JPS60137820A - New method for separation and purification - Google Patents

Abstract

PURPOSE:To separate efficiently an element of Group IIIB, by utilizing an acceptor agent and an eliminating agent, and chromatography with a chelate resin. CONSTITUTION:A solution of an acceptor agent, a substance having a lower adsorptibity for a chelate resin than the aimed element of Group IIIB is passed through a packed column packed with the chelate resin (exchange capacity; about >=0.5 millimole amount of copper ions based on 1g dried resin; particle diameter; about 5-500 mesh) to adsorb the acceptor agent in the resin. A solution containing the aimed element of Group IIIB is then passed through the column to replace the element of Group IIIB with the acceptor agent to form a beltlike adsorption zone of the element adsorbed on the resin. A solution of an eliminating agent (a substance having a higher adsorptibity for the resin than the aimed element of Group IIIB) is then passed through the column to move the above-mentioned beltlike adsorption zone of the element of Group IIIB to the downstream side of the resin one after another and discharged from the lower end of the packed column. The resultant solution in this part is then separated to give the desired element of Group IIIB in high purity.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for separating and purifying a group 3B element from a mixture containing the group 3B element, using a packed column filled with a chelate resin.

Group 3B elements are B, AI, Ga, In, and TI.

The need to separate and purify these elements occurs throughout the industry. Examples include the separation of boron from magnesia clinker, the separation of aluminum and gallium from Bayer's liquid, and the separation of indium and krillam from natural raw stones.

These industrial meanings are becoming more and more important due to the rapid development of high-purity element application technology in recent years, including the electronic industry.

Under these circumstances, various separation and purification methods have been attempted.

Chemical separation methods such as precipitation methods and solvent extraction methods are representative, but these are extremely disadvantageous techniques from the point of view of high purity. Also known is a method of adsorbing and separating desired elements in batches using a chelate resin having a specific structure. However, these methods also have extremely poor separation efficiency, making it difficult to obtain highly pure products.

The present inventors have conducted intensive research on methods for separating Group 3B elements with high purity. As a result, the present inventors have discovered that Group 3B elements can be efficiently separated by chromatography using a chelate resin, acceptor, and/or desorbing liquid. The chelate resin in the present invention is a resin that has a functional group that can form a chelate compound with a group 3B element, and the functional group is, for example, polyaminocarboxylic acid, various oximes, etc. and has an oxine structure in its molecule.

As an example of polyaminocarboxylic acid, °C is generally a compound represented by the following structural formula (1) or a compound in which any hydrogen atom in formula (1') is substituted with a hydrocarbon group.

These polyaminocarboxylic acids include iminodiacetic acid, N
- Polyaminocarboxylic acids having one nitrogen atom such as iminodiacetic acid and nitrilotriacetic acid having substituents such as methyliminodiacetic acid, N-cyclohexyliminodiacetic acid, N-phenyliminodiacetic acid, etc., ethylenediamine-N, N, N
1N'4 acetic acid, 1,2-propylenediamine-N,N,
N', N'4 acetic acid, ■-phenylethylenediamine-N
, N, N', N'4 acetic acid, cyclohexyldiamine-N
, N, N', N'4 Ethylenediamine-N, N, N' having a substituent such as acetic acid; N'4 acetic acid and polyaminocarboxylic acid having two nitrogen atoms, diethylenetriamine-N, N, N', N ';N''5 acetic acid,
Diethylenetriamine-N, N, N7 N'4 acetic acid Diethylenetriamine-N, N, N, N4 acetic acid, etc., substituted products of these with various substituents introduced, and triethylenetetramine-N, N, N', N';':'N#'6 Examples include polyaminocarboxylic acid groups having three or more nitrogen atoms, such as acetic acid, polyethyleneimine, and polyethyleneimine into which acetic acid groups have been introduced. Furthermore, N-hydroxyethylenediamine-N, N', N'-3 acetic acid, 1,3-diaminopropane-N, N, N', N'4 acetic acid, ■, 4-
Polyaminocarboxylic acids such as diaminobutane-N, N, N', N'4 acetic acid can also be used per se in the present invention.

Among these, more preferable polyaminocarboxylic acid groups are:
These are iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriamine-N,N,N';N''4acetic acid, diethylenetriamine-H,H', N/;N/J4acetic acid, and substituted products thereof.

These chelate compounds are contained in the chelate resin as a radical group obtained by removing one or more hydrogen atoms at arbitrary positions from the compound.

The skeleton resin forming the chelate resin is not particularly limited, and may include naturally occurring polymer compounds or addition polymers, polycondensation polymers, and addition condensation polymers of various polymerizable monomers alone or in the coexistence. , polyaddition polymers, ring-opening polymers, etc., and are insoluble in the medium used. For example, a known resin skeleton such as a styrene-divinylbenzene copolymer can be used, and preferably one having a structure in which various substituents are introduced into a styrene-divinylbenzene copolymer.

The most preferred typical structure of the chelate resin used in the present invention is one containing repeating units represented by structural formulas (n) to (III). Examples of methods for producing these chelate resins include the reaction of chloromethylstyrene-divinylbenzene copolymer with iminodiacetic acid ethyl ester (structural formula (H>)), (1°2-dibromoethyl)styrene-divinylbenzene Method by reaction of copolymer and iminodiacetic acid (structural formula (III)), chloromethylstyrene-
A method involving the reaction of a divinylbenzene copolymer with diethylene I-liamine followed by chloroacetic acid (Structural formula: )).

Structural Formula (I[) Structural Formula (I[[) A typical example of an oxime is one obtained by reacting a polymer having a carbonyl group with hydroxylamine.

Further, as those containing oxine, those obtained by addition condensation reaction of oxine and formalin are typical. Further, a chelate resin having an oxine skeleton can also be synthesized by reacting it with a polymer having an aldehyde group or a hydroxyl group.

The exchange capacity of the chelate resin used in the present invention is as follows: dry resin 1
It is preferable that the amount of copper ion adsorbed per gram is 0.5 mmol or more, and if it is less than that, sufficient separation cannot be achieved. The number of particles i is not particularly limited, but it is preferably 5 to 500 meshes (4 mm to 0.03 mm in diameter), and more preferably 50 to 400 meshes. If the particle size is too large, the separation efficiency will decrease, and if it is too small, the pressure loss in the packed column will increase, making it impractical.

In the present invention, the element to be separated is usually used in a solution state.

The acceptor used in the present invention generally refers to a substance that has lower adsorption to the chelate resin than the target group 3B element, and is a substance that is easily replaced by contact with the element while adsorbed to the chelate resin. collectively. Also, what is a release agent?
Generally, it is a substance that has higher adsorptivity to the chelate resin than the target element, and it is a substance that easily replaces and desorbs the metal element when it comes into contact with the chelate resin that has adsorbed the metal element.

The acceptor and the desorbing agent can be appropriately selected depending on the desired element and the combination of the chelate resin used.

As an acceptor, when separating with a polyaminocarboxylic acid type chelate resin, Li, Na, K, Rb,
Group I metals such as Cs, Group I metals such as Be, Mg, Ca, Sr, and metal ions such as Ag % Fe % Mn and Zn, or ammonium cations and other organic ions can be used. Further, there is no particular restriction on the pH of the acceptor/other agent solution containing the acceptor, and it can be selected depending on the combination with the acceptor used.

A preferred acceptor solution contains Li'', Na as an acceptor.
", K", NH: alone or in combination, pl+5
-10, and in this case, the amount of Group 3B elements adsorbed onto the chelate resin increases, and the separation efficiency is significantly improved.

As a desorption agent, Pb (II), Pd (11)
, N1(II), Cu(II), V(II[), V(
Metal ions such as IV), Ti(]III, Fe(III) or II" ions can be used, with H+ ions being particularly preferred.

The acceptor solution, Group 3B element-containing solution, and release agent solution used in the present invention generally use water as a solvent, but various solvents,
Additives such as stabilizers can also be used. For example, acetone, methyl ethyl ketone, dioxane, imidazole, 2-mercaptoethanol, ethylenediamine, thioglycolic acid, methanesulfonic acid, ace]nylacetone, sulfamic acid, nitromethane, dimethylacecool, diethylene glycol, picolinic acid, ethylene glycol, propyl alcohol, Tetrahydrofuran, pyridine, monoethanolamine, 2-aminopyridine, 3-amino-1,2,4-triazole, piperazine, methylcellosolve, L-butyl alcohol porumamide, acetonitrile, acetylacetone, urea, oxine, etc. . Furthermore, it is also possible to add complexing agents such as citric acid and malic acid.

Next, the separation method will be described.

The present invention, which separates Group 3B elements, uses a method generally called displacement chromatography, and typically performs separation by a series of the following operations. That is, (1) Fill a jacketed packed tower with KIRE-1 resin.

■ Supply an acceptor solution containing an acceptor to enable the chelate resin to accept and adsorb the element to be separated.

(2) A solution containing Group 3B elements is supplied to form an adsorption zone for the substance to be separated.

(2) A desorption liquid containing a desorption agent is supplied to form a band-shaped adsorption zone and move it (at this time, both the front and rear interfaces of the adsorption zone are kept clear).

■ As the desorbed liquid is supplied, the solution flowing out from the bottom of the packed column is separated.

In this series of operations, it is also possible to separate them by omitting the operations ① and ②. In this case, the number of interfaces is one each.

However, in general, it can be said that it is industrially more advantageous to carry out all the operations from (1) to (2).

Through this so-called chromatography, substances to be separated are adsorbed and/or adsorbed depending on the selectivity for each chelate resin.
Or move while repeatedly attaching and detaching. By appropriately separating the liquid flowing out from the packed column in this manner, the purpose of separation and purification can be achieved.

There is no particular restriction on the temperature at which the present invention is carried out, but it is usually -10
The temperature is between 10°C and 200°C, preferably 10°C and 120°C.

There are no particular restrictions on the speed of liquid flowing into the packed tower, but
Generally, if the linear velocity is increased, the separation performance decreases, and if it is decreased, the amount of liquid to be treated decreases, which is industrially disadvantageous.

Under these circumstances, it can be said that the speed is preferably about 10 to 100 m/hour.

The method of the present invention is superior to conventional methods in that it can separate Group 3B elements with extremely high purity in one step.

Examples are shown below, but these are not intended to limit the scope of the present invention.

Example 4 Using about 35 ml of a chelate resin obtained by reacting di(aminoethyl)aminoethyl)styrene-divinylbenzene copolymer with chloroacetic acid, gallium-
An aluminum separation experiment was conducted.

After filling the above column with the chelate resin, the chelate resin was made into a receptor type using a regeneration solution (pH 6) containing NTi" ions. Next, a hydrochloric acid solution containing 5 mM gallium and 5 mM aluminum, and then a dilute hydrochloric acid solution were added. Deployment separation was performed as a desorption agent.

The eluate was divided into each fraction and analyzed for gallium and aluminum using a conventional method. As a result, the purity of the front fraction with the highest aluminum purity was 90% or more, and the rear fraction with the highest gallium purity was found. With a purity of 90% or more,
Each was separated and recovered.

Alternatively, without using a regenerating solution, a similar gallium-aluminum solution is sufficiently supplied to a chelate resin-packed column and then developed and separated using dilute hydrochloric acid. Separated liquids of Ga and AI were also obtained by the two feeding methods.

Patent applicant: Asahi Kasei Industries, Ltd. Agent: Patent Attorney Tohru Saturn

Claims (3)

[Claims] (1) A packed tower filled with chelate resin is used, and a solution containing an acceptor is passed through the packed tower, followed by a solution containing a group 3B element, thereby replacing and adsorbing the acceptor. A method for separating and purifying Group 3B elements. (2) Using a packed tower filled with a chelate resin, a solution containing a group 3B element is passed through the packed tower, and then a solution containing a desorbing agent is passed through the packed tower to perform replacement with a desorbing agent and desorption. A method for separating and purifying group 3B elements, characterized by: (3) Using a packed tower filled with a chelate resin, by flowing a solution containing an acceptor into the packed tower, followed by a solution containing a group 3B element, and further flowing a desorption liquid containing a desorption agent. , a method for separating and purifying a Group 3B element, which comprises forming a band-shaped adsorption region for a liquid containing the Group 3B element, and moving the solution through the region while causing an adsorption reaction within the region.