to obtain a titanium hydrated ferrite powder. Place 20g of hydrated titanium ferrite powder in a beaker and add isophthalic acid-based unsaturated polyester resin (manufactured by Takeda Pharmaceutical Company Limited; Polymer
6709) Add 20gr and mix thoroughly with a stirring rod.
Next, add 0.1gr of cobalt naphthenate and 0.2gr methyl ethyl ketone peroxide, mix well, and harden. Curing time is approximately 30-60 minutes. Next, the solidified material was taken out from the beaker, crushed into an appropriate size, and then refined into particles of 8 to 32 mesh to obtain an adsorbent. Example 2 1 0.05 mol aqueous solution of zirconium oxychloride
adjust. This solution contains 4.55gr of metal ions as Zr. 27.8 gr of ferrous sulfate crystals (FeSO ₄ .7H ₂ O) are added to this aqueous solution and dissolved with stirring. This amount is as iron ion
Equivalent to 0.1mol. Next, add 15% by weight to this aqueous solution.
While stirring the sodium hydroxide solution of
If the solution is dropped until the concentration reaches 11, a bluish-green precipitate will form.
Next, while heating this aqueous solution to 50 to 80℃,
Blow air at a flow rate of /hour. Continuing to blow air will lower the pH of the aqueous solution, so in this case, add a 15% by weight sodium hydroxide solution dropwise.
Keep PH at 10. If air is continued to be blown until the pH no longer decreases, a black zirconium hydrated ferrite precipitate will form. Next, this black precipitate is suctioned off, washed with deionized water until the liquid becomes neutral, and then dried at below 50°C.
This is ground in a mortar to a size of 120 microns or less to obtain zirconium hydrated ferrite powder. Next, 10g of this zirconium hydrated ferrite powder was placed in a beaker, and then, in the same manner as in Example 1, it was mixed with 10g of isophthalic acid-based unsaturated polyester resin and cured to obtain an adsorbent. Example 3 14g of the zirconium hydrated ferrite powder prepared in Example 2 was placed in a beaker, and the same procedure as in Example 1 was carried out to prepare an isophthalic acid-based unsaturated polyester resin.
Add 6gr of cobalt naphthenate, 0.03gr of cobalt naphthenate, and 0.06gr of methyl ethyl ketone peroxide, stir thoroughly, and then leave to harden in about 60 minutes. After crushing this to an appropriate size, it was refined into particles of 8 to 32 mesh to obtain an adsorbent. Example 4 1 0.05 mol aqueous solution of zirconium oxychloride
adjust. This solution contains 4.55gr of metal ions as Zr. Add 153 gr of ferrous sulfate crystals (FeSO ₄ .7H ₂ O) to this aqueous solution and dissolve while stirring. This amount is 0.55mol as iron ion
corresponds to Next, a 15% by weight sodium hydroxide solution was added to this aqueous solution while stirring until the pH of the solution was adjusted.
If the solution is added dropwise until the concentration reaches 9.5, a bluish-green precipitate will form. Next, air is blown into the aqueous solution at a flow rate of 10/hour while heating it to 40 to 70°C. If you continue to blow air, the pH of the aqueous solution will drop, so at this time, drop a 15% by weight sodium hydroxide solution.
Keep PH at 10. If air blowing is continued until no decrease in pH is observed, a precipitate of a mixture of black hydrated zirconium ferrite and hydrated iron oxide is formed. It contains approximately 27% by weight of hydrated ferrite of zirconium. Thereafter, an adsorbent was obtained by processing in the same manner as in Example 1. Example 5 In the same manner as in Example 2, 16 gr of zirconium hydrated ferrite powder was obtained. Next, 7gr of bisphenol-based unsaturated polyester resin (Prominate P-350 manufactured by Takeda Pharmaceutical Company Limited) was added to this powder.
After stirring and mixing thoroughly, add 0.035gr of 1% by weight cobalt naphthenate solution, 0.07gr methyl ethyl ketone peroxide, and further add dimethylaniline.
Add 0.007gr, mix thoroughly under nitrogen gas flow, and cure. Curing time is 35-45 minutes.
The solid material obtained in this way is crushed and refined, and
A 32mesh adsorbent was obtained. Example 6 In the same manner as in Example 2, 16 gr of zirconium hydrated ferrite powder was obtained. While suspending this powder in 10 ml of water, 10 ml (approximately 10 gr) of a hydrophilic urethane polymer (hydrophilic polyether polyol made by copolymerizing ethylene oxide and propylene oxide with tolylene diisocyanate added to both ends) is mixed. while dripping. The reaction between the hydrophilic urethane polymer and water immediately begins, and a foamable gel of the polyurethane resin is formed while generating carbon dioxide gas. In this gel, zirconium hydrated ferrite powder is dispersed and retained. This gel was cut into an appropriate size to obtain an adsorbent. Example 7 The adsorbent obtained in Example 2 was crushed to 120mesh.
A sieved product was obtained. Next, the above adsorbent powder was added in the amount shown in the table below to 100 ml of simulated wastewater (PH = 3) containing 500 ppm of phosphate ions prepared using monosodium phosphate, and after shaking all day and night (24 hours),
Table 1 shows the results of measuring the phosphate ion concentration in the simulated wastewater and measuring the amount of phosphate ion adsorbed by the adsorbent. Note that this table also includes the amount of adsorption of activated alumina powder, which has been known as an adsorbent for phosphate ions.

[Table] Adsorbents
4 Commercial activity 0.8 500 50 56
Alumina Example 8 The adsorbent obtained in the same manner as in Example 3 was granulated into 32 to 60 meshes, and a column of 10 gr (approximately 14
ml) filled. Here, simulated wastewater containing 300 ppm of phosphate ions adjusted using monosodium phosphate (adjusted to PH = 4 with dilute sulfuric acid) was added to SV3 (1/
The liquid was passed at a flow rate of (Hr). Then, the column effluent was sampled at regular intervals and the phosphate ion concentration was measured. The results are shown in Table 2.

[Table] The amount of phosphate ion adsorbed by the adsorbent after 2.5 liquid passages was approximately 65 mgPO ₄ /g adsorbent. When 30 ml of 15 wt% NaOH solution was passed through this at SV=1 (1/hr), it was found that about 95% of the adsorbed phosphate ions were desorbed. Example 9 The adsorbent obtained in the same manner as in Example 3 was granulated into 8 to 32 meshes, and 20gr (approx.
30ml) filled. Add 380ppm phosphate ion here
SV = activated sludge treated water 5 adjusted to contain
The liquid was passed at a flow rate of 2 (1/Hr). The amount of phosphate ions adsorbed by the adsorbent after 5 passes was approximately 52 mgPO ₄ /g adsorbent. Add 40ml of 15% NaOH solution to this.
It was found that approximately 94% of the adsorbed phosphate ions were desorbed when the liquid was passed at SV = 1 (1/Hr). Next, 2% by weight of H ₂ SO ₄ was added to the adsorbent after desorption.
After regenerating by passing 40 ml of the solution at SV=10 (1/Hr), the activated sludge treated water of No. 5 was passed under the same conditions as above, and repeated use was continued. The results are shown in Table 3.

[Table] As is clear from this table, the adsorbent of the present invention has a
It was found that the adsorption capacity hardly decreased even after repeated use. Example 10 2% by weight H ₂ SO ₄ was added to a test solution containing 500 ppm of phosphate ions prepared using monosodium phosphate.
100 ml of each simulated wastewater was prepared by adding the solution or 2% by weight NaOH solution to adjust the pH to 1, 2, 3, 5, 8, 10, and 12. Next, the adsorbent obtained in Example 2 was pulverized into 120-mesh sieved products, and 300 mg of each was added to the above simulated wastewater. After shaking for a day and a night (24 hours), the phosphate ion concentration in the simulated wastewater was measured, and the amount of phosphate ion adsorbed by the adsorbent was measured. The results are shown in Table 4 and FIG.

[Table] As is clear from Table 4 and Figure 1,
It can be seen that the adsorbent of the present invention adsorbs a large amount of phosphate ions especially in the pH range of 2 to 5, but hardly adsorbs on the alkaline side where the pH is 10 or more. Example 11 A 0.15 mol aqueous solution of titanium tetrachloride is prepared. This solution contains 7gr of metal ions as Ti. 75.6g of ferrous sulfate crystals (FeSO ₄ .7H ₂ O) are added to this aqueous solution and dissolved with stirring. This amount corresponds to 0.27 moles of ferrous ion. Next, when this aqueous solution is heated to 60 to 70°C and a 15% by weight sodium hydroxide solution is added dropwise with stirring, a blue-green to gray-green precipitate is produced. Continue dropping until the pH of the aqueous solution reaches 10. Next, while heating this aqueous solution to 60 to 70°C, air is blown in at a flow rate of 10/hour. If you continue blowing air, the pH of the aqueous solution will decrease, so
In this case, keep the pH at 10 by adding 15% by weight sodium hydroxide solution. Air is blown for about 2 hours to form a precipitate of a mixture of black hydrated ferrite and hydrated oxide of titanium. Next, this black precipitate is separated by suction, washed with deionized water until the liquid becomes neutral, and then dried at 70°C or lower. This was ground in a mortar to a size of 120 microns or less to obtain a mixture of hydrated titanium ferrite and metal oxide hydrate in powder form. Mixture powder of hydrated ferrite and hydrated oxide of titanium in a beaker (97.2% by weight of hydrated ferrite of titanium, 2.8% by weight of hydrated oxide of titanium)
Take 20gr, add 20gr of isophthalic acid-based unsaturated polyester resin (manufactured by Takeda Pharmaceutical Co., Ltd.; Polymer 6709), and mix thoroughly with a stirring rod. Next, add 0.1gr of cobalt naphthenate and 0.2gr methyl ethyl ketone peroxide, mix thoroughly and harden. Curing time is approximately 30-60 minutes. Next, the solid material was taken out from the beaker, crushed to an appropriate size, and then refined to a size of 24 to 80 mesh to obtain an adsorbent. Example 12 1 0.05 mol aqueous solution of zirconium oxychloride
adjust. This solution contains 4.55gr of metal ions as Zr. 25g of ferrous sulfate crystals (FeSO ₄ .7H ₂ O) are added to this aqueous solution and dissolved with stirring. This amount is as iron ion
Equivalent to 0.09mol. Next, add a 15% by weight sodium hydroxide solution to this aqueous solution while stirring to adjust the pH of the solution.
When added dropwise until the value reaches 10, a bluish-green precipitate is produced. Next, while heating this aqueous solution to 50 to 80°C, air is blown in at a flow rate of 10/hour. If you continue blowing air, the pH of the aqueous solution will decrease, so
In this case, 15% by weight sodium hydroxide solution is added dropwise to maintain the pH at 10. When air blowing is continued until no decrease in pH is observed, a black mixture of hydrated ferrite of zirconium and hydrated oxide of zirconium is precipitated. Next, this black precipitate is suctioned off, washed with deionized water until the liquid becomes neutral, and then dried at a temperature below 50°C. Grind this in a mortar to less than 120 microns,
A powder mixture of hydrated ferrite of zirconium and hydrated oxide of zirconium was obtained. The hydrated ferrite content of the zirconium was 95% by weight. Next, 10g of this powder was placed in a beaker, mixed with 10g of isophthalic acid-based unsaturated polyester resin in the same manner as in Example 11, and cured to obtain an adsorbent. Example 13 14g of a powder mixture of hydrated ferrite of zirconium and hydrated oxide of zirconium prepared in the same manner as in Example 12 was placed in a beaker, and the following Example 11 was prepared.
In the same manner as above, add 6g of isophthalic acid-based unsaturated polyester resin, 0.03gr of cobalt naphthenate, and 0.06gr of methyl ethyl ketone peroxide, stir thoroughly, and then leave to cure in about 60 minutes. This was crushed to an appropriate size and then refined into particles of 8 to 80 mesh to obtain an adsorbent. Example 14 In the same manner as in Example 12, 16 gr of a powder mixture of hydrated ferrite of zirconium and hydrated oxide of zirconium (content of hydrated ferrite of 95%) was obtained. Next, a bisphenol-based unsaturated polyester resin (Prominate P- manufactured by Takeda Pharmaceutical Co., Ltd.) was added to this powder.
350) After adding 7gr and stirring thoroughly, 1% by weight
Add 0.035 gr of cobalt naphthenate solution, 0.07 gr of methyl ethyl ketone peroxide, and further 0.007 gr of dimethylaniline, mix thoroughly under a nitrogen gas stream, and harden. Curing time is 30-60 minutes. The solid material obtained in this way is crushed and refined,
An 8-80 mesh adsorbent was obtained. Example 15 In the same manner as in Example 12, 16 gr of hydrated zirconium ferrite and hydrated zirconium oxide (hydrated ferrite content: 95% by weight) were obtained. 10 times this powder
ml of water while mixing 10 ml (approximately 10 gr) of a hydrophilic urethane polymer (a hydrophilic polyether polyol made by copolymerizing ethylene oxide and propylene oxide with tolylene diisocyanate added to both ends). Drip. Immediately, the reaction between the hydrophilic urethane prepolymer and water begins, and a foamable gel of polyurethane resin is formed while generating carbon dioxide gas. In this gel,
A powder mixture of hydrated ferrite of zirconium and hydrated oxide of zirconium is held dispersed.
This gel was cut into an appropriate size to obtain an adsorbent. Example 16 Five 0.5 mol aqueous solutions of zirconium sulfate are prepared. Divide this into 5 equal parts and place 1 part each in a beaker and call it A, B, C, D, and E. Each beaker contains 45.5 gr of metal ions as Zr. Next, add ferrous sulfate crystals ( _FeSO4 .
7H ₂ O) to A is 556gr, B is 278gr, C is
Add 136gr, 91.7gr to D, and 34.8gr to E, and dissolve while stirring. Next, each beaker is transferred to a water bath and heated to 70°C, and then a 15% by weight sodium hydroxide solution is added dropwise while stirring until the pH of each beaker reaches 9. At this time, keep the internal temperature of each beaker at 70℃. As the pH increases, a blue-green precipitate is formed in the beaker, and as the pH further increases, the precipitate changes to a blackish brown color. For each beaker, stop adding alkali when the pH reaches 9, maintain the internal temperature at 70°C, and blow in air at a flow rate of 10/hour while continuing to stir. If air is continued to be blown into each beaker, the pH of each beaker will drop slightly, so in this case, a 15% by weight sodium hydroxide solution is added dropwise to maintain the pH at 10. If you continue blowing air until there is no longer a drop in pH, a black color will appear in each beaker.
A black-gray precipitate of a mixture of hydrated ferrite of zirconium and hydrated oxide of zirconium forms.
Next, each of the precipitates is suctioned off, washed with deionized water until the liquid becomes neutral, and then dried at below 50°C. This was ground in a mortar to a size of 120 microns or less to obtain five types of powder. The compositions of the five types of powder were as follows. Hydrous ferrite content Hydrated oxide content A...45.6% by weight 54.4% by weight B...100〃 0〃 C...68.6〃 31.4〃 D...41.7〃 58.3〃 E......23.5〃 76.5〃 Next Put 30g of these five types of powder into a beaker, and add 10g of isophthalic acid-based unsaturated polyester resin and 40g of cobalt naphthenate in the same manner as in Example 11.
After adding 80 mg of methyl ethyl ketone peroxide and stirring thoroughly, leave it to harden within about 60 minutes. After crushing this to an appropriate size,
Granulated into 24-80mesh, 5 of A, B, C, D, E
Various types of adsorbents were obtained. Example 17 Regarding the five types of adsorbents obtained in Example 16,
100ml of simulated wastewater containing 500ppm of phosphate ions created using monosodium phosphate (PH=3)
After adding 0.2 g of each of these five types of adsorbent powder to the mixture and shaking it all day and night (24 hours), the phosphate ion concentration in the simulated wastewater was measured, and the amount of phosphate ion adsorbed by the adsorbent was measured. The results are shown in Table 5.

[Table] Example 18 Adsorbent B prepared by the same method as Example 16
(24-80mesh) was packed into a column with an inner diameter of 25 mmφ. This column was prepared using monosodium phosphate. A simulated wastewater (PH=4.5) containing 1000 ppm of phosphate ions was passed through the tube at a flow rate of SV=5 1/Hr. After 12 hours of liquid flow, the column effluent was sampled and the phosphate ion concentration was measured. Immediately after sampling, the following treatments were performed. 10% sodium hydroxide solution at SV=2 1/Hr
200 ml of liquid was passed through the tube to desorb phosphate ions. Through this operation, 94% of the adsorbed phosphate ions were desorbed. After desorption, add 100ml of water to SV = 2 1/
The solution was passed through with Hr to push out the sodium hydroxide.
Next, add 500 ml of dilute sulfuric acid solution with PH = 2 to SV = 10 (1/
The adsorbent was made acidic by circulating the solution through the column using Hr). After this treatment, phosphate ions are added again.
Simulated wastewater containing 1000ppm at SV = 5 1/Hr 12
After passing water for a period of time, the column effluent was sampled and the phosphate ion concentration was measured. The above operation was repeated, and the concentration of phosphate ions in the column effluent after water flow for 12 hours was measured. The results are shown in Table 6.

【table】 [Brief explanation of the drawing]

In Figure 1, the horizontal axis shows the pH of an aqueous solution containing phosphate ions.
The vertical axis shows the amount of phosphate ion adsorbed by the adsorbent of Example 2 of the present invention.

Claims (1)

[Claims] 1 At least one of the hydrated ferrites of titanium, zirconium, and tin, or a mixture of these and at least one of the hydrated oxides of titanium, zirconium, tin, and iron, in an amount approximately 1/10 to 3 times the amount (weight) An adsorbent made by mixing with unsaturated polyester resin or polyurethane resin and curing it.