CN1255562C - Separating column for separating rare earth - Google Patents
Separating column for separating rare earth Download PDFInfo
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- CN1255562C CN1255562C CNB021592330A CN02159233A CN1255562C CN 1255562 C CN1255562 C CN 1255562C CN B021592330 A CNB021592330 A CN B021592330A CN 02159233 A CN02159233 A CN 02159233A CN 1255562 C CN1255562 C CN 1255562C
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- silicon ball
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Abstract
The present invention relates to a separating column for separating rare earth, which comprises a liquid inlet, a liquid outlet and a cylinder body. The present invention is characterized in that the cylinder body is filled with silicon balls carried with di(2, 4, 4-trimethylpentyl)phosphonate, the silicon balls are silanized silicon balls, the length range of surface silanized carbon chains is from C1 to C8, and the particle size range of the silicon balls is 50 to 400 meshes (American standards). The column greatly decreases the operational acidity, and can shorten the separating period and reduce the consumption. The separating column can be connected with the instruments, such as ICP-MS, ICP-AES, etc., to analyze impurities in high purity rare earth, and can be also be applied to the industrial preparation of the high purity rare earth after being amplified.
Description
Technical field
The present invention relates to a kind of column liquid chromatographic, particularly a kind of what be used for separation of rare earth elements is the C272 load silicon ball separator column of carrier with the silicon ball.
Background technology
The rare earth element separation method is a lot, as column liquid chromatographic, Thin-layer separation, wherein column liquid chromatographic has using value most in the high-purity rare-earth analysis, and wherein extraction chromatography is owing to have the two-fold advantage of the big and high efficiency of separation factor, and the separation of high-purity rare-earth is had unique advantage, especially P507 is the system of stationary phase, but since the reextraction acidity height of this system extraction, the cost height, and produce a large amount of spent acid to environment generation pollution.High acidity solution after the separation need spend a large amount of chemical raw materials and complicated technology is carried out aftertreatment, and whole separation cycle is prolonged.
Summary of the invention
The purpose of this invention is to provide a kind of separator column that is used for separation of rare earth elements, this post reduces operation acidity and can shorten separation cycle greatly, reduces consuming, and separator column can carry out impurity analysis in the high-purity rare-earth with instruments such as ICP-MS, ICP-AES are online.This separator column also can be applicable to the industrial preparation of high-purity rare-earth after amplifying.
For achieving the above object, the present invention takes following design: this separator column that is used for rare-earth separating, and it comprises a fluid inlet, a liquid outlet, and cylinder, filling load in this cylinder has two (2,4, the 4-tri-methyl-amyl) phosphonic silicon ball.
The degree of load of described silicon ball is 5-60%.
Silicon spherolite degree scope 50-400 order (USS).Described silicon ball means that through silanization silicon ball its surface silicon alkanisation carbon chain lengths scope is C1-C8.
In the described cylinder, can there be a tectum top of load silicon ball, and tectum can be sponge, industrial fiber cloth etc.
Bed diameter/height of bed=1: the 1.5-1 of load silicon ball in the described cylinder: 10.
Employed C272, owing to do not contain the ester Sauerstoffatom in its molecule, and the C-P key increases than P507, the electronic action that pushes away of alkyl makes that the hydrogen ion on the P-OH is difficult to ionization among the C272, therefore its Pka value is than P507 height, be C272 acidity than P507 a little less than, the aqueous phase acidity that needs when getting rare earth and other high price key metal ion with the C272 base is low, strip (wash-out) is easy.
Description of drawings
Fig. 1 is the elution curve of rare earth element on the 5% load silicon ball
Fig. 2 is the elution curve of rare earth element on the 10% load silicon ball
Fig. 3 is the elution curve of rare earth element on the 15% load silicon ball
Fig. 4 is the elution curve of rare earth element on the 20% load silicon ball
Fig. 5 a, Fig. 5 b are 5% load silicon ball image
Fig. 6 a, Fig. 6 b are 10% load silicon ball image
Fig. 7 a, Fig. 7 b are 15% load silicon ball image
Fig. 8 a, Fig. 8 b are 20% load silicon ball image
Fig. 9 is a C272 load silicon ball separation of rare earth elements elution curve
Figure 10 is a separator column structural representation of the present invention
Among Figure 10,1 is import, and 2 is spongy layer, and 3 are load silicon ball, and 4 are outlet.
Embodiment
The wash-out situation of each drip washing element of table 1
Table 1
| HCl concentration (mol/L) | The wash-out element |
| 0.03 | La、Ce、Pr、Nd、Sm、Eu、Gd |
| 0.06 | Tb、Dy、Ho、Y |
| 0.12 | Er、Tm、Yb |
| 0.50 | Lu |
One, the preparation of separator column:
1, the preparation of load silicon ball
Silanization silicon ball: granularity 200-250 order (0.061-0.074 μ m), packing density 0.35-0.55g/ml, specific surface area is not less than 250m
2/ g.Use pickling process, C272 is adsorbed on the silicon ball, make load silicon ball, load silicon ball only forms the very thin stationary phase of one deck on the surface, method is to take by weighing 2gC272, and 10g silicon ball moves into C272 in the 300ml furnace pot with the 35ml ether in stink cupboard and stirs, the limit is stirred and is slowly added the silicon ball, C272 is carried on the silicon ball, volatilizees substantially totally to ether, under infrared lamp, continue oven dry, drive the residue ether away, standby.
2, dress post
Get an amount of exsiccant load silicon ball, make slurries in order to the rear pillar first kind of mobile phase (0.06mol/LHCL) that will use in service.Constantly stir the gained slurries, till all bubble collapses.Then, they are transferred in the pillar of vertical placement.During transfer, only pour into a small amount of slurries at every turn.During filler, rock solution in the post gently.The general natural sedimentation that adopts makes the slurries natural subsidence, and this method spended time is longer.This test adopts peristaltic pump from post lower port suction filtration between the slurries sedimentation period, makes slurries very fast, is settled down to desired height equably.Upper end at the post bed is fixing with sponge covering, and the dress post finishes.
3, the pre-treatment of separator column:
(1) pickling: install the separator column of load silicon ball with 4mol/L HCL drip washing, in the liquid fluid, do not have Fe
3+Till.(use NH
4The check of SCN solution).
(2) washing:, approaching neutral until effluent liquid with secondary deionized water drip washing separator column.
(3) balance:, consistent, standby with this drip washing acidity until effluent liquid acidity with the post hydrochloric acid drip washing separator column that needs first kind of drip washing acidity of use in service.
Two, degree of load
Degree of load be often referred to every gram not load support that how many physical efficiency loads restrains stationary phase, represents with per-cent.The length of diffusion path in the capacity factor of degree of load decision pillar and the stationary phase, its size and the component retention time on separator column is contacted directly.Below made degree of load respectively and be 5%, 10%, 20% and 40% C272 load silicon ball, with wet method dress post.
1, sample solution: preparation contains Eu
2O
3, Tm
2O
3, Lu
2O
3The mixed rare earth chlorides aqueous solution of each 2 μ m/ml, pH value of solution 5-6.
2, separation condition
Post bed: 31mm * 9mmi.d., separator column after pre-treatment with deionized water balance, standby.Column temperature:
Room temperature (22 ± 1 ℃).
Drip washing acidity: adopt gradient elution, progressively with 0.03mol/L, 0.06mol/L, 0.12mol/L and 0.50mol/L HCL drip washing successively.
Flow velocity: sample introduction and drip washing are 1ml/min in the test.
Elution curve is seen Fig. 1, Fig. 2, Fig. 3, Fig. 4
By elution curve as can be seen, in different loads degree separator column, all by wash-out, but quantitatively elution time differs greatly Eu in 0.03mol/L HCL lessivation.
It for degree of load 5% load silicon ball separator column, rare earth element all flows out together in 0.03mol/L HCL begins the 3min of drip washing, obviously all not have the extraction exchange process to take place with stationary phase and with leacheate directly flow out post outward, in degree of load is 10%, 20% and 40% load silicon ball separator column, Eu has all obtained well separating with Tm, Yb, Lu, but the quantitative elution time difference of Eu, wash-out is incomplete yet to be followed successively by 6min, 8min and 13min, when leacheate HCL concentration switched to 0.06mol/L by 0.03mol/L, a small peak appearred in Eu once more.
For silicon ball degree of load is 40% separator column, because load metric is big, the retention time of Eu is the longest.In addition, it is serious that dress can find that 40% load silicon ball is stained with sticking phenomenon during post, is state of aggregation and is suspended in the dilute hydrochloric acid, is difficult to sedimentation.We estimate that degree of load is that this sticking situation of being stained with has also appearred in 40% load silicon ball.
It for degree of load 5% silicon ball, may be because fixedly liquid measure very little, because its capillary effect fails to form complete liquid film at silicon ball surface, solution passes through from the gap of bare silicon ball during sample introduction, causes all rare earth elements can not upper prop and directly flow out.For this reason, we observe the configuration of surface of these 4 kinds of load silicon balls with JSM-840 type scanning electron microscope, see Fig. 5, Fig. 6, Fig. 7, Fig. 8.
Can't show even extraction agent liquid film among the figure, only see adherent C272 between the silicon ball attached to silicon ball surface.As seen from Figure 8, degree of load is obviously to have adhered to a large amount of C272 on 40% the silicon ball, can see the netted and banded liquid film of C272 between the silicon ball, and do not find tangible adhesion phenomenon on 5% load silicon ball.Also found the C272 adhesion phenomenon on 10% and 20% the load silicon ball, but with 40% compare, the adhesion situation obviously reduces.Illustrated thus degree of load be on 5% the silicon ball really because do not superscribe C272, cause rare earth element directly not flow out outside the post with stationary phase generation permutoid reaction.40% silicon ball is then because the too many C272 of load prolongs the elution time of Eu, and it is serious to be stained with sticking phenomenon during with the fashionable dress post, and the silicon ball is state of aggregation and is suspended in the dilute hydrochloric acid, is difficult to sedimentation, has strengthened the difficulty of dress post.
From the quantitative elution time of Eu, silicon ball degree of load is that 10% and 20% separator column drip washing is all very fast, the former is fast 2min, and this conforms to our result previously discussed.But from the capacity of load silicon ball, the latter will exceed 1 times, considers the loss of extraction agent C272 in process of the test, the latter's longer service life, and therefore, the employing degree of load is 20% load silicon ball.
Three, column type
Separating column type directly influences separating effect and velocity of separation, and liquid chromatography is generally used straight type post, and it is easy to fill, and post is imitated high.
1, column diameter: column diameter obviously influences post imitates, and this is mainly owing to column internal diameter causes to diffusion and wall effect.
2, post height
The height of bed is one of most important parameter of column extracting stratographic: elution volume, disengaging time and theoretical tray number average form the increase of rectilinearity ground with the increase of the height of bed.For filling good chromatographic column, the theoretical plate height and the height of bed are irrelevant, but resolving power is directly proportional with the square root of the height of bed.Can improve separating effect though increase the height of bed, disengaging time also increases, and owing to the post pressure drop is directly proportional with column length, post is pressed and is increased rapidly, therefore, and under the situation of the resolution that suits the requirements, should use short column, to reach sharp separation and to reduce the purpose that post is pressed as far as possible.
This test is carried out generality to the distribution behavior of rare earth element (except that Sc, Pm) on the C272 load silicon ball and is investigated employing gradient elution drafting elution curve.
1, test conditions:
Sample solution: get an amount of mixed rare-earth elements standard reserving solution and be diluted to 2ug/ml, pH value of solution 5-6.Other test conditions is post bed 31mm * 9mm i.d, separator column after pre-treatment with (22 ± 1 ℃ of deionized water balance column temperatures.)
2, result and discussion:
Separation case is seen Fig. 9 and table 1
By above chart as can be known, all rare earth elements is sequentially eluting between 0.03-0.50mol/L HCL, compares with P507, drip washing acidity reduces significantly, and it is detected that elutriant can directly enter mass spectrum, can save to contain Tm parting liquid aftertreatment link, simplify operation, saved the time.
According to the drip washing situation of Eu, Tm, Eu flows out during with 0.03-0.50mol/L HCL drip washing, and Eu is adsorbed hardly under 0.06mol/L HCl condition, and Tm just occurs when 0.12mol/L HCl drip washing, and Tm/Eu is easy to separate.
Adopt separator column provided by the invention to carry out post and separate, the inductively coupled plasma mass spectroscopy is separated high-purity Tb
4O
7Middle trace Lu.
Adopt miniature extracting chromatographic column (post bed 16mm * 9mm i.d), the ICP-MS instrument.
With Tb
4O
7Concentration is 2mg/ml, the sample solution of each 2 μ g/ml of other rare earth impurities, selected 0.08mol/L HCL acidity drip washing Tb, the drip washing condition of Tb be with the 1.5ml/min flow velocity, drip washing 20min, Lu employing 0.9ml/min flow velocity, during wash-out in 5min wash-out finish Tb
4O
7Sample size is 5.0mg.
Measurement result is that Lu measures isotropic substance 175, abundance 97.4%, and detection limit (μ g/g) is 0.1, measuring lower limit (μ g/g) is 0.4.
Advantage of the present invention: this post reduces operation acidity and can shorten separation cycle greatly, reduces consuming, and splitter can carry out impurity analysis in the high-purity rare-earth with the instruments such as ICP-MS, ICP-AES are online. This splitter also can be applicable to the industry preparation of high-purity rare-earth after amplifying.
Claims (2)
1, a kind of separator column that is used for rare-earth separating, it comprises a fluid inlet, a liquid outlet, and cylinder, filling load in this cylinder has two (2,4,4 one tri-methyl-amyls) phosphonic silicon ball, there is a tectum top of silicon ball, bed diameter/height of bed=1: the 1.5-1 of load silicon ball in the cylinder: 10, and it is characterized in that: the degree of load of described silicon ball is 20%.
2, a kind of application of separator column according to claim 1 is characterized in that: carry out post by separator column and separate, the inductively coupled plasma mass spectroscopy is separated high-purity Tb
4O
7Middle trace Lu is with Tb
4O
7Concentration is 2mg/ml, the sample solution of each 2 μ g/ml of other rare earth impurities, and the bed diameter of load silicon ball is 9mm, height of bed 16mm in the described cylinder, Tb
4O
7Sample size is 5.0mg, and the drip washing acidity of Tb is 0.08mol/L HCL, flow velocity 1.5ml/min, drip washing 20 minutes, Lu adopts the 0.9ml/min flow velocity, during wash-out in 5min wash-out finish.
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|---|---|---|---|
| CNB021592330A CN1255562C (en) | 2002-12-27 | 2002-12-27 | Separating column for separating rare earth |
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|---|---|---|---|
| CNB021592330A CN1255562C (en) | 2002-12-27 | 2002-12-27 | Separating column for separating rare earth |
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| CN1255562C true CN1255562C (en) | 2006-05-10 |
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| CN101870506B (en) * | 2010-06-08 | 2012-04-18 | 龙南县南裕稀土资源综合利用有限责任公司 | Process for recovering rare earth from rare earth mining wastewater by resin adsorption method |
| CN102949973B (en) * | 2011-08-19 | 2014-12-10 | 中国核动力研究设计院 | Uranium and rare earth element separation method in fuel element burn-up measurement |
| CN103449568B (en) * | 2013-09-05 | 2014-11-26 | 南昌大学 | Method for treating wastewater with extremely low rare earth concentration by using coarse-grained clay in ionic rare-earth tailings |
| CN103616433B (en) * | 2013-12-09 | 2016-01-20 | 通标标准技术服务（天津）有限公司 | A kind of method utilizing ICP-MS to measure oil rare earth elements |
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Effective date of registration: 20160530 Address after: Yang Yanlu 101407 Beijing city Huairou District Yanqi Economic Development Zone No. 88 Patentee after: National standard (Beijing) inspection & Certification Co., Ltd. Address before: 100088, 2, Xinjie street, Beijing Patentee before: General Research Institute for Nonferrous Metals |
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Granted publication date: 20060510 Termination date: 20161227 |
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