CN109374602A - Method for determination of neodymium fluoride and lithium fluoride content in neodymium production electrolytes - Google Patents
Method for determination of neodymium fluoride and lithium fluoride content in neodymium production electrolytes Download PDFInfo
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- CN109374602A CN109374602A CN201811348925.XA CN201811348925A CN109374602A CN 109374602 A CN109374602 A CN 109374602A CN 201811348925 A CN201811348925 A CN 201811348925A CN 109374602 A CN109374602 A CN 109374602A
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- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000003792 electrolyte Substances 0.000 title claims abstract description 70
- 229910052779 Neodymium Inorganic materials 0.000 title claims abstract description 68
- XRADHEAKQRNYQQ-UHFFFAOYSA-K trifluoroneodymium Chemical compound F[Nd](F)F XRADHEAKQRNYQQ-UHFFFAOYSA-K 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 20
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 title claims description 94
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 46
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000012488 sample solution Substances 0.000 claims abstract description 27
- 238000004458 analytical method Methods 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 77
- 239000000243 solution Substances 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 26
- 229910052582 BN Inorganic materials 0.000 claims description 18
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 18
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- 239000012086 standard solution Substances 0.000 claims description 12
- 238000009616 inductively coupled plasma Methods 0.000 claims description 8
- 238000005259 measurement Methods 0.000 claims description 8
- 238000004090 dissolution Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000003556 assay Methods 0.000 claims 9
- 238000009472 formulation Methods 0.000 claims 2
- 239000000523 sample Substances 0.000 abstract description 38
- 230000008878 coupling Effects 0.000 abstract description 13
- 238000010168 coupling process Methods 0.000 abstract description 13
- 238000005859 coupling reaction Methods 0.000 abstract description 13
- 230000001939 inductive effect Effects 0.000 abstract description 13
- 238000003682 fluorination reaction Methods 0.000 abstract description 10
- 238000001514 detection method Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000001419 dependent effect Effects 0.000 abstract description 2
- 238000007405 data analysis Methods 0.000 abstract 1
- 229910017557 NdF3 Inorganic materials 0.000 description 18
- 238000012360 testing method Methods 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 229910052571 earthenware Inorganic materials 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- 239000012803 melt mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 239000006210 lotion Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000008236 heating water Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012113 quantitative test Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/73—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using plasma burners or torches
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
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Abstract
The present invention relates to the measuring methods of neodymium fluoride and fluorination lithium content in a kind of neodymium production electrolyte, comprising steps of formulating lithium standard working curve and neodymium standard working curve, being prepared as soluble compound, prepare sample solution and be measured analysis using inductive coupling plasma emission spectrograph neodymium production electrolyte.The present invention carries out working curve comparison using inductive coupling plasma emission spectrograph and automatically analyzes calibrating, have many advantages, such as that linear detection range is wide, analysis speed is fast, accuracy is high, check and approve the standard working curve of lithium and neodymium solution automatically by instrument analysis software, so that the linearly dependent coefficient of sample and standard curve is greater than 99.99%, reliable data analysis can be quickly and accurately provided.
Description
Technical field
The present invention relates to electrolysis tech fields, and in particular to neodymium fluoride and fluorination lithium content in a kind of neodymium production electrolyte
Measuring method.
Background technique
Electrolyte used in commercial production of metals neodymium is the mixture of neodymium fluoride and lithium fluoride, the initial quality percentage of mixture
Than being usually 10-20% lithium fluoride, remaining is neodymium fluoride.But with the progress of electrolysis, the group branch of electrolyte changes.
Under normal conditions, it since reduction reaction can occur for the neodymium fluoride in electrolyte, will lead in electrolyte under the content of neodymium fluoride
Drop.This directly affects the neodymia solubility in the electrolyte as raw material, and then influences current efficiency.Since electrolysis is
One continuous production process, therefore the content of neodymium fluoride and lithium fluoride needs to be monitored in electrolyte.But current neodymium metal
Manufacturing enterprise rely primarily on worker micro-judgment electrolyte composition, without carrying out accurate chemical analysis.This is main
It is but also also there was only low-down solubility in common acid, for example lithium fluoride can only lack since fluoride is not only not soluble in water
Amount is dissolved in acid, and neodymium fluoride cannot all dissolve in hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, can only be slightly soluble in perchloric acid.
The content of neodymium fluoride and lithium fluoride in electrolyte is measured therefore, it is necessary to a kind of accurate chemical analysis method.
Summary of the invention
For the defects in the prior art, it is an object of that present invention to provide neodymium fluoride and fluorinations in a kind of neodymium production electrolyte
The measuring method of lithium content, be one kind that a kind of Rare Earth Electrolysis enterprise can apply is convenient, analysis speed is fast, accuracy is high,
Convenient for the measuring method of the small content of fluoride of operation, environmental pollution.
To achieve the above object, the present invention provides the measurements of neodymium fluoride and fluorination lithium content in a kind of neodymium production electrolyte
Method, comprising steps of formulating lithium standard working curve and neodymium standard working curve, neodymium production electrolyte being prepared as dissolvableization
Object is closed, sample solution is prepared and analysis is measured using inductive coupling plasma emission spectrograph.The characteristics of this method is
By solubility very low LiF and NdF3It is converted into it can be dissolved completely in the compound of hydrochloric acid, then lead to by chemically reacting
The method for crossing ICP-AES accurately measures the content of Li and Nd in solution, to calculate LiF and NdF in electrolyte3Contain
Amount.
Formulate lithium standard working curve and specifically include step: pipette 0.00 respectively, 0.50,1.00,2.00,5.00,
10.00mL lithium standard solution is that 5% nitric acid solution is settled to scale (100mL) with volumetric concentration into 6 100mL volumetric flasks,
It shakes up, obtained solution is introduced into inductive coupling plasma emission spectrograph, lithium standard working curve is made.
Formulate neodymium standard working curve and specifically include step: pipette 0.00 respectively, 0.50,1.00,5.00,10.00,
20.00,50.00mL neodymium standard solution is that 5% nitric acid solution is settled to scale with volumetric concentration into 7 100mL volumetric flasks
(100mL), shakes up, and obtained solution is introduced into inductive coupling plasma emission spectrograph, and neodymium standard working curve is made.
Neodymium production electrolyte is prepared as soluble compound and specifically includes step: by neodymium production electrolyte and excessive oxygen
Change neodymium to be uniformly mixed, be subsequently placed in boron nitride crucible；Boron nitride crucible is put into vacuum tube furnace, is kept the temperature after heating；It
Boron nitride crucible is taken out afterwards, quenching, soluble compound is prepared.
Preferably, the temperature of heat preservation is 700 DEG C, and the time of heat preservation is 3 hours.
It prepares sample solution and specifically includes step: soluble compound being ground uniformly, then takes 0.3g to be placed in respectively dense
Degree for 0.5,1.0,2.0, dissolve in the excessive hydrochloric acid of 4.0mol/L, obtain sample solution.
Preferably, dissolution is dissolved under the conditions of sonic oscillation.
Preferably, dissolution is dissolved under 50 DEG C of condition of water bath heating.
Preferably, dissolution is dissolved under the conditions of being stored at room temperature.
Technical solution provided by the invention, with following the utility model has the advantages that the invention firstly uses fluorides and Nd2O3Instead
Oxyfluoride should be generated, then is completely dissolved the oxyfluoride of generation with HCl, emits light finally by inductively coupled plasma body
Spectrometer carries out working curve comparison and automatically analyzes calibrating, has the characteristics that analysis speed is fast, accuracy is high；It is analyzed by instrument soft
Part checks and approves the standard working curve of lithium and neodymium solution automatically, and sample and standard curve linearly dependent coefficient is made to be greater than 99.99%, can
Reliable analysis data are rapidly and accurately provided.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Detailed description of the invention
Fig. 1 is 20%LiF-80%NdF in the embodiment of the present invention3The XRD spectra of sample after mixture melting is cooling；
Fig. 2 is LiF-NdF in the embodiment of the present invention3-Nd2O3The XRD spectra of solid phase reaction prepare compound.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description.The following examples are only intended to illustrate the technical solution of the present invention more clearly, therefore is intended only as example, without
It can be limited the scope of the invention with this.
Experimental method in following embodiments is unless otherwise specified conventional method.Examination as used in the following examples
Material is tested, is to be commercially available from regular shops unless otherwise specified.Quantitative test in following embodiment, is respectively provided with three
Secondary to repeat to test, data are the average value or mean+SD of three repeated experiments.
The present invention provides the measuring method of neodymium fluoride and fluorination lithium content in a kind of neodymium production electrolyte, including walks as follows
It is rapid:
(1) pipette 0.00 respectively, 0.50,1.00,5.00,10.00,20.00,50.00mL neodymium standard solution is to 7
In 100mL volumetric flask, it is that 5% nitric acid solution is settled to scale with volumetric concentration, shakes up, obtained solution is introduced into inductive coupling
In plasma emission spectrometer, neodymium standard working curve is made；
(2) 0.00,0.50,1.00,2.00,5.00,10.00mL lithium standard solution to 6 100mL volumetric flasks are pipetted respectively
In, it is that 5% nitric acid solution is settled to scale with volumetric concentration, shakes up, obtained solution is introduced into inductively coupled plasma body hair
It penetrates in spectrometer, lithium standard working curve is made；
(3) according to the composition of neodymium production electrolyte, 6g LiF (mass fraction 20%) and 24.0g NdF is weighed3(quality point
Number 80%), by LiF and NdF3After mixing, it is dried in vacuo 12 hours at 400 DEG C, removes possible moisture, obtain drying
Mixture afterwards；
(4) mixture after drying is placed in boron nitride crucible, is placed in vacuum tube furnace, be warming up to industrial production
1050 DEG C of temperature, melt mixture completely needed for neodymium, keep the temperature 4 hours, cool to room temperature with the furnace；
(5) electrolyte that will be cooled to room temperature crushes, and is ground uniformly with agate crucible, takes out 4g and passes through X-ray diffractometer
(XRD) test sample structure；
(6) the mixture 5g after taking out step (5) grinding, it is assumed that all neodymium fluorides of mixture, according to molar percentage
NdF3: Nd2O3Excessive neodymia 10g is added in=1:1.2, with agate crucible ground and mixed it is uniform after, be placed in boron nitride crucible
In, crucible is put into vacuum tube furnace and is heated to 700 DEG C, keeps the temperature 3 hours；
(7) boron nitride crucible is taken out from vacuum tube furnace, is quenched crucible with liquid nitrogen, then takes out sample agate earthenware
Crucible grinding uniformly, takes out 4g and passes through X-ray diffractometer (XRD) test sample structure；
(8) 12 parts of sample after weighing grinding, every part of 0.3g；It is 0.5,1.0,2.0,4.0mol/L that sample, which is placed in concentration,
In excessive hydrochloric acid, dissolved respectively in ultrasonic vibration, 50 DEG C of heating water baths and under being stored at room temperature three kinds of different conditions, to
After sample is completely dissolved, by carrying out inductive coupling plasma emission spectrograph (ICP-AES) test analysis to sample solution
The content of Li and Nd in sample；By the content of Li in sample solution, the content of LiF in original electrolyte is calculated；By solution
The content of middle Nd subtracts addition Nd2O3The content of middle Nd calculates NdF in original electrolyte3Content.
Combined with specific embodiments below to the survey of neodymium fluoride and fluorination lithium content in neodymium provided by the invention production electrolyte
The method of determining is described further.
Embodiment 1
The present embodiment provides a kind of measuring methods for preparing neodymium fluoride and fluorination lithium content in neodymium production electrolyte, including such as
Lower step.
(1) pipette 0.00 respectively, 0.50,1.00,5.00,10.00,20.00,50.00mL neodymium standard solution is to 7
In 100mL volumetric flask, it is that 5% nitric acid solution is settled to scale with volumetric concentration, shakes up, obtained solution is introduced into inductive coupling
In plasma emission spectrometer, neodymium standard working curve is made.
(2) 0.00,0.50,1.00,2.00,5.00,10.00mL lithium standard solution to 6 100mL volumetric flasks are pipetted respectively
In, it is that 5% nitric acid solution is settled to scale with volumetric concentration, shakes up, obtained solution is introduced into inductively coupled plasma body hair
It penetrates in spectrometer, lithium standard working curve is made.
(3) according to the composition of neodymium production electrolyte, 6g LiF (mass fraction 20%) and 24.0g NdF is weighed3(quality point
Number 80%), by LiF and NdF3After mixing, it is dried in vacuo 12 hours at 400 DEG C, removes possible moisture, obtain drying
Mixture afterwards.
(4) mixture after drying is placed in boron nitride crucible, is placed in vacuum tube furnace, be warming up to industrial production
1050 DEG C of temperature, melt mixture completely needed for neodymium, keep the temperature 4 hours, cool to room temperature with the furnace.
(5) electrolyte that will be cooled to room temperature crushes, and is ground uniformly with agate crucible, takes out 4g and passes through X-ray diffractometer
(XRD) test sample structure.The XRD spectra that measurement obtains in step (5) from the diffraction maximum of XRD as shown in Figure 1, can be seen that
The structure of electrolyte is LiF and NdF3。
(6) the mixture 5g after taking out step (5) grinding, it is assumed that all neodymium fluorides of mixture, according to molar percentage
NdF3: Nd2O3Excessive neodymia 10g is added in=1:1.2, with agate crucible ground and mixed it is uniform after, be placed in boron nitride crucible
In, crucible is put into vacuum tube furnace and is heated to 700 DEG C, keeps the temperature 3 hours.
(7) boron nitride crucible is taken out from vacuum tube furnace, is quenched crucible with liquid nitrogen, then takes out sample agate earthenware
Crucible grinding uniformly, takes out 4g and passes through X-ray diffractometer (XRD) test sample structure.The XRD spectra that measurement obtains in step (7)
As shown in Fig. 2, having been converted into NdOF from the primary structure that the diffraction maximum of XRD can be seen that electrolyte.
(8) 4 parts of sample after weighing grinding, every part of 0.3g (including 0.2g neodymia and 0.1g electrolyte)；By sample point
It is not placed in four 100mL beakers, being separately added into concentration is 0.5,1.0,2.0, the excessive hydrochloric acid of 4.0mol/L；
Four samples are placed under conditions of ultrasonic vibration and are dissolved；0.5,1.0,2.0,4.0mol/L it is excessive
In hydrochloric acid, the time required for four samples are completely dissolved is 12h, 7h, 3h and 2.5h respectively；
Sample solution after being completely dissolved is transferred in 1000mL volumetric flask, and elutes beaker with the hydrochloric acid of same concentrations
Three times, then with deionized water elution beaker three times, all washing lotions are all transferred in 1000mL volumetric flask, will be molten after constant volume shakes up
Liquid is transferred to constant volume in 100mL volumetric flask；
Sample solution is introduced into inductive coupling plasma emission spectrograph and is measured, lithium and neodymium element in sample solution
Intensity is calculated by instrument according to the lithium and neodymium standard working curve of deposit automatically；By carrying out ICP-AES test analysis to solution
Four samples obtain: in the sample solution for 1. using 0.5mol/L dissolving with hydrochloric acid, Concentration of Neodymium Ion in Czochralski 228.71mg/L, and lithium ion
Concentration is 5.33mg/L；2. using 1.0mol/L dissolving with hydrochloric acid sample solution in, Concentration of Neodymium Ion in Czochralski 228.79mg/L, lithium from
Sub- concentration is 5.35mg/L；3. using in the sample solution of 2.0mol/L dissolving with hydrochloric acid, Concentration of Neodymium Ion in Czochralski 228.68mg/L, lithium
Ion concentration is 5.28mg/L；4. using 4.0mol/L dissolving with hydrochloric acid solution in, Concentration of Neodymium Ion in Czochralski 228.78mg/L, lithium from
Sub- concentration is 5.30mg/L；
Lithium fluoride is converted by lithium concentration, Concentration of Neodymium Ion in Czochralski is subtracted into 0.2gNd2O3The content of contained neodymium
After 171.48mg/L, it is then converted to neodymium fluoride；It is computed and obtains: 1. using in the 0.3g sample of 0.5mol/L dissolving with hydrochloric acid, containing
There are 0.01992gLiF and 0.07984gNdF3；Contain mass percent 19.97%LiF and 80.03%NdF i.e. in electrolyte3；②
Using in the 0.3g sample of 1.0mol/L dissolving with hydrochloric acid, contain 0.01999gLiF and 0.07996gNdF3, i.e., contain in electrolyte
Mass percent 20.00%LiF and 80.00%NdF3；3. containing using in the 0.3g sample of 2.0mol/L dissolving with hydrochloric acid
0.01974gLiF and 0.07980gNdF3, i.e., contain mass percent 19.83%LiF and 80.17%NdF in electrolyte3；4. adopting
With in the 0.3g sample of 4.0mol/L dissolving with hydrochloric acid, contain 0.01981gLiF and 0.07994gNdF3, i.e., contain matter in electrolyte
Measure percentage 19.86%LiF and 80.14%NdF3。
Using detection method provided by the invention, test result and the content one for preparing lithium fluoride and neodymium fluoride in electrolyte
It causes, it was demonstrated that the method is reliable.
Embodiment 2
The present embodiment provides a kind of measuring methods for preparing neodymium fluoride and fluorination lithium content in neodymium production electrolyte, including such as
Lower step.
(1) pipette 0.00 respectively, 0.50,1.00,5.00,10.00,20.00,50.00mL neodymium standard solution is to 7
In 100mL volumetric flask, it is that 5% nitric acid solution is settled to scale with volumetric concentration, shakes up, obtained solution is introduced into inductive coupling
In plasma emission spectrometer, neodymium standard working curve is made.
(2) 0.00,0.50,1.00,2.00,5.00,10.00mL lithium standard solution to 6 100mL volumetric flasks are pipetted respectively
In, it is that 5% nitric acid solution is settled to scale with volumetric concentration, shakes up, obtained solution is introduced into inductively coupled plasma body hair
It penetrates in spectrometer, lithium standard working curve is made.
(3) according to the composition of neodymium production electrolyte, 6g LiF (mass fraction 20%) and 24.0g NdF is weighed3(quality point
Number 80%), by LiF and NdF3After mixing, it is dried in vacuo 12 hours at 400 DEG C, removes possible moisture, obtain drying
Mixture afterwards.
(4) mixture after drying is placed in boron nitride crucible, is placed in vacuum tube furnace, be warming up to industrial production
1050 DEG C of temperature, melt mixture completely needed for neodymium, keep the temperature 4 hours, cool to room temperature with the furnace.
(5) electrolyte that will be cooled to room temperature crushes, and is ground uniformly with agate crucible, takes out 4g and passes through X-ray diffractometer
(XRD) test sample structure.The XRD spectra that measurement obtains in step (5) from the diffraction maximum of XRD as shown in Figure 1, can be seen that
The structure of electrolyte is LiF and NdF3。
(6) the mixture 5g after taking out step (5) grinding, it is assumed that all neodymium fluorides of mixture, according to molar percentage
NdF3: Nd2O3Excessive neodymia 10g is added in=1:1.2, with agate crucible ground and mixed it is uniform after, be placed in boron nitride crucible
In, crucible is put into vacuum tube furnace and is heated to 700 DEG C, keeps the temperature 3 hours.
(7) boron nitride crucible is taken out from vacuum tube furnace, is quenched crucible with liquid nitrogen, then takes out sample agate earthenware
Crucible grinding uniformly, takes out 4g and passes through X-ray diffractometer (XRD) test sample structure.The XRD spectra that measurement obtains in step (7)
As shown in Fig. 2, having been converted into NdOF from the primary structure that the diffraction maximum of XRD can be seen that electrolyte.
(8) 4 parts of sample after weighing grinding, every part of 0.3g (including 0.2g neodymia and 0.1g electrolyte)；By sample point
It is not placed in four 100mL beakers, being separately added into concentration is 0.5,1.0,2.0, the excessive hydrochloric acid of 4.0mol/L；
Four samples are placed under conditions of 50 DEG C of heating water baths and are dissolved；In 0.5,1.0,2.0,4.0mol/L mistake
In the hydrochloric acid of amount, the time required for four samples are completely dissolved is 13h, 8.5h, 5h and 4h respectively；
Sample solution after being completely dissolved is transferred in 1000mL volumetric flask, and elutes beaker with the hydrochloric acid of same concentrations
Three times, then with deionized water elution beaker three times, all washing lotions are all transferred in 1000mL volumetric flask, will be molten after constant volume shakes up
Liquid is transferred to constant volume in 100mL volumetric flask；
Sample solution is introduced into inductive coupling plasma emission spectrograph and is measured, lithium and neodymium element in sample solution
Intensity is calculated by instrument according to the lithium and neodymium standard working curve of deposit automatically；By carrying out ICP-AES test analysis to solution
Four samples obtain: in the sample solution for 1. using 0.5mol/L dissolving with hydrochloric acid, Concentration of Neodymium Ion in Czochralski 228.66mg/L, and lithium ion
Concentration is 5.27mg/L；2. using 1.0mol/L dissolving with hydrochloric acid sample solution in, Concentration of Neodymium Ion in Czochralski 228.80mg/L, lithium from
Sub- concentration is 5.37mg/L；3. using in the sample solution of 2.0mol/L dissolving with hydrochloric acid, Concentration of Neodymium Ion in Czochralski 228.71mg/L, lithium
Ion concentration is 5.25mg/L；4. using 4.0mol/L dissolving with hydrochloric acid solution in, Concentration of Neodymium Ion in Czochralski 228.78mg/L, lithium from
Sub- concentration is 5.35mg/L；
Lithium fluoride is converted by lithium concentration, Concentration of Neodymium Ion in Czochralski is subtracted into 0.2gNd2O3The content of contained neodymium
After 171.48mg/L, it is then converted to neodymium fluoride.It is computed and obtains: 1. using in the 0.3g sample of 0.5mol/L dissolving with hydrochloric acid, containing
There are 0.01970gLiF and 0.07977gNdF3, i.e., contain mass percent 19.80%LiF and 80.20%NdF in electrolyte3；②
Using in the 0.3g sample of 1.0mol/L dissolving with hydrochloric acid, contain 0.02007gLiF and 0.07997gNdF3, i.e., contain in electrolyte
Mass percent 20.06%LiF and 79.94%NdF3；3. containing using in the 0.3g sample of 2.0mol/L dissolving with hydrochloric acid
0.01962gLiF and 0.07984gNdF3, i.e., contain mass percent 19.73%LiF and 80.57%NdF in electrolyte3；4. adopting
With in the 0.3g sample of 4.0mol/L dissolving with hydrochloric acid, contain 0.02000gLiF and 0.07994gNdF3, i.e., contain matter in electrolyte
Measure percentage 20.01%LiF and 79.99%NdF3。
Using detection method provided by the invention, test result and the content one for preparing lithium fluoride and neodymium fluoride in electrolyte
It causes, it was demonstrated that the method is reliable.
Embodiment 3
The present embodiment provides a kind of measuring methods for preparing neodymium fluoride and fluorination lithium content in neodymium production electrolyte, including such as
Lower step.
(1) pipette 0.00 respectively, 0.50,1.00,5.00,10.00,20.00,50.00mL neodymium standard solution is to 7
In 100mL volumetric flask, it is that 5% nitric acid solution is settled to scale with volumetric concentration, shakes up, obtained solution is introduced into inductive coupling
In plasma emission spectrometer, neodymium standard working curve is made.
(2) 0.00,0.50,1.00,2.00,5.00,10.00mL lithium standard solution to 6 100mL volumetric flasks are pipetted respectively
In, it is that 5% nitric acid solution is settled to scale with volumetric concentration, shakes up, obtained solution is introduced into inductively coupled plasma body hair
It penetrates in spectrometer, lithium standard working curve is made.
(3) according to the composition of neodymium production electrolyte, 6g LiF (mass fraction 20%) and 24.0g NdF is weighed3(quality point
Number 80%), by LiF and NdF3After mixing, it is dried in vacuo 12 hours at 400 DEG C, removes possible moisture, obtain drying
Mixture afterwards.
(4) mixture after drying is placed in boron nitride crucible, is placed in vacuum tube furnace, be warming up to industrial production
1050 DEG C of temperature, melt mixture completely needed for neodymium, keep the temperature 4 hours, cool to room temperature with the furnace.
(5) electrolyte that will be cooled to room temperature crushes, and is ground uniformly with agate crucible, takes out 4g and passes through X-ray diffractometer
(XRD) test sample structure.The XRD spectra that measurement obtains in step (5) from the diffraction maximum of XRD as shown in Figure 1, can be seen that
The structure of electrolyte is LiF and NdF3。
(6) the mixture 5g after taking out step (5) grinding, it is assumed that all neodymium fluorides of mixture, according to molar percentage
NdF3: Nd2O3Excessive neodymia 10g is added in=1:1.2, with agate crucible ground and mixed it is uniform after, be placed in boron nitride crucible
In, crucible is put into vacuum tube furnace and is heated to 700 DEG C, keeps the temperature 3 hours.
(7) boron nitride crucible is taken out from vacuum tube furnace, is quenched crucible with liquid nitrogen, then takes out sample agate earthenware
Crucible grinding uniformly, takes out 4g and passes through X-ray diffractometer (XRD) test sample structure.The XRD spectra that measurement obtains in step (7)
As shown in Fig. 2, having been converted into NdOF from the primary structure that the diffraction maximum of XRD can be seen that electrolyte.
(8) 4 parts of sample after weighing grinding, every part of 0.3g (including 0.2g neodymia and 0.1g electrolyte)；By sample point
It is not placed in four 100mL beakers, being separately added into concentration is 0.5,1.0,2.0, the excessive hydrochloric acid of 4.0mol/L；
Four sample placements are dissolved at room temperature；In 0.5,1.0,2.0, the excessive hydrochloric acid of 4.0mol/L
In, the time required for four samples are completely dissolved is 80h, 48h, 30h and 13h respectively；
Sample solution after being completely dissolved is transferred in 1000mL volumetric flask, and elutes beaker with the hydrochloric acid of same concentrations
Three times, then with deionized water elution beaker three times, all washing lotions are all transferred in 1000mL volumetric flask, will be molten after constant volume shakes up
Liquid is transferred to constant volume in 100mL volumetric flask；
Sample solution is introduced into inductive coupling plasma emission spectrograph and is measured, lithium and neodymium element in sample solution
Intensity is calculated by instrument according to the lithium and neodymium standard working curve of deposit automatically；By carrying out ICP-AES test analysis to solution
Four samples obtain: in the sample solution for 1. using 0.5mol/L dissolving with hydrochloric acid, Concentration of Neodymium Ion in Czochralski 228.59mg/L, and lithium ion
Concentration is 5.25mg/L；2. using 1.0mol/L dissolving with hydrochloric acid sample solution in, Concentration of Neodymium Ion in Czochralski 228.77mg/L, lithium from
Sub- concentration is 5.35mg/L；3. using in the sample solution of 2.0mol/L dissolving with hydrochloric acid, Concentration of Neodymium Ion in Czochralski 228.93mg/L, lithium
Ion concentration is 5.38mg/L；4. using 4.0mol/L dissolving with hydrochloric acid solution in, Concentration of Neodymium Ion in Czochralski 228.87mg/L, lithium from
Sub- concentration is 5.28mg/L；
Lithium fluoride is converted by lithium concentration, Concentration of Neodymium Ion in Czochralski is subtracted into 0.2gNd2O3The content of contained neodymium
After 171.48mg/L, it is then converted to neodymium fluoride；It is computed and obtains: 1. using in the 0.3g sample of 0.5mol/L dissolving with hydrochloric acid, containing
There are 0.01962gLiF and 0.07968gNdF3, i.e., contain mass percent 19.76%LiF and 80.24%NdF in electrolyte3；②
Using in the 0.3g sample of 1.0mol/L dissolving with hydrochloric acid, contain 0.02000gLiF and 0.07993gNdF3, i.e., contain in electrolyte
Mass percent 20.01%LiF and 79.99%NdF3；3. containing using in the 0.3g sample of 2.0mol/L dissolving with hydrochloric acid
0.02011gLiF and 0.08015gNdF3, i.e., contain mass percent 20.06%LiF and 79.94%NdF in electrolyte3；4. adopting
With in the 0.3g sample of 4.0mol/L dissolving with hydrochloric acid, contain 0.01974gLiF and 0.08007gNdF3, i.e., contain matter in electrolyte
Measure percentage 19.77%LiF and 20.23%NdF3。
Using detection method provided by the invention, test result and the content one for preparing lithium fluoride and neodymium fluoride in electrolyte
It causes, it was demonstrated that the method is reliable.
It should be noted that unless otherwise indicated, technical term or scientific term used in this application should be this hair
The ordinary meaning that bright one of ordinary skill in the art are understood.Unless specifically stated otherwise, it otherwise illustrates in these embodiments
Component and opposite step, numerical expression and the numerical value of step are not limit the scope of the invention.It is illustrated and described herein
In all examples, unless otherwise prescribed, any occurrence should be construed as merely illustratively, not as limitation, because
This, other examples of exemplary embodiment can have different values.
In the description of the present invention, it is to be understood that, term " first ", " second " are used for description purposes only, and cannot
It is interpreted as indication or suggestion relative importance or implicitly indicates the quantity of indicated technical characteristic.Define as a result, " the
One ", the feature of " second " can explicitly or implicitly include one or more of the features.In the description of the present invention,
The meaning of " plurality " is two or more, unless otherwise specifically defined.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme should all cover in protection scope of the present invention.
Claims (9)
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