JPH0432761B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method of 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, Al, Ga, In, and Tl.
The need to separate and purify these elements arises throughout industry. Examples include the separation of boron in magnesia chrysicar, the separation of aluminum and gallium in Bayer's liquid, and the separation of indium and thallium 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 slow techniques from the standpoint of achieving 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. As a result of extensive research into methods for separating Group 3B elements with high purity, the present inventors have discovered that Group 3B elements can be efficiently separated by chromatography using a chelate resin, an acceptor, and a desorbing liquid. They discovered what they could do and completed the present invention. 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 has a polyaminocarboxylic acid structure in its molecule, and is an example of a polyaminocarboxylic acid. is generally a compound represented by the following structural formula () and a compound in which any hydrogen atom in the formula () is replaced with a hydrocarbon group. [However, each of R ₁ , R ₂ , and R ₃ is a hydrogen group -
CH ₂ COOR ₅ is represented, and R ₅ represents hydrogen, a metal, or a hydrocarbon compound group having 1 to 4 carbon atoms. _A1 , _A2 , _A3
are each

[Formula] or

[Formula], and i, j, and k each represent 0, 1, 2, or 3. However, the compound () shall contain at least _{one -CH2COOR5} . ] These polyaminocarboxylic acids include imino 2
Polyaminocarboxylic acids having one nitrogen atom such as iminodiacetic acid and nitrilotriacetic acid having a substituent such as acetic acid, N-methyliminodiacetic acid, N-cyclohexyliminodiacetic acid, N-phenyliminodiacetic acid, N-phenyliminodiacetic acid, etc., ethylenediamine-N,N , N′, N′4 acetic acid,
1,2-propylenediamine-N,N,N',N'4
Acetic acid, 1-phenylethylenediamine-N,N,
N′, N′4acetic acid, cyclohexyldiamine-N,
N,N',N'4Ethylenediamine-N,N,N',N', having a substituent such as acetic acid, and polyaminocarboxylic acid having two nitrogen atoms, diethylenetriamine-N,N,N',N ″,N″5 acetic acid, diethylenetriamineN,N,N″,N″4 acetic acid Diethylenethomiamine-N,N′,N″,N″4acetic acid etc., substituted products with various substituents introduced therein, and triethylenetetramine-N, N, N'N'', N
〓,N〓6 Nitrogen atom 3 of acetic acid, polyethyleneimine, or polyethyleneimine with an acetic acid group introduced
There are polyaminocarboxylic acid groups having 1 or more. Furthermore, N-hydroxyethylenediamine-
Amino acids such as N,N',N'-3acetic acid, 1,3-diaminopropane-N,N,N',N'4acetic acid, 1,4-diaminobutaneN,N,N',N'4acetic acid, etc. Carboxylic acids can also be used per se in the present invention. Among these, a more preferable polyaminocarboxylic acid group is imino 2
These are acetic acid, ethylenediaminetetraacetic acid, diethylenetriamine-N,N,N'',N''4acetic acid, diethylenetriamine-N,N',N'',N''4acetic 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 of various polymerizable monomers alone or in the coexistence;
Polycondensation polymers, addition condensation polymers, polyaddition polymers,
There are ring-opened polymers, etc., which 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 () to (). An example of a method for producing these chelate resins is a method by reacting a chloromethylstyrene-divinylbenzene copolymer with iminodiacetic acid ethyl ester (structural formula (), (1,2
-dibromoethyl)styrene-divinylbenzene copolymer and iminodiacetic acid (structural formula formula()),
This is a method (structural formula ()) based on the reaction of para(diaminoethyl)aminoethyl)styrene-dinylbenzene copolymer and chloroacetic acid. Structural formula() [ _A1 , _A2 :

[Formula] or

[Formula] R ₁ , R ₂ : H or -CH ₂ COOR ₅ i, j: 0, 1, 2 or 3 k: 1, 2 or 3 R ₅ : H, metal or hydrocarbon group having 1 to 4 carbon atoms However, in this structure, at least one -
Contains ₅ CH ₂ COOR groups. 〕 Structural formula() [ _A1 , _A2 :

[Formula] or

[Formula] R ₁ , R ₂ , R ₃ , R ₄ : H or -CH ₂ COOR ₅ i, j: 0, 1, 1 or 3 R ₅ : Hydrogen, metal, or hydrocarbon having 1 to 4 carbon atoms , at least one or more - in this structure
Contains ₅ CH ₂ COOR groups. ] The exchange capacity of the chelate resin used in the present invention is 0.5 mmol or more as the amount of copper ions adsorbed per gram of dry resin. If it is less than that, sufficient separation cannot be achieved. In addition, there is no particular restriction on the particle size, but 5
The mesh size is preferably 500 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 referred to in the present invention generally refers to
A general term for substances that have lower adsorption to chelate resins than Group 3B elements, and which are easily displaced by contact with the element while adsorbed to the chelate resin. In addition, a desorption agent is a substance that generally has higher adsorption to the chelate resin than the target element, and easily replaces and desorbs the metal element by coming into contact with the chelate resin that has adsorbed the metal element. It is a substance. The acceptor and the desorbing agent can be appropriately selected depending on the desired element and the combination of the chelate resin used. When separating with a polyaminocarboxylic acid type chelate resin, acceptors include Li, Na, K,
Group metals such as Rb, Cs, group metals such as Be, Mg, Ca, Sr, and metal ions such as Ag, Fe, Mn, Zn,
Alternatively, ammonium cations and other organic ions can be used. Further, the pH of the acceptor solution containing the acceptor is not particularly limited and can be selected depending on the combination with the acceptor used. Preferred acceptor solutions include Li ⁺ , Na ⁺ , K ⁺ ,
It contains NH ₄ ⁺ alone or in combination, and has a composition with a pH in the range of 5 to 10. In this case, the amount of Group 3B elements adsorbed to the chelate resin increases, and the separation efficiency is significantly improved. As desorption agents, Pb (), Pd (), Ni (),
Metal ions such as Cu(), V(), V(), Ti(), Fe() or H ⁺ ions can be used, especially H ⁺
Ions are 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 and additives such as stabilizers can also be used. For example, acetone, methyl ethyl ketone, dioxane, imidazole, 2-mercaptoethanol, ethylene diamine, thioglycolic acid, methanesulfonic acid, acetonylacetone, sulfamic acid, nitromethane, dimethyl acetal, diethylene glycol, picolinic acid, ethylene glycol, propyl alcohol, tetrahydrocarbon Furan, pyridine, monoethanolamine,
2-aminopyridine, 3-amino-1,2,4-
triazole, piperazine, methylcellosolve,
t-butyl alcohol, dimethylformamide,
N-methylformamide, 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, a jacketed packed tower is filled with chelate resin. An acceptor solution containing an acceptor is supplied so that the chelating resin can accept and adsorb the element to be separated. A solution containing Group 3B elements is supplied to form an adsorption zone for the substance to be separated. 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 collected. By such so-called chromatography, the substance to be separated moves while repeating adsorption and desorption depending on the selectivity for each chelate resin. By appropriately fractionating the liquid flowing out from the packed column in this manner, the objectives 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 between -10°C and 200°C, preferably between 10°C and 120°C.
is within the range of There is no particular restriction on the velocity of the liquid flowing into the packed column, but generally speaking, increasing the linear velocity will reduce the separation performance, while decreasing it will reduce the amount of liquid to be treated, 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 Using approximately 35 ml of a chelate resin (copper ion adsorption amount per 1 g of dry resin: 1.2 mmol) obtained by reacting para(diaminoethylaminoethyl)styrene-divinylbenzene copolymer with chloroacetic acid, a Pyrex glass column (inner diameter 10mmφ×50cm)
A gallium-aluminum separation experiment was conducted using the following methods. After filling the above column with chelate resin,
The chelate resin was made into a receptor type using a regenerating solution (PH6) containing NH ₄ ⁺ ions. Next, gallium 5m
M, a hydrochloric acid solution containing 5mM of aluminum, and a diluted hydrochloric acid solution were used as desorbing agents to perform development separation. The eluate was collected separately for 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 over 90%, and the rear fraction with the highest gallium purity was found. Separation and recovery were carried out at a purity of 90% or higher.

Claims (1)

[Claims] 1. Filled with a chelate resin having a polyaminocarboxylic acid structure represented by the following structural formula () as a functional group, and having an adsorption amount of copper ions of 0.5 mmol or more per 1 g of dry resin. A packed column is used, the packed column is fed with a solution containing an acceptor, and then
Supplying a solution containing a group 3B element, further supplying a desorption liquid containing a desorption agent, and having an interface between a region where the acceptor exists and a region where the desorption agent exists.
3B, which is characterized by forming a band-shaped adsorption region for a liquid containing group 3B elements, moving the region while performing an adsorption reaction within this region, and fractionating the liquid flowing out from the packed column. Separation and purification method of group elements. [However, R ₁ , R ₂ , R ₃ are each hydrogen or -
CH ₂ COOR ₅ is represented, and R ₅ represents hydrogen, a metal, or a hydrocarbon compound group having 1 to 4 carbon atoms. _A1 , _A2 , _A3
represents [Formula] or [Formula], respectively, and i, j, and k represent 0, 1, 2, or 3, respectively. However, the compound () shall contain at least one -CH ₂ COOR ₅ . ]