CN117169196A - Method for measuring calcium fluoride in dolomite-containing ore - Google Patents
Method for measuring calcium fluoride in dolomite-containing ore Download PDFInfo
- Publication number
- CN117169196A CN117169196A CN202311143583.9A CN202311143583A CN117169196A CN 117169196 A CN117169196 A CN 117169196A CN 202311143583 A CN202311143583 A CN 202311143583A CN 117169196 A CN117169196 A CN 117169196A
- Authority
- CN
- China
- Prior art keywords
- calcium fluoride
- calcium
- acid
- sample
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 title claims abstract description 88
- 229910001634 calcium fluoride Inorganic materials 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000010459 dolomite Substances 0.000 title claims abstract description 32
- 229910000514 dolomite Inorganic materials 0.000 title claims abstract description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000001514 detection method Methods 0.000 claims abstract description 40
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 35
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 32
- 238000004448 titration Methods 0.000 claims abstract description 31
- 238000005259 measurement Methods 0.000 claims abstract description 24
- 239000011575 calcium Substances 0.000 claims abstract description 23
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 claims abstract description 20
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 19
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 16
- 238000004458 analytical method Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 15
- 238000004090 dissolution Methods 0.000 claims description 15
- 239000007790 solid phase Substances 0.000 claims description 13
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004327 boric acid Substances 0.000 claims description 9
- 230000029087 digestion Effects 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- 230000003595 spectral effect Effects 0.000 claims description 5
- 238000003556 assay Methods 0.000 claims 1
- 238000000691 measurement method Methods 0.000 claims 1
- 229960000583 acetic acid Drugs 0.000 abstract description 20
- 239000012362 glacial acetic acid Substances 0.000 abstract description 10
- 238000012360 testing method Methods 0.000 abstract description 9
- 238000010998 test method Methods 0.000 abstract description 3
- IXAIKEKMZXIEKF-UHFFFAOYSA-N S(O)(O)(=O)=O.Cl.B(O)(O)O Chemical compound S(O)(O)(=O)=O.Cl.B(O)(O)O IXAIKEKMZXIEKF-UHFFFAOYSA-N 0.000 abstract description 2
- 238000002203 pretreatment Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 45
- 239000000523 sample Substances 0.000 description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000010436 fluorite Substances 0.000 description 17
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 14
- 239000000292 calcium oxide Substances 0.000 description 14
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 14
- 239000012086 standard solution Substances 0.000 description 14
- 235000011054 acetic acid Nutrition 0.000 description 12
- 239000000395 magnesium oxide Substances 0.000 description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 12
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 239000000706 filtrate Substances 0.000 description 9
- 238000010561 standard procedure Methods 0.000 description 9
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000012490 blank solution Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- UOFRJXGVFHUJER-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;hydrate Chemical compound [OH-].OCC[NH+](CCO)CCO UOFRJXGVFHUJER-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- DEGAKNSWVGKMLS-UHFFFAOYSA-N calcein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC(CN(CC(O)=O)CC(O)=O)=C(O)C=C1OC1=C2C=C(CN(CC(O)=O)CC(=O)O)C(O)=C1 DEGAKNSWVGKMLS-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 229960002378 oftasceine Drugs 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000007781 pre-processing Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 150000001243 acetic acids Chemical class 0.000 description 2
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 235000014380 magnesium carbonate Nutrition 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 208000001490 Dengue Diseases 0.000 description 1
- 206010012310 Dengue fever Diseases 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 208000025729 dengue disease Diseases 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 239000010437 gem Substances 0.000 description 1
- 229910001751 gemstone Inorganic materials 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention belongs to the technical field of calcium fluoride detection, and relates to a method for measuring calcium fluoride in dolomite-containing ores. The invention adopts a calcium-containing glacial acetic acid solution to separate calcium carbonate, and after residues are dissolved by boric acid-hydrochloric acid-sulfuric acid, ICP-AES is used for measurement, and then EDTA titration method is used for secondary analysis of samples with calcium fluoride results higher than 15 wt%. The pretreatment method is simple and quick, saves cost, and improves the test accuracy by combining the two test methods.
Description
Technical Field
The invention belongs to the technical field of calcium fluoride detection, and relates to a method for measuring calcium fluoride in dolomite-containing ores.
Background
The fluorite comprises calcium fluoride (CaF) 2 ) The calcium fluoride crystal is colorless and transparent originally, and is easy to be filled by other ions due to the cavity existing in the crystal structure of fluorite. This structural defect also makes fluorite the most colorful stone, and because of the iron, magnesium, copper and other ions, the green, purple, yellow, blue, brown, orange and powder … … fluorite can almost take on any color, so many people refer to fluorite as rainbow precious stone. Dolomite is a double salt composed of calcium carbonate and magnesium carbonate, where 50% of the Ca is located in a structural position that is exactly occupied by Mg. When fluorite and dolomite are coexistent, the calcium-magnesium double salt in the dolomite is difficult to separate and remove by dilute acetic acid as pure calcium carbonate, so that part of calcium carbonate is left in the residue. Therefore, the measurement result is higher than the actual content of calcium fluoride by adopting the current national standard method GB/T5195.1-2017.
Disclosure of Invention
In view of the above, the invention provides a method for determining calcium fluoride in dolomite-containing ores, and the method provided by the invention can accurately determine the content of calcium fluoride in dolomite-containing samples.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for determining calcium fluoride in dolomite-containing ores, which comprises the following steps of:
dissolving dolomite in a sample to be detected by using a calcium-containing acetic acid solution, and then carrying out solid-liquid separation to obtain a solid phase;
mixing the solid phase with the mixed acid, and carrying out digestion to obtain a liquid to be tested; the mixed acid comprises hydrochloric acid, boric acid and sulfuric acid;
performing ICP-AES detection on the liquid to be detected to obtain an initial detection result of the mass content of calcium fluoride in the sample to be detected;
if the initial measurement result is that the mass content of the calcium fluoride is more than 15%, re-measuring the liquid to be measured by adopting an EDTA titration method to obtain a re-measurement result of the mass content of the calcium fluoride in the sample to be measured, and taking the re-measurement result as a final detection result;
and if the initial detection result is that the mass content of the calcium fluoride is less than or equal to 15%, taking the initial detection result as a final detection result.
Preferably, the concentration of calcium carbonate in the calcium-containing acetic acid solution is 4-6 mg/L.
Preferably, the concentration of hydrochloric acid in the mixed acid is 295g/L; the mass concentration of boric acid of the mixed acid is 12.5g/L.
Preferably, the volume concentration of sulfuric acid in the mixed acid is 46g/L.
Preferably, the mass of the solid phase and the volume ratio of the mixed acid is 1g:100mL.
Preferably, the digestion is carried out at a temperature of 150℃for a period of 30 minutes.
Preferably, the temperature of dissolution is 100 ℃ and the time is 40min.
Preferably, the conditions for the ICP-AES method include: the analysis spectral line is Ca 317.933nm; the radio frequency emission power is 1.15KW; sample rinse time was 30s; the gas flow rate of the atomizer is 0.7L.min -1 。
The invention provides a method for determining calcium fluoride in dolomite-containing ores, which comprises the following steps of: dissolving dolomite in a sample to be detected by using a calcium-containing acetic acid solution, and then carrying out solid-liquid separation to obtain a solid phase; mixing the solid phase with the mixed acid, and carrying out digestion to obtain a liquid to be tested; the mixed acid comprises hydrochloric acid, boric acid and sulfuric acid; performing ICP-AES detection on the liquid to be detected to obtain an initial detection result of the mass content of calcium fluoride in the sample to be detected; if the initial measurement result is that the mass content of the calcium fluoride is more than 15%, re-measuring the liquid to be measured by adopting an EDTA titration method to obtain a re-measurement result of the mass content of the calcium fluoride in the sample to be measured, and taking the re-measurement result as a final detection result; and if the initial detection result is that the mass content of the calcium fluoride is less than or equal to 15%, taking the initial detection result as a final detection result.
The method adopts the calcium-containing glacial acetic acid solution to separate the calcium carbonate, and the pretreatment method is simple and quick after the residue is dissolved by boric acid-hydrochloric acid-sulfuric acid, so that the cost is saved; then, the ICP-AES is used for measuring, a low-content sample (the calcium fluoride detection result is less than or equal to 15 wt%) is screened, the titration error of the low-content sample is avoided, and then, the EDTA titration method is used for secondary analysis of a high-content sample (the calcium fluoride detection result is higher than 15 wt%) and has higher accuracy compared with the ICP-AES method. Therefore, the combination of the two test methods improves the test accuracy.
Drawings
FIG. 1 shows the dissolution of calcium fluoride in example 4;
FIG. 2 shows the dissolution of calcium oxide and magnesium oxide in example 4.
Detailed Description
The invention provides a method for determining calcium fluoride in dolomite-containing ores, which comprises the following steps of:
dissolving dolomite in a sample to be detected by using a calcium-containing acetic acid solution, and then carrying out solid-liquid separation to obtain a solid phase;
mixing the solid phase with the mixed acid, and carrying out digestion to obtain a liquid to be tested; the mixed acid comprises hydrochloric acid, boric acid and sulfuric acid;
performing ICP-AES detection on the liquid to be detected to obtain an initial detection result of the mass content of calcium fluoride in the sample to be detected;
if the initial measurement result is that the mass content of the calcium fluoride is more than 15%, re-measuring the liquid to be measured by adopting an EDTA titration method to obtain a re-measurement result of the mass content of the calcium fluoride in the sample to be measured, and taking the re-measurement result as a final detection result; and if the initial detection result is that the mass content of the calcium fluoride is less than or equal to 15%, taking the initial detection result as a final detection result.
In the present invention, unless otherwise specified, the reagents used are commercially available products well known to those skilled in the art.
According to the method, the dolomite in the sample to be detected is dissolved by using the calcium-containing acetic acid solution, and then solid-liquid separation is carried out to obtain a solid phase.
In the present invention, the concentration of calcium carbonate in the calcium-containing acetic acid solution is preferably 4 to 6mg/L, more preferably 5mg/L. In the present invention, the calcium-containing acetic acid solution is preferably obtained by mixing calcium carbonate and glacial acetic acid.
In the invention, the dolomite is preferably a calcium-magnesium double salt, specifically calcium oxide and magnesium oxide.
In the present invention, the temperature of the dissolution is preferably 100℃and the time is preferably 40 minutes.
After a solid phase is obtained, the solid phase and the mixed acid are mixed and digested to obtain a liquid to be measured; and detecting the liquid to be detected by an ICP-AES method to obtain an initial detection result of the mass content of the calcium fluoride in the sample to be detected.
In the invention, the concentration of hydrochloric acid in the mixed acid is 295g/L; the mass concentration of boric acid of the mixed acid is 12.5g/L; the concentration of sulfuric acid in the mixed acid is preferably 46g/L.
In the present invention, the temperature of the digestion is preferably 150 ℃; the time is preferably 30 minutes.
In the present invention, after the digestion, the method preferably further comprises the step of fixing the volume of the system obtained by digestion. In embodiments of the present invention, a constant volume of up to 100mL is preferred.
After the liquid to be detected is obtained, the liquid to be detected is detected by an ICP-AES method, and the mass content of the calcium fluoride in the sample to be detected is obtained.
In the present invention, the analytical line detected by the ICP-AES method is preferably Ca 317.933nm.
In the present invention, the conditions for the ICP-AES method are shown in Table 1.
TABLE 1 conditions for ICP-AES detection
| Instrument operating parameters | Setting value | Instrument operating parameters | Setting value |
| Radio frequency transmit power/KW | 1.15 | Auxiliary air flow (L.min) -1 ) | 0.5 |
| Sample lift pump speed/rpm | 75 | Flushing pump speed/rpm | 75 |
| Atomizer gas flow (L.min) -1 ) | 0.7 | Atomizer gas pressure/MPa | 0.2 |
| Cooling air flow (L.min) -1 ) | 15 | Sample rinse time/s | 30 |
| Integration time (long wave)/s | 5 | Reading time/s | 20 |
If the initial measurement result is that the mass content of the calcium fluoride is more than 15%, re-measuring the liquid to be measured by adopting an EDTA titration method to obtain a re-measurement result of the mass content of the calcium fluoride in the sample to be measured, and taking the re-measurement result as a final detection result;
and if the initial detection result is that the mass content of the calcium fluoride is less than or equal to 15%, taking the initial detection result as a final detection result.
In the invention, the testing method of the EDTA titration method comprises the following steps:
transferring the solution to be measured into a 150mL conical flask, adding water to 50mL, adding 2 drops of 5g/L magnesium sulfate solution, 5mL triethanolamine water solution (the volume ratio of triethanolamine to water is 1:2), a small amount of hydroxylamine hydrochloride, 10mL 200g/L potassium hydroxide solution and a proper amount of calcein indicator, and titrating the solution with EDTA standard until fluorescence green disappears, wherein the solution takes pure purple as an end point. 3 parts of the calibration are calibrated in parallel, the difference between the calibration volumes cannot exceed 0.10mL, otherwise, the calibration is carried out again. The mass of calcium fluoride is calculated according to formula (1).
In the formula (1): w is the content of calcium fluoride in the sample,%;
t is 1mL of EDTA standard titration solution, which is equivalent to the mass of calcium fluoride, mg/mL;
V 4 the volume of EDTA standard titration solution is consumed for titrating the sample, and the volume is mL;
V 3 sample volume, mL;
V 01 the volume of EDTA standard titration solution is consumed for titrating blank solution, and mL is obtained;
m is the sample amount, g.
The method for obtaining T preferably includes the steps of:
10.0mL of a 1.0000mg/mL calcium fluoride standard solution is removed into a 150mL conical flask, water is added to 50mL, 2 drops of 5g/L magnesium sulfate solution, 5mL of triethanolamine water solution (the volume ratio of the triethanolamine to the water is 1:2), a small amount of hydroxylamine hydrochloride, 10mL of 200g/L potassium hydroxide solution and a proper amount of calcein indicator are added, and EDTA standard titration solution is used until fluorescence green disappears, and the solution takes pure purple as an end point. 3 parts of the calibration are calibrated in parallel, the difference between the calibration volumes cannot exceed 0.10mL, otherwise, the calibration is carried out again. The 1mL EDTA standard solution calculated according to formula (2) corresponds to the mass of calcium fluoride.
Wherein: t is 1mL of EDTA standard titration solution, which is equivalent to the mass of calcium fluoride, mg/mL;
ρ is the mass concentration of the standard solution of calcium fluoride, 1.0000mg/mL;
v is the volume of the standard solution of the sucked calcium fluoride, 10.0mL;
V 1 the average volume of EDTA standard titration solution is consumed for titrating the calcium fluoride standard solution, and the volume is mL; v (V) 0 To titrate the blank solution, the volume of EDTA standard titration solution, mL, was consumed.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
The inductively coupled plasma emission spectrometer in the embodiment of the invention is an iCAP6300 inductively coupled plasma emission spectrometer provided by Siemens' Feier science and technology company in U.S.A.;
the intelligent electric heating plate is provided for Tianjin Zhuiming experimental instrument technology development limited company;
the water for experiments is secondary water prepared by an ion exchange method, and the resistivity is not less than 18.2MΩ & cm.
Example 1
1.1 reagent Material
Calcium-containing acetic acid: 5g of calcium carbonate is weighed into a 500mL beaker, 200mL (1+9) glacial acetic acid is added, the mixture is heated and boiled, cooled and transferred into a 1000mL volumetric flask, and the volume is fixed to a scale by the (1+9) glacial acetic acid.
Mixed acid: weighing 25g boric acid in a 400mL beaker, adding about 200mL water, slowly adding 50mL concentrated sulfuric acid, continuously stirring, and slightly cooling; transferring into a reagent bottle which is pre-filled with 500mL of concentrated hydrochloric acid and 1000mL of water, stirring continuously until boric acid is completely dissolved and cooled to room temperature; diluting to 2L with water, and storing in polyethylene reagent bucket for use.
Standard calcium fluoride solution (1.0000 mg/mL): weighing 1.2819g of high-purity calcium carbonate (omega > 99.99%) dried at 120 ℃ for 2 hours, placing the high-purity calcium carbonate in a 400mL beaker, adding a little water for wetting, covering a watch glass, slowly adding 40mL of hydrochloric acid aqueous solution (the volume ratio of concentrated hydrochloric acid to water is 1:1) along a beaker mouth, boiling for 2 minutes to drive out carbon dioxide after complete dissolution, taking down, flushing the watch glass and the beaker wall, cooling to room temperature, transferring the cooled high-purity calcium carbonate into a 1000mL volumetric flask, diluting to a scale with water, and shaking uniformly to obtain the calcium carbonate;
EDTA standard titration solution: 9.3g of disodium ethylenediamine tetraacetate is weighed into a 1000mL beaker, 400mL of water is added, the mixture is dissolved slightly by heating and transferred into a 5000mL lower mouth bottle, water is added to 5L, and the mixture is uniformly shaken to obtain EDTA standard titration solution with the concentration of 0.005 mol/L.
1.2 sample pretreatment
Accurately weighing 0.2000g of a sample in a 50mL conical flask, adding 10mL of calcium-containing acetic acid solution, shaking the sample, placing a phi 40mm funnel at a bottleneck, heating for 40min at 100 ℃ on a temperature-controlled electric hot plate, taking down and purging the funnel, filtering with slow quantitative filter paper, washing the conical flask and residues for 4 times, putting the filter paper and residues back into the original conical flask, adding 20mL of mixed acid, placing the phi 40mm funnel at the bottleneck, boiling and keeping micro-boiling for 30min on the temperature-controlled electric hot plate, taking down and cooling, purging the funnel, transferring the solution into a 100mL colorimetric tube, fixing the volume to a scale, shaking the colorimetric tube uniformly, and placing the colorimetric tube for clarification to obtain the liquid to be measured.
1.3 test
(1) The conditions for the ICP-AES method are shown in Table 1.
(2) Test method of EDTA titration:
transferring the solution to be measured into a 150mL conical flask, adding water to 50mL, adding 2 drops of 5g/L magnesium sulfate solution, 5mL triethanolamine water solution (the volume ratio of triethanolamine to water is 1:2), a small amount of hydroxylamine hydrochloride, 10mL 200g/L potassium hydroxide solution and a proper amount of calcein indicator, and titrating the solution with EDTA standard until fluorescence green disappears, wherein the solution takes pure purple as an end point. 3 parts of the calibration are calibrated in parallel, the difference between the calibration volumes cannot exceed 0.10mL, otherwise, the calibration is carried out again. The mass of calcium fluoride is calculated according to formula (1).
In the formula (1): w is the content of calcium fluoride in the sample,%;
t is 1mL of EDTA standard titration solution, which is equivalent to the mass of calcium fluoride, mg/mL;
V 4 the volume of EDTA standard titration solution is consumed for titrating the sample, and the volume is mL;
V 3 sample volume, mL;
V 01 the volume of EDTA standard titration solution is consumed for titrating blank solution, and mL is obtained;
m is the sample amount, g.
Acquisition of T: 10.0mL of a 1.0000mg/mL calcium fluoride standard solution is removed into a 150mL conical flask, water is added to 50mL, 2 drops of 5g/L magnesium sulfate solution, 5mL of triethanolamine water solution (the volume ratio of the triethanolamine to the water is 1:2), a small amount of hydroxylamine hydrochloride, 10mL of 200g/L potassium hydroxide solution and a proper amount of calcein indicator are added, and EDTA standard titration solution is used until fluorescence green disappears, and the solution takes pure purple as an end point. 3 parts of the calibration are calibrated in parallel, the difference between the calibration volumes cannot exceed 0.10mL, otherwise, the calibration is carried out again.
The 1mL EDTA standard solution calculated according to formula (2) corresponds to the mass of calcium fluoride.
Wherein: t is 1mL of EDTA standard titration solution, which is equivalent to the mass of calcium fluoride, mg/mL;
ρ is the mass concentration of the standard solution of calcium fluoride, 1.0000mg/mL;
v is the volume of the standard solution of the sucked calcium fluoride, 10.0mL;
V 1 EDTA standard for titrating calcium fluoride standard solution consumptionTitrating the average volume of the solution, mL;
V 0 to titrate the blank solution, the volume of EDTA standard titration solution, mL, was consumed.
Example 2
Examining the influence of Ca and Mg in ore on detection when fluorite and different ores coexist
The conditions when fluorite coexists with different ores were determined according to the national standard method (GB/T5195.1-2017) and the industry standard method (DZG 93-05):
experiment 1, limestone standard GBW07214a (wca0= 55.34%, wMg 0=0.29%); 2. dolomite standard GBW07217a (wca0=32.11%, wMg 0= 20.37%); 3. silicate standard GBW07364 (wca0=16.4%, wMg 0=1.94%); 4. copper ore standard GBW07233 (wca0=9.61%, wMg 0=3.91%); 5. magnesite standard GBW07867 (wca0=2.51%, wMg 0=43.64%) was mixed with two fluorite standards YSB14791-02 (wCaF) 2 =59.99%) and GBW07253 (wCaF 2 =85.21%) at 4:1, and the results are shown in Table 2 according to the national standard method (GB/T5195.1-2017) and the industry standard method (DZG 93-05).
TABLE 2 determination results when fluorite coexists with different ores
As can be seen from table 2, when fluorite and other ores coexist, the calcium and magnesium in the ores have no obvious influence on the measurement result, the result is reliable, and the measurement result of the national standard method is superior to the industry standard.
Example 2
Investigation of calcium dissolution in dolomite and fluorite by glacial acetic acid of different concentrations
4 parts of fluorite standard substance GBW07250 and dolomite standard substance GBW07217a (wca0=32.11%, wMg 0= 20.37%) are weighed, and four glacial acetic acids with different concentrations of 1+9, 2+8, 3+7 and 4+6 are respectively added into the mixture, the mixture is heated on a temperature-controlled electric plate at 100 ℃ for 5min, filtered, and a 100mL volumetric flask is used for receiving filtrate, wherein the measurement results of calcium oxide and magnesium oxide in the filtrate are shown in Table 3.
TABLE 3 determination of calcium oxide and magnesium oxide in the filtrate at different acidity
As can be seen from Table 3, when the glacial acetic acid concentration is 1+9, the calcium loss in the fluorite standard substance is minimum, the solubility of the calcium oxide in the dolomite standard substance is highest, the dissolution rate is 85.77%, the dissolution rate of the magnesium oxide is 82.62%, but 4% -5% of the calcium oxide still remains in the residue at this time, so that the analysis result is high.
Example 3
Examining the dissolution conditions of calcium oxide and magnesium oxide in the filtrate at different heating times
4 parts of fluorite standard substance GBW07250 and dolomite standard substance GBW07217a (wca0=32.11%, wMg 0= 20.37%) are weighed, and four glacial acetic acids with different concentrations of 1+9, 2+8, 3+7 and 4+6 are respectively added into the mixture, and the mixture is heated on a temperature-controlled electric plate at 100 ℃ for different times, taken down, filtered and the filtrate is received, wherein the measurement results are shown in Table 4.
TABLE 4 determination of calcium oxide and magnesium oxide in different dissolution time filtrates
As can be seen from Table 4, the solubility of calcium oxide and magnesium oxide in dolomite increases with time, and when the time reaches 40min, the dissolution rate of calcium oxide and magnesium oxide in dolomite reaches 99.5% or more, and the residue is substantially free of residue.
Example 4
After treatment of calcium-containing glacial acetic acid with different concentrations, the dissolution conditions of calcium oxide and magnesium oxide in the filtrate are examined
Weighing 5 parts of fluorite standard substance GBW07250 and dolomite standard substance GBW07217a respectively, adding 10mL of glacial acetic acid (1+9) with different calcium contents respectively, heating on a temperature-controlled electric plate at 100 ℃ for 40min, filtering, and receiving filtrate, wherein the dissolution condition of calcium fluoride in the filtrate is shown in figure 1; the results of the dissolution of calcium oxide and magnesium oxide are shown in FIG. 2.
As can be seen from FIGS. 1-2, when the calcium carbonate concentration in glacial acetic acid is greater than 4mg/L, the solubility change of calcium fluoride is not obvious, and at this time, the solubility of calcium oxide and magnesium oxide in dolomite is not obvious, so that the experimental selection of the calcium carbonate concentration is 5mg/L.
Example 5
Investigation of test interference conditions of different analysis spectral lines
The 100. Mu.g/mL calcium oxide standard solution and reagent blank solution were measured, inductively coupled plasma mass spectrometry was performed according to the parameters set in Table 1, peak patterns of spectral lines at different wavelengths were observed, and each analysis spectral line and interference condition selected are shown in Table 5. In combination with Table 5, and considering that the EDTA titration method was selected again to determine the calcium fluoride content of 15% or more, 317.933{106} nm, which is high in sensitivity, was selected as the analysis line in this experiment.
TABLE 5 analysis lines and interference conditions
Example 6
Determination of detection and quantification limits:
at ρ (CaF) 2 ) Standard solution of 1.0000mg/mL is used as mother solution, and the mother solution is diluted step by step into standard solution series with the mass concentration of calcium fluoride of 0, 2.0, 20.0, 100, 200 and 500 mug/mL respectively, and hydrochloric acid (10+90, V/V) medium.
The standard solution series was measured under the working conditions set in table 1, and a calcium fluoride calibration curve was drawn with the mass concentration of calcium fluoride as the cross-beam coordinate and the emission intensity as the ordinate. The linear equation is y=796.96x+2846.5, the correlation coefficient is 0.9998, meanwhile, the blank sample is continuously measured for 11 times, the detection limit of the method is calculated to be 0.063% by 3 times of standard deviation, the quantitative limit is calculated to be 0.25% by 4 times of detection limit, and the detection limit of the method is far lower than the detection limit of national standard GB/T5195.1-2017 and industry standard DZG 93-05, so that the quantitative limit is reduced.
Example 7
The sample to be tested is a sample which is sent by the Harjaden mining area and is symbiotic with dolomite, and the particle size is 0.074mm.
Mixing a sample to be tested with fluorite standard substances YSB14791-02, GBW07253 and GBW07250 with different weights, and preprocessing according to 1.2 sample pretreatment to obtain a liquid to be tested;
the liquid to be tested is detected by ICP-AES method according to the conditions of table 1, the liquid to be tested with the mass concentration of calcium fluoride higher than 15% is screened out, then the liquid to be tested is measured again by EDTA titration method, and the measurement result is shown in table 6.
TABLE 6 precision and labeling recovery test results
Test II
Determining critical values of ICP-AES method and EDTA titration method:
selecting a sample (lithology is an ore with dolomite coexistence) sent from a Ha Yake dengue area and 3 national first-grade standard substances, and preprocessing according to 1.2 sample preprocessing to obtain a liquid to be detected; the test solutions were tested according to the "1.3 test" respectively, and the results are shown in Table 7.
Table 7 comparison of results of measurement of calcium fluoride
As can be seen from table 7: when the result of calcium fluoride is lower than 20%, there is no obvious difference between ICP-AES and EDTA titration, but when the result is higher than 60%, EDTA titration is significantly better than ICP-AES. The boundary grade of calcium fluoride is 15%, so that when the measurement result of ICP-AES is more than 15% for safety, the EDTA titration method is adopted for re-analysis, and the accuracy of the result is ensured.
Test three
5 actual samples are selected for experiment, and are respectively measured by national standard GB/T5195.1-2017, industry standard DZG 93-05 and the method, and comparison results are shown in Table 8:
table 8 results comparison and summary
As can be seen from the comparison data, when the sample contains dolomite, the national standard method has a result which is obviously higher than the theoretical value, the line standard method is similar to the result of the method, but the line standard method has a result which is obviously lower than the theoretical value when the standard sample with higher content is measured, and the method can accurately measure the sample containing dolomite and the national standard substance, so that the result is satisfactory.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. A method for determining calcium fluoride in dolomite-containing ores, comprising the steps of:
dissolving dolomite in a sample to be detected by using a calcium-containing acetic acid solution, and then carrying out solid-liquid separation to obtain a solid phase;
mixing the solid phase with the mixed acid, and carrying out digestion to obtain a liquid to be tested; the mixed acid comprises hydrochloric acid, boric acid and sulfuric acid;
performing ICP-AES detection on the liquid to be detected to obtain an initial detection result of the mass content of calcium fluoride in the sample to be detected;
if the initial measurement result is that the mass content of the calcium fluoride is more than 15%, re-measuring the liquid to be measured by adopting an EDTA titration method to obtain a re-measurement result of the mass content of the calcium fluoride in the sample to be measured, and taking the re-measurement result as a final detection result;
and if the initial detection result is that the mass content of the calcium fluoride is less than or equal to 15%, taking the initial detection result as a final detection result.
2. The method according to claim 1, wherein the concentration of calcium carbonate in the calcium-containing acetic acid solution is 4 to 6mg/L.
3. The method according to claim 1, wherein the concentration of hydrochloric acid in the mixed acid is 295g/L; the mass concentration of boric acid of the mixed acid is 12.5g/L.
4. The method according to claim 1, wherein the concentration of sulfuric acid in the mixed acid is 46g/L.
5. The method according to claim 1 or 4, wherein the ratio of the mass of the solid phase to the volume of the mixed acid is 1g:100mL.
6. The assay of claim 1, wherein the digestion is carried out at a temperature of 150 ℃ for a period of 30 minutes.
7. The method according to claim 1, wherein the dissolution temperature is 100 ℃ and the time is 40min.
8. The measurement method according to claim 1, wherein the conditions for the ICP-AES method include: the analysis spectral line is Ca 317.933nm; the radio frequency emission power is 1.15KW; sample rinse time was 30s; the gas flow rate of the atomizer is 0.7L.min -1 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311143583.9A CN117169196A (en) | 2023-09-06 | 2023-09-06 | Method for measuring calcium fluoride in dolomite-containing ore |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311143583.9A CN117169196A (en) | 2023-09-06 | 2023-09-06 | Method for measuring calcium fluoride in dolomite-containing ore |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117169196A true CN117169196A (en) | 2023-12-05 |
Family
ID=88935016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311143583.9A Pending CN117169196A (en) | 2023-09-06 | 2023-09-06 | Method for measuring calcium fluoride in dolomite-containing ore |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117169196A (en) |
-
2023
- 2023-09-06 CN CN202311143583.9A patent/CN117169196A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8796032B2 (en) | Method for analyzing and detecting calcium element in ore | |
| CN102621090B (en) | Method for measuring iron content in kaolin through using spectrophotometer | |
| CN103115920A (en) | Method for measuring iron/calcium ratio in iron-calcium core-spun yarn | |
| CN108872203A (en) | The detection method of elemental composition in a kind of vanadium chromium slag and its digestion procedure and a kind of measurement vanadium chromium slag | |
| CN109916882B (en) | Method for measuring contents of niobium, silicon and phosphorus in niobium-manganese-iron | |
| CN113504191A (en) | Method for measuring content of trace iron and aluminum in nickel-based solution | |
| CN117169196A (en) | Method for measuring calcium fluoride in dolomite-containing ore | |
| CN108037088A (en) | The accurate measuring method of titanium carbide in carbide slag | |
| CN111650194A (en) | Method for determining phosphorus content in iron ore by bismuth-phosphorus-molybdenum blue | |
| CN110672577A (en) | Method for measuring selenium content in rice | |
| CN111220598A (en) | Method for rapidly measuring content of titanium dioxide in ilmenite | |
| CN115032327A (en) | Method for determining content of nickel, cobalt and manganese in positive electrode material | |
| CN108872106A (en) | A kind of method of trace sulphite in measurement water body | |
| CN103940944A (en) | Method for detecting content of calcium oxide in limestone by using DBC (Dibromochloro)-arsenazo indicator | |
| CN105067605A (en) | Method for continuously determining calcium content and iron content in limestone powder | |
| CN110514644B (en) | ICP-AES rapid determination of MnO in metal manganese powder2Method (2) | |
| CN110763672A (en) | Method for measuring total sulfur in soil or water system sediment | |
| CN116482091A (en) | Method for accurately measuring content of calcium carbonate in dolomite-containing fluorite | |
| CN109612980A (en) | Silicon, manganese, method for measuring phosphor content in reduced iron powder in a kind of iron-calcium core-spun yarn | |
| CN110530852B (en) | Method for analyzing barite by mixed flux decomposition inductively coupled plasma spectrometer | |
| CN112444554B (en) | Method for determining trace elements in oil sample | |
| CN109425609B (en) | Color plate for quantitatively determining humic acid and preparation method and application thereof | |
| CN113933288A (en) | Method for detecting contents of silicon and calcium elements in silicon-calcium alloy by utilizing ICP (inductively coupled plasma) | |
| CN112161970A (en) | Method for determining total phosphorus content in water | |
| CN115684136A (en) | Method for measuring content of calcium oxide in samarium oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |