JPH08196805A - Adsorption treatment of antimony-containing solution - Google Patents

Abstract

PURPOSE: To efficiently adsorb and separate Sb from an Sb-contg. soln. and to reduce the concn. of Sb in treated water. CONSTITUTION: An Sb-contg. soln. is brought into contact with an adsorbent obtd. by carrying a compd. of at least one kind of metal selected from among Ti, Zr, Hf, La, Ce, Pr, Nd, Sm, Eu and Gd on a carrier to adsorb and separate the Sb in the Sb-contg. soln.

Description

Detailed Description of the Invention

[0001]

The present invention relates to the production of antimony and its compounds, which are widely used as soft metal curing agents, polyester fiber polymerization catalysts, flame retardants, glass clarifying agents, and the use and disposal of these antimony-containing products. The present invention relates to an adsorption treatment method for an antimony-containing solution capable of separating the antimony in the discharged antimony-containing solution in such cases.

[0002]

2. Description of the Related Art Conventionally, as a method for separating antimony from an antimony-containing solution, for example, a method is known in which sodium sulfide is added to an antimony-containing solution under acidic conditions to separate a precipitate that forms a sparingly soluble antimony sulfide. There is.

[0003]

However, it is difficult to control the amount of sodium sulfide added by the method of adding sodium sulfide under acidic conditions to the solution containing antimony sulfide and separating the precipitate that has produced antimony sulfide, as described above. However, when excessive sodium sulfide is added, there is a problem that antimony sulfide is redissolved, processing accuracy is poor, and antimony cannot be separated efficiently.
It is an object of the present invention to provide an adsorption treatment method for an antimony-containing solution, which is capable of efficiently adsorbing and separating antimony from an antimony-containing solution and reducing the concentration of antimony in treated water. It is a thing.

[0004]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that elements of titanium, zirconium, hafnium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, and gadolinium. Based on this finding, it was found that the above problem can be solved by contacting an adsorbent having at least one metal compound selected from the group supported on a carrier with an antimony-containing solution. Reached
That is, the present invention provides an adsorbent in which at least one metal compound selected from the group of elements of titanium, zirconium, hafnium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, and gadolinium is supported on a carrier, and an antimony-containing material. The gist is an adsorption treatment method of an antimony-containing solution, which is characterized in that an antimony in the antimony-containing solution is adsorbed and separated by contacting the solution.

The present invention will be described in detail below. As the adsorbent used in the present invention, at least one metal compound selected from the element group of titanium, zirconium, hafnium, lanthanum, cerium, praseodymium, neodymium, samarium, europium and gadolinium is supported on a carrier. Yes, especially at least 1 selected from the group of elements titanium, zirconium, hafnium, cerium
It is preferable to support a metal compound of a kind on a carrier. The carrier used in the present invention is preferably granular, and its particle size is suitably 0.2 to 2 mm.
Organic polymer materials such as phenol resin and polystyrene are preferable as such materials, and natural zeolite, synthetic zeolite, acid clay, silica gel,
Examples thereof include silica-alumina gel, granular activated carbon, molecular adsorbent resin, synthetic granular activated carbon, ion exchange resin and chelate resin.

The metal compound may be supported on the carrier in the form of a metal chloride or oxide. At this time, the amount of the metal compound supported on the carrier is preferably 50 to 500 g, and more preferably 100 to 300 g, per liter of the adsorbent. Further, as a method for supporting the metal compound on the carrier used in the present invention, a solution or slurry of the metal compound and the carrier are put in a container and stirred or mixed, or
Alternatively, it is preferable that the metal compound is supported on a carrier by passing a solution of the metal compound through a column packed with the carrier and bringing them into contact with each other. The adsorbent used in the present invention may be a commercially available product, and a preferable specific example thereof is zirconium oxychloride (Zr
A granular adsorbent “UNISELEC UR-3700S” (manufactured by Unitika Ltd.) in which polystyrene is supported by OCl ₂ 8H ₂ O) is used.

The antimony-containing solution to which the present invention is applied includes, for example, the production of antimony and its compounds widely used in soft metal curing agents, polyester fiber polymerization catalysts, flame retardants, glass clarifying agents, etc., and these antimony compounds. The antimony-containing solution is discharged when the contained product is used or discarded. In addition, in the present invention, p of the antimony-containing solution which is brought into contact with the above adsorbent is added.
It is preferable to adjust with H or hydrochloric acid or caustic soda so that H becomes 13 or more. When the pH of the antimony-containing solution is less than 13, antimony is less likely to dissolve, and the antimony is not adsorbed by the adsorbent packed in the column and is easily blocked.

In the present invention, it is necessary to bring the adsorbent into contact with the antimony-containing solution.
It is preferable that the adsorbent is packed in a column, and the antimony-containing solution is passed through at a downward flow of space velocity (SV) = 2 to 20 hr ⁻¹ to contact the adsorbent. At this time, when the suspended matter is contained in the antimony-containing solution,
It is preferable to contact the adsorbent after solid-liquid separation by filtration or precipitation to remove suspended substances.

Next, in the present invention, in order to elute the antimony adsorbed on the adsorbent, for example, a concentration of 36.
5 g / l or more hydrochloric acid (HCl) or 49 g /
2 liters / volume of sulfuric acid (H ₂ SO ₄ )
Liter-adsorbent or higher, downward space velocity (S
V) = 5 hr ⁻¹ or less, the antimony can be eluted by passing it through the adsorbent that has adsorbed the antimony.

[0010]

In the present invention, although the detailed adsorption mechanism is unknown, for example, the granular adsorbent "Uniselec UR-370" is used.
When the adsorption treatment is carried out by bringing antimony-containing solution adjusted to pH 13 or higher into contact with “0S” (manufactured by Unitika Ltd.),
It is considered that Cl and Sb are replaced and Sb is adsorbed as shown in the following formula, so that a strong “—Zr—Sb” bond is formed and antimony can be adsorbed and removed.

[0011]

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[0012]

EXAMPLES Next, the present invention will be described in detail with reference to examples. Example 1 First, 2.63 g of diantimony trioxide (Sb ₂ O ₃ ),
12.8 g of sodium sulfate (Na ₂ SO ₄ ) and 720 g of 97 wt% caustic soda (NaOH) were dissolved in water, and p
18 liters of an antimony-containing solution containing H of 13.6, less than 1 mg / liter of suspended solids (SS), 122 mg / liter of antimony (Sb), and 710 mg / liter of sodium sulfate (Na ₂ SO ₄ ) were prepared.

Next, a commercially available granular adsorbent "Uniselec U" is used.
60 ml of "R-3700S" (manufactured by Unitika Ltd.) was packed in a glass column having a diameter of 9 mm.

The above antimony-containing solution was passed through a glass column in a downward flow at a space velocity (SV) = 5 hr ⁻¹ (0.3 liter / hr) for adsorption treatment, and a flow rate of 25 liters. / L-The treated water was sampled for each adsorbent (1.5 L), and the antimony concentration was measured by the atomic absorption spectrophotometry.

Further, a granular adsorbent "UNISEREC UR-3700S" having adsorbed antimony was added to 146 g / liter of hydrochloric acid (HCl) 3 liter / liter-adsorbent (0.18 liter) and water 1 liter / liter-adsorbent Space velocity (S
V) = 2 hr ⁻¹ (0.12 liter / hr) was passed to elute antimony to obtain an eluent, and the concentration of antimony in the obtained eluent was measured.

As a result, the antimony concentration of the treated water was as low as 0.001 mg / liter up to the flow rate of 200 liters / liter-adsorbent (12 liters), and the granular adsorbent "Uniselec UR-" was used. 3700S "
24.4 g of antimony could be adsorbed and separated per liter. The antimony concentration in the eluent was 5960 mg / liter, and the elution rate was 97.7%.

[0017]

According to the present invention, antimony can be efficiently adsorbed and separated from an antimony-containing solution, and the concentration of antimony in treated water can be reduced.

Claims (1)

[Claims] 1. An adsorbent in which at least one metal compound selected from the group of elements of titanium, zirconium, hafnium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, and gadolinium is supported on a carrier, and an antimony-containing solution. An adsorption treatment method for an antimony-containing solution, which comprises contacting with and adsorbing and separating antimony in the antimony-containing solution.