CN110044999A - The detection method of 14 kinds of trace impurity rare earth ion contents in a kind of ultra-pure cerium compound - Google Patents

The detection method of 14 kinds of trace impurity rare earth ion contents in a kind of ultra-pure cerium compound Download PDF

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CN110044999A
CN110044999A CN201910372958.6A CN201910372958A CN110044999A CN 110044999 A CN110044999 A CN 110044999A CN 201910372958 A CN201910372958 A CN 201910372958A CN 110044999 A CN110044999 A CN 110044999A
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solution
sample
rare earth
kinds
concentration
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张衍
蔡华强
潘忠奔
段太成
焦鹏冲
居佳
何亭
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SICHUAN RESEARCH CENTER OF NEW MATERIALS
Institute of Chemical Material of CAEP
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    • G—PHYSICS
    • G01—MEASURING; TESTING
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    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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Abstract

The invention discloses a kind of detection methods of 14 kinds of trace impurity rare earth ion contents in ultra-pure cerium compound, comprising the following steps: the first step prepares solution needed for testing；Step 2: sample pre-treatments；Step 3: sample matrices separate；Step 4: preparation work curve solution；Step 5: drawing working curve；Step 6: 14 kinds of impurity rare earth ion contents in measurement sample solution；Step 7: calculating.Each rare-earth impurity element detection is limited to 0.0024~0.0057ng/mL in the method for the present invention, quantitatively it is limited to 0.008~0.019 μ g/g, meet the ultra-pure cerium compound purity detecting demand of 7N, solves the problems, such as that dirt content test in the ultra-pure cerium of 7N rank can not be applied to since the virtualization disposition matter of cerium forms the interference such as oxide and hydroxide in existing inductivity coupled plasma mass spectrometry method.Measuring method of the invention, easy to operate, high-efficient, high sensitivity.

Description

14 kinds of trace impurity rare earth ion contents in a kind of ultra-pure cerium compound Detection method
Technical field
The present invention relates to superelevation pure rare-earth metals trace element analysis detection technique fields, and in particular to ultra-pure cerium (cerium Detection method of the content greater than 14 kinds of trace impurity rare earth ion contents in 99.99999%, 7N) compound.
Background technique
" high-purity rare-earth " refers to that purity is greater than the rare earth metal and its compound of 99.99% (4N), with electronics, optics and swashs The development of the national defence advanced science technology such as light, the demand of high pure rare earth metals material increasingly increase, in order to develop higher performance Advanced material, purity higher than 99.9999% (6N) ultra-pure rare earth compound exploitation dynamics be gradually increased, especially in recent years To have developed ultra-pure rare earth compound of higher purity (purity be higher than 99.99999%, 7N) for using.As characterization Means, the accuracy of method for detecting purity are exploitation and the premise using ultra-pure rare earth compound.In ultra-pure cerium compound In method for detecting purity, since matrix cerium has spectral emission lines more abundant and multimass isotopic characteristic, it is based on Inductively coupled plasma atomic emission (ICP-OES), the inductivity coupled plasma mass spectrometry of conventional even high resolution mode (ICP-MS) etc. analytical technologies are difficult to meet the direct purity analysis of the high-purity cerium compound of 4N or more, particularly, for by dry The elements such as serious La, Pr, Tb, Gd, Dy are disturbed, accurate analysis usually requires to combine multiple matrix isolation technics, so that entirely Analysis process is cumbersome and tediously long, so as to cause test result inaccuracy.Triple quadrupole bar inductivity coupled plasma mass spectrometry (ICP- QQQ or ICP-MS/MS) it is the inorganic mass spectrum new technology occurred in recent years, core is ingenious bond quality screening and matter Collision/reaction the pool technology for measuring transfer realizes unique chemical high resolution, provides to solve strong compound ion mass spectrum interference A kind of very effective technological approaches.
Summary of the invention
It is a primary object of the present invention to provide traces in a kind of ultra-pure cerium (purity is greater than 99.99999%, 7N) compound Measure triple level four bars series inductive coupling plasma mass (ICP-MS/MS) detection methods of impurity rare earth ion, energy Trace impurity rare earth ion contains in the enough accurate quantitative analysis detection ultra-pure cerium of 7N (cerium content is greater than 99.99999%) compounds Amount improves detection sensitivity, solves in existing detection method since the multi-atomic ion that cerium matrix is formed generates tested element Serious mass spectrum interference problem.
Core of the invention content is using new and effective extractant, by matrix separation method, using anti-with collision Triple level four bars series inductive coupling plasma mass spectrographs of Ying Chi, to the trace impurity rare earth in the ultra-pure cerium compound of 7N Tenor is detected.
Instrument used in the present invention are as follows: with the triple level four bars series inductive coupling plasma constitutions of collision/reaction tank Spectrometer (G3663A#100, Agilent company, the U.S.), instrument configuration x type lens system, nickel sampling spiroid and interception cone, glass are same Heart atomizer, subsidiary resistance to high matrix sampling system (High Matrix Introduction, HMI).
The technical scheme adopted by the invention is that: 14 kinds of trace impurity rare earth ions contain in ultra-pure cerium compound The detection method of amount, 14 kinds of rare earth ions be yttrium Y, lanthanum La, praseodymium Pr, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, terbium Tb, dysprosium Dy, Holmium Ho, erbium Er, thulium Tm, ytterbium Yb, lutetium Lu, comprising the following steps:
Required solution is detected step 1: preparing
Refer to (the resistivity 18.2M Ω of level-one water as defined in GB/T 6682 when water used in this detection method does not explain .cm), prepared through ELGAPURELAB ultrapure water production system (Britain)；
The nitric acid of ρ=1.4g/mL: super trace levels of metal (MOS,II, J.T.Baker, the U.S.)；
5% (V/V) nitric acid solution and 2% (V/V) nitric acid solution: it is prepared in proportion by nitric acid with ultrapure water, 5% (V/V) Nitric acid solution is made of 5 parts of nitric acid and 95 parts of ultrapure waters, and 2% (V/V) nitric acid solution is made by 2 parts of nitric acid and 98 parts of ultrapure waters, V/V refers to volume ratio.
PH=4.0 buffer solution: taking sodium acetate trihydrate 54.4g to dissolve with ultrapure appropriate amount of water, adds 92ml glacial acetic acid, ultrapure water Dilution, is settled to 1000ml；
2% (m/V) sodium hydroxide solution: accurately weighing 10.0g sodium hydroxide and be transferred to volumetric flask after suitable quantity of water dissolution, Ultrapure water dilution, is settled to 500mL；
Liquor potassic permanganate: concentration is 1.0~10.0g/L, is prepared with potassium permanganate and ultrapure water；
Cyanex272 extractant: two (2,4,4- tri-methyl-amyl) phosphinic acids, concentration is 0.01~0.10mol/L；
0.05mol/L Cyanex272/ cyclohexane solution: two (2,4,4- tri-methyl-amyl) phosphinic acids are accurately weighed 14.52g is dissolved with hexamethylene, is settled to 1000mL and is made；
The sodium acetate trihydrate, glacial acetic acid, sodium hydroxide, potassium permanganate, two (2,4,4- tri-methyl-amyl) phosphinic acids and Hexamethylene is excellent pure grade；
Step 2: sample pre-treatments
The sample for accurately weighing quality m=0.1000g is added 1.0mL nitric acid (MOS), heating makes in PFA counteracting tank Sample is completely dissolved, and volumetric flask is transferred to after cooling, and deionized water is added and is settled to 50mL (volume V0), it is molten to obtain sample Liquid makes sample blank solution with process；
Step 3: sample matrices separate
Accurately pipette 5.0mL (volume V1) on walk obtained sample solution and sample blank solution in quartz beaker In, 2% (m/V) sodium hydroxide solution is added and adjusts pH value of solution to 3.0~6.0, solution is transferred in separatory funnel respectively, according to Secondary addition 20.0mL pH=4.0 buffer solution, the liquor potassic permanganate of 1.0~5.0mL 5.0mg/mL, 5~30mL Cyanex272/ cyclohexane solution shakes 1~10min, discards water layer after standing, is added 1%~30% into remaining organic phase (V/V) aqueous solution of nitric acid 10mL carries out back extraction, separates organic phase, water phase evaporated under reduced pressure to about 2mL, Zhi Houyong after standing 5% (V/V) nitric acid solution is accurately settled to 10.0mL, sample solution (the volume V after obtaining matrix separation2) and sample blank Solution (volume V3), it is to be measured；
Step 4: preparation work curve solution
The multielement rare earth element containing yttrium, lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium is taken to mix mark Quasi- stock solution (holding national standard reference certificate, provided by State Standard Matter Research Centre), 100mg/L, by the standard inventory Liquid is diluted step by step with 2% (V/V) nitric acid solution obtains the solution of 3~10 concentration gradients, and concentration gradient is distributed in 0.0~ Working curve solution is made in 100.0ng/mL；Cesium element (Cs) standard reserving solution is taken, is diluted to 0.01~10.0 μ with ultrapure water G/mL makees inner mark solution；
Step 5: drawing working curve
It is carried out using triple level four bars series inductive coupling plasma mass spectrographs (ICP-MS/MS) with crash response pond Measurement, using argon gas (Ar) as carrier gas, helium (He), oxygen (O2) and ammonia (NH3) it is used as collision/reaction tank gas, it sets The measurement parameter of instrument, wherein yttrium Y, lanthanum La, praseodymium Pr, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, holmium Ho, erbium Er, thulium Dy, ytterbium Yb, lutetium Lu element use oxygen quality transfer mode (O2Mode) it is measured, terbium Tb element uses ammonia mass transfer mode (NH3Mode) make online internal standard using 1.0 μ g/mL Cs solution in test process, difference obtained in the 4th step is measured respectively The concentration of 14 kinds of rare earth ions in the working curve solution of concentration, with the multielement rare earth element mixed solution of each element Signal strength is ordinate, using multielement rare earth element mixed solution concentration as abscissa, carries Software on Drawing using instrument and obtains To 14 kinds of rare earth ion concentration and signal strength working curve；
Step 6: 14 kinds of rare earth ion contents in measurement sample solution
It is carried out using triple level four bars series inductive coupling plasma mass spectrographs (ICP-MS/MS) with crash response pond Measurement, using argon gas as carrier gas, helium, oxygen and ammonia set the measurement parameter of instrument as collision/reaction tank gas, Make online internal standard using 1.0 μ g/mL Cs solution in test process, it is molten to sample solution obtained in third step and sample blank 14 kinds of rare earth ion concentration in liquid are measured, and test result carries software using instrument and draws according in the 5th step Working curve be directly calculated, in sample each element content measuring result be cx1, each element test result in sample blank For cx0, wherein x represents each element；
Step 7: calculating
The mass fraction of each rare-earth impurity element is in primary sample with ωxIt indicates, and is calculated according to following formula:
That is:
Wherein:
M --- sample quality obtained by precise in second step, unit are gram (g)；
V2--- analysis sample solution volume obtained in third step, unit are milliliter (mL)；
V3--- sample blank liquor capacity is made in third step, unit is milliliter (mL)；
cx1--- rare earth metal content in the 6th step Instrumental test gained sample solution, unit is nanograms per milliliter (ng/ mL)；
cx0--- rare earth metal content, unit are nanograms per milliliter (ng/ in test gained sample blank solution in the 6th step mL)；
V0--- sample solution total volume in second step, unit are milliliter (mL)；
V1--- divide in third step and take sample solution volume, unit is milliliter (mL).
Ce elements content ω in primary sample cerium compoundCeAre as follows:
Wherein:
∑ωx--- each rare earth metal impurity content summation in sample；
MCe--- Ce elements atomic mass in sample, unit are gram every mole (g/mol)；
Ms--- sample molecule quality, unit are gram every mole (g/mol).
The detection method of 14 kinds of trace impurity rare earth ion contents in ultra-pure cerium compound uses New and effective extractant Cyanex272 is by matrix separation method, using the triple level four bars series electricals for having crash response pond Feel couple plasma mass spectrometer, it is miscellaneous to the Trace Rare Earth metal in 7N (purity is greater than 99.99999%) ultra-pure cerium compound It is upright to tap into capable detection.
The detection method of 14 kinds of trace impurity rare earth ion contents in ultra-pure cerium compound, first The concentration that step prepares liquor potassic permanganate is 5.0mg/mL.
The detection method of 14 kinds of trace impurity rare earth ion contents in ultra-pure cerium compound, second The quality of sample described in step weighs according to the following rules: when sample purity is between 99.999999%~99.99999%, weighing Sample quality is 0.1000g, and 0.0001g is accurate to when weighing, and the temperature of heating PFA counteracting tank is 70 DEG C~130 DEG C.
The detection method of 14 kinds of trace impurity rare earth ion contents, third in ultra-pure cerium compound In step, the pH=4.0 of solution is adjusted, liquor potassic permanganate dosage is 2.0mL, Cyanex272/ cyclohexane solution volume when extraction For 20mL, extraction shaking time 5min, aqueous solution of nitric acid volumetric concentration is 5% when back extraction and constant volume, back extraction shaking 1~10min of time.
The detection method of 14 kinds of trace impurity rare earth ion contents in ultra-pure cerium compound, the 4th In step, element working curve concentration gradient to be measured be 4, concentration be respectively 0.0ng/mL, 0.1ng/mL, 0.2ng/mL, 0.5ng/mL, online inner mark solution concentration are 1 μ g/mL.
The detection method of 14 kinds of trace impurity rare earth ion contents in ultra-pure cerium compound, the 5th In step, when being measured using oxygen quality transfer mode, specific apparatus measures parameter are as follows: scan pattern MS/MS, RF power 1550W, pond gas are oxygen, and oxygen concentration 5~40% (He balance), pond 0.5~10.0mL/min of gas flow rate, eight grades of bars are inclined Voltage -18V is set, kinetic energy discriminates against voltage 5V, reaction tank exit potential -60V, deflection lens voltage 10V, plate lens voltage -80V, 3 dot pattern of peak shape is acquired, scanning/number of repetition 100 times, data analysing method is external standard method；Using ammonia mass transfer mode When being measured, specific apparatus measures parameter are as follows: scan pattern MS/MS, RF power 1550W, pond gas are ammonia/helium mix Gas, ammonia concentration 5~40% (He balance), pond 0.5~10.0mL/min of gas flow rate, eight grades of bar bias voltage -18V are moved Voltage 5V, reaction tank exit potential -60V, deflection lens voltage 10V, plate lens voltage -80V can be discriminated against, acquire 3 moulds of peak shape Formula, scanning/number of repetition 100 times, data analysing method is external standard method；Wherein online inner mark solution element is Cs, online internal standard Solution concentration is 0.01~10.0 μ g/mL.
The detection method of 14 kinds of trace impurity rare earth ion contents in ultra-pure cerium compound, the 6th In step, using triple level four bars series inductive coupling plasma mass spectrographs with crash response pond to 14 kinds of rare-earth impurity elements Content is measured, and specific apparatus measures parameter is respectively as follows: oxygen quality with the 5th step, each element measurement isotope and ion pair Transfer mode: yttrium89Y → 105, lanthanum139La → 155, praseodymium141The neodymium of Pr → 157,144Nd → 160, samarium147Sm → 161, europium151Eu→ 167, gadolinium160Gd → 176, dysprosium162Dy → 178, holmium165Ho → 181, erbium166Er → 182, thulium169Tm → 185, ytterbium172Yb→188、 Lutetium175Lu→191；Ammonia mass transfer mode: terbium159Tb→175。
The present invention is based on ICP-MS/MS technologies, by resistance to sampling system (the High Matrix with high salt for sufficiently combining instrument Introduction, HMI) aerosol dilution function possessed by oxide yield rejection ability, realize the ultra-pure cerium of 7N It is measured while 14 kinds of ultra trace rare earth impurities ions in compound.
Compared with prior art, the present invention at least has the advantages that the ultra-pure cerium of a kind of 7N provided by the invention Triple level four bars inductively coupled plasma bodies of trace impurity rare earth ion in (purity is greater than 99.99999%) compound Tandem mass spectrum (ICP-MS/MS) detection method, it is easy to operate, measurement sensitivity is high.
In method, cerium concentration is as shown in table 1 in a stripping workshop after cerium concentration is separated with matrix in original solution, as a result Show that this method reaches 99.9% or more to cerium matrix single separative efficiency, hence it is evident that higher than using the single of other extractants to be stripped Take separative efficiency.
1 cerium matrix separative efficiency of table
* separative efficiency calculation formula is (100%-C1*V1/C0*V0), wherein C1It is dense to test Ce in solution after after being stripped Degree, V1For final strip liquor volume, C0For Ce concentration, V in original solution0For original solution volume.
Each element detection limit is respectively yttrium >=0.0057ng/mL, lanthanum >=0.0048ng/mL, praseodymium >=0.0036ng/ in method ML, neodymium >=0.0036ng/mL, samarium >=0.0049ng/mL, europium >=0.0036ng/mL, gadolinium >=0.0033ng/mL, terbium >= 0.0052ng/mL, dysprosium >=0.0024ng/mL, holmium >=0.0026ng/mL, erbium >=0.0033ng/mL, thulium >=0.0027ng/mL, Ytterbium >=0.0024ng/mL, lutetium >=0.0024ng/mL；In method each element quantitative limit be respectively yttrium >=0.019 μ g/g, lanthanum >= 0.016 μ g/g, praseodymium >=0.012 μ g/g, neodymium >=0.012 μ g/g, samarium >=0.016 μ g/g, europium >=0.012 μ g/g, gadolinium >=0.011 μ G/g, terbium >=0.017 μ g/g, dysprosium >=0.008 μ g/g, holmium >=0.009 μ g/g, erbium >=0.011 μ g/g, thulium >=0.009 μ g/g, ytterbium >=0.008 μ g/g, lutetium >=0.008 μ g/g, it was demonstrated that this method is suitable for the ultra-pure cerium compound purity detecting of 7N.
As shown in table 2, method whole process each element recovery of standard addition is 93.6~102.7%, solves existing detection side Serious mass spectrum interference problem of the multi-atomic ion to be generated to tested element in method due to the formation of cerium matrix.
Table 2ICP-MS/MS is to impurity thulium assay recovery of standard addition in high-purity cerium dioxide
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to Limit the present invention.
The present invention measures 14 kinds of impurity rare earth metals in the ultra-pure cerium of 7N (cerium content is greater than 99.99999%) compound Ion (yttrium Y, lanthanum La, praseodymium Pr, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, terbium Tb, dysprosium Dy, holmium Ho, erbium Er, thulium Tm, ytterbium Yb, lutetium Lu) Content.
Embodiment one
The present embodiment measures ultra high purity nitric oxide cerium (CeO2) in 14 kinds of impurity rare earth ion contents, include following step It is rapid:
Required solution is tested step 1: preparing
Solution needed for method prepares following test is described according to specification
5% (V/V) nitric acid solution；2% (V/V) nitric acid solution；PH=4.0 buffer solution；2% (m/V) sodium hydroxide is molten Liquid；5.0mg/mL liquor potassic permanganate；0.05mol/L Cyanex272/ cyclohexane solution.
Step 2: sample pre-treatments
2 30mL PFA counteracting tanks are taken, CeO is accurately weighed2Sample quality m=0.1000g (being accurate to 0.0001g) is in it In in a PFA counteracting tank, another PFA counteracting tank is added without sample as process blank, is added respectively into 2 counteracting tanks The super trace levels of metal nitric acid of 1.0mL ρ=1.4g/mL and the super trace levels of metal H of 1.0mL2O2, heated 30 minutes in 120 DEG C, until sample It is completely dissolved, is transferred to volumetric flask after cooling respectively, deionized water is added and is settled to 50.0mL (V0), CeO is made respectively2Sample Solution and sample blank solution.
Step 3: sample matrices separate
5.0mL (V is accurately pipetted respectively1) on walk obtained sample solution and sample blank solution in quartz beaker, add Enter 2% (m/V) sodium hydroxide solution and adjust pH value of solution to 4.0, solution is transferred in separatory funnel respectively, is sequentially added 20.0mL buffer solution (pH=4.0), 2.0mL liquor potassic permanganate (5.0mg/mL), 20.0mL Cyanex272/ hexamethylene are molten Liquid shakes 2 minutes, water layer is discarded after standing, and 10mL 5% (V/V) aqueous solution of nitric acid is added into remaining organic phase, carries out anti- To extraction, organic phase is separated after standing, water phase is evaporated under reduced pressure to about 2mL, is accurately settled to 5% (V/V) nitric acid solution 10.0mL, sample solution (the volume V after obtaining matrix separation2) and sample blank solution (volume V3), it is to be measured.
Step 4: preparation work curve solution
Multielement rare earth element hybrid standard stock solution is taken (to hold national standard reference certificate, studied by national standard substance Center provides), contain yttrium (Y), lanthanum (La), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), 100mg/L dilute above-mentioned solution with 2% (V/V) nitric acid solution step by step For 0.0ng/mL, 0.1ng/mL, 0.2ng/mL, 0.5ng/mL solution, working curve solution is made.
Caesium (Cs) elemental standards stock solution is taken (to hold national standard reference certificate, mentioned by State Standard Matter Research Centre For), 100mg/L is diluted to 1.0 μ g/mL with ultrapure water, makees inner mark solution.
Step 5: drawing working curve
It is carried out using triple level four bars series inductive coupling plasma mass spectrographs (ICP-MS/MS) with crash response pond Measurement, using argon gas (Ar) as carrier gas, helium (He), oxygen (O2) and ammonia (NH3) it is used as collision/reaction tank gas, it sets The measurement parameter of instrument, wherein yttrium Y, lanthanum La, praseodymium Pr, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, holmium Ho, erbium Er, thulium Dy, ytterbium Yb, lutetium Lu element use oxygen quality transfer mode (O2Mode) it is measured, terbium Tb element uses ammonia mass transfer mode (NH3Mode) make online internal standard using 1.0 μ g/mL Cs solution in test process, difference obtained in the 4th step is measured respectively The concentration of 14 kinds of rare earth ions in the working curve solution of concentration, with the multielement rare earth element mixed solution of each element Signal strength is ordinate, using multielement rare earth element mixed solution concentration as abscissa, carries Software on Drawing using instrument and obtains To 14 kinds of rare earth ion concentration and signal strength working curve；
When being measured using oxygen quality transfer mode, specific apparatus measures parameter are as follows: scan pattern MS/MS, RF function Rate 1550W, pond gas are oxygen, oxygen concentration 25%, pond gas flow rate 3.0mL/min, eight grades of bar bias voltage -18V, kinetic energy Discriminate against voltage 5V, reaction tank exit potential -60V, deflection lens voltage 10V, plate lens voltage -80V, acquire 3 dot pattern of peak shape, Scanning/number of repetition 100 times, data analysing method is external standard method；Wherein online inner mark solution element is Cs, online inner mark solution Concentration is 3.0 μ g/mL；When being measured using ammonia mass transfer mode, specific apparatus measures parameter are as follows: scan pattern MS/ MS, RF power 1550W, pond gas are ammonia/helium mix gas, ammonia concentration 25% (He balance), pond gas flow rate 5.0mL/min, eight grades of bar bias voltage -18V, kinetic energy discriminate against voltage 5V, reaction tank exit potential -60V, deflection lens voltage 10V, plate lens voltage -80V acquire 3 dot pattern of peak shape, and scanning/number of repetition 100 times, data analysing method is external standard method；Its In online inner mark solution element be Cs, online inner mark solution concentration is 6.0 μ g/mL.
Step 6: 14 kinds of rare earth ion contents in measurement sample solution
It is carried out using triple level four bars series inductive coupling plasma mass spectrographs (ICP-MS/MS) with crash response pond Measurement, using argon gas as carrier gas, helium, oxygen and ammonia set the measurement parameter of instrument as collision/reaction tank gas, Make online internal standard using 1.0 μ g/mL Cs solution in test process, it is molten to sample solution obtained in third step and sample blank 14 kinds of rare earth ion concentration in liquid are measured, and test result carries software using instrument and draws according in the 5th step Working curve be directly calculated, in sample each element content measuring result be cx1, each element test result in sample blank For cx0, wherein x represents each element；
Specific apparatus measures parameter is respectively as follows: oxygen quality transfer with the 5th step, each element measurement isotope and ion pair Mode: yttrium89Y → 105, lanthanum139La → 155, praseodymium141The neodymium of Pr → 157,144Nd → 160, samarium147Sm → 161, europium151Eu→167、 Gadolinium160Gd → 176, dysprosium162Dy → 178, holmium165Ho → 181, erbium166Er → 182, thulium169Tm → 185, ytterbium172Yb → 188, lutetium175Lu→191；Ammonia mass transfer mode: terbium159Tb→175。
Step 7: calculating
The mass fraction of each rare-earth impurity element is in primary sample with ωx(%) is indicated, and is calculated according to following formula:
That is:
Wherein:
M --- sample quality obtained by precise in second step, unit are gram (g)；
V2--- analysis sample solution volume obtained in third step, unit are milliliter (mL)；
V3--- sample blank liquor capacity is made in third step, unit is milliliter (mL)；
cx1--- rare earth metal content in the 6th step Instrumental test gained sample solution, unit is nanograms per milliliter (ng/ mL)；
cx0--- rare earth metal content, unit are nanograms per milliliter (ng/ in test gained sample blank solution in the 6th step mL)；
V0--- sample solution total volume in second step, unit are milliliter (mL)；
V1--- divide in third step and take sample solution volume, unit is milliliter (mL).
Ce elements content ω in primary sample cerium compoundCe(%) are as follows:
Wherein:
∑ωx--- each rare earth metal impurity content summation in sample；
MCe--- Ce elements atomic mass in sample, unit are gram every mole (g/mol)；
Ms--- sample molecule quality, unit are gram every mole (g/mol).
By calculating, various impurity rare earth ion contents are as follows in the present embodiment:
It is computed, the cerium oxide (CeO2) Ce elements content is 99.999986% in sample.
Embodiment two
The present embodiment measures ultra-high pure nitric acid cerium (Ce (NO3)3) in 14 kinds of impurity rare earth ion contents, comprising with Lower step:
Step 1:: prepare solution needed for testing
Solution needed for method prepares following test is described according to specification
5% (V/V) nitric acid solution；2% (V/V) nitric acid solution；PH=4.0 buffer solution；2% (m/V) sodium hydroxide is molten Liquid；5.0mg/mL liquor potassic permanganate；0.05mol/L Cyanex272/ cyclohexane solution.
Step 2: sample pre-treatments
2 30mL PFA counteracting tanks are taken, Ce (NO is accurately weighed3)3Sample quality m=0.1000g (is accurate to 0.0001g) In one of PFA counteracting tank, another PFA counteracting tank is added without sample as process blank, respectively into 2 counteracting tanks 20.0mL deionized water to sample is added to be completely dissolved, is transferred to volumetric flask, deionized water is added and is settled to 50.0mL (V0), point It Zhi get not Ce (NO3)3Sample solution and sample blank solution.
Step 3: sample matrices separate
5.0mL (V is accurately pipetted respectively1) on walk obtained sample solution and sample blank in quartz beaker, be added 2% Sodium hydroxide solution adjusts pH value of solution to 4.0, and solution is transferred in separatory funnel respectively, sequentially adds 20.0mL buffer solution (pH=4.0), 2.0mL liquor potassic permanganate (5.0mg/mL), 20.0mL P507/ hexane solution shakes 1 minute, after standing Water layer is discarded, 5% aqueous solution of nitric acid of 10.0mL is added into remaining organic phase, back extraction is carried out, is separated after standing organic Phase, water phase are accurately settled to 10.0mL with 5% nitric acid solution, sample solution (the volume V after obtaining matrix separation2) and sample Blank solution (volume V3), it is to be measured.
Step 4: preparation work curve solution
Multielement rare earth element hybrid standard stock solution is taken (to hold national standard reference certificate, studied by national standard substance Center provides), contain yttrium (Y), lanthanum (La), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), above-mentioned solution is diluted to 0.0ng/ with 2% nitric acid by erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), 100mg/L step by step Working curve solution is made in mL, 0.1ng/mL, 0.2ng/mL, 0.5ng/mL solution.
Caesium (Cs) elemental standards stock solution is taken (to hold national standard reference certificate, mentioned by State Standard Matter Research Centre For), 100mg/L is diluted to 1.0 μ g/mL with ultrapure water, makees inner mark solution.
Step 5: drawing working curve
It is carried out using triple level four bars series inductive coupling plasma mass spectrographs (ICP-MS/MS) with crash response pond Measurement, using argon gas (Ar) as carrier gas, helium (He), oxygen (O2) and ammonia (NH3) it is used as collision/reaction tank gas, it sets The measurement parameter of instrument, wherein yttrium Y, lanthanum La, praseodymium Pr, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, holmium Ho, erbium Er, thulium Dy, ytterbium Yb, lutetium Lu element use oxygen quality transfer mode (O2Mode) it is measured, terbium Tb element uses ammonia mass transfer mode (NH3Mode) make online internal standard using 1.0 μ g/mL Cs solution in test process, difference obtained in the 4th step is measured respectively The concentration of 14 kinds of rare earth ions in the working curve solution of concentration, with the multielement rare earth element mixed solution of each element Signal strength ordinate carries Software on Drawing using instrument and obtains using multielement rare earth element mixed solution concentration as abscissa 14 kinds of rare earth ion concentration and signal strength working curve.
Step 6: 14 kinds of rare earth ion contents in measurement sample solution
It is carried out using triple level four bars series inductive coupling plasma mass spectrographs (ICP-MS/MS) with crash response pond Measurement, using argon gas as carrier gas, helium, oxygen and ammonia set the measurement parameter of instrument as collision/reaction tank gas, Make online internal standard using 1.0 μ g/mL Cs solution in test process, it is molten to sample solution obtained in third step and sample blank 14 kinds of rare earth ion concentration in liquid are measured, and test result carries software using instrument and draws according in the 5th step Working curve be directly calculated, in sample each element content measuring result be cx1, each element test result in sample blank For cx0, wherein x represents each element；
The instrument parameter of 5th step and the 6th step is arranged with embodiment 1.
Step 7: calculating
The mass fraction of each rare-earth impurity element is in primary sample with ωx(%) is indicated, and is calculated according to following formula:
That is:
Wherein:
M --- sample quality obtained by precise in second step, unit are gram (g)；
V2--- analysis sample solution volume obtained in third step, unit are milliliter (mL)；
V3--- sample blank liquor capacity is made in third step, unit is milliliter (mL)；
cx1--- rare earth metal content in the 6th step Instrumental test gained sample solution, unit is nanograms per milliliter (ng/ mL)；
cx0--- rare earth metal content, unit are nanograms per milliliter (ng/ in test gained sample blank solution in the 6th step mL)；
V0--- sample solution total volume in second step, unit are milliliter (mL)；
V1--- divide in third step and take sample solution volume, unit is milliliter (mL).
Ce elements content ω in primary sample cerium compoundCe(%) are as follows:
Wherein:
∑ωx--- each rare earth metal impurity content summation in sample；
MCe--- Ce elements atomic mass in sample, unit are gram every mole (g/mol)；
Ms--- sample molecule quality, unit are gram every mole (g/mol).
By calculating, various impurity rare earth ion contents are as follows in the present embodiment:
It is computed, the Ce (NO3)3Ce elements content is 99.999987% in sample.
Embodiment three
The present invention measures ultra-pure four (DPM dpm,dipivalomethane) ceriums (Ce (TMHD)4) in 14 kinds it is miscellaneous Matter rare earth ion content comprising the steps of:
Required solution is tested step 1: preparing
Solution needed for method prepares following test is described according to specification
5% (V/V) nitric acid solution；2% (V/V) nitric acid solution；PH=4.0 buffer solution；2% (m/V) sodium hydroxide is molten Liquid；5.0mg/mL liquor potassic permanganate；0.05mol/L Cyanex272/ cyclohexane solution.
Step 2: sample pre-treatments
2 30mL PFA counteracting tanks are taken, Ce (TMHD) is accurately weighed4Sample quality m=0.1000g (is accurate to 0.0001g) in one of PFA counteracting tank, another PFA counteracting tank is added without sample as process blank, respectively to 2 The super trace levels of metal nitric acid of 1.0mL ρ=1.4g/mL is added in counteracting tank, is heated 30 minutes in 120 DEG C, until sample is completely dissolved, Volumetric flask is transferred to after cooling respectively, deionized water is added and is settled to 50.0mL (V0), Ce (TMHD) is made respectively4Sample solution And sample blank solution.
Step 3: sample matrices separate
5.0mL (V is accurately pipetted respectively1) on walk obtained sample solution and sample blank in quartz beaker, be added 2% Sodium hydroxide solution adjusts pH value of solution to 4.0, and solution is transferred in separatory funnel respectively, sequentially adds 20.0mL buffer solution (pH=4.0), 2.0mL liquor potassic permanganate (5.0mg/mL), 20.0mL Cyanex272/ cyclohexane solution shake 1 minute, Water layer is discarded after standing, 5% aqueous solution of nitric acid is added into remaining organic phase, is carried out back extraction, is separated organic phase after standing, Water phase is accurately settled to 20.0mL with 5% nitric acid, sample solution (the volume V after obtaining matrix separation2) and sample blank it is molten Liquid (volume V3), it is to be measured.
Step 4: preparation work curve solution
Multielement rare earth element hybrid standard stock solution is taken (to hold national standard reference certificate, studied by national standard substance Center provides), contain yttrium (Y), lanthanum (La), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), above-mentioned solution is diluted to 0.0ng/ with 2% nitric acid by erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), 100mg/L step by step Working curve solution is made in mL, 1.0ng/mL, 2.0ng/mL, 5.0ng/mL solution.
Caesium (Cs) elemental standards stock solution is taken (to hold national standard reference certificate, mentioned by State Standard Matter Research Centre For), 100mg/L is diluted to 1.0 μ g/mL with ultrapure water, makees inner mark solution.
Step 5: drawing working curve
It is carried out using triple level four bars series inductive coupling plasma mass spectrographs (ICP-MS/MS) with crash response pond Measurement, using argon gas (Ar) as carrier gas, helium (He), oxygen (O2) and ammonia (NH3) it is used as collision/reaction tank gas, it sets The measurement parameter of instrument, wherein yttrium Y, lanthanum La, praseodymium Pr, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, holmium Ho, erbium Er, thulium Dy, ytterbium Yb, lutetium Lu element use oxygen quality transfer mode (O2Mode) it is measured, terbium Tb element uses ammonia mass transfer mode (NH3Mode) make online internal standard using 1.0 μ g/mL Cs solution in test process, difference obtained in the 4th step is measured respectively The concentration of 14 kinds of rare earth ions in the working curve solution of concentration, with the multielement rare earth element mixed solution of each element Signal strength ordinate carries Software on Drawing using instrument and obtains using multielement rare earth element mixed solution concentration as abscissa 14 kinds of rare earth ion concentration and signal strength working curve.
Step 6: 14 kinds of rare earth ion contents in measurement sample solution
It is carried out using triple level four bars series inductive coupling plasma mass spectrographs (ICP-MS/MS) with crash response pond Measurement, using argon gas as carrier gas, helium, oxygen and ammonia set the measurement parameter of instrument as collision/reaction tank gas, Make online internal standard using 1.0 μ g/mL Cs solution in test process, it is molten to sample solution obtained in third step and sample blank 14 kinds of rare earth ion concentration in liquid are measured, and test result carries software using instrument and draws according in the 5th step Working curve be directly calculated, in sample each element content measuring result be cx1, each element test result in sample blank For cx0, wherein x represents each element；
The instrument parameter of 5th step and the 6th step is arranged with embodiment 1.
Step 7: calculating
The mass fraction of each rare-earth impurity element is in primary sample with ωx(%) is indicated, and is calculated according to following formula:
That is:
Wherein:
M --- sample quality obtained by precise in second step, unit are gram (g)；
V2--- analysis sample solution volume obtained in third step, unit are milliliter (mL)；
V3--- sample blank liquor capacity is made in third step, unit is milliliter (mL)；
cx1--- rare earth metal content in the 6th step Instrumental test gained sample solution, unit is nanograms per milliliter (ng/ mL)；
cx0--- rare earth metal content, unit are nanograms per milliliter (ng/ in test gained sample blank solution in the 6th step mL)；
V0--- sample solution total volume in second step, unit are milliliter (mL)；
V1--- divide in third step and take sample solution volume, unit is milliliter (mL).
Ce elements content ω in primary sample cerium compoundCe(%) are as follows:
Wherein:
∑ωx--- each rare earth metal impurity content summation in sample；
MCe--- Ce elements atomic mass in sample, unit are gram every mole (g/mol)；
Ms--- sample molecule quality, unit are gram every mole (g/mol).
By calculating, various impurity rare earth ion contents are as follows in the present embodiment:
It is computed, the Ce (TMHD)4Ce elements content is 99.999973% in sample.
Although reference be made herein to invention has been described for explanatory embodiment of the invention, however, it is to be understood that ability Field technique personnel can be designed that a lot of other modification and implementations, these modifications and implementations will fall in the application public affairs Within the scope and spirit opened.It more specifically, can be to the group of theme combination layout in range disclosed in the present application A variety of variations and modifications are carried out at component and/or layout.In addition to variations and improvements to the component parts and or layout, To those skilled in the art, other purposes also will be apparent.

Claims (8)

1. the detection method of 14 kinds of trace impurity rare earth ion contents in a kind of ultra-pure cerium compound, 14 kinds of rare earths Metal ion is yttrium, lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, it is characterised in that the following steps are included:
Required solution is detected step 1: preparing
Refer to level-one water as defined in GB/T 6682 (resistivity 18.2M Ω .cm) when water used in this detection method does not explain；
The nitric acid of ρ=1.4g/mL: super trace levels of metal；
5% (V/V) nitric acid solution and 2% (V/V) nitric acid solution: it is prepared in proportion by nitric acid with ultrapure water；
PH=4.0 buffer solution: taking sodium acetate trihydrate 54.4g to dissolve with ultrapure appropriate amount of water, adds 92ml glacial acetic acid, ultrapure water dilution To 1000ml；
2% (m/V) sodium hydroxide solution: accurately weighing 10.0g sodium hydroxide and be transferred to volumetric flask after suitable quantity of water dissolution, ultrapure Water is diluted to 500mL；
Liquor potassic permanganate: concentration is 1.0~10.0g/L, is prepared with potassium permanganate and ultrapure water；
Cyanex272 extractant: two (2,4,4- tri-methyl-amyl) phosphinic acids, concentration is 0.01~0.10mol/L；
0.05mol/L Cyanex272/ cyclohexane solution: accurately weighing two (2,4,4- tri-methyl-amyl) phosphinic acids 14.52g, It is dissolved with hexamethylene, is settled to 1000mL and is made；
The sodium acetate trihydrate, glacial acetic acid, sodium hydroxide, potassium permanganate, two (2,4,4- tri-methyl-amyl) phosphinic acids and hexamethylene Alkane is excellent pure grade；
Step 2: sample pre-treatments
The sample for accurately weighing quality m=0.1000g is added 1.0mL nitric acid (MOS) in PFA counteracting tank, and heating makes sample It is completely dissolved, volumetric flask is transferred to after cooling, deionized water is added and is settled to 50mL (volume V0), sample solution is obtained, together Process makes sample blank solution；
Step 3: sample matrices separate
Accurately pipette 5.0mL (volume V1) on walk obtained sample solution and sample blank solution in quartz beaker, be added 2% (m/V) sodium hydroxide solution adjusts pH value of solution to 3.0~6.0, and solution is transferred in separatory funnel respectively, is sequentially added 20.0mL pH=4.0 buffer solution, the liquor potassic permanganate of 1.0~5.0mL 5.0mg/mL, 5~30mL Cyanex272/ ring Hexane solution shakes 1~10min, discards water layer after standing, and it is water-soluble that 1%~30% (V/V) nitric acid is added into remaining organic phase Liquid 10mL carries out back extraction, separates organic phase after standing, water phase evaporated under reduced pressure to about 2mL is molten with 5% (V/V) nitric acid later Liquid is accurately settled to 10.0mL, sample solution (the volume V after obtaining matrix separation2) and sample blank solution (volume V3), It is to be measured；
Step 4: preparation work curve solution
The multielement rare earth element hybrid standard containing yttrium, lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium is taken to store up Standby liquid (holding national standard reference certificate, provided by State Standard Matter Research Centre), 100mg/L, by the standard reserving solution with 2% (V/V) nitric acid solution dilutes step by step obtains the solution of 3~10 concentration gradients, and concentration gradient is distributed in 0.0~100.0ng/ Working curve solution is made in mL；Cesium element standard reserving solution is taken, 0.01~10.0 μ g/mL is diluted to ultrapure water, it is molten to make internal standard Liquid；
Step 5: drawing working curve
It is surveyed using triple level four bars series inductive coupling plasma mass spectrographs (ICP-MS/MS) with crash response pond Fixed, using argon gas as carrier gas, helium, oxygen and ammonia set the measurement parameter of instrument as collision/reaction tank gas, Middle yttrium, lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium element are measured using oxygen quality transfer mode, terbium Tb Element is measured using ammonia mass transfer mode, makees online internal standard using 1.0 μ g/mL caesium solution in test process, respectively The concentration of 14 kinds of rare earth ions in the working curve solution of various concentration obtained in the 4th step is measured, with each element Multielement rare earth element mixed solution signal strength be ordinate, with multielement rare earth element mixed solution concentration be horizontal seat Mark, carries Software on Drawing using instrument and obtains 14 kinds of rare earth ion concentration and signal strength working curve；
Step 6: 14 kinds of rare earth ion contents in measurement sample solution
It is surveyed using triple level four bars series inductive coupling plasma mass spectrographs (ICP-MS/MS) with crash response pond Fixed, using argon gas as carrier gas, helium, oxygen and ammonia set the measurement parameter of instrument as collision/reaction tank gas, survey Make online internal standard using 1.0 μ g/mL caesium solution during examination, in sample solution obtained in third step and sample blank solution 14 kinds of rare earth ion concentration be measured, test result carries software according to the work drawn in the 5th step using instrument Make curve to be directly calculated, each element content measuring result is c in samplex1, each element test result is in sample blank cx0, wherein x represents each element；
Step 7: calculating
The mass fraction of each rare-earth impurity element is in primary sample with ωxIt indicates, and is calculated according to following formula:
That is:
Wherein:
M --- sample quality obtained by precise in second step, unit are gram (g)；
V2--- analysis sample solution volume obtained in third step, unit are milliliter (mL)；
V3--- sample blank liquor capacity is made in third step, unit is milliliter (mL)；
cx1--- rare earth metal content in the 6th step Instrumental test gained sample solution, unit is nanograms per milliliter (ng/mL)；
cx0--- rare earth metal content, unit are nanograms per milliliter (ng/mL) in test gained sample blank solution in the 6th step；
V0--- sample solution total volume in second step, unit are milliliter (mL)；
V1--- divide in third step and take sample solution volume, unit is milliliter (mL)；
Ce elements content ω in primary sample cerium compoundCeAre as follows:
Wherein:
∑ωx--- each rare earth metal impurity content summation in sample；
MCe--- Ce elements atomic mass in sample, unit are gram every mole (g/mol)；
Ms--- sample molecule quality, unit are gram every mole (g/mol).
2. the detection of 14 kinds of trace impurity rare earth ion contents in ultra-pure cerium compound according to claim 1 Method, it is characterised in that new and effective extractant Cyanex272 is used, by matrix separation method, using with crash response Triple level four bars series inductive coupling plasma mass spectrographs in pond are greater than 99.99999% ultra-pure cerium compound to purity In Trace Rare Earth metal impurities directly detected, be not necessarily to mathematical formulae correction data.
3. the detection of 14 kinds of trace impurity rare earth ion contents in ultra-pure cerium compound according to claim 1 Method, it is characterised in that the concentration that the first step prepares liquor potassic permanganate is 5.0mg/mL.
4. the detection of 14 kinds of trace impurity rare earth ion contents in ultra-pure cerium compound according to claim 1 Method, it is characterised in that the quality of sample described in second step weighs according to the following rules: sample purity 99.999999%~ When between 99.9999%, weighing sample quality is 0.10g, and 0.0001g is accurate to when weighing, and the temperature of heating PFA counteracting tank is 80 DEG C~120 DEG C.
5. the detection of 14 kinds of trace impurity rare earth ion contents in ultra-pure cerium compound according to claim 1 Method, it is characterised in that in third step, adjust the pH=4.0 of solution, liquor potassic permanganate dosage is 2.0mL, when extraction Cyanex272/ cyclohexane solution volume is 20mL, extraction shaking time 2min, aqueous solution of nitric acid body when back extraction and constant volume Product concentration is 5%, and back extraction shakes 1~10min of time.
6. the detection of 14 kinds of trace impurity rare earth ion contents in ultra-pure cerium compound according to claim 1 Method, it is characterised in that in the 4th step, element working curve concentration gradient to be measured be 4, concentration be respectively 0.0ng/mL, 0.1ng/mL, 0.2ng/mL, 0.5ng/mL, online inner mark solution concentration are 1.0 μ g/mL.
7. the detection of 14 kinds of trace impurity rare earth ion contents in ultra-pure cerium compound according to claim 1 Method, it is characterised in that in the 5th step, when being measured using oxygen quality transfer mode, specific apparatus measures parameter are as follows: sweep Mode MS/MS, RF power 1550W are retouched, pond gas is oxygen, oxygen concentration 5~40%, pond 1.0~10.0mL/ of gas flow rate Min, eight grades of bar bias voltage -18V, kinetic energy discriminate against voltage 5V, reaction tank exit potential -60V, deflection lens voltage 10V, and plate is saturating Mirror voltage -80V acquires 3 dot pattern of peak shape, and scanning/number of repetition 100 times, data analysing method is external standard method；It is wherein online interior Mark solution elements are Cs, and online inner mark solution concentration is 0.01~10.0 μ g/mL；It is measured using ammonia mass transfer mode When, specific apparatus measures parameter are as follows: scan pattern MS/MS, RF power 1550W, pond gas are ammonia/helium mix gas, ammonia Gas concentration 5~40% (He balance), pond 0.5~10.0mL/min of gas flow rate, eight grades of bar bias voltage -18V, kinetic energy discriminate against electricity 5V, reaction tank exit potential -60V, deflection lens voltage 10V, plate lens voltage -80V are pressed, 3 dot pattern of peak shape is acquired, scan/ Number of repetition 100 times, data analysing method is external standard method；Wherein online inner mark solution element is Cs, online inner mark solution concentration For 0.01~10.0 μ g/mL.
8. the detection of 14 kinds of trace impurity rare earth ion contents in ultra-pure cerium compound according to claim 7 Method, it is characterised in that in the 6th step, use triple level four bars series inductive coupling plasma mass with crash response pond Instrument is measured rare-earth impurity element content, and specific apparatus measures parameter measures isotope and ion with the 5th step, each element To being respectively as follows: oxygen quality transfer mode: yttrium89Y → 105, lanthanum139La → 155, praseodymium141The neodymium of Pr → 157,144Nd → 160, samarium147Sm → 161, europium151Eu → 167, gadolinium160Gd → 176, dysprosium162Dy → 178, holmium165Ho → 181, erbium166Er → 182, thulium169Tm → 185, ytterbium172Yb → 188, lutetium175Lu→191；Ammonia mass transfer mode: terbium159Tb→175。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111206162A (en) * 2020-02-25 2020-05-29 中国科学院金属研究所 Rare earth metal purification method and purification equipment
CN114836623A (en) * 2021-12-31 2022-08-02 中国工程物理研究院核物理与化学研究所 A kind of 160 Gd、 161 Tb、 161 Dy synchronous separation method

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101781706A (en) * 2009-01-15 2010-07-21 有研稀土新材料股份有限公司 Process for separating rare-earth element by extraction
CN102851501A (en) * 2011-06-27 2013-01-02 信越化学工业株式会社 Method for extracting and separating light rare earth element
WO2013155638A2 (en) * 2012-04-18 2013-10-24 Eth Zurich Reference materials
WO2014000404A1 (en) * 2012-06-28 2014-01-03 荆门市格林美新材料有限公司 Process for recycling rare earths in permanent magnet scrap of electronic waste
CN104515796A (en) * 2013-10-08 2015-04-15 北京有色金属研究总院 Measurement method of trace-amount rare earth impurity element in W-La alloy
CN106153711A (en) * 2016-08-26 2016-11-23 内蒙古包钢钢联股份有限公司 The assay method of rare earth aluminium alloy Rare Earth Element Contents
CN106811598A (en) * 2015-11-30 2017-06-09 北京有色金属研究总院 A kind of low content nickel cobalt biochemical lixivium high-efficient purification process for separating and purifying
CN107385242A (en) * 2017-07-07 2017-11-24 中国科学院过程工程研究所 A kind of system and method for solvent extraction dynamics packet rare-earth separating ion
CN108680564A (en) * 2018-05-18 2018-10-19 中国工程物理研究院化工材料研究所 The detection method of 14 kinds of trace impurity rare earth ion contents in a kind of high-purity cerium compound
CN108693168A (en) * 2018-05-18 2018-10-23 中国工程物理研究院化工材料研究所 The detection method of 14 kinds of trace impurity rare earth metals and the non-rare earth ion content of ten kinds of trace impurities in ultra-pure ytterbium compound

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101781706A (en) * 2009-01-15 2010-07-21 有研稀土新材料股份有限公司 Process for separating rare-earth element by extraction
CN102851501A (en) * 2011-06-27 2013-01-02 信越化学工业株式会社 Method for extracting and separating light rare earth element
WO2013155638A2 (en) * 2012-04-18 2013-10-24 Eth Zurich Reference materials
WO2014000404A1 (en) * 2012-06-28 2014-01-03 荆门市格林美新材料有限公司 Process for recycling rare earths in permanent magnet scrap of electronic waste
CN104515796A (en) * 2013-10-08 2015-04-15 北京有色金属研究总院 Measurement method of trace-amount rare earth impurity element in W-La alloy
CN106811598A (en) * 2015-11-30 2017-06-09 北京有色金属研究总院 A kind of low content nickel cobalt biochemical lixivium high-efficient purification process for separating and purifying
CN106153711A (en) * 2016-08-26 2016-11-23 内蒙古包钢钢联股份有限公司 The assay method of rare earth aluminium alloy Rare Earth Element Contents
CN107385242A (en) * 2017-07-07 2017-11-24 中国科学院过程工程研究所 A kind of system and method for solvent extraction dynamics packet rare-earth separating ion
CN108680564A (en) * 2018-05-18 2018-10-19 中国工程物理研究院化工材料研究所 The detection method of 14 kinds of trace impurity rare earth ion contents in a kind of high-purity cerium compound
CN108693168A (en) * 2018-05-18 2018-10-23 中国工程物理研究院化工材料研究所 The detection method of 14 kinds of trace impurity rare earth metals and the non-rare earth ion content of ten kinds of trace impurities in ultra-pure ytterbium compound

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
吴伟明等: "三重串联电感耦合等离子体质谱法直接测定高纯氧化钕中14种稀土杂质元素", 《分析化学》 *
张瑞华等: "新型萃取剂Cyanex272在萃取分离稀土中的应用", 《江西有色金属》 *
张衍等: "三重串联四极杆等离子体质谱法测定激光光纤用超高纯铈螯合物中痕量金属杂质离子", 《分析测试学报》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111206162A (en) * 2020-02-25 2020-05-29 中国科学院金属研究所 Rare earth metal purification method and purification equipment
CN114836623A (en) * 2021-12-31 2022-08-02 中国工程物理研究院核物理与化学研究所 A kind of 160 Gd、 161 Tb、 161 Dy synchronous separation method
CN114836623B (en) * 2021-12-31 2023-06-09 中国工程物理研究院核物理与化学研究所 The method comprises the following steps of 160 Gd、 161 Tb、 161 Dy synchronous separation method

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Application publication date: 20190723