JPS5923246A - Demarcation method of chromatographic liquid - Google Patents

Abstract

PURPOSE:To obtain the demarcated material having high purity by drawing dividely part of the outflow liquid from an ion exchange resin column in front of a multiway dividing valve, subjecting the same continuously to plasma emission analysis, detecting the change in the concn. of various metallic elements and operating the multiway dividing valve according to the information thereon. CONSTITUTION:The outflow liquid from an ion exchange chromatographic column 1 is partly sampled by a needle valve 9 in front of a multiway dividing valve 16, and the sample is fed at a specified flow rate by using a flow rate control valve 11 and a flowmeter 12 to a plasma emission analytical device 14 coupled to frequency induction, by which the change in the concn. of various metallic elements is measured continuously. When the concn. of the elements attains a prescribed concn., the valve 16 is changed over to feed the sample to respective dispensing liquid tanks 17-23. The excess flow of the measuring sample is discharged from a diversion point 10 through a pipe 13. The demarcation and sampling of the various metallic elements from particularly the mixture of rare earth elements with high accuracy is thus made possible.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides an ion exchange chromatographic separation method for isolating each element from a mixture of metal elements using an ion exchange resin.
This invention relates to a new method for fractionating each component of liquid flowing out from an ion exchange tower.

For example, as a method for separating rare earth elements, a complexing agent and a complexing agent receiving agent are used, and a mixture of rare earth elements is expanded in an ion exchange tower in a displacement manner to form an adsorption zone for each element, which is then separated and obtained. method is known. In this separation operation, in order to accurately determine the details of the separation situation and efficiently obtain a rare earth element solution of high purity, it is necessary to accurately detect the time-series composition change of the liquid flowing out from the ion exchange tower during elution. It becomes necessary to fractionate it.

In order to detect changes in the composition of the effluent from the ion exchange tower and perform fractionation, a fraction collector is conventionally installed at the bottom of the tower, and the composition of rare earth elements in each fraction is sequentially measured using a spectrophotometer, redox 7C, 1 ! polar, fluorescent X-ray analyzer,
There is a method of measuring using an emission spectrometer or the like, determining which fraction should be fractionated based on the results, and performing the fractionation. However, the analytical work using these analytical methods requires a long time to determine the analytical value, and
The method of collecting fractions with a fraction collector and analyzing each fraction was not satisfactory in terms of workability and separation efficiency when the scale increased.

A known method for directly detecting the effluent is to install a flow cell at the bottom of the ion exchange tower and measure the absorption spectrum of rare earth elements with a spectrophotometer to detect changes in the composition of the effluent. This method has the disadvantage that only some metal elements can be detected and the detection sensitivity m'' is false and is not completely satisfactory.

Taking the above points into consideration, the present inventors have attempted to accurately and quickly detect time-series compositional changes in the liquid flowing out from the ion exchange tower, and to enable simple fractionation operations. As a result of examining 5 different fractionation methods, we decided to use a plasma emission spectrometer 4, such as a high-frequency inductively coupled plasma emission spectrometer (hereinafter referred to as
Ill (denoted as 311-OE S) can be used to quickly and accurately analyze even very low levels of concentration (even the stream Ill from an ion exchange column).
The liquid is directly introduced into the device through branch piping, analyzed continuously, and based on the information of the analysis results, the effluent is fractionated by switching the multi-way dividing valve installed in the main piping line. Then, they discovered scales by accurately and easily fractionating the effluent, and completed the present invention.

That is, the present invention provides a main piping line consisting of piping from the ion exchange tower outlet to a plurality of separation tanks via a multi-way dividing valve connected to the ion exchange tower outlet when separating FrV metal element mixtures by ion exchange chromatography. A branch tributary is taken from the front of the multi-way dividing valve, and a part of the effluent is directly and continuously introduced into a plasma emission spectrometer to detect the time-series concentration changes of each metal element in the effluent. This is a method for fractionating a chromatographic fluid, which is characterized by operating a nuclear multi-way dividing valve based on information.

An example of this method will be specifically explained with reference to the drawings.

In FIG. 1, the inlet of an ion exchange tower l filled with ion exchange resin is connected via a valve 2 to a solution tank 6 for a metal element mixture, a developing eluent tank 7, a resin regenerating liquid tank 8, and each liquid feed. Pumps 3, 4.5 are piped, and the ion exchange tower 1 is a trench.
A separation liquid tank 17 is connected to the outlet of the separation liquid tank 17 via a multi-way dividing valve 16.
23 and a pipe for taking out a small Jjt branched water flow from the front of the multi-way dividing valve 16 are connected to the sample introduction section 10 of the plasma emission spectrometer 14 via the needle valve 9.

A solution of the metal element mixture is supplied to the ion exchange column 1, and after forming an adsorption bed on the ion exchange resin, a developing eluent is supplied, and the metal ions are separated into individual component elements by chromatographic development and flow out from the column outlet. do. When a portion of the effluent is directly and continuously supplied to the sample introduction section of the plasma emission spectrometer, the concentration of each element is continuously transferred to the printer 15 at arbitrary set intervals. While checking this measurement result, when the desired concentration value is reached, the multi-way dividing valve 1
By switching 6, it is possible to obtain a fraction containing a single metal element with a desired purity.

FIG. 2 shows an example of a sample introduction section of a high-frequency coupling plasma emission spectrometer that can be suitably used as a detection device for this method.

The chromatographic eluate taken out through the needle valve is
While maintaining a constant flow rate with the separation control valve shown in Fig. 11,
It flows to the connector in FIG. 24 at a flow rate of approximately +51 nl/man. At that time, the flow rate is being measured by the flow meter 12. On the other hand, the sample introduction tube 25 comes out from the 10P-OES, so when that tube is inserted into the connector, the sample is sucked into the TOP nebulizer 26 at a flow rate of about 2 me/min, and is transferred to the plasma. and will be introduced. The flow of sweet excess is drei/
The number of picks is increasing to 13. The time required for analysis is 10 to 15 seconds, including the integration time of luminescence intensity, the time required for data processing, and the time for printing out. It is possible to carry out measurements continuously. Various methods can be considered for determining the timing of data pre/l/out and multi-way valve switching.
For example, if you set a certain measurement interval, you can know the time of each measurement, so you can know the time required for the liquid to flow from the empty outlet and the time required for the liquid to flow into the branch pipe and +OF.
If you calculate the time required in advance, you can calculate how long it will take for the measured liquid to reach the multi-way valve ridge after the data is input/output. There is a method of performing multi-way valve switching based on this.

The suitable measurement method used in the present invention is plasma emission spectroscopy, which uses argon plasma as a light source. For elements in solution (1, 1
It is capable of detecting concentrations below m9/L. Among these, 1-OP-OIE, 9, which generates plasma by introducing high frequency waves, is commonly used. The wavelength of the emission line that should be adopted for each element during measurement is usually in the range of 200 nm to 500 nm, and within that range, the wavelength considered to be optimal is selected, taking into account the sensitivity and degree of interference of coexisting elements. select. Although the performance of the device is not limited to 1, it is preferable that the spectrometer has good performance and the software is excellent in order to correct interference of coexisting elements, especially when rare earth elements are to be targeted.

FIG. 3 shows an example of a multi-way split valve used in the present invention. This figure shows a hexagonal split valve as an example, (1 shows a three-dimensional view, and (b) shows a plan view from directly above. It has a double structure with the main pipe line #B and the inner pipe #B.The liquid that flows through the main pipe line /A flows through the piping that passes through the inner pipe B, and then flows through the six pipes E l of the outer pipe C. ”-E6 in the diagram.
3), and the pipe that comes out from there will reach the receiving tank. Next, when switching the split valve, the inner cylinder B rotates and the piping is connected to another pipe (for example, E4) in the outer cylinder O, and the liquid at that time reaches another receiving tank.

By using a multi-way dividing valve, it is possible to collect fractions of one chromatographic solution without mixing different types of solutions, which makes it possible to illegally obtain high-purity metal solutions. linked.

Switching of the multi-way split valve may be done manually after checking the results issued to the control computer, or depending on the taste of the control computer, the person, etc. So-called automatic switching may be performed by sending the information.

In the present invention, [W contact and continuous ('(introduced into plasma emission spectrometer 1~)), h' from the ymen exchange tower: flj 711: is collected once with a flux collector/collector, etc. and accumulated. Instead of introducing the liquid into the plasma emission spectrometer, the liquid flowing out should be poured directly into the plasma emission spectrometer7.
This shows that nuclear devices will be introduced and introduced. As for the introduction method, as mentioned above, a branch pipe is connected to the lower part of the column, and a part of the eluate is taken out from there.

The ion exchange chromatography method to which this method can be applied includes all known separation force methods for isolating and producing fc gold r1 elements using a di/d exchange resin.

A typical example of ion-exchange chromatography is to flow a metal element mixture as an aqueous solution (~, to form adsorption of metal ions) onto a receptor resin solution, and then to flow an eluent solution. This is a method of performing chromatographic development using and.

The type of ion exchange resin, acceptor, eluent, chromatography method, conditions, etc. can be selected from known methods suitable for separating the target element.

The metal element mixture in the present invention may be any metal element as long as it becomes an aqueous solution in an ionic state. When the substance to be separated is a cation, a cation exchanger can be used, and when the substance to be separated is an anion, an anion exchanger can be used. Specifically, Li, B
e, Na, Mg, At, 5ilK, OB.

8c, Ti, V, Or, Mu(n, Fe, Co
, Ni, Ou, Zn, Ga, Gc, n,
b.

Sr, Y, Zr, Nb, Mo, Tc, Ru
, I'th, Pd, Ag, Cd, In, S
n.

Sb, Te, Os, I3a, lanthanides, Hf
, Ta, W., 几e, Us.

Tr, Pt, Au, )Ig, Tt, Pi),
Examples include mixtures of two or more of Bi+Po, Fr, Ra, actinide groups, and the like.

Among the metal elements mentioned above, separation of the lanthanide group elements from each other and trace analysis of other lanthanide group elements in the separated elements are particularly difficult targets because of their similar properties.
This method is suitably used in a method for separating rare earth element mixtures containing the lanthanide group.

In the present invention, rare earth elements and t:11, rank 2 F group bf) elements, namely uranium/tan, cerium, noraceonomum, neodymium, promethium, zamarium, europium, gadolinium, terbium, dysprosium, holminium, erbium, thulium, It is a general term for 17 elements, including the 15 elements ytterbium and lutetium, plus scandium and yttrium.

As a mutual separation method for rare earth elements, a displacement expansion ion exchange chromatography method using a sulfonic acid type cationic exchange resin as an ion exchange resin and a complex forming agent as an eluent is known. Since this is a suitable example, the present invention will be explained below using the above-mentioned example of separation of rare earth elements.

Of course, the principles in this explanation should also apply to the separation of other metal element mixtures.

A complexing agent, a complexing agent acceptor (hereinafter referred to as acceptor), and a cation/exchange resin are used to separate rare earth elements.

Preferred complexing agents include citric acid, lactic acid, glycolic acid, malic acid, tartaric acid, and the like. /acids,
Ethylenediaminetetraacetic acid, 1,2-diaminocyclohexanetetraacetic acid, N-hydroxyethylethylenediamino I
JilE acid, ethylenochlicol bis(2-aminoethyl)ether-'N, N, N', N'
-tetraacetic acid, diethylenetetraamide/acetic acid, bis(2-
aminoethyl)ether-N,N.

Aminopolyacetic acids such as NL, N/-tetraacetic acid, di)IJ-triacetic acid, and iminodiacetic acid are mentioned, and preferred acceptors include pb(b) ion, Pd(Illlliono, i(n)iono, V (N)O ion, 0u(II
) ion, )I r (■) ion, Zn(II) ion, z r (■) ion, lt ion, Ga(I[l
l ion, Ti (I [ll ion, I n (III)
There are iono, Fe, (In)io/, v (ml ion, etc.).

An actual operation example will be explained using FIG. 1, which was previously described in detail.In column 1, a porous cation exchange resin with a crosslinking degree of 20 obtained by sulfonating a styrene-divinylpenzeno copolymer was used. The column was filled with hydrogen ionized hydrogen ions, and the temperature inside the column was maintained at 95°C by passing hot water through the jacket.
o! , / /, , europium sulfate 0.0025 ma
l/t1 sulfuric acid-limariuno, 0.005 mol/1
1 ethylene/diami/tetraacetic acid (EDT) 0.010
Contains an aqueous solution containing mO1/L and adjusted to pH 3. Also, on evening/return 7, El) TA O,
(Contains 125mo7/L f, po 8.s aqueous solution. In evening/liquid 8, 0.5N for resin regeneration.
It contains sulfuric acid. Activate pump 3 and empty the aqueous solution containing rare earth elements, li'A, and gold in Kunkuro!・
1 to 40 of the charged cation/f-on exchange resin are fed to form an adsorption zone of the rare earth element. Therefore, pop 3 is stopped, pop 4 is made, and EDT in tack 7 is
Feed A solution 0 (1) to Karano. At that time, open the needle valve 9 and remove some of the liquid that is eluted from Karano.
Flowed through the min+17ξ pipe at a flow rate of 15 ml/min and introduced into the I OP-OE S, Ru 272.78
nm, (id 310.05 nm, Sn+ 44
2.4: (++ When we start the simultaneous measurement of the emission intensity of m,
Continuously, the concentration of each element is outputted to the silicon/tar 15 as well as Jl.

The order is 1, the lI type 1yx) T aqueous solution elutes,
Subsequently, ErJTA bodies of 9-linin, europium, and yamarium are eluted in this order. The IOP preprinter 15 displays the results of continuous measurement of the vorticity of rare earth elements in the continuously introduced column eluate at regular intervals. No rare earth elements are detected in the liquid.

At this time, the eluate enters the receiving tank 17.

Eventually, when cadrinium was detected,
switch so that the eluate enters the receiving tank 18. Next, I looked at the cylinder and realized that the proportion of europium mixed into the gadolinium was 0. When the O1 staff confirms that the eluate is present, the dividing valve 16 is switched to allow the eluate to enter the fractionating tank 19. After this, the concentration of europium gradually increases, and the concentration of gadolinium gradually decreases.
The proportion of gadolinium contained in europium is o, o
When it reaches os %, the dividing valve 16 is switched to allow the eluate to enter the fractionating tank 20. Next, when the concentration of monosmarium contained in europium reaches o, oOs%, the dividing valve 16 is switched to allow the eluate to enter the fractionating tank 21. After this, the concentration of samarium is gradually increased and the concentration of europium is decreased, but when the ratio of europium contained in samarium J becomes 0.01, the dividing valve 16 is switched and the eluate is The liquid is placed in the separation/separation tank 22. Eventually, the outer claws of the samarium will become lower, so when it is no longer detected, the dividing valve 16 is switched to allow the eluate to enter the fractionating tank 23. As a result, the pure type 14 ITA aqueous solution containing almost no rare earth elements is in the preparative tank 17.
, 22 contains an aqueous solution containing gallium, europium, and modern malium with a purity of 99% or more, and 119 contains an aqueous solution containing gallium 50% and gallium 5061. ) is collected in the preparative tank 21.
2, there is an aqueous solution containing 50% europium and 50% samarium, and the same ED as in tank 7 is in the preparative tank 23.
A TA aqueous solution was obtained.

The above shows one embodiment of the fractionation method according to the present invention, and I OP -OES is 0.1 mq/l.
It is possible to detect rare earth elements at the following concentrations, and as shown in the example above, the multi-way dividing valve is used to measure the concentration of rare earth elements by checking the results printed on the printer. By switching, a highly pure rare earth element aqueous solution can be obtained with little loss. Still, the present invention has the advantage that, as in the above example, it is possible to collect a pure aqueous solution of EI)TA, which is advantageous for reuse.

The diameter of the branch piping should be as small and short as possible so that the column eluate can be quickly introduced into the 10P-OES. Therefore, the inner diameter is preferably around 1wn.

In addition, the time it takes to enter the branch pipe and get the concentration results,
It is necessary to measure in advance the time it takes for the same liquid to reach the multi-way dividing valve, and to determine the timing between ejection to the printer and switching of the dividing valve. Furthermore, when using something other than H ions as the acceptor, it is not necessary to keep the branch piping warm or mix ammonia water.

In the separation of rare earth elements, the cation exchange resin is a porous cation exchange resin with a volume porosity of 40% or more and a degree of crosslinking of 1 to 99, preferably 5 to 80, more preferably 21 to 50. It has been found that the preferred temperature for carrying out the separation is between -10 DEG C. and 150 DEG C., and the seed temperature of the complexing agent and acceptor can be selected. In particular, when 11 ions are used as acceptors, it is more preferable to use 6 ions.
It is 0-130°C. In this case, if the temperature is lower than 60°C, the solubility of the complex between the acceptor 11 and the complex forming agent will be low, resulting in poor efficiency.2 Conversely, if the temperature is higher than 130°C, it will be uneconomical in terms of energy. Yes, it also causes deterioration of cation exchange resins and complex forming agents.

When carrying out separation, there is no particular restriction on the length of the adsorption zone, and the length of the adsorption zone may be adjusted to a value of j quotient depending on the type and composition of the rare earth element to be separated, the type and concentration of the complex forming agent, the flow rate of the liquid, etc.

☆ preferred pl of the complexing agent aqueous solution used in the present invention
(is 1-14, more preferably 2-10, and the preferred pH of the acceptor aqueous solution is 8 or less, more preferably 0.0
01 to 6, and the preferable p of the rare earth element mixture aqueous solution is
i is 0.001-14, more preferably 0.01-7.

The present invention has improved the various shortcomings of conventional ion exchange column eluate fractionation methods, and established a fractionation system that is fully satisfactory in terms of workability, efficiency of separation operations, detection sensitivity, etc. . In addition, the fractionation system of the present invention not only makes it possible to obtain a highly pure metal element solution, but also allows the complex forming agent solution eluted at the beginning and end of separation to be
It can be collected in a pure state that does not contain the four elements,
The present invention has great industrial significance since it is also advantageous in terms of the complexing agent solution adhesive cycle.

Examples will be described below, but the present invention is not limited to the following examples.

Example 1 A porous cation with a degree of crosslinking of 21 obtained by sulfonating a styrene divinylbenzene copolymer into a filter with an inner diameter of 4 cm and a height of 3 NL and a jacket (with a needle valve attached to the bottom). The column was filled with exchange resin and maintained at 90° C. by passing hot water into the jacket of the column.

Next, a 0.5N aqueous solution of sulfuric acid was flowed from the second part of the column to convert the ion exchange resin in the column to the hydrogen ion type.

Next, gadolinium sulfate (■) octahydrate 0,004
mot/l, erbium sulfate (1■) octahydrate 0.00
4 mol/L, ethylenediaminotetraacetic acid 0.01
An aqueous solution prepared so that mol/1% pal was 3 was flowed from the top of the column.

Next, 0,015 mol of ethylenediaminotetraacetic acid
/L.

An aqueous solution prepared to have a pal of 8.5 was diluted with 0,3
4/n) in, and the knee at the bottom of the column.
(Inner diameter 1mm kept warm with 1000ml laser.

A Teflon branch pipe was connected, through which the eluate -714 was taken out and introduced into the 101°-OIS.
I OP K Yoruga 1 Simultaneous quantification of linium and erbium has begun.

We measured the time it took for the eluate to reach the switching valve from the empty outlet, and the time it took for some of the eluate to exit the needle valve, be introduced into the ICP, and display the measurement results, and found that they were 40 seconds and 20 seconds, respectively. Therefore, while looking at the printer, I decided to operate the switching valve 20 seconds after the density to be switched was printed.

In this way, (■ the beginning of erbium, ■ the point where trinium in erbiut reaches 0.01%, ■ the point where erbium in gadolinium reaches 0.01%, and ■ the end of gadolinium, respectively). After performing the switching operation, the eluate was collected separately into five fractionation tanks.That is, the fractionation positions are as shown in Figures 4 and 5.The high-purity rare earth element solution collected in this manner The composition was as shown in Table 1.

Table 1 Example 2 A styrene divinylbenzene copolymer was added to a filter with an inner diameter of 4 cm and a height of 1 m and a no-V butt (t'a:/J ram (with a needle valve attached to the bottom)). The resulting porous cation exchange resin with a degree of crosslinking of 21 was filled, and Y11λ water was passed into the jacket of this collar (kept at 0°CK).

Next, a 0.5N aqueous solution of sulfuric acid was flowed from the top of the column to change the ion exchange resin in the column to a hydrogen ion type.

Then sulfuric acid imt[I)5 aqueous product (1,+13 mo
An aqueous solution prepared to have a pH of 3 at t/j% is poured from the top of the column, and the ion exchange resin in the column is heated to 0n (II
I made it into a J shape.

Next, gadolinium sulfate (■) 8 water I 11 0.004
mol/l.

Erbium sulfate (■) octahydrate +1,004 mn/
, /, /, , ethylenediaminotetraacetic acid 0.01 mO
The aqueous solution prepared by 1/l 1 pl+ becomes 3; tl, 'll was poured into the upper part of the column at 1:35.

Next, 0.015 mot/t of ethylenediaminotetraacetic acid
, While flowing an aqueous solution prepared at % 171 so that pi (is 8) at a bIL speed of 0.25 t/min, a branch pipe made of Teflon with an inner diameter of 1+ nm was connected to the knee IF of the columnar section, and a branch pipe made of Teflon. A part of the eluate was taken out through this and introduced into 10P-OES, and simultaneous determination of copper, gadolinium, and erbium by IOP was started.

We measured the time it took for the eluate to reach the switching point from the empty outlet and the time it took for some of the eluate to exit the needle valve, be introduced into the IOP, and display the measurement results, and found that they were 50 seconds and 20 seconds, respectively. Therefore, while looking at the printer, I decided to perform the switching/lube operation 30 seconds after the density to be changed was printed.

In this way, ■ When copper in erbium became 0.01%, ■ When gadolinium in erbium became 0.01%, ■ When erbium in gadolinium became @-0
, 01% and ■ At the point where gadolinium comes out, perform the Z-lube switching operation and reduce the eluate to 5%.
The samples were collected separately into two preparative tanks. The composition of the high purity rare earth element solution thus separately collected was as shown in Table 2.

Table 2 Example 3 A crosslinking degree of 20 obtained by sulfonating a styrene-divinylbenzene copolymer □ on a filter with an inner diameter of 20 cnr and a height of 3 m, and a tube with a jacket (with a needle valve at the bottom). The tube was filled with a porous cation exchange resin and maintained at 90° C. by passing hot water into the jacket of the tube.

Next, a 0.5 N aqueous solution of sulfuric acid was flowed from the top of the column to convert the ion exchange resin in the column to a hydrogen ion type.

Then yttrium iltate (+nl 8 aquarium 0.0
05mo bamboo, terbium sulfate (■) octahydrate 0,00
25 mat/l, gal sulfate: 'linium (■) 8 water 11th substance 0.0 (15 mol, / L, :f-chi L
/7 diaminotetraacetic acid 0,025 mol/t,
An aqueous solution prepared to have a pH of 3 was poured into the column from the top of the column.

Next, 0.025 mot/l of ethylenediaminotetraacetic acid,
Adjust the pH to 8! ! ! ! 1 to 5 aqueous solution
While flowing at a flow rate of t/m+n, the inner diameter x mm was kept warm with a steam tracer in the needle/lube at the bottom of the column.
A branch pipe made of Teflon is connected, and a part of the eluate is taken out through this and introduced into IO'P-OR3.
Simultaneous determination of yttrium, terbium, and gadolinium using P was started.

When we measured the time it took for the eluate to reach the switching valve from the empty outlet, and the time it took for some of the eluate to exit the needle and be introduced into the IOP and display the measurement results, they were 60 seconds and 20 seconds, respectively. 2 seconds, so while looking at the printer, I decided to perform the switching operation after 40 seconds had elapsed since the density to be changed was printed.

In this way, ■ yttrium begins to appear, ■ terbium in yttrium reaches 0.01%, ■ yttrium in terbium reaches 0.01%, and ■
When gadolinium in terbium reaches 0.01%, ■ When terbium in gadolinium reaches 0.01%, and when [F]gallinium has finished coming out, the valves are switched to drain the eluate. The samples were collected separately into seven fractionation tanks. In other words, the portions are as shown in FIG. 6. The composition of the purified rare earth element solution thus separately collected is as shown in Table 3.

Table 3 Example 4 A filter with an inner diameter of 20 m and a height of 3771 cm and a jacketed column (with a needle/lube at the bottom) were filled with the degree of crosslinking obtained by sulfonating a styrene-divinylben-+;/copolymer. A porous cation exchange resin of 20 mm was packed, and heated water was passed into the jacket of the column to 8 mm.
It was kept at 5°C.

Next, a 0.5 N aqueous solution of sulfuric acid was flowed from the top of the column, converting the ion exchange resin in the column to a hydrogen ion type.

Then (jfj Fa yttrium (u+) 8 water il
l qt/JO, 025mat/l.

Dysprosium sulfate (rfi) octahydrate 0. O1mol
1504/l of aqueous solution was flowed from the top of the column. Next, diethylenetetraaminepentaacetic acid 0.05 mol/l,
An aqueous solution prepared to have a pH-1 of 8.5 was
At the same time as flowing at a flow rate of t/m+n, a Teflon branch pipe with an inner diameter of one tube kept warm with a steam tracer was connected to the needle valve at the bottom of the column, and a part of the eluate was taken out through this and sent to 10P-OR3. and IOP
Simultaneous quantification of yttrium and dysprosium was started.

We measured the time it took for the eluate to reach the switching valve from the empty outlet, and the time it took for some of the eluate to exit the needle valve, be introduced into the IOP, and display the measurement results, and each time was 30 seconds. 20 seconds, so while looking at the printer, I decided to perform the switching and lubricant operations 10 seconds after the dark bar to be switched was printed.

In this way, ■ when dysprosium begins to come out, ■ when the yttrium in the dysprosium reaches 0.1%, ■ when the dysprosium in the yttrium becomes over 0.01, and ■ when the yttrium stops coming out, the nonolube is switched. The eluate was collected separately into five receiver tanks. The composition of the high-purity rare earth element solution thus separately collected was as shown in Table 4.

Table 4

[Brief explanation of the drawing]

FIG. 1 is a flowchart showing one embodiment of the present invention. FIG. 2 shows an example of the sample introduction part to the IOI)-0ES, and FIG. 3 shows an example of the multi-way dividing valve used in the present invention [(a) 3D view, (b) plan view]. FIG. 4, FIG. 5, and FIG. 6 are diagrams showing changes in the rare earth element composition in the eluate with respect to the amount of eluate and the switching position of the split valve in Examples of the rare earth element composition, and FIG. 5 and 5 correspond to the first embodiment, and FIG. 6 corresponds to the third embodiment, respectively. Figure 1 Figure 2 [ Figure 3 (a) Δ (b) A

Claims (1)

[Claims] (1) When performing isolation and purification of metal element mixtures by ion exchange chromatography, the main piping line consisting of the ion exchange tower outlet or C] connected to multiple separation tanks via a multi-way dividing valve. A branched tributary stream is taken from the front of the multi-way dividing valve, and a portion of the effluent is directly and continuously introduced into a plasma emission spectrometer to detect time-series concentration changes of each metal element in the effluent. and operating the multi-way dividing valve based on the information. (2) Claim 1, characterized in that the metal element mixture is a rare earth element mixture. Chromatography solution method described