CN116287788B - Method for efficiently separating high-purity W from geological sample - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000000523 sample Substances 0.000 claims abstract description 53
- 239000011347 resin Substances 0.000 claims abstract description 47
- 229920005989 resin Polymers 0.000 claims abstract description 47
- 238000000926 separation method Methods 0.000 claims abstract description 32
- 239000012488 sample solution Substances 0.000 claims abstract description 15
- GPGMRSSBVJNWRA-UHFFFAOYSA-N hydrochloride hydrofluoride Chemical compound F.Cl GPGMRSSBVJNWRA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000011068 loading method Methods 0.000 claims abstract description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 52
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 15
- 238000002386 leaching Methods 0.000 claims description 10
- 230000029087 digestion Effects 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 7
- 239000012498 ultrapure water Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000007781 pre-processing Methods 0.000 claims description 3
- XWROUVVQGRRRMF-UHFFFAOYSA-N F.O[N+]([O-])=O Chemical compound F.O[N+]([O-])=O XWROUVVQGRRRMF-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- QWARLPGIFZKIQW-UHFFFAOYSA-N hydrogen peroxide;nitric acid Chemical compound OO.O[N+]([O-])=O QWARLPGIFZKIQW-UHFFFAOYSA-N 0.000 claims description 2
- YLYIXDZITBMCIW-UHFFFAOYSA-N n-hydroxy-n-phenylbenzamide Chemical compound C=1C=CC=CC=1N(O)C(=O)C1=CC=CC=C1 YLYIXDZITBMCIW-UHFFFAOYSA-N 0.000 description 25
- 229910052721 tungsten Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000000100 multiple collector inductively coupled plasma mass spectrometry Methods 0.000 description 7
- 230000002452 interceptive effect Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000011435 rock Substances 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- VRZYWIAVUGQHKB-UHFFFAOYSA-N 2-[2-(dioctylamino)-2-oxoethoxy]-n,n-dioctylacetamide Chemical compound CCCCCCCCN(CCCCCCCC)C(=O)COCC(=O)N(CCCCCCCC)CCCCCCCC VRZYWIAVUGQHKB-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003957 anion exchange resin Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 101100328463 Mus musculus Cmya5 gene Proteins 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000011097 chromatography purification Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000000155 isotopic effect Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000000918 plasma mass spectrometry Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000000176 thermal ionisation mass spectrometry Methods 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 238000013055 trapped ion mobility spectrometry Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention relates to isotope astrochemistry (isoppe cosmo-chemistry), isotope geochemistry (isotope geochemistry) and isotope geology, and provides a method for efficiently separating high-purity W from a geological sample, which comprises the following steps: s1, dissolving a sample in a hydrochloric acid-hydrofluoric acid medium to obtain a sample solution; s2, loading the sample solution into a BPHA resin-loaded exchange column, and separating W; for 1-2g samples, the BPHA resin was used in an amount of 1mL. Through the technical scheme, the problem of low separation efficiency of separating W in the prior art is solved.
Description
Technical Field
The present invention relates to isotope astrochemistry (isotope cosmo-chemistry), isotope geochemistry (isotope geochemistry) and isotope geology, and in particular, to a method for efficiently separating high purity W from geologic samples.
Background
The formation of the planet nuclei can be limited by using the high-precision W isotope for studying the formation and early evolution of the earth, moon, etc. High-precision W isotope analysis first requires separation of high purity W from a geological sample and then measurement using multi-receiver plasma mass spectrometry (MC-ICP-MS) or negative ion thermionic mass spectrometry (NTIMS).
In order to obtain W of high purity, the existing W separation method generally employs 2 or more cation exchange or (/ and) anion exchange resin methods (e.g., documents 1, 2). Multiple passes over the column not only consume large amounts of acid solution, which is time consuming and laborious, but also results in reduced recovery (< 90%) and high risk of contamination.
In addition to the interfering elements Mo, ta, hf and Zr, analytical separation of Ti and W is particularly necessary as it may prevent accurate measurement of isotopes. In particular, ti inhibits ionization of W in the NTIMS method. In order to improve the purity of W, some special types of resins have also been applied to the separation step, such as TEVA resin (document 3), TODGA resin (document 4). There is still a need to eliminate a large number of matrix elements in combination with cationic resins.
For low W content samples, such as basalt, a larger sample size (> 1 g) is typically required in order to obtain a sufficient amount of W for testing. Because of the limitation of the bearing capacity of the resin column, the samples are often required to be separated into 2-4 parts and then combined, so that the workload and the risk are doubled.
The method for rapidly separating the high-purity W from the geological sample (patent number ZL 202010460136.6) can realize the separation of the high-purity W from the geological sample with larger sample quantity, reduce the problem of repeated column passing in the prior art, but the method needs to adopt resin and large leaching liquid volume, can cause the waste of reagents and has lower W extraction efficiency.
Document 1: touboul m.and Walker r.j. (2012) High precision tungsten isotope measurement by thermalionization Mass spectrum, int.j. Mass spectrum.309, 109-117.
Document 2: peters b.j., mundl-peter a., horan m.f., carlson r.w., and Walker r.j. (2019) ChemicalSeparation of Tungsten and Other Trace Elements for TIMS Isotope Ratio Measurements Using Organic acids geotand. Geoanal. Res.43,245-259.
Document 3: mei q.f., yang j.h. and Yang y.h. (2018) An improved extraction chromatographicpurification of tungsten from a silicate matrix for high precision isotopic measurements using MC-icpms.j. anal At. spectrum, 33, 569-577.
Document 4: zhu-Yin Chu, jun-Jie Xu, chao-Feng Li, yue-Heng Yang, and jin-Hui guo AChromatographic Method for Separation of Tungsten (W) from Silicate Samples for High-Precision Isotope Analysis Using Negative Thermal Ionization massspectrum, animal, chem 2020, 92, 11987-11993.
Disclosure of Invention
The invention provides a method for efficiently separating high-purity W from a geological sample, which solves the problem of low separation efficiency of separating W in the prior art.
The technical scheme of the invention is as follows:
a method for efficiently separating high purity W from a geological sample, comprising the steps of:
s1, dissolving a sample in a hydrochloric acid-hydrofluoric acid medium to obtain a sample solution;
s2, loading the sample solution into a BPHA resin-loaded exchange column, and separating W;
the BPHA resin was used in an amount of 1mL relative to 1-2g of sample.
As a further technical scheme, before dissolving the sample in the hydrochloric acid-hydrofluoric acid medium, the method further comprises the steps of digesting the sample: dissolving a sample by using a nitric acid-hydrofluoric acid mixed solution, and then sequentially digesting the sample by using the nitric acid-hydrogen peroxide mixed solution, hydrochloric acid and the hydrofluoric acid-hydrochloric acid mixed solution to obtain a mixture.
As a further technical scheme, after digestion, the mixture obtained by digestion is dissolved in 3mol/L hydrochloric acid-0.1 mol/L hydrofluoric acid medium to obtain a sample solution.
As a further technical scheme, the sample is digested twice by using a mixed solution of nitric acid and hydrogen peroxide, is digested twice by using hydrochloric acid, and is digested once by using a mixed solution of hydrofluoric acid and hydrochloric acid.
As a further technical scheme, for 1-2g of sample, digestion is specifically:
s01, dissolving a sample by using 5mL 15mol/L nitric acid and 15mL 22mol/L hydrofluoric acid;
s02, adding 10mL of 15mol/L nitric acid and 0.5mL of 30% hydrogen peroxide solution with volume concentration for digestion twice;
s03, adopting 10mL of 6mol/L hydrochloric acid to digest twice;
s04, digestion is carried out by adopting 3mL of 1mol/L hydrofluoric acid and 3mL of 6mol/L hydrochloric acid.
As a further technical scheme, for 1-2g of sample, the mixture obtained by digestion is added with 0.2mL of 1mol/L hydrofluoric acid, 1mL of 6mol/L hydrochloric acid and 0.8mL of ultrapure water for dissolution, so as to obtain a sample solution.
As a further technical scheme, the exchange column is Bio-rad Bio-Spin ® A chromatographic column.
As a further technical scheme, the BPHA resin is prepared by soaking DOW AMBERCHROM CG resin in 5wt% of ethanol solution of N-benzoyl-N-phenylhydroxylamine (BPHA) in an oscillating way.
As a further technical solution, the S2 includes:
s21, preprocessing a column loaded with BPHA resin;
s22, loading the sample solution on a column;
s23, adding hydrochloric acid-hydrofluoric acid for leaching, and leaching out the interference elements;
s24, eluting by adopting hydrofluoric acid to obtain W receiving liquid.
As a further technical solution, the preprocessing in S21 is as follows: the exchange column loaded with the BPHA resin is pre-cleaned by ultrapure water, and is cleaned again by 1mol/L hydrochloric acid-6 mol/L hydrofluoric acid, and the exchange column is balanced by 3mol/L hydrochloric acid-0.1 mol/L hydrofluoric acid.
As a further technical scheme, for 1-2g of the sample, 1mL of 3mol/L hydrochloric acid-0.1 mol/L hydrofluoric acid is adopted for leaching for 4 times in S23, and the interference element is leached out.
As a further technical scheme, for 1-2g of the sample, the solution is eluted 5 times by 1mL of 1mol/L hydrofluoric acid in S24 to obtain W receiving solution.
As a further technical solution, after the S24 eluting, the method further includes: drying the W receiving solution and adding H 2 O 2 Digestion is carried out at 120 ℃ to obtain high-purity W.
The working principle and the beneficial effects of the invention are as follows:
1. according to the invention, the BPHA resin column is adopted for W separation for the first time, for 1-2g geological samples, W separation can be efficiently completed by only 1mL of BPHA resin, and high-purity W can be rapidly separated from geological samples with larger sample quantity by only one resin column. Compared with the prior art, the method realizes the separation of Ti-W, ta-W, has good separation effect, and can also realize the thorough removal of Zr-Hf.
2. Compared with the existing anion or anion exchange resin separation method or TEVA resin and TODGA resin methods, the method for separating W has the characteristics of good W separation effect, high separation speed and low separation background. By adopting the existing method, the matrix elements are required to be separated by an anion column or a cation column, then the separation of W and Ti, zr, ta and the like is further realized by an anion column or TEVA resin or TODGA resin, and before the W with high purity is obtained, the resin column is required to be leached by more than 100mL of inorganic acid or organic acid and is required to be separated by the resin column for 2-3 times.
3. According to the invention, elements such as 3mol/L HCl-0.1mol/L HF medium, fe, mg, la, ti, hf, zr and the like are very weak in retention on the BPHA resin column, and W is relatively strong in retention, so that after a sample solution is loaded on the column, only 4mL of 3mol/L HCl-0.1mol/L HF is required to be used for eluting elements interfering with a test, and the W is still retained on the resin column. Subsequently, with higher concentrations of HF to form complexes with W, >98% of W can be eluted with 6ml 1mol/L HF, while Ta is not eluted, thus achieving effective separation of W from the matrix element and the mass spectrometry interfering elements. The separation method provided by the invention has the advantages of small resin amount, small acid amount, high separation speed, high efficiency and easiness in purification.
4. The method can realize the separation of high-purity W through the resin column once, and then adopts NTIMS or MC-ICP-MS to carry out ultra-high precision W isotope analysis, thereby being particularly suitable for W isotope analysis of basalt samples.
Drawings
The invention will be described in further detail with reference to the drawings and the detailed description.
FIG. 1 is a graph showing the flow-out curve of W obtained in example 1 of the present invention;
FIG. 2 is a graph showing the W flow-out curve obtained in comparative example 1 of the present invention;
FIG. 3 is a W flow-out curve obtained in comparative example 2 of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Basalt international rock standard USGS BHVO-2W isotope analysis (determination of W isotope using MC-ICP-MS).
Using 2g BHVO-2 samples, the isotope analysis procedure is as follows:
s1, dissolving a sample:
s01, taking 2g of rock powder sample, and dissolving the rock powder sample by using 5mL of 15mol/L nitric acid and 15mL of 22mol/L hydrofluoric acid;
s02, adding 10mL of 15mol/L nitric acid and 0.5mL of 30% (V/V) hydrogen peroxide solution to digest twice;
s03, adopting 10mL of 6mol/L hydrochloric acid to digest twice;
s04, digesting with 3mL of 1mol/L hydrofluoric acid and 3mL of 6mol/L hydrochloric acid;
s11, 0.2mL of 1mol/L hydrofluoric acid, 1mL of 6mol/L hydrochloric acid and 0.8mL of ultrapure water were added for dissolution, to obtain a sample solution dissolved in 3mol/L hydrochloric acid-0.1 mol/L hydrofluoric acid medium.
S2, separating the BPHA resin column into W:
BPHA resin column: 1mL of AMBERCHROM CG71 resin produced by DOW corporation in the United states was immersed in an ethanol solution of 6% N-benzoyl-N-phenylhydroxylamine (BPHA) and shaken for 2 hours to prepare a BPHA resin, and 1mL of the BPHA resin was packed in a Bio-Spin chromatography column having an inner diameter of 0.8cm produced by Bio-Rad corporation in the United states;
s21, pre-cleaning for 2 times by adopting 1mL of ultrapure water, and pre-cleaning for 4 times by adopting 1mL of 1mol/L of hydrochloric acid-6 mol/L of hydrofluoric acid; 1mL of 3mol/L hydrochloric acid-0.1 mol/L hydrofluoric acid balance exchange column for 4 times;
s22, loading a sample solution dissolved in 3mol/L hydrochloric acid-0.1 mol/L hydrofluoric acid medium on a column;
s23, adding 1mL of 3mol/L hydrochloric acid-0.1 mol/L hydrofluoric acid, leaching for 4 times, and leaching out Fe, ca, mg, al, K, na, cr, ba, ti, zr, hf, os, pb and other interference elements;
s24, eluting with 1mL of 1mol/L hydrofluoric acid for 5 times to obtain W receiving solution;
TABLE 1 flow of BPHA resin column separation W
The principle of the invention for efficiently separating high-purity W from a geological sample is as follows:
FIG. 1 is a graph showing the W flow-out curve (color image, see substantial examination reference) obtained by processing a geological sample according to the method, wherein on a BPHA resin column, under the condition of 3mol/L HCl-0.1mol/L HF medium, fe, ca, mg, al, K, na, cr, ba, ti, zr, hf and other interference elements exist in a cationic form, the column is basically not arranged, and W, ta element forms chelate with BPHA, and the column is reserved; therefore, after loading and 4 times of 1mL of 3mol/L HCl-0.1mol/L HF leaching of the exchange column, fe, ca, mg, al, K, na, cr, ba, ti, zr, hf and other interference elements are basically eluted completely by 100%, W, ta is not eluted, then 5mL of 1mol/L HF is adopted to leach the resin column, W can be basically eluted completely, and Ta is still reserved on the resin column, so that separation of W, sample interference elements and Ta is realized.
S3, MC-ICP-MS determination of W isotope
The obtained W receiving solution was evaporated to dryness and then 0.02mL of H was added 2 O 2 And (3) digesting the organic matters for 2 times at 120 ℃ to obtain a sample to be detected, and then carrying out high-precision W isotope analysis on the MC-ICP-MS or NTIMS.
The instrument used was a Neptune Plus multi-receiver inductively coupled plasma mass spectrum produced by Thermo-fisher company, usa. The measurement method is described in reference to document 3, and comprises the following steps:
adding proper amount of 1mol/L HF and 15mol/L HNO into the sample 3 And diluted to 10mL of 0.5mol/L HNO with ultrapure water 3 -0.2mol/L HF. The cup structure used for mass spectrometry is shown in Table 2. The Integration time (Integration time) was measured to be 8s, and the skip waiting time (Idletime) was measured to be 3s. Each sample collects 200-600 sets (Cycles) of data. To be used for 186 W/ 184 W= 0.92767 or 186 W/ 183 W= 1.9859 isotope fractionation correction calculation was performed using an exponential correction method. The test is performed using the method of standard-sample crossover (standard sample bracketing, SSB), i.e. measuring the standard sample NIST3163 before and after the measurement of the unknown sample, respectively. The ratio of the samples is expressed as
ε 182/184 W=（ 182/184 W sample / 182/184 W NIST3163 -1) 10000, wherein 182/184 W NIST3163 Is the average of the two samples, NIST3163, before and after the sample.
TABLE 2 MC-ICP-MS determination of W isotope cup Structure
Accuracy and repeatability of determination results of BHVO-2W isotope
The results of the W isotope test for basalt standard USGS BHVO-2 are shown in Table 3, ε 182/184 W= -0.12±0.07 (2sd, n=4), consistent with the results reported in documents 2, 3, 4 within the error range.
TABLE 3W isotope test results for basalt standard sample USGS BHVO-2
Wherein n is the number of samples
Example 2
Compared with example 1, the experiment was performed using 1g of the same rock sample, and the test results were not much different from those of example 1, and will not be described in detail here.
Comparative example 1
The difference from example 1 is that the flow of separation of W by BPHA resin column is different, and the specific procedure is shown in Table 4.
TABLE 4 BPHA resin column separation flow Process for W
Comparative example 2
The difference from example 1 is that the flow of separation of W by BPHA resin column is different, and the specific procedure is shown in Table 5.
TABLE 5 BPHA resin column separation flow Process for W
FIGS. 2 and 3 are the W flow-out curves obtained in comparative examples 1 and 2, respectively (color drawings see substantial examination reference), and it can be seen from FIGS. 2 and 3 that changing the concentration of HF when eluting the interfering elements causes Ti, zr, hf to be adsorbed on the resin column, and then when 1mol/L HF is further used, these elements are eluted together with W and cannot be effectively separated, and that comparative examples 1 and 2 cannot achieve better separation of W from other elements than in example 1.
Comparative example 3
The difference from example 1 is that the flow of the separation W of the BPHA resin column is different, and the specific procedure is shown in table 6.
TABLE 6 BPHA resin column separation flow Process for W
In comparative example 3, the concentration of HF was increased when the interfering element was eluted, and W eluted together with the interfering element, and separation of W from other elements was not achieved.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (7)
1. A method for efficiently separating high purity W from a geological sample, comprising the steps of:
s1, dissolving a sample in a hydrochloric acid-hydrofluoric acid medium to obtain a sample solution;
s2, loading the sample solution into a BPHA resin-loaded exchange column, and separating W;
the step S2 comprises the following steps:
s21, preprocessing a column loaded with BPHA resin;
s22, loading the sample solution on a column;
s23, adding hydrochloric acid-hydrofluoric acid for leaching, and leaching out the interference elements;
s24, eluting with hydrofluoric acid to obtain W receiving solution;
for 1-2g of sample, the dosage of the BPHA resin is 1mL, and 1mL of 3mol/L hydrochloric acid-0.1 mol/L hydrofluoric acid is adopted for leaching for 4 times in S23, so that the interference element is leached out.
2. The method of claim 1, wherein prior to dissolving the sample in the hydrochloric acid-hydrofluoric acid medium, further comprising digesting the sample: dissolving a sample by using a nitric acid-hydrofluoric acid mixed solution, and then sequentially digesting the sample by using the nitric acid-hydrogen peroxide mixed solution, hydrochloric acid and the hydrofluoric acid-hydrochloric acid mixed solution to obtain a mixture.
3. The method for efficiently separating high-purity W from a geological sample according to claim 2, wherein after digestion, the digested mixture is dissolved in 3mol/L hydrochloric acid-0.1 mol/L hydrofluoric acid medium to obtain a sample solution.
4. The method for efficiently separating high-purity W from a geological sample according to claim 3, wherein for 1-2g of the sample, 0.2mL of 1mol/L hydrofluoric acid, 1mL of 6mol/L hydrochloric acid and 0.8mL of ultrapure water are added to the digested mixture for dissolution to obtain a sample solution.
5. The method for efficient separation of high purity W from geologic samples according to claim 1, wherein the pretreatment in S21 is: the exchange column loaded with the BPHA resin is pre-cleaned by ultrapure water, and is cleaned again by 1mol/L hydrochloric acid-6 mol/L hydrofluoric acid, and the exchange column is balanced by 3mol/L hydrochloric acid-0.1 mol/L hydrofluoric acid.
6. The method for efficiently separating high-purity W from a geological sample according to claim 1, wherein for 1-2g of the sample, the W-receiving solution is obtained by eluting 5 times with 1mL of 1mol/L hydrofluoric acid in S24.
7. The method for efficiently separating high purity W from a geologic sample according to claim 1, further comprising, after said S24 eluting: drying the W receiving solution and adding H 2 O 2 Digestion is carried out at 120 ℃ to obtain high-purity W.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2003222619A (en) * | 2001-07-16 | 2003-08-08 | Mitsui Mining & Smelting Co Ltd | Method and apparatus for analyzing impurity in tantalum-based material, and tantalum oxide powder |
| CN103357389A (en) * | 2013-07-03 | 2013-10-23 | 中国科学院广州地球化学研究所 | BPHA levextrel resin and method for separating and enriching molybdenum in environmental and geological samples by using same |
| CN111610247A (en) * | 2020-05-27 | 2020-09-01 | 中国科学院地质与地球物理研究所 | Method for quickly separating high-purity W from geological sample |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2003222619A (en) * | 2001-07-16 | 2003-08-08 | Mitsui Mining & Smelting Co Ltd | Method and apparatus for analyzing impurity in tantalum-based material, and tantalum oxide powder |
| CN103357389A (en) * | 2013-07-03 | 2013-10-23 | 中国科学院广州地球化学研究所 | BPHA levextrel resin and method for separating and enriching molybdenum in environmental and geological samples by using same |
| CN111610247A (en) * | 2020-05-27 | 2020-09-01 | 中国科学院地质与地球物理研究所 | Method for quickly separating high-purity W from geological sample |
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