CN110376148B - Method for measuring content of tungsten trioxide in high-phosphorus scheelite - Google Patents
Method for measuring content of tungsten trioxide in high-phosphorus scheelite Download PDFInfo
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- CN110376148B CN110376148B CN201910822142.9A CN201910822142A CN110376148B CN 110376148 B CN110376148 B CN 110376148B CN 201910822142 A CN201910822142 A CN 201910822142A CN 110376148 B CN110376148 B CN 110376148B
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- tungsten trioxide
- hydrochloric acid
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- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 title claims abstract description 219
- 239000011574 phosphorus Substances 0.000 title claims abstract description 87
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 57
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 184
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 75
- 238000010438 heat treatment Methods 0.000 claims description 69
- 239000000706 filtrate Substances 0.000 claims description 62
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 44
- 239000000463 material Substances 0.000 claims description 44
- 239000007788 liquid Substances 0.000 claims description 40
- 239000007864 aqueous solution Substances 0.000 claims description 39
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 34
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 34
- 238000001914 filtration Methods 0.000 claims description 33
- 229910052697 platinum Inorganic materials 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 28
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 24
- 229910017604 nitric acid Inorganic materials 0.000 claims description 24
- 238000007865 diluting Methods 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 22
- 229910021529 ammonia Inorganic materials 0.000 claims description 17
- 238000002835 absorbance Methods 0.000 claims description 16
- 238000002791 soaking Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 12
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 10
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 10
- 229940116357 potassium thiocyanate Drugs 0.000 claims description 10
- ZXNIRGPMYQWIJS-UHFFFAOYSA-O azanium azane nitrate Chemical compound [N+](=O)([O-])[O-].[NH4+].N ZXNIRGPMYQWIJS-UHFFFAOYSA-O 0.000 claims description 8
- 238000004737 colorimetric analysis Methods 0.000 claims description 8
- 238000010304 firing Methods 0.000 claims description 7
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 7
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 7
- 239000012085 test solution Substances 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052721 tungsten Inorganic materials 0.000 abstract description 20
- 239000010937 tungsten Substances 0.000 abstract description 20
- 238000000975 co-precipitation Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000004458 analytical method Methods 0.000 abstract description 2
- 238000001514 detection method Methods 0.000 abstract description 2
- 238000005406 washing Methods 0.000 description 24
- 239000012086 standard solution Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 9
- 239000001096 (4-ethenyl-1-azabicyclo[2.2.2]octan-7-yl)-(6-methoxyquinolin-4-yl)methanol hydrochloride Substances 0.000 description 8
- NNKXWRRDHYTHFP-HZQSTTLBSA-N (r)-[(2s,4s,5r)-5-ethenyl-1-azabicyclo[2.2.2]octan-2-yl]-(6-methoxyquinolin-4-yl)methanol;hydron;dichloride Chemical compound Cl.Cl.C([C@H]([C@H](C1)C=C)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 NNKXWRRDHYTHFP-HZQSTTLBSA-N 0.000 description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 8
- 229910052750 molybdenum Inorganic materials 0.000 description 8
- 239000011733 molybdenum Substances 0.000 description 8
- 229960001811 quinine hydrochloride Drugs 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- RFVVBBUVWAIIBT-UHFFFAOYSA-N beryllium nitrate Chemical compound [Be+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O RFVVBBUVWAIIBT-UHFFFAOYSA-N 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- SFBLKWGYRDDITM-UHFFFAOYSA-J [Ti+4].[O-]S([O-])=O.[O-]S([O-])=O Chemical compound [Ti+4].[O-]S([O-])=O.[O-]S([O-])=O SFBLKWGYRDDITM-UHFFFAOYSA-J 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 3
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229930013930 alkaloid Natural products 0.000 description 2
- 150000003797 alkaloid derivatives Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- KMPWYEUPVWOPIM-UHFFFAOYSA-N cinchonidine Natural products C1=CC=C2C(C(C3N4CCC(C(C4)C=C)C3)O)=CC=NC2=C1 KMPWYEUPVWOPIM-UHFFFAOYSA-N 0.000 description 2
- KMPWYEUPVWOPIM-LSOMNZGLSA-N cinchonine Chemical compound C1=CC=C2C([C@@H]([C@H]3N4CC[C@H]([C@H](C4)C=C)C3)O)=CC=NC2=C1 KMPWYEUPVWOPIM-LSOMNZGLSA-N 0.000 description 2
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229960003540 oxyquinoline Drugs 0.000 description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910004829 CaWO4 Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910003893 H2WO4 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- UYDPQDSKEDUNKV-UHFFFAOYSA-N phosphanylidynetungsten Chemical compound [W]#P UYDPQDSKEDUNKV-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
-
- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/3103—Atomic absorption analysis
-
- 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
Abstract
The invention provides a method for measuring the content of tungsten trioxide in high-phosphorus scheelite, belonging to the technical field of analysis and detection. According to the method provided by the invention, dilute hydrochloric acid is adopted to soak the high-phosphorus scheelite sample, so that tungsten and phosphorus separation is realized, the problem that in the prior art, phosphorus cannot be effectively removed, and the accurate determination of the content of tungsten trioxide is influenced due to the coprecipitation of a large part of phosphorus and tungsten is solved, and the accurate determination of the content of tungsten trioxide in the high-phosphorus scheelite can be realized.
Description
Technical Field
The invention relates to the technical field of analysis and detection, in particular to a method for determining the content of tungsten trioxide in high-phosphorus scheelite.
Background
The tungsten reserves in China are huge, wherein tungsten and molybdenum resources in Henan are abundant and are tungsten and molybdenum associated ores, molybdenum in the ores is separated to form molybdenum concentrate after dressing and smelting, tailings are reprocessed to form scheelite, the content of tungsten trioxide in the scheelite is 20-40%, the content of phosphorus is 5-10%, and the scheelite also contains molybdenum, calcium, silicon and a small amount of elements such as iron, sulfur and tin, and is mainly used as a raw material for producing ammonium paratungstate, ammonium metatungstate, blue tungsten and the like.
For samples with tungsten trioxide content of more than 20%, the traditional determination method usually adopts a gravimetric method, including ammonium tungstate burning method, cinchonine precipitation method and 8-hydroxyquinoline precipitation method. Cinchonine and 8-hydroxyquinoline are organic reagents, harm is caused to operators and the environment, and the two methods are complicated in operation steps. The ammonium tungstate burning method is suitable for determining a sample with the phosphorus content of less than 2%, and beryllium nitrate coprecipitation phosphorus (GB/T26019-2010) needs to be added when the phosphorus content in the sample is more than 0.3%, so that the toxicity of beryllium is high, and the environmental pollution is serious.
The scheelite has high phosphorus content, belongs to high-impurity tungsten concentrate, can not completely remove phosphorus according to the traditional method, and has the defect that a large part of phosphorus can be coprecipitated with tungsten to be weighed, so that the measurement result of the tungsten trioxide content is influenced.
At present, researchers measure the content of tungsten trioxide in tungsten ore by adopting an X-ray fluorescence method, and the method has the advantages of rapidness, simplicity, convenience and high precision, but an X-ray fluorescence spectrometer is expensive and difficult to popularize.
In summary, a method for measuring the content of tungsten trioxide in high-phosphorus scheelite, which is accurate and easy to popularize, is lacking at present.
Disclosure of Invention
The invention aims to provide a method for measuring the content of tungsten trioxide in high-phosphorus scheelite, which can realize accurate measurement of the content of tungsten trioxide in high-phosphorus scheelite.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for measuring the content of tungsten trioxide in high-phosphorus scheelite, which comprises the following steps:
soaking high-phosphorus scheelite by using first hydrochloric acid, and performing first filtration on the obtained soaked material to obtain first filter residue and first filtrate; the first hydrochloric acid is prepared by diluting 4.5-5.5 mL of analytically pure hydrochloric acid with water to 1000mL, and the dosage ratio of the first hydrochloric acid to the high-phosphorus scheelite is (80-120) mL: 0.2 g; the temperature of the soaking treatment is room temperature, and the time is 2-4 h;
mixing the first filter residue with nitric acid, perchloric acid and second hydrochloric acid, performing I heat treatment, and performing second filtration on the obtained I heat treatment material to obtain a second filter residue and a second filtrate;
mixing the ammonia water-ammonium nitrate mixed solution with the second filter residue, performing third filtration to obtain a third filter residue and a third filtrate, evaporating the third filtrate to dryness, and then firing, wherein the remainder is tungsten trioxide, so as to obtain the content of the tungsten trioxide in the third filtrate;
mixing the third filter residue with phosphoric acid and third hydrochloric acid, and then carrying out II heat treatment, mixing the obtained II heat treatment material with a sodium hydroxide aqueous solution, and then carrying out III heat treatment to obtain a III heat treatment material;
mixing the first filtrate, the second filtrate and the III heat treatment material, and measuring the content of tungsten trioxide in the obtained mixed feed liquid by a colorimetric method to obtain the content of tungsten trioxide in the mixed feed liquid;
and obtaining the content of the tungsten trioxide in the high-phosphorus scheelite according to the content of the tungsten trioxide in the third filtrate and the content of the tungsten trioxide in the mixed feed liquid.
Preferably, the first hydrochloric acid is prepared by diluting 5mL of analytically pure hydrochloric acid with water to 1000mL, and the dosage ratio of the first hydrochloric acid to the high-phosphorus scheelite is 100 mL: 0.2 g; the temperature of the soaking treatment is 20 ℃, and the time is 3 h.
Preferably, in the heat treatment process of the first step I, the dosage ratio of the first filter residue to the nitric acid, the perchloric acid and the second hydrochloric acid is (0.17-0.21) g: 20mL of: 10mL of: 50 mL; the nitric acid is analytically pure nitric acid, the perchloric acid is analytically pure perchloric acid, and the second hydrochloric acid is analytically pure hydrochloric acid.
Preferably, the temperature of the I heat treatment is 180-220 ℃, and the time is 15-35 min.
Preferably, the ammonia water-ammonium nitrate mixed solution is prepared by diluting 195-205 mL of analytically pure ammonia water and 9-11 g of ammonium nitrate with water to 1000 mL; the dosage ratio of the ammonia water-ammonium nitrate mixed solution to the second filter residue is (25-40) mL: (0.04-0.09) g.
Preferably, in the heat treatment process of the second step II, the usage ratio of the third filter residue to the phosphoric acid and the third hydrochloric acid is (0.004-0.009) g: 3mL of: 40 mL; the phosphoric acid is prepared by diluting 48-52 mL of analytically pure phosphoric acid with water to 200mL, and the third hydrochloric acid is analytically pure hydrochloric acid.
Preferably, the temperature of the II heat treatment is 100-200 ℃ and the time is 20-30 min.
Preferably, the concentration of the sodium hydroxide aqueous solution is 190-210 g/L, and the volume ratio of the sodium hydroxide aqueous solution to the II-th heat treatment material is 18: 10.
preferably, the temperature of the III heat treatment is 300-350 ℃, and the time is 10-20 min.
Preferably, the method for measuring the content of the tungsten trioxide in the mixed feed liquid by using a colorimetric method comprises the following steps:
mixing the mixed feed liquid, sulfuric acid and nitric acid, evaporating to dryness, and mixing the obtained residue with a sodium hydroxide aqueous solution, a potassium thiocyanate aqueous solution, hydrochloric acid and a titanium sulfate aqueous solution to obtain a solution to be detected;
and measuring the absorbance of the solution to be measured, and obtaining the content of the tungsten trioxide in the mixed feed liquid according to the working curve of the tungsten trioxide and the absorbance of the obtained solution to be measured.
The invention provides a method for measuring the content of tungsten trioxide in high-phosphorus scheelite, which comprises the following steps: soaking high-phosphorus scheelite by using first hydrochloric acid, and performing first filtration on the obtained soaked material to obtain first filter residue and first filtrate; the first hydrochloric acid is prepared by diluting 4.5-5.5 mL of analytically pure hydrochloric acid with water to 1000mL, and the dosage ratio of the first hydrochloric acid to the high-phosphorus scheelite is (80-120) mL: 0.2 g; the temperature of the soaking treatment is room temperature, and the time is 2-4 h; mixing the first filter residue with nitric acid, perchloric acid and second hydrochloric acid, performing I heat treatment, and performing second filtration on the obtained I heat treatment material to obtain a second filter residue and a second filtrate; mixing the ammonia water-ammonium nitrate mixed solution with the second filter residue, performing third filtration to obtain a third filter residue and a third filtrate, evaporating the third filtrate to dryness, and then firing, wherein the remainder is tungsten trioxide, so as to obtain the content of the tungsten trioxide in the third filtrate; mixing the third filter residue with phosphoric acid and third hydrochloric acid, and then carrying out II heat treatment, mixing the obtained II heat treatment material with a sodium hydroxide aqueous solution, and then carrying out III heat treatment to obtain a III heat treatment material; mixing the first filtrate, the second filtrate and the III heat treatment material, and measuring the content of tungsten trioxide in the obtained mixed feed liquid by a colorimetric method to obtain the content of tungsten trioxide in the mixed feed liquid; and obtaining the content of the tungsten trioxide in the high-phosphorus scheelite according to the content of the tungsten trioxide in the third filtrate and the content of the tungsten trioxide in the mixed feed liquid. According to the method provided by the invention, the dilute hydrochloric acid is adopted to soak the high-phosphorus scheelite sample under specific conditions, phosphorus in the high-phosphorus scheelite sample usually exists in the form of calcium phosphate, and can react with the dilute hydrochloric acid to generate phosphoric acid which enters a solution, so that tungsten and phosphorus separation is realized, the problem that in the prior art, phosphorus cannot be effectively removed, and the accurate determination of the tungsten trioxide content is influenced due to the coprecipitation of a large part of phosphorus and tungsten is solved, and the accurate determination of the tungsten trioxide content in the high-phosphorus scheelite can be realized.
Detailed Description
The invention provides a method for measuring the content of tungsten trioxide in high-phosphorus scheelite, which comprises the following steps:
soaking high-phosphorus scheelite by using first hydrochloric acid, and performing first filtration on the obtained soaked material to obtain first filter residue and first filtrate; the first hydrochloric acid is prepared by diluting 4.5-5.5 mL of analytically pure hydrochloric acid with water to 1000mL, and the dosage ratio of the first hydrochloric acid to the high-phosphorus scheelite is (80-120) mL: 0.2 g; the temperature of the soaking treatment is 20-30 ℃, and the time is 2-4 h;
mixing the first filter residue with nitric acid, perchloric acid and second hydrochloric acid, performing I heat treatment, and performing second filtration on the obtained I heat treatment material to obtain a second filter residue and a second filtrate;
mixing the ammonia water-ammonium nitrate mixed solution with the second filter residue, performing third filtration to obtain a third filter residue and a third filtrate, evaporating the third filtrate to dryness, and then firing, wherein the remainder is tungsten trioxide, so as to obtain the content of the tungsten trioxide in the third filtrate;
mixing the third filter residue with phosphoric acid and third hydrochloric acid, and then carrying out II heat treatment, mixing the obtained II heat treatment material with a sodium hydroxide aqueous solution, and then carrying out III heat treatment to obtain a III heat treatment material;
mixing the first filtrate, the second filtrate and the III heat treatment material, and measuring the content of tungsten trioxide in the obtained mixed feed liquid by a colorimetric method to obtain the content of tungsten trioxide in the mixed feed liquid;
and obtaining the content of the tungsten trioxide in the high-phosphorus scheelite according to the content of the tungsten trioxide in the third filtrate and the content of the tungsten trioxide in the mixed feed liquid.
According to the invention, high-phosphorus scheelite is soaked by first hydrochloric acid, and the obtained soaked material is subjected to first filtration to obtain first filter residue and first filtrate; the first hydrochloric acid is prepared by diluting 4.5-5.5 mL of analytically pure hydrochloric acid with water to 1000mL, and the dosage ratio of the first hydrochloric acid to the high-phosphorus scheelite is (80-120) mL: 0.2 g; the temperature of the soaking treatment is room temperature, and the time is 2-4 hours. In the invention, the mass content of tungsten trioxide in the high-phosphorus scheelite is preferably 20-40%, and the mass content of phosphorus is preferably 5-10%; the source of the high-phosphorus scheelite is not specially limited, specifically, tungsten and molybdenum associated ores are sorted and smelted, molybdenum concentrate and tailings are obtained through separation, the scheelite formed by reprocessing the tailings is the high-phosphorus scheelite provided by the invention, and the scheelite contains tungsten trioxide, phosphorus, molybdenum, calcium, silicon, a small amount of iron, sulfur, tin and other elements. In the embodiment of the invention, Henan high-phosphorus scheelite is adopted.
In the invention, the first hydrochloric acid is prepared by diluting 4.5-5.5 mL of analytically pure hydrochloric acid with water to 1000mL, preferably by diluting 5mL of analytically pure hydrochloric acid with water to 1000 mL; the dosage ratio of the first hydrochloric acid to the high-phosphorus scheelite is (80-120) mL: 0.2g, preferably 100 mL: 0.2 g; the temperature of the soaking treatment is room temperature, i.e. no additional heating or cooling is needed, preferably 20 ℃; the soaking time is 2-4 h, preferably 3 h. In the invention, the soaking treatment is preferably carried out under the condition of stirring, and is specifically stirred once every 30 min; the container used for the soaking treatment is preferably a beaker. According to the invention, dilute hydrochloric acid is adopted to soak the high-phosphorus scheelite under specific conditions, phosphorus in a high-phosphorus scheelite sample generally exists in the form of calcium phosphate, and can react with the dilute hydrochloric acid to generate phosphoric acid to enter a solution, so that tungsten-phosphorus separation is realized, the problem that in the prior art, phosphorus cannot be effectively removed, and the accurate determination of the tungsten trioxide content is influenced by the coprecipitation of a large part of phosphorus and tungsten is solved, and the accurate determination of the tungsten trioxide content in the high-phosphorus scheelite is favorably realized.
The first filtration is not particularly limited in the present invention, and a filtration method well known to those skilled in the art may be adopted; the present invention preferably employs medium speed quantitative filter paper for the first filtration.
After the first filtration is completed, the beaker and the first filter residue are preferably washed by first hydrochloric acid 7 times respectively, washing liquid obtained after washing is combined with the first filtrate for subsequent treatment, and the filter paper used by the first filtrate and the washed first filter residue are placed in the beaker for subsequent treatment.
Mixing the first filter residue with nitric acid, perchloric acid and second hydrochloric acid, performing I heat treatment, and performing second filtration on the obtained I heat treatment material to obtain second filter residue and second filtrate. In the invention, in the heat treatment process of the item I, the dosage ratio of the first filter residue to the nitric acid, the perchloric acid and the second hydrochloric acid is preferably (0.17-0.21) g: 20mL of: 10mL of: 50 mL; the nitric acid is preferably analytically pure nitric acid, the perchloric acid is preferably analytically pure perchloric acid, and the second hydrochloric acid is preferably analytically pure hydrochloric acid. In the invention, the temperature of the I heat treatment is preferably 180-220 ℃, and more preferably 200 ℃; the time is preferably 15-35 min, and more preferably 25 min.
In the invention, the first heat treatment is preferably to add nitric acid and perchloric acid into a beaker containing the filter paper and the first filter residue, heat the beaker for 15-35 min at 180-220 ℃ in an electric furnace, stop heating, add the second hydrochloric acid into the beaker, heat the beaker for 25-35 min in a boiling water bath, heat the beaker at 180-220 ℃ in the electric furnace to concentrate the filtrate to 1/4 of the original volume, stop heating, and cover the beaker with the watch glass in the whole heating process. In the present invention, the I-th heat treatmentIn the course of treatment, nitric acid and perchloric acid can destroy organic matters in the filter paper, and decompose the filter paper and the first filter residue, and hydrochloric acid can further decompose the first filter residue, so that each element in the first filter residue is changed from a solid state to a soluble state, such as CaWO4+2HCl＝H2WO4+CaCl2。
After the I heat treatment is completed, the invention preferably adopts quinine hydrochloride solution with the temperature of 85 ℃ and the concentration of 4g/L to wash the inner walls of the watch glass and the beaker, uses water to dilute the materials in the beaker to 3.5 times of the volume of the materials when the heating is stopped, and evenly stirs the materials and heats the materials until the materials are boiled to obtain the I heat treatment materials.
After the first heat-treated material is obtained, the first heat-treated material is subjected to second filtration to obtain second filter residue and second filtrate. The second filtration is not particularly limited in the present invention, and a filtration method well known to those skilled in the art may be adopted; the present invention preferably employs medium speed quantitative filter paper for the second filtration. In the invention, the second filtrate and the first filtrate are combined for subsequent treatment, the filter paper for the second filtration is preferably kept as it is, and the second filter residue is placed in a beaker for subsequent treatment.
After the second filtration is finished, the beaker and the second filter residue in the filter paper are preferably washed by a quinine hydrochloride solution at 90 ℃ and 4g/L for 4 times respectively, then the beaker and the second filter residue in the filter paper are washed by an ammonium nitrate solution at 90 ℃ and 5g/L for 5 times respectively, and washing liquid obtained after washing is combined with the first filter solution for subsequent treatment. The invention preferably utilizes the quinine hydrochloride solution to wash away some impurities (such as iron) which form the chloro complexes, and further utilizes the ammonium nitrate solution to wash away chloride ions and alkaloid (the chloride ions generate reduction action during subsequent ignition to lead the ignited tungsten trioxide to be green, and the existence of the alkaloid can wrap the tungstic acid, so that the tungstic acid can not be completely dissolved in the subsequent ammonia water-ammonium nitrate mixed solution dissolving process).
After the second filter residue is obtained, mixing an ammonia water-ammonium nitrate mixed solution with the second filter residue, performing third filtration to obtain a third filter residue and a third filtrate, evaporating the third filtrate to dryness, and then firing, wherein the remainder is tungsten trioxide, so as to obtain the content of the tungsten trioxide in the third filtrate. In the invention, the ammonia water-ammonium nitrate mixed solution is preferably prepared by diluting 195-205 mL of analytically pure ammonia water and 9-11 g of ammonium nitrate with water to 1000mL, more preferably by diluting 200mL of analytically pure ammonia water and 10g of ammonium nitrate with water to 1000 mL; the preferable dosage ratio of the ammonia water-ammonium nitrate mixed solution to the second filter residue is (25-40) mL: (0.04-0.09) g.
In the invention, preferably, a weighed platinum dish is placed below a funnel (containing filter paper) for second filtration, the beaker and the second filter residue in the filter paper are flushed by ammonia water-ammonium nitrate mixed solution at the temperature of 85 ℃, pouring the washed materials in the beaker into a funnel, continuously washing the beaker for 3 times by using the ammonia-ammonium nitrate mixed solution, pouring the obtained washing solution into the funnel, washing the residue on the filter paper in the funnel for 1 time by using the ammonia-ammonium nitrate mixed solution, taking the filter paper (containing the residue) on the funnel down and placing the filter paper in the beaker, and then washing the inner wall of the funnel by using the ammonia water-ammonium nitrate mixed solution, wherein the washing and filtering process by using the ammonia water-ammonium nitrate mixed solution is a third filtering process, the liquid collected in the platinum dish is a third filtrate (corresponding to the volume of the ammonia water-ammonium nitrate mixed solution), and the residue on the filter paper is a third filter residue (the filter paper and the third filter residue are placed in a beaker for subsequent treatment).
After the third filtrate is obtained, the third filtrate is evaporated to dryness and then burned, and the remainder is tungsten trioxide, so that the content of the tungsten trioxide in the third filtrate is obtained. Preferably, a platinum dish containing the third filtrate is placed on a boiling water bath to be dried by distillation, then the platinum dish is transferred to an electric furnace, the platinum dish is heated for 10min at the temperature of 200-300 ℃ to remove ammonium salt, then the platinum dish is transferred to a muffle furnace at the temperature of 780-800 ℃ to be fired for 10-15 min, the platinum dish is taken out and cooled, hydrofluoric acid (with the mass concentration of 40 percent, the silicon is removed) is added, the platinum dish is placed on the boiling water bath to be dried by distillation, then the platinum dish is transferred to the muffle furnace at the temperature of 780-800 ℃ to be fired for 10min, the platinum dish is taken out and cooled to the room temperature, tungsten trioxide is left in the platinum dish, and the tungsten trioxide content in the third filtrate is obtained by weighing (the total mass of the platinum dish and the tungsten trioxide obtained after firing).
After the third filter residue is obtained, the third filter residue is mixed with phosphoric acid and third hydrochloric acid and then subjected to II heat treatment, and the obtained II heat treatment material is mixed with a sodium hydroxide aqueous solution and then subjected to III heat treatment to obtain a III heat treatment material. In the invention, in the heat treatment process of the second step II, the usage ratio of the third filter residue to the phosphoric acid and the third hydrochloric acid is preferably (0.004-0.009) g: 3mL of: 40 mL; the phosphoric acid is preferably prepared by diluting 48-52 mL of analytically pure phosphoric acid with water to 200mL, and more preferably prepared by diluting 50mL of analytically pure phosphoric acid with water to 200mL (1: 3 phosphoric acid); the third hydrochloric acid is preferably analytically pure hydrochloric acid. In the invention, the temperature of the II heat treatment is preferably 100-200 ℃, and the time is preferably 20-30 min. In the invention, the concentration of the sodium hydroxide aqueous solution is preferably 190-210 g/L, more preferably 200g/L, and the volume ratio of the sodium hydroxide aqueous solution to the II-th heat treatment material is preferably 18: 10. in the invention, the temperature of the III heat treatment is preferably 300-350 ℃, and the time is preferably 10-20 min.
According to the invention, analytically pure hydrochloric acid and 1:3 phosphoric acid are preferably added into a beaker containing filter paper and third filter residue, the beaker is placed on an electric furnace and heated and decomposed for 20-30 min at 100-200 ℃, the volume of a system in the beaker is concentrated into 1/4 of the original volume, the beaker is taken down and cooled, water is blown along the wall of the beaker, salts and solution attached to the wall of the beaker are blown to the bottom of the beaker, then a sodium hydroxide aqueous solution with the concentration of 190-210 g/L is added, the beaker is uniformly shaken and then placed on the electric furnace to be boiled and kept for 1 min; then removed and cooled to obtain the third heat-treated material (i.e., all the feed in the beaker).
After the third heat-treated material is obtained, the third heat-treated material and the first filtrate are combined, and the content of the tungsten trioxide in the obtained mixed feed liquid is measured by a colorimetric method to obtain the content of the tungsten trioxide in the mixed feed liquid. In the present invention, the mixed liquid further contains a second filtrate, and preferably further contains a washing liquid generated in the foregoing process (see the foregoing related matters for details).
In the present invention, the method for measuring the content of tungsten trioxide in the mixed feed liquid by colorimetry preferably includes the steps of:
mixing the mixed feed liquid, sulfuric acid and nitric acid, evaporating to dryness, and mixing the obtained residue with a sodium hydroxide aqueous solution, a potassium thiocyanate aqueous solution, hydrochloric acid and a titanium sulfate aqueous solution to obtain a solution to be detected;
and measuring the absorbance of the solution to be measured, and obtaining the content of the tungsten trioxide in the mixed feed liquid according to the working curve of the tungsten trioxide and the absorbance of the obtained solution to be measured.
Preferably, the mixed feed liquid, sulfuric acid and nitric acid are mixed and then evaporated to dryness, and the obtained residue is mixed with a sodium hydroxide aqueous solution, a potassium thiocyanate aqueous solution, hydrochloric acid and a titanium sulfite aqueous solution to obtain a solution to be detected. In the embodiment of the invention, specifically, 10mL of mixed material liquid is placed in a beaker, 4mL of sulfuric acid (the sulfuric acid is prepared by diluting 50mL of analytically pure sulfuric acid to 100mL with water and is recorded as 1:1 sulfuric acid), a few drops (such as 3-8 drops) of analytically pure nitric acid are added dropwise, the mixture is evaporated on an electric furnace to dryness (obtain a white residue), 10mL of a 34g/L sodium hydroxide aqueous solution is taken down, after the white residue in the beaker is completely dissolved, 1.5mL of a 250g/L potassium thiocyanate aqueous solution and 13.5mL of hydrochloric acid (the hydrochloric acid is prepared by diluting 60mL of analytically pure hydrochloric acid to 100mL with water and is recorded as 3:2 hydrochloric acid) and 1mL of a 10g/L titanium sulfate aqueous solution are added, and the mixture is shaken uniformly and placed for 15min to obtain a solution to be detected.
After the solution to be detected is obtained, the absorbance of the solution to be detected is preferably measured, and the content of the tungsten trioxide in the mixed material liquid is obtained according to the working curve of the tungsten trioxide and the absorbance of the solution to be detected. In the embodiment of the invention, the solution to be detected is transferred into a 25mL colorimetric tube, part of the solution to be detected is transferred into a 1cm cuvette, and the absorbance of the solution is measured at 400nm of a spectrophotometer by taking a reagent blank (namely, the solution without the solution to be detected and only the solution added with various reagents) as a reference; and obtaining the content of the tungsten trioxide in the mixed feed liquid according to the working curve of the tungsten trioxide and the absorbance of the obtained solution to be detected.
The method for drawing the working curve of tungsten trioxide in the present invention is not particularly limited, and a method known to those skilled in the art may be used. In the present invention, the method for drawing the working curve of tungsten trioxide preferably comprises the following steps:
transferring 0.00mL, 0.50mL, 1.00mL, 2.00mL, 3.00mL, 4.00mL, 5.00mL and 6.00mL of tungsten trioxide standard solutions (the concentration is 100mg/L), respectively placing the tungsten trioxide standard solutions in a group of 25mL colorimetric tubes, supplementing 10mL with a 34g/L sodium hydroxide aqueous solution, adding 1.5mL of a 250g/L potassium thiocyanate aqueous solution, 13.5mL of 3:2 hydrochloric acid and 1mL of a 10g/L titanium sulfate aqueous solution, shaking uniformly, placing for 15min to obtain a standard solution to be measured, transferring part of the standard solution to a 1cm cuvette, measuring the absorbance of the standard solution at 400nm of a spectrophotometer by taking the reagent as a blank reference, taking the mass of the tungsten trioxide as an abscissa and the absorbance as an ordinate, and drawing a working curve.
After the content of the tungsten trioxide in the third filtrate and the content of the tungsten trioxide in the mixed feed liquid are obtained, the content of the tungsten trioxide in the high-phosphorus scheelite is obtained according to the content of the tungsten trioxide in the third filtrate and the content of the tungsten trioxide in the mixed feed liquid.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The preparation method of each solution required in the following examples is as follows:
preparing first hydrochloric acid: transferring 5mL of analytically pure hydrochloric acid into a 2000mL measuring cup, diluting with water to 1000mL, and shaking up;
preparing a quinine hydrochloride solution with the concentration of 4 g/L: weighing 4g of analytically pure quinine hydrochloride into a beaker, adding 20mL of analytically pure quinine hydrochloride to dissolve, transferring into a 1000mL volumetric flask, fixing the volume with water, and shaking up;
preparing an ammonium nitrate solution with the concentration of 5 g/L: weighing 5g of analytically pure ammonium nitrate in a beaker, adding 20mL of analytically pure nitric acid for dissolution, transferring into a 1000mL volumetric flask, fixing the volume with water, and shaking up;
preparing ammonia water-ammonium nitrate mixed solution: transferring 200mL of analytically pure ammonia water into a beaker, adding 10g of analytically pure ammonium nitrate to dissolve, transferring into a 1000mL volumetric flask, fixing the volume with water, and shaking up;
preparing 1:3 phosphoric acid: transferring 50mL of analytically pure phosphoric acid into a 200mL volumetric flask, fixing the volume with water, and shaking up;
preparing a sodium hydroxide aqueous solution with the concentration of 200 g/L: weighing 200g of analytically pure sodium hydroxide in a beaker, adding 200mL of water for dissolving, transferring into a 1000mL volumetric flask, fixing the volume with water, and shaking up;
preparing 1:1 sulfuric acid: transferring 50mL of analytically pure sulfuric acid into a 100mL volumetric flask, fixing the volume with water, and shaking up;
preparing a sodium hydroxide aqueous solution with the concentration of 34 g/L: weighing 34g of analytically pure sodium hydroxide in a beaker, adding 100mL of water for dissolving, transferring into a 1000mL volumetric flask, fixing the volume with water, and shaking up;
preparing a potassium thiocyanate aqueous solution with the concentration of 250 g/L: weighing 250g of analytically pure potassium thiocyanate in a beaker, adding 200mL of water for dissolving, transferring into a 1000mL volumetric flask, fixing the volume with water, and shaking up;
preparing 3:2 hydrochloric acid: transferring 60mL of analytically pure hydrochloric acid into a 100mL volumetric flask, fixing the volume with water, and shaking up;
preparing a titanium sulfate aqueous solution with the concentration of 10 g/L: weighing 10g of analytically pure titanium sulfite into a beaker, adding 200mL of water for dissolving, transferring into a 1000mL volumetric flask, fixing the volume with water, and shaking up;
example 1
(1) 0.2000g (the mass is denoted m) is weighed0) Placing a Henan high-phosphorus scheelite sample into a 300mL beaker (marked as beaker A), adding 100mL of first hydrochloric acid, uniformly stirring, stirring once every 30min, and soaking for 3h at room temperature (20 ℃).
(2) Performing first filtration on the soaked system by using medium-speed quantitative filter paper (marked as filter paper A) to obtain first filtrate and first filter residue, placing the first filtrate in a 200mL volumetric flask (marked as volumetric flask A), washing the beaker A and the first filter residue by using first hydrochloric acid for 7 times respectively, placing washing liquid obtained after washing in the volumetric flask A, and placing the filter paper A and the first filter residue obtained after washing in the beaker A;
(3) adding 20mL of analytically pure nitric acid and 10mL of analytically pure perchloric acid into a beaker A, heating the beaker A for 25min at 200 ℃ on an electric furnace, stopping heating, adding 50mL of analytically pure hydrochloric acid into the beaker A, heating the beaker A on a boiling water bath for 30min to further decompose first filter residue, heating the beaker A on the electric furnace at 200 ℃ and concentrating the filter residue to 20mL, and covering a watch glass A with the watch glass in the whole heating process; after heating, washing the surface dish and the wall of the beaker A by 4g/L quinine hydrochloride solution at 90 ℃, diluting the material in the beaker A to 70mL by water, stirring uniformly, and heating to boiling;
performing second filtration on the material heated to be boiled in the beaker A by using medium-speed quantitative filter paper (marked as filter paper B) to obtain second filtrate and second filter residue, placing the second filtrate in the volumetric flask A, washing the second filter residue in the beaker A and the filter paper B4 times respectively by using quinine hydrochloride solution with the concentration of 4g/L at the temperature of 90 ℃, washing the second filter residue in the beaker A and the filter paper B5 times respectively by using ammonium nitrate solution with the concentration of 5g/L at the temperature of 90 ℃, and placing washing liquid obtained after washing in the volumetric flask A;
weighed platinum dish (the mass is recorded as m)3) Placing the filter cake below a funnel (containing filter paper B) used for second filtration, flushing second filter residues in a beaker A and the filter paper B by using an ammonia-ammonium nitrate mixed solution at the temperature of 85 ℃, pouring a washing material in the beaker A into the funnel, continuously washing the beaker A for 3 times by using the ammonia-ammonium nitrate mixed solution, pouring a washing solution into the funnel, washing residues on the filter paper B in the funnel by using the ammonia-ammonium nitrate mixed solution for 1 time, taking the filter paper B (containing residues) on the lower funnel into the beaker A, flushing the inner wall of the funnel by using the ammonia-ammonium nitrate mixed solution, wherein the washing and filtering process by using the ammonia-ammonium nitrate mixed solution is third filtration, the liquid collected in a platinum dish is third filtrate (35mL), and the residues on the filter paper B are third filter residues; placing a platinum dish on a boiling water bath for evaporating to dryness, then transferring the platinum dish to an electric furnace, heating the platinum dish for 10min at the temperature of 250 ℃ to remove ammonium salt, then transferring the platinum dish to a muffle furnace at the temperature of 790 ℃ for burning for 13min, taking out the platinum dish for cooling, adding 5mL hydrofluoric acid (the concentration is 40%), placing the platinum dish on the boiling water bath for evaporating to dryness, then transferring the platinum dish to the muffle furnace at the temperature of 790 ℃ for burning for 10min, taking out the platinum dish, cooling the platinum dish to the room temperature in a drier, weighing tungsten trioxide as the residue in the platinum dish (the mass is recorded as m), and weighing the tungsten trioxide2The total mass of the platinum vessel and the tungsten trioxide obtained after firing) to obtain the content of the tungsten trioxide in the third filtrate;
(4) adding analytical reagent into the beaker A containing the filter paper B and the third filter residue40mL of hydrochloric acid and 3mL of 1:3 phosphoric acid are placed on an electric furnace and heated and decomposed for 25min at 150 ℃, the volume of the system in the beaker A is concentrated to about 10mL, the beaker A is taken down and cooled, about 20mL of water is blown along the wall of the beaker A, salts and solution attached to the wall of the beaker A are blown to the bottom of the beaker, 18mL of sodium hydroxide aqueous solution with the concentration of 200g/L is added, the beaker is uniformly shaken and then placed on the electric furnace to be boiled and kept for 1 min; then taking off and cooling, transferring all the feed liquid in the beaker A into a volumetric flask A, and fixing the volume (the volume is marked as V)0I.e., 200 mL);
10mL of the test solution in the measuring flask A was aspirated (the volume was denoted as V)110mL) is placed in a beaker A, 4mL of 1:1 sulfuric acid is added, several drops of analytically pure nitric acid are added dropwise, the mixture is evaporated on an electric furnace to dryness (to obtain a white residue), 10mL of a sodium hydroxide aqueous solution with the concentration of 34g/L is taken down, 1mL of a potassium thiocyanate aqueous solution with the concentration of 250g/L, 13.5mL of 3:2 hydrochloric acid and 1mL of a titanium sulfite aqueous solution with the concentration of 10g/L are added after the white residue in the beaker A is completely dissolved, the mixture is shaken uniformly and placed for 15min to obtain a solution to be detected, the solution to be detected is transferred into a 25mL colorimetric tube, a part of the solution to be detected is transferred into a 1cm cuvette, a reagent blank is used as a reference, and the absorbance of the solution is measured at 400nm of a spectrophotometer;
(5) drawing a working curve: transferring 0.00mL, 0.50mL, 1.00mL, 2.00mL, 3.00mL, 4.00mL, 5.00mL and 6.00mL of tungsten trioxide standard solutions (the concentration is 100mg/L), respectively placing the tungsten trioxide standard solutions in a group of 25mL colorimetric tubes, supplementing 10mL with a 34g/L sodium hydroxide aqueous solution, adding 1.5mL of a 250g/L potassium thiocyanate aqueous solution, 13.5mL of 3:2 hydrochloric acid and 1mL of a 10g/L titanium sulfate aqueous solution, shaking uniformly, placing for 15min to obtain a standard solution to be measured, transferring part of the standard solution to a 1cm cuvette, measuring the absorbance of the standard solution at 400nm of a spectrophotometer by taking the reagent as a blank reference, taking the mass of the tungsten trioxide as an abscissa and the absorbance as an ordinate, and drawing a working curve.
(6) Obtaining the mass (m) of the tungsten trioxide in the liquid to be detected according to the absorbance and the working curve of the liquid to be detected1) And calculating the content (%) of the tungsten trioxide in the high-phosphorus scheelite sample according to the formula I:
in formula I:
m0-mass of the high phosphorus scheelite sample in g;
m1-the mass of tungsten trioxide found from the working curve is in mg;
m2-the mass of tungsten trioxide and platinum pan in g;
m3-mass of platinum dish in g;
V0the total volume of the test solution is 200 mL;
V1the volume of the test solution is 10 mL.
Comparative examples 1 to 7
The content of tungsten trioxide in the high-phosphorus scheelite sample was measured according to the method of example 1, except for the operating parameters in step (1), which are specifically listed in table 1; and the phosphorus removal effect and the tungsten precipitation effect in example 1 and comparative examples 1 to 7 are specifically shown in table 1.
TABLE 1 data of the respective operating parameters, phosphorus removal effect and tungsten precipitation effect in example 1 and comparative examples 1 to 7
Note: in Table 1, hydrochloric acid is shown as a column, a hydrochloric acid was prepared by diluting 2.5mL of analytically pure hydrochloric acid with water to 1000mL, and b hydrochloric acid was the first hydrochloric acid, i.e., was prepared by diluting 5mL of analytically pure hydrochloric acid with water to 1000 mL.
As can be seen from Table 1, 0.2g of Henan high-phosphorus scheelite sample is soaked for 3 hours at room temperature by 100mL of first hydrochloric acid and then filtered, the content of phosphorus in the first filtrate accounts for 98% of the content of phosphorus in the sample, and phosphorus is basically separated from tungsten in the first filter residue; the phosphorus content of the burned tungsten trioxide in the platinum dish (measured according to GB/T6150.3-2009) was found to be 0.12% (referring to the difference between the total phosphorus content of the sample and the phosphorus content of the first filtrate, as measured in example 1). The phosphorus content in the Henan high-phosphorus scheelite is generally 5-10%, so when the phosphorus content in the scheelite reaches 10% at most, the phosphorus removal rate reaches 98% after the scheelite is soaked by dilute hydrochloric acid by adopting the method disclosed by the invention, and the residual phosphorus content in the first filter residue is less than 0.2%. GB/T26019-2010 states that beryllium nitrate is added for phosphorus removal when P in ore is more than 0.3%, otherwise phosphorus does not affect the result of tungsten determination, so it can be concluded that the invention adopts 100mL of first hydrochloric acid to soak 0.2g of sample for 3h at room temperature and then filter, phosphorus and tungsten are separated, and residual phosphorus does not affect the determination of tungsten.
As can be seen from table 1, although a part of tungsten trioxide remains in the first filtrate obtained in example 1, the part of tungsten is recovered and measured in the subsequent steps, and thus, there is no influence on the measurement result.
Method comparison
The content of tungsten trioxide in the high-phosphorus scheelite sample was measured according to the method of example 1 and the method of GB/T26019-2010, and the content of tungsten trioxide in the solution to be measured in step (4) was examined, and the results are shown in Table 2.
TABLE 2 measurement results of the method of example 1 and GB/T26019-2010 method
| Method | Content of tungsten trioxide in sample (%) | Content of tungsten trioxide (%) |
| GB/T26019-2010 method | 22.26 | 6.82 |
| Method of example 1 | 22.78 | 0.45 |
As can be seen from Table 2, the tungsten trioxide content of the high-phosphorus scheelite sample measured by the GB/T26019-2010 method is low, the tungsten trioxide content of the solution to be measured is high, the ratio of the tungsten trioxide content in the high-phosphorus scheelite sample is large, and the influence on the result is large. By adopting the method of the embodiment 1, the content of the tungsten trioxide in the solution to be measured is small, and the influence on the result is small, so that the measurement result of the content of the tungsten trioxide is more accurate.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. A method for measuring the content of tungsten trioxide in high-phosphorus scheelite is characterized by comprising the following steps:
soaking high-phosphorus scheelite by using first hydrochloric acid, and performing first filtration on the obtained soaked material to obtain first filter residue and first filtrate; the first hydrochloric acid is prepared by diluting 4.5-5.5 mL of analytically pure hydrochloric acid with water to 1000mL, and the dosage ratio of the first hydrochloric acid to the high-phosphorus scheelite is (80-120) mL: 0.2 g; the temperature of the soaking treatment is room temperature, and the time is 2-4 h;
mixing the first filter residue with nitric acid, perchloric acid and second hydrochloric acid, performing I heat treatment, and performing second filtration on the obtained I heat treatment material to obtain a second filter residue and a second filtrate;
mixing the ammonia water-ammonium nitrate mixed solution with the second filter residue, performing third filtration to obtain a third filter residue and a third filtrate, evaporating the third filtrate to dryness, and then firing, wherein the remainder is tungsten trioxide, so as to obtain the content of the tungsten trioxide in the third filtrate;
mixing the third filter residue with phosphoric acid and third hydrochloric acid, and then carrying out II heat treatment, mixing the obtained II heat treatment material with a sodium hydroxide aqueous solution, and then carrying out III heat treatment to obtain a III heat treatment material;
mixing the first filtrate, the second filtrate and the III heat treatment material, and measuring the content of tungsten trioxide in the obtained mixed feed liquid by a colorimetric method to obtain the content of tungsten trioxide in the mixed feed liquid;
obtaining the content of the tungsten trioxide in the high-phosphorus scheelite according to the content of the tungsten trioxide in the third filtrate and the content of the tungsten trioxide in the mixed feed liquid;
in the process of the I heat treatment, the nitric acid is analytically pure nitric acid, the perchloric acid is analytically pure perchloric acid, and the second hydrochloric acid is analytically pure hydrochloric acid;
the temperature of the first heat treatment is 180-220 ℃, and the time is 15-35 min;
in the process of the second heat treatment, the phosphoric acid is prepared by diluting 48-52 mL of analytically pure phosphoric acid with water to 200mL, and the third hydrochloric acid is analytically pure hydrochloric acid;
the temperature of the second heat treatment is 100-200 ℃, and the time is 20-30 min;
the temperature of the third heat treatment is 300-350 ℃, and the time is 10-20 min;
the method for measuring the content of the tungsten trioxide in the mixed feed liquid by adopting a colorimetric method comprises the following steps:
mixing the mixed feed liquid, sulfuric acid and nitric acid, evaporating to dryness, and mixing the obtained residue with a sodium hydroxide aqueous solution, a potassium thiocyanate aqueous solution, hydrochloric acid and a titanium sulfate aqueous solution to obtain a solution to be detected;
measuring the absorbance of the solution to be measured, and obtaining the content of the tungsten trioxide in the mixed feed liquid according to the working curve of the tungsten trioxide and the absorbance of the obtained solution to be measured;
calculating the content (%) of the tungsten trioxide in the high-phosphorus scheelite sample according to the formula I:
in formula I:
m0-mass of the high phosphorus scheelite sample in g;
m1-the mass of tungsten trioxide found from the working curve is in mg;
m2-the mass of tungsten trioxide and platinum pan in g;
m3-mass of platinum dish in g;
V0the total volume of the test solution is 200 mL;
V1the volume of the test solution is 10 mL.
2. The method according to claim 1, wherein the first hydrochloric acid is prepared by diluting 5mL of analytically pure hydrochloric acid to 1000mL with water, and the dosage ratio of the first hydrochloric acid to the high-phosphorus scheelite is 100 mL: 0.2 g; the temperature of the soaking treatment is 20 ℃, and the time is 3 h.
3. The method as claimed in claim 1, wherein during the heat treatment I, the dosage ratio of the first filter residue to the nitric acid, perchloric acid and second hydrochloric acid is (0.17-0.21) g: 20mL of: 10mL of: 50 mL.
4. The method according to claim 1, wherein the ammonia-ammonium nitrate mixed solution is prepared by diluting 195-205 mL of analytically pure ammonia and 9-11 g of ammonium nitrate with water to 1000 mL; the dosage ratio of the ammonia water-ammonium nitrate mixed solution to the second filter residue is (25-40) mL: (0.04-0.09) g.
5. The method according to claim 1, wherein in the heat treatment process of the second stage II, the dosage ratio of the third filter residue to the phosphoric acid and the third hydrochloric acid is (0.004-0.009) g: 3mL of: 40 mL.
6. The method according to claim 1, wherein the concentration of the aqueous sodium hydroxide solution is 190-210 g/L, and the volume ratio of the aqueous sodium hydroxide solution to the II th heat-treated material is 18: 10.
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