CN114371166A - Detection method for measuring different valence state iron of niobium-containing metallurgical slag system in hydrochloric acid-based solution - Google Patents
Detection method for measuring different valence state iron of niobium-containing metallurgical slag system in hydrochloric acid-based solution Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000002893 slag Substances 0.000 title claims abstract description 76
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000010955 niobium Substances 0.000 title claims abstract description 53
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052758 niobium Inorganic materials 0.000 title claims abstract description 51
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 34
- 238000001514 detection method Methods 0.000 title claims abstract description 11
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 32
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims abstract description 32
- 235000003270 potassium fluoride Nutrition 0.000 claims abstract description 16
- 239000011698 potassium fluoride Substances 0.000 claims abstract description 16
- 238000004448 titration Methods 0.000 claims abstract description 15
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 10
- 239000001119 stannous chloride Substances 0.000 claims abstract description 10
- 235000011150 stannous chloride Nutrition 0.000 claims abstract description 10
- DGXTZMPQSMIFEC-UHFFFAOYSA-M sodium;4-anilinobenzenesulfonate Chemical compound [Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=CC=C1 DGXTZMPQSMIFEC-UHFFFAOYSA-M 0.000 claims abstract description 9
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 146
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000002253 acid Substances 0.000 claims description 15
- 239000012086 standard solution Substances 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 239000000523 sample Substances 0.000 claims description 2
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 6
- 238000004458 analytical method Methods 0.000 abstract description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 9
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 6
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 6
- 235000010703 Modiola caroliniana Nutrition 0.000 description 6
- 244000038561 Modiola caroliniana Species 0.000 description 6
- 238000009835 boiling Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- JSABTPDNEXHNOQ-UHFFFAOYSA-N n-phenylaniline;sodium Chemical compound [Na].C=1C=CC=CC=1NC1=CC=CC=C1 JSABTPDNEXHNOQ-UHFFFAOYSA-N 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005485 electric heating Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007705 chemical test Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- -1 iron ion Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- XMXNVYPJWBTAHN-UHFFFAOYSA-N potassium chromate Chemical compound [K+].[K+].[O-][Cr]([O-])(=O)=O XMXNVYPJWBTAHN-UHFFFAOYSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
- G01N21/79—Photometric titration
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
- G01N31/162—Determining the equivalent point by means of a discontinuity
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Molecular Biology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention belongs to the technical field of metallurgical analysis, and provides a detection method for measuring different valence state iron of niobium-containing metallurgical slag system in hydrochloric acid-based solution. Aiming at a difficult-to-dissolve niobium-containing metallurgical slag system, the invention selects concentrated hydrochloric acid and potassium fluoride to heat and dissolve a sample, reduces ferric iron in slag by stannous chloride and titanium trichloride under an acidic condition, takes sodium diphenylamine sulfonate as an indicator, and can respectively detect total iron and ferrous iron in slag by titration by adopting potassium dichromate. The method can be used for niobium-containing metallurgical slag systems, so that the accurate determination of the iron content in the difficult-to-dissolve niobium-containing metallurgical slag systems can be realized; and the required reagent has low cost, high safety, thorough dissolving of slag samples, high analysis speed and accurate result.
Description
Technical Field
The invention relates to the technical field of metallurgical analysis, in particular to a detection method for measuring different valence state iron of niobium-containing metallurgical slag system in hydrochloric acid-based solution.
Background
The mineral resources in the inner Mongolia Baiyunebo mining area are rich, and the storage amount of the niobium element is the first in China. In the comprehensive utilization and production process of niobium resources, a large amount of niobium-containing metallurgical slag system is generated. Data such as components, physicochemical properties and the like of valuable elements in a niobium-containing metallurgical slag system need to be mastered aiming at deep separation and reduction of the valuable elements in the niobium-containing metallurgical slag system, so that a precise detection method for iron with different valence states in the niobium-containing metallurgical slag system becomes a focus of attention. The determination and the definition of different valence states and contents of iron in the niobium-containing metallurgical slag system have important guiding significance for the comprehensive utilization of niobium resources.
There are many methods for detecting the iron content in iron ore that have been disclosed so far, and potassium dichromate titration, EDTA photometric titration, titanium trichloride titration, and the like are known (CN112179899A/2021, CN110426391A/2019, CN 113049738A/2021). However, no complex detection method for niobium-containing metallurgical slag systems is reported at present.
The main principle for the determination of iron in the slag in different valence states is well known, based on the strong oxidizing properties of potassium dichromate, and on Fe2+Oxidation-reduction reaction takes place until Fe is in solution2+Is completely oxidized and the titration endpoint is determined according to the indicator color reaction. The currently common method for dissolving iron ore is as follows: various acids were mixed for the purpose of dissolution, including mixed sulfuric and phosphoric acid (CN107340359A/2017), mixed sulfuric and phosphoric acid + perchloric acid (CN112179899A/2021), hydrochloric acid + potassium fluoride solution (CN 111257500A/2020). However, the dissolution process of niobium-containing metallurgical slag systems is a great problem due to the corrosion resistance of niobium-containing compounds, and the inaccurate dissolution of slag samples can lead to inaccurate iron content measurement in the process.
Disclosure of Invention
The invention aims to solve the problem of dissolving the niobium-containing metallurgical slag system, can accurately measure the contents of iron with different valence states in the niobium-containing metallurgical slag system, and provides a feasible way for separating and recovering beneficial metal elements; meanwhile, the defect that iron is easily oxidized in the ferrous content determination process can be overcome, and the oxidation process of ferrous ions is effectively inhibited by adding a reagent.
The general technical scheme of the invention is as follows: a detection method for measuring different valence state iron of niobium-containing metallurgical slag system in hydrochloric acid-based solution comprises the following steps;
the first step is as follows: the niobium-containing metallurgical slag sample and potassium fluoride are mixed according to the mass ratio of 1: 10, dissolving the mixture in a hydrochloric acid solution with the mass concentration of 37%, and heating the solution at the temperature of 100 ℃ until a slag sample is completely dissolved to form a solution A;
niobium-containing metallurgical slag sample, potassium fluoride and hydrogen carbonate according to the mass ratio of 1: 10: 10, dissolving the mixture in a hydrochloric acid solution with the mass concentration of 37%, immediately covering the hydrochloric acid solution, and heating the hydrochloric acid solution at the temperature of 100 ℃ until a slag sample is completely dissolved to form a solution B;
in the solution A and the solution B, 20ml of hydrochloric acid solution corresponds to every 1g of potassium fluoride;
the second step is that: dropwise adding a stannous chloride solution into the solution A, and stirring until the solution is reduced to be light yellow to form a solution C; respectively adding water to dilute the solution C and the solution B, and cooling to room temperature; respectively obtaining a diluted solution C and a diluted solution B; the ratio of the volume of added water to the volume of each of solution C and solution B was 4: 1.
the third step: dropwise adding a sodium tungstate solution into the diluted solution C, wherein the volume ratio of the sodium tungstate solution to the diluted solution C is 1: 250 of (a); dropwise adding a titanium trichloride solution, wherein the solution is changed from colorless to blue and does not fade within 20 s; continuously dripping copper sulfate solution, and continuously shaking the conical flask in the process until the tungsten blue completely fades to form solution D; respectively dripping sodium diphenylamine sulfonate into the solution D and the diluted solution B, wherein the volume ratio of the sodium diphenylamine sulfonate to the volume ratio of the solution D to the diluted solution B is 1: 200 of a carrier; respectively adding mixed acid to obtain a solution E and a solution F; the volume ratio of the mixed acid to the volume of each of the solution D and the diluted solution B was 1: 10.
the seventh step: titrating the solution E and the solution F respectively by using a potassium dichromate standard solution until stable purple red appears, recording the volume V of potassium dichromate consumed in the titration process of the two solutions of the solution F and the solution G after the titration is finished1And V2；
The content of T.Fe in the niobium-containing metallurgical slag sample is as follows:
the content of FeO in the niobium-containing metallurgical slag sample is as follows:
fe in niobium-containing metallurgical slag sample2O3The content of (A) is as follows:
in the formula, C is the concentration of a potassium dichromate standard solution, moL/L; v1Consuming a volume of potassium dichromate mL for solution F; v2Consuming a volume of potassium dichromate mL for solution G; (ii) a MFe、MFeO、MFeO1.5Are Fe, FeO and FeO respectively1.5Relative molecular mass of (a); m is the mass of the dissolved slag sample, g.
The mass ratio of the niobium-containing metallurgical slag samples forming the solution A and the solution B is 1: 1.
The mixed acid is formed by mixing a sulfuric acid solution with the mass concentration of 98% and a phosphoric acid solution with the mass concentration of 85% in a volume ratio of 1: 1.
Preparing reagents used in the above process:
(1) the preparation method of the sulfur-phosphorus mixed acid comprises the following steps: slowly injecting 150mL of sulfuric acid into 700mL of water under stirring, cooling, adding 150mL of phosphoric acid, and uniformly mixing;
(2) the preparation method of the stannous chloride solution comprises the following steps: weighing 6g of stannous chloride, dissolving the stannous chloride in 20mL of hot concentrated hydrochloric acid, adding water to dilute the stannous chloride to 100mL, and uniformly mixing;
(3) the preparation method of the sodium tungstate solution comprises the following steps: weighing 25g of sodium tungstate, dissolving in a proper amount of water, adding 5mL of phosphoric acid, diluting with water to 100mL, and uniformly mixing;
(4) the preparation method of the titanium trichloride solution comprises the following steps: taking 10mL of titanium trichloride solution with the mass concentration of 15% -20%, adding 22.5mL of concentrated hydrochloric acid, adding water to dilute to 100mL, and uniformly mixing;
(5) the preparation method of the copper sulfate solution comprises the following steps: weighing 0.5g of copper sulfate, dissolving in water, continuously adding water to dilute to 100mL, and uniformly mixing;
(6) the preparation method of the diphenylamine sodium sulfonate comprises the following steps: weighing 0.2g of sodium diphenylamine sulfonate reagent, dissolving in water, continuously adding water to dilute to 100mL, and uniformly mixing;
(7) the preparation method of the potassium dichromate standard solution C is 0.008338 mol/L: 2.4515g of potassium dichromate which is previously dried at 150 ℃ for 1h are weighed and dissolved in water, transferred into a 1000mL volumetric flask, diluted to the scale with water and mixed uniformly.
The invention has the beneficial effects that: compared with other acid dissolution methods, the method has the advantages of low reagent cost, high safety, thorough dissolving of slag samples and accurate analysis result; compared with the alkali fusion method, the method has the advantages of simple operation process, less types of used chemical reagents and higher analysis speed. The method for detecting and analyzing the iron with different valence states can be used for niobium-containing metallurgical slag systems, so that the accurate determination of the iron content in the niobium-containing metallurgical slag systems which are difficult to dissolve can be realized.
Detailed Description
Example 1
The niobium-containing metallurgical slag system is prepared from the components of the bayan obo tailings and is CaO-SiO2-Nb2O5-TiO2-FeO basic slag system, and determining the content of iron element with different valence states in the slag sample, the specific steps are as follows:
weighing 0.1g of the niobium-containing metallurgical slag sample, accurately weighing the niobium-containing metallurgical slag sample to 0.0001g, adding 1g of potassium fluoride into a conical flask, and continuously adding 20mL of hydrochloric acid to heat on an electric heating plate for 15min, wherein the solution is in a boiling state. And (3) dropwise adding a stannous chloride solution while the solution is hot until the solution is reduced to light yellow, washing the bottle neck and the bottle wall with a small amount of water, adding water to dilute the solution to 100mL, and cooling the solution to room temperature in a water bath kettle. 8 drops of sodium tungstate solution are added, and each drop is 0.05 mL; dropwise adding a titanium trichloride solution until the solution turns blue, continuously adding copper sulfate, and continuously shaking the conical flask in the dropwise adding process until the tungsten blue completely fades. Continuously adding 10 drops of sodium diphenylamine sulfonate into the solution, wherein each drop is 0.05 mL; 10mL of sulfur-phosphorus mixed acid is titrated by potassium dichromate standard solution, and the volume V of consumed potassium dichromate is recorded when stable mauve appears as the titration end point1The T.Fe in the slag is measured.
Weighing 0.1g of slag sample into a conical flask, adding 1g of potassium fluoride and 1g of sodium bicarbonate, continuously adding 20mL of hydrochloric acid, rapidly placing a porcelain crucible at the bottle mouth, and generating CO in the process2The gas can exhaust the air in the bottle completely, the bottle is placed on a heating plate and heated for 15min until the sample is completely dissolved, the bottle is taken down, the bottle opening and the bottle wall are cleaned by a small amount of water and diluted until the volume of the solution is 100mL, and the solution is cooled to the room temperature by a water bath kettle after being sealed by a rubber plug. Taking down the rubber plug, and adding 10 drops of sodium diphenylamine sulfonate, wherein each drop is 0.05 mL; 10mL of sulfur-phosphorus mixed acid is titrated by potassium dichromate standard solution, and the consumed heavy metal is recorded when stable mauve appears as the titration end pointVolume V of potassium chromate2Is Fe in slag2+The measurement of (1).
T.Fe and Fe in the sample were calculated as follows2+、Fe3+The content of (A):
content of t.fe in slag:
FeO content in slag:
fe in slag2O3The content is as follows:
in the formula, C is the concentration of the standard potassium dichromate solution, moL/L;
V1、V2respectively, the volume of potassium dichromate consumed is mL;
MFe、MFeO、MFeO1,5are Fe, FeO and FeO respectively1.5Relative molecular mass of (a);
m is the mass of the dissolved slag sample, g.
Example 2
The niobium-containing metallurgical slag system is prepared from the components of the bayan obo tailings and is CaO-SiO2-Nb2O5-TiO2-FeO basic slag system, and determining the content of iron element with different valence states in the slag sample, the specific steps are as follows:
weighing 0.15g of the niobium-containing metallurgical slag sample, accurately placing the niobium-containing metallurgical slag sample into a conical flask until the weight of the niobium-containing metallurgical slag sample is 0.0001g, adding 1.5g of potassium fluoride, and continuously adding 30mL of hydrochloric acid to heat on an electric heating plate for 15min, wherein the solution is in a boiling state. And (3) dropwise adding a stannous chloride solution while the solution is hot until the solution is reduced to light yellow, washing the bottle neck and the bottle wall with a small amount of water, adding water to dilute the solution to 150mL, and cooling the solution to room temperature in a water bath kettle. 0.6ml of sodium tungstate solution is added dropwise,dropwise adding a titanium trichloride solution until the solution turns blue, continuously adding copper sulfate, and continuously shaking the conical flask in the dropwise adding process until the tungsten blue completely fades. Then continuously adding 0.75mL of diphenylamine sodium sulfonate and 15mL of sulfur-phosphorus mixed acid into the solution, then titrating by using a potassium dichromate standard solution, and recording the volume V of the consumed potassium dichromate when stable mauve appears as a titration end point1The T.Fe in the slag is measured.
Weighing 0.15g of slag sample into a conical flask, adding 1.5g of potassium fluoride and 1.5g of sodium bicarbonate, continuously adding 30mL of hydrochloric acid, rapidly placing a porcelain crucible at the bottle mouth, and generating CO in the process2The gas can exhaust the air in the bottle completely, the bottle is placed on a heating plate and heated for 15min until the sample is completely dissolved, the bottle is taken down, the bottle opening and the bottle wall are cleaned by a small amount of water and diluted until the volume of the solution is 100mL, and the solution is cooled to the room temperature by a water bath kettle after being sealed by a rubber plug. Taking down the rubber plug, adding 0.75mL of diphenylamine sodium sulfonate and 15mL of sulfur-phosphorus mixed acid, titrating by using a potassium dichromate standard solution, and recording the volume V of consumed potassium dichromate when stable mauve appears as a titration end point2Is Fe in slag2+The measurement of (1).
Example 3
Preparing a standard iron ion solution containing a small amount of chromium and nickel metal elements, and detecting the content of the iron elements:
1mL of the standard solution was put in a conical flask, 1g of potassium fluoride was added, and 20mL of hydrochloric acid was further added and heated on an electric heating plate for 15min, at which time the solution was in a boiling state. And (3) dropwise adding a stannous chloride solution while the solution is hot until the solution is reduced to light yellow, washing the bottle neck and the bottle wall with a small amount of water, adding water to dilute the solution to 100mL, and cooling the solution to room temperature in a water bath kettle. 8 drops of sodium tungstate solution are added, and each drop is 0.05 mL; dropwise adding a titanium trichloride solution until the solution turns blue, continuously adding copper sulfate, and continuously shaking the conical flask in the dropwise adding process until the tungsten blue completely fades. Continuously adding 10 drops of sodium diphenylamine sulfonate into the solution, wherein each drop is 0.05 mL; 10mL of sulfur-phosphorus mixed acid is titrated by potassium dichromate standard solution, and the volume V of consumed potassium dichromate is recorded when stable mauve appears as the titration end point1The T.Fe in the slag is measured.
And (3) putting another 1mL of standard solution into a conical flask, adding 1g of potassium fluoride and 1g of sodium bicarbonate, continuously adding 20mL of hydrochloric acid, quickly placing a porcelain crucible at the bottle mouth, placing the porcelain crucible on a heating plate, heating for 15min till boiling, taking down, cleaning the bottle wall of the bottle mouth with a small amount of water, diluting until the volume of the solution is 100mL, sealing with a rubber plug, and cooling to room temperature by using a water bath kettle. Taking down the rubber plug, and adding 10 drops of diphenylamine sodium sulfonate indicator, wherein each drop is 0.05 mL; 10mL of sulfur-phosphorus mixed acid is titrated by potassium dichromate standard solution, and the volume V of consumed potassium dichromate is recorded when stable mauve appears as a titration end point2Is Fe in slag2+The measurement of (1).
The comparison of the sample detection result and the chemical detection result in the invention is shown in Table 1, the detection errors of the contents of iron with different valence states are less than 0.5 percent, and the method can be used for accurately measuring the iron with different valence states in the niobium-containing metallurgical slag system.
TABLE 1 comparison of the results of the experiments of the present invention with those of the chemical tests
Claims (10)
1. A detection method for measuring different valence state iron of niobium-containing metallurgical slag system in hydrochloric acid-based solution is characterized by comprising the following steps;
the first step is as follows: mixing a niobium-containing metallurgical slag sample and potassium fluoride, dissolving the mixture in a hydrochloric acid solution with the mass concentration of 37%, and heating the mixture at the temperature of 100 ℃ until the slag sample is completely dissolved to form a solution A;
mixing a niobium-containing metallurgical slag sample, potassium fluoride and hydrogen carbonate, dissolving the mixture in a hydrochloric acid solution with the mass concentration of 37%, immediately covering the hydrochloric acid solution, and heating the hydrochloric acid solution until the slag sample is completely dissolved to form a solution B;
in the solution A and the solution B, 20ml of hydrochloric acid solution corresponds to every 1g of potassium fluoride;
the second step is that: dropwise adding a stannous chloride solution into the solution A, and stirring until the solution is reduced to be light yellow to form a solution C; respectively adding water to dilute the solution C and the solution B, and cooling to room temperature; respectively obtaining a diluted solution C and a diluted solution B;
the third step: dropwise adding a sodium tungstate solution into the diluted solution C; dropwise adding a titanium trichloride solution, wherein the solution is changed from colorless to blue and does not fade within 20 s; continuously dripping copper sulfate solution, and continuously shaking the conical flask in the process until the tungsten blue completely fades to form solution D; respectively dropwise adding sodium diphenylamine sulfonate into the solution D and the diluted solution B; respectively adding mixed acid to obtain a solution E and a solution F;
the fourth step: titrating the solution E and the solution F respectively by using a potassium dichromate standard solution until stable purple red appears, recording the volume V of potassium dichromate consumed in the titration process of the two solutions of the solution E and the solution F respectively after titration is finished1And V2。
2. The method for detecting iron in different valence states of niobium-containing metallurgical slag system according to claim 1, wherein the heating temperature is 100 ℃.
3. The method for detecting iron in different valence states in the niobium-containing metallurgical slag system according to claim 1 or 2, wherein the niobium-containing metallurgical slag sample and the potassium fluoride are mixed according to a mass ratio of 1: 10, and mixing.
4. The method for detecting iron in different valence states in the hydrochloric acid-based solution according to claim 3, wherein the niobium-containing metallurgical slag sample, the potassium fluoride and the hydrogen carbonate are mixed according to a mass ratio of 1: 10: 10, and mixing.
5. The method for detecting iron in different valence states in the niobium-containing metallurgical slag system according to claim 4, wherein the mass ratio of the niobium-containing metallurgical slag samples forming the solution A to the solution B is 1: 1.
6. The method for detecting iron in different valence states of niobium-containing metallurgical slag system in hydrochloric acid-based solution according to claim 5, wherein in the second step, the ratio of the volume of the added water to the volume of each of solution C and solution B in the process of diluting with water is 4: 1.
7. the method for detecting iron with different valence states in the hydrochloric acid-based solution according to claim 6, wherein in the third step, the volume ratio of the sodium tungstate solution to the diluted solution C is 1: 250 of (a); the volume ratio of the sodium diphenylamine sulfonate to the volume ratio of the solution D to the volume ratio of the diluted solution B is 1: 200.
8. the method for detecting iron with different valence states in the hydrochloric acid-based solution according to claim 7, wherein in the third step, the volume ratio of the mixed acid to the volume ratio of the solution D to the diluted solution B is 1: 10.
9. the method for detecting iron in different valence states in the hydrochloric acid-based solution according to claim 8, wherein the mixed acid is a sulfuric acid solution with a mass concentration of 98% and a phosphoric acid solution with a mass concentration of 85% mixed in a volume ratio of 1: 1.
10. The method for detecting iron in different valence states in niobium-containing metallurgical slag system according to claim 1, wherein V is1And V2Used for calculating the content of each valence iron in the niobium-containing metallurgical slag sample,
the content of T.Fe in the niobium-containing metallurgical slag sample is as follows:
the content of FeO in the niobium-containing metallurgical slag sample is as follows:
fe in niobium-containing metallurgical slag sample2O3The content of (A) is as follows:
in the formula, C is the concentration of a potassium dichromate standard solution, moL/L; v1Consuming a volume of potassium dichromate mL for solution F; v2Consuming a volume of potassium dichromate mL for solution G; mFe、MFeO、MFeO1.5Are Fe, FeO and FeO respectively1.5Relative molecular mass of (a); m is the mass of the dissolved slag sample, g.
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