CN107101905A - A kind of method of Se content in measure impure selenium - Google Patents
A kind of method of Se content in measure impure selenium Download PDFInfo
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- CN107101905A CN107101905A CN201710270326.XA CN201710270326A CN107101905A CN 107101905 A CN107101905 A CN 107101905A CN 201710270326 A CN201710270326 A CN 201710270326A CN 107101905 A CN107101905 A CN 107101905A
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- selenium
- impure
- acid
- impure selenium
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- 239000011669 selenium Substances 0.000 title claims abstract description 147
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 123
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 238000000034 method Methods 0.000 title claims abstract description 45
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical group OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims abstract description 34
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 31
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical group [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 27
- 239000007800 oxidant agent Substances 0.000 claims abstract description 26
- 230000001590 oxidative effect Effects 0.000 claims abstract description 26
- 238000001556 precipitation Methods 0.000 claims abstract description 24
- 239000013049 sediment Substances 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 22
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 20
- 230000001376 precipitating effect Effects 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000004364 calculation method Methods 0.000 claims abstract description 10
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910001626 barium chloride Inorganic materials 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 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 6
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 6
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical group Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000012535 impurity Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052785 arsenic Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 238000002386 leaching Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- 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 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims 2
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- 238000004458 analytical method Methods 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000003556 assay Methods 0.000 abstract description 3
- 238000001514 detection method Methods 0.000 abstract description 3
- 235000011649 selenium Nutrition 0.000 description 103
- 239000000523 sample Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 11
- 238000006722 reduction reaction Methods 0.000 description 9
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 9
- 235000019345 sodium thiosulphate Nutrition 0.000 description 9
- 239000010949 copper Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 238000004448 titration Methods 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 235000019504 cigarettes Nutrition 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000012937 correction Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 2
- 241001062009 Indigofera Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 102000004316 Oxidoreductases Human genes 0.000 description 1
- 108090000854 Oxidoreductases Proteins 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000012472 biological sample Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003342 selenium Chemical class 0.000 description 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- -1 thio sulphur Chemical compound 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N5/00—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
- G01N5/04—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid by removing a component, e.g. by evaporation, and weighing the remainder
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a kind of method for determining Se content in impure selenium, comprise the following steps：A) by impure selenium and water Hybrid Heating, add reducing agent and reacted, obtain sediment；B the sediment) is added into oxidant progress oxidation reaction with after acid dissolving, the oxidant is selected from perchloric acid and composite oxidant, potassium permanganate or the potassium bichromate of hydrogen peroxide formation；C) by step B) oxidation product carry out adding precipitating reagent after salinization and reacted, precipitated, obtain the content of selenium in impure selenium according to the Mass Calculation of precipitation, the precipitating reagent is selected from barium nitrate or barium chloride.The method of Se content is simple in the measure impure selenium that the present invention is provided, flow is short, and result is accurate, and operating personnel are easy to grasp.The reagent used in method is cheap and easy to get, and avoids, using multi-method instruments such as ICP spectrometers, reducing assay cost.This can be suitably used for impure selenium production detection and analysis, be conducive to Instructing manufacture.Also it can be suitably used for trade settlement analysis.
Description
Technical field
The invention belongs to non-ferrous metal metallurgy technical field, and in particular to a kind of method of Se content in measure impure selenium.
Background technology
Selenium is a kind of non-metal chemical element, and chemical symbol is Se.Selenium is a kind of important raw material of industry, may be used as light
Quick material, electrolytic manganese industry catalyst etc..Purposes is quite varied.
Current 90% primary selenium is occurred mainly with the earth of positive pole of cupric electrolysis, and crude product is exactly impure selenium.Electrolysis production is cloudy
In the process for copper of pole, the copper anode mud of generation passes through pyrometallurgical smelting, produces the flue gas containing selenium, and flue gas is handled by cleaning system, is used
The reduction generation impure selenium such as reducing agent such as sodium sulfite.Wherein Se content is substantially in 80-99%.
Impure selenium is important byproduct in Copper making, and selenium is most important of which valuation element.The measure of selenium, to production work
Skill Con trolling index, trade settlement has larger directive significance.
At present, the measure of selenium does not issue the standard method of analysis of execution also in impure selenium, partly may be referred to purity higher
Selenium chemical analysis method, the analysis method of selenium dioxide, the assay method of the impure selenium of part document report, and thio sulphur
Sour sodium titration and hydroxylamine hydrochloride reduction gravimetric method etc..
Specifically disclosed in the People's Republic of China (PRC) non-ferrous metal industry YST 226.12-2009 selenium chemical analysis method-
12 parts-selenium measures fixed-sodium thiosulfate volumetric method (measurement range 98.0-99.0%), and specific method is：Sample is through salt
After acid, nitric acid are decomposed, in sulfuric acid medium, titrated with sodium thiosulfate standard titration solution.Iodine is added when closing on terminal
Change potassium, react the iodine separated out using starch as indicator, continuation is titrated with sodium thiosulfate standard titration solution, is titrated to indigo plant
Decoloration is terminal.Calculate the content of selenium in sample.This method is primarily adapted for use in the measure for determining selenium amount in the higher selenium of purity,
Measurement range 98.0-99.0%.This selenium material is compared with impure selenium, and matrix composition is simple, and sample is only needed after simply dissolving, so that it may
To be titrated with sodium thiosulfate.And the matrix composition of impure selenium is complicated, containing more impurity element, directly dripped with sodium thiosulfate
Surely larger error is had.
The specific method of sodium thiosulfate titration is：Sample is containing tartaric acid after nitric acid, sulfuric acid decomposition
In 6moL/L hydrochloric acid solutions, monomer selenium, filtering and other element sepatations are separated out with hydroxylamine hydrochloride reduction, monomer selenium acid dissolves,
In sulfuric acid medium, titrated with sodium thiosulfate standard titration solution.KI is added when closing on terminal, what reaction was separated out
Iodine is using starch as indicator, and continuation is titrated with sodium thiosulfate standard titration solution, and it is terminal to be titrated to blueness and disappear.Should
Method is reacted because early stage adds sodium thiosulfate with most selenium, and KI is added when closing on terminal, so needing to shift to an earlier date
Know the substantially content of Selenium In Some Selenium-rich Biological Samples, for unknown content impure selenium sample, determining has certain inconvenience.Further, since
The reaction speed of KI and selenium be not quickly, when close to reaction end, sodium thiosulfate with generation Iod R it is complete after,
Blueness is disappeared, and directing terminal is reached, but the KI iodine newly-generated with selenium reaction can make solution return color, it is necessary to titrate repeatedly again,
Comparatively laborious, endpoint is more difficult, and error is also big.If simultaneously reaction solution standing time it is longer after, the iodide ion in solution
Also have a small amount of oxidized, and cause and return color, increase titration error.
The measure of standard YS/T1084.3 impure seleniums chemical analysis method-third portion-selenium amount discloses hydroxylamine hydrochloride also original weight
Amount method, specific method is：Sample aqua regia dissolution, in 3mol/L~4mol/L hydrochloric acid medium, selenium is reduced with hydroxylamine hydrochloride
Separate, filtered with glass sand core crucible with other impurities for elemental stage, precipitation is washed with water and ethanol, is weighed after constant weight.Receive
Collect filtrate, the selenium amount remained in filtrate is determined with ICP-OES methods and is maked corrections.
Application No. 201310545957.X Chinese patent discloses a kind of method for analyzing Se content in impure selenium, specifically
For：Sample nitric acid and dissolving with hydrochloric acid, filtering, the insoluble element disturbance of separating acid；Hydrazine hydrate reduction, filtering, separate section interference
Element；Precipitation is again through acid dissolving, and ICP spectrophotometer telluriums exclude main interference element；Filtrate through spectrophotometer Se content,
Analysis result is maked corrections.
But, need the selenium in impure selenium is reduced into elemental selenium with hydroxylamine hydrochloride or hydrazine hydrate in above two method and sink
Form sediment, most selenium is all dissolved by acid oxidase in solution before reduction, and the reduction reaction time is long.Also, it is molten in reduction reaction
The impurity such as tellurium, copper, lead, bismuth, arsenic, iron has a certain degree of reduction in liquid, forms co-precipitation.So sometimes for rinsing repeatedly
Many times.If impurity content is higher in impure selenium sample, this influence will be apparent from, and Gao Shineng reaches 0.05-0.1% ratio
Example.Influence the measurement result degree of accuracy.Deducted sometimes for impurity content is determined with ICP-OES.In addition, Application No.
201310545957.X Chinese patent uses different reducing agent hydrazine hydrates, but reduction effect is different, is introduced more in precipitation
Many impurity.Not only need to be maked corrections with the selenium amount remained in ICP-OES measure filtrates, in addition it is also necessary to determined and precipitated with ICP-OES
In tellurium deducted.Continuous mode is more cumbersome.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of method for determining Se content in impure selenium, this
Invent the method provided simply, flow is short, and result is accurate.
The invention provides a kind of method for determining Se content in impure selenium, comprise the following steps：
A) by impure selenium and water Hybrid Heating, add reducing agent and reacted, obtain sediment；
B) sediment is added oxidant and carry out oxidation reaction, the oxidant is selected from (perchloric acid with after acid dissolving
And hydrogen peroxide), the one or more in potassium permanganate and potassium bichromate；
C) by step B) oxidation product carry out salinization after add precipitating reagent reacted, precipitated, according to precipitation
Mass Calculation obtains the content of selenium in impure selenium, and the precipitating reagent is selected from barium nitrate or barium chloride.
It is preferred that, the oxidant is selected from perchloric acid and the composite oxidant of hydrogen peroxide formation, the composite oxidant
The volume ratio of middle perchloric acid and hydrogen peroxide is (4~6)：(4~6).
It is preferred that, the reducing agent is selected from hydroxylamine hydrochloride, sulphuric acid leaching, hydrazine hydrate or stannous chloride.
It is preferred that, the acid is selected from nitric acid or hydrochloric acid.
It is preferred that, by step B) oxidation product mixed with sodium hydroxide, potassium hydroxide or sodium carbonate progress salinization.
It is preferred that, the precipitating reagent is selected from barium nitrate.
It is preferred that, step A) temperature of reaction is about 90~100 DEG C, time of reaction is 30~60 minutes；
Step B) oxidation reaction temperature be 90~100 DEG C, the time be 20~40 minutes；
Step C) reaction temperature be 90~100 DEG C, the time be 1.5~2 hours.
It is preferred that, comprise the following steps：
By impure selenium and water Hybrid Heating, add hydroxylamine hydrochloride and reacted, obtain sediment；
The sediment is subjected to oxidation reaction with addition perchloric acid after acid dissolving with hydrogen peroxide；
Above-mentioned oxidation product is reacted with sodium hydroxide and barium nitrate successively, precipitated, according to the quality meter of precipitation
Calculate the content for obtaining selenium in impure selenium.
It is preferred that, shown in the calculation formula such as formula (I)：
In formula (I), w be impure selenium in selenium percentage composition, %,
m1For the quality of precipitation,
m0For the quality of impure selenium.
It is preferred that, the major impurity element that the impure selenium is included in selenium and impurity component, the impurity component includes
Pb, S, Cu, Te, Fe, As and Sb.
Compared with prior art, the invention provides a kind of method for determining Se content in impure selenium, comprise the following steps：A)
By impure selenium and water Hybrid Heating, add reducing agent and reacted, obtain sediment；B after) sediment is dissolved with acid,
Add oxidant and carry out oxidation reaction, the oxidant is selected from composite oxidant, the permanganic acid of perchloric acid and hydrogen peroxide formation
Potassium or potassium bichromate；C) by step B) oxidation product carry out salinization after add precipitating reagent reacted, precipitated, according to sink
The Mass Calculation in shallow lake obtains the content of selenium in impure selenium, and the precipitating reagent is selected from barium nitrate or barium chloride.The measure that the present invention is provided
The method of Se content is simple in impure selenium, flow is short, and result is accurate, and operating personnel are easy to grasp.The reagent used in method
It is cheap and easy to get, and avoid, using multi-method instruments such as ICP spectrometers, reducing assay cost.This can be suitably used for impure selenium life
Production detection and analysis, is conducive to Instructing manufacture.Also it can be suitably used for trade settlement analysis.
Embodiment
The invention provides a kind of method for determining Se content in impure selenium, comprise the following steps：
A) by impure selenium and water Hybrid Heating, add reducing agent and reacted, obtain sediment；
B) sediment is added oxidant and carry out oxidation reaction, the oxidant is selected from perchloric acid with after acid dissolving
With composite oxidant, potassium permanganate or the potassium bichromate of hydrogen peroxide formation；
C) by step B) oxidation product carry out salinization after add precipitating reagent reacted, precipitated, according to precipitation
Mass Calculation obtains the content of selenium in impure selenium, and the precipitating reagent is selected from barium nitrate or barium chloride.
The present invention adds reducing agent and reacted, obtain sediment first by impure selenium and water Hybrid Heating.The impure selenium
The generation after copper anode mud flue gas during smelting purified treatment is a kind of Se content substantially in 80wt%~99wt% selenium material.
In the present invention, the Se content that the impure selenium includes in selenium and impurity component, the impure selenium is 80wt%~99wt%, described
Major impurity element in impurity component includes Pb, S, Cu, Te, Fe, As and Sb.The content of the impurity element accounts for the impure selenium
In mass percent be：Pb：0.001wt%~2wt%；S：0.01wt%~3wt%；Cu：0.001wt%~1wt%；
Te：0.001wt%~1wt%；Fe：0.001wt%~0.5wt%；As：0.001wt%~0.05wt%；Sb：0.001wt%
~0.05wt%.
The present invention is by above-mentioned impure selenium and water Hybrid Heating, and the temperature of the heating is preferably 90~100 DEG C, is heated to micro-boiling
Afterwards, add reducing agent to be reacted, obtain sediment.The reducing agent is selected from hydroxylamine hydrochloride, sulphuric acid leaching, hydrazine hydrate, two
Stannic chloride, preferably hydroxylamine hydrochloride.The temperature of the reaction is preferably 90~100 DEG C, keeps micro-boiling, the time of the reaction is
30~60 minutes.
Obtain after sediment, washed after the sediment is filtered.Then the acid of the sediment after the washing is dissolved.
Wherein, the acid is preferably nitric acid or hydrochloric acid, more preferably nitric acid.The temperature of the dissolving is preferably 90~100 DEG C.
After sediment dissolving completely, add oxidant and carry out oxidation reaction, the oxidant is selected from perchloric acid and peroxidating
Composite oxidant, potassium permanganate or the potassium bichromate of hydrogen formation, preferably perchloric acid and the composite oxidant of hydrogen peroxide formation,
The volume ratio of perchloric acid and hydrogen peroxide is (4~6) in the composite oxidant：(4~6), preferably 5:5.The oxidation is anti-
The temperature answered is preferably 90~100 DEG C, and the time is preferably 20~40 minutes.
Then, above-mentioned oxidation product is subjected to salinization, the specific method of the salinization is：By above-mentioned oxidation product and hydrogen-oxygen
Change sodium, potassium hydroxide or sodium carbonate mixing and carry out salinization, it is preferred that above-mentioned oxidation product is mixed into progress salt with sodium hydroxide
Change.
Finally, add precipitating reagent to be reacted, precipitated, containing for selenium in impure selenium is obtained according to the Mass Calculation of precipitation
Amount, the precipitating reagent is selected from barium nitrate or barium chloride.In the present invention, the precipitating reagent is selected from barium nitrate or barium chloride, preferably
For barium nitrate.The temperature of the reaction is preferably 90~100 DEG C, keeps micro-boiling, the time is preferably 1.5~2h.Dried according to precipitation
Mass Calculation after dry obtains the content of selenium in impure selenium.
In the present invention, the mass ratio of impure selenium and reducing agent is preferably 1:(6~10), more preferably 1：(7~9).Impure selenium
Mass volume ratio with acid is preferably 1g：(30~50) ml, more preferably 1g：(35~45) ml.
The mass volume ratio of impure selenium and oxidant is 1g：(16~24) ml, preferably 1g：(18~22) ml；
The aqueous solution mass volume ratio of material of the impure selenium with oxidation product to be carried out to salinization is preferably 1g：(70~90) ml,
More preferably 1g：(75~85) ml, wherein, the concentration that oxidation product is carried out to the aqueous solution of the material of salinization is 180~220g/
L；
The mass volume ratio 1g of the aqueous solution of impure selenium and precipitating reagent：(36~50) ml, preferably 1g：(40~45) ml, institute
The concentration for stating the aqueous solution of precipitating reagent is 130~170g/L.
In certain specific embodiments of the invention, Se content method in the measure impure selenium comprises the following steps：
By impure selenium and water Hybrid Heating, add hydroxylamine hydrochloride and reacted, obtain sediment；
The sediment is subjected to oxidation reaction with addition perchloric acid after acid dissolving with hydrogen peroxide；
Above-mentioned oxidation product is reacted with sodium hydroxide and barium nitrate successively, precipitated, according to the quality meter of precipitation
Calculate the content for obtaining selenium in impure selenium.
Wherein, shown in the calculation formula such as formula (I)：
In formula (I), w be impure selenium in selenium percentage composition, %,
m1For the quality of precipitation,
m0For the quality of impure selenium,
0.2817 is coefficient, 0.2817=78.96/280.3, and 78.96 be Se molecular weight, and 280.3 be BaSeO4Point
Son amount.
The method of Se content is simple in the measure impure selenium that the present invention is provided, flow is short, and result is accurate, and operating personnel are easy
In grasp.The reagent used in method is cheap and easy to get, and avoids, using multi-method instruments such as ICP spectrometers, reducing chemical examination point
Analyse cost.This can be suitably used for impure selenium production detection and analysis, be conducive to Instructing manufacture.Also it can be suitably used for trade settlement analysis.
For a further understanding of the present invention, the side of Se content in the measure impure selenium provided with reference to embodiment the present invention
Method is illustrated, and protection scope of the present invention is not limited by the following examples.
Impure selenium sample used in following examples is produced after copper anode mud flue gas during smelting purified treatment, and Se content is big
Cause major impurity element in 80wt%~99wt%, the impurity component in addition to selenium include Pb, S, Cu, Te, Fe, As and
Sb.The mass percent that the content of the impurity element is accounted in the impure selenium is：Pb：0.001wt%~2wt%；S：
0.01wt%~3wt%；Cu：0.001wt%~1wt%；Te：0.001wt%~1wt%；Fe：0.001wt%~
0.5wt%；As：0.001wt%~0.05wt%；Sb：0.001wt%~0.05wt%.
Embodiment 1
Weigh impure selenium sample 0.5022g (m0), it is placed in 250mL conical flasks.About 100mL water is added, micro-boiling is heated, added
4g hydroxylamine hydrochlorides.Low-temperature heat.Filtered with quantitative filter paper at a slow speed.Precipitation and beaker 3 times is washed with water.Precipitation is transferred to former beaker
In, add 19mLHNO3, in low-temperature heat on electric hot plate, treat that brown cigarette emits to the greatest extent, remove, cool down.Add 4.5mL hydrogen peroxide and
4mL perchloric acid, low-temperature heat is complete to reaction.Remove, be slowly added to about 40mL sodium hydroxide (200g/L), regulation solution to
Faintly acid, low-temperature heat is slightly cold.About 21mL barium nitrates solution (150g/L) is slowly added dropwise, low-temperature heat is cold to reacting complete
But.Filtered with quantitative filter paper at a slow speed, rinsed and precipitated with dust technology.Precipitation is dried about through 105 DEG C ± 5 DEG C of Constant Temp. Oven
2 hours, weighed (m after cooling1), the content of selenium in sample is calculated by formula (I).
Embodiment 2
Weigh impure selenium sample 0.4981g (m0), it is placed in 250mL conical flasks.About 110mL water is added, micro-boiling is heated, added
3.5g hydroxylamine hydrochloride.Low-temperature heat.Filtered with quantitative filter paper at a slow speed.Precipitation and beaker 3 times is washed with water.Precipitation is transferred to former beaker
In, 22mL hydrochloric acid is added, in low-temperature heat on electric hot plate, treats that brown cigarette emits to the greatest extent, removes, cool down.Add 5mL hydrogen peroxide and
5mL perchloric acid, low-temperature heat is complete to reaction.Remove, be slowly added to about 45mL potassium hydroxide (220g/L), regulation solution to
Faintly acid, low-temperature heat is slightly cold.About 23mL barium nitrates solution (150g/L) is slowly added dropwise, low-temperature heat is cold to reacting complete
But.Filtered with quantitative filter paper at a slow speed, rinsed and precipitated with dust technology.Precipitation is dried about through 105 DEG C ± 5 DEG C of Constant Temp. Oven
2 hours, weighed (m after cooling1), the content of selenium in sample is calculated by formula (I).
Embodiment 3
Weigh impure selenium sample 0.5009g (m0), it is placed in 250mL conical flasks.About 100mL water is added, micro-boiling is heated, added
5g hydrazine hydrates.Low-temperature heat.Filtered with quantitative filter paper at a slow speed.Precipitation and beaker 3 times is washed with water.Precipitation is transferred in former beaker,
Add 20mLHNO3, in low-temperature heat on electric hot plate, treat that brown cigarette emits to the greatest extent, remove, cool down.6g potassium permanganate is added, low temperature adds
Heat is complete to reaction.Remove, be slowly added to about 42mL sodium hydroxide (200g/L), regulation solution to faintly acid, low-temperature heat,
It is slightly cold.About 20mL barium chloride solutions (170g/L) are slowly added dropwise, low-temperature heat is cooled down to reacting complete.With quantitative filter paper at a slow speed
Filtering, is rinsed with dust technology and precipitated.Precipitation is dried about 2 hours through 105 DEG C ± 5 DEG C of Constant Temp. Oven, is weighed after cooling
(m1), the content of selenium in sample is calculated by formula (I).
The Precision Experiment of embodiment 4
With selenium amount 4 times in the different impure selenium sample of the method parallel determination two of embodiment 1, measurement result is then calculated
Relative standard deviation.It the results are shown in Table 1.
The Precision Experiment result of table 1
The rate of recovery of embodiment 5 is tested
Take impure selenium sample (background Se contents：85.01%) content of selenium, is determined with the method for embodiment 1, and by quantitative
Addition pure selenium (Se >=99.99%), carry out recovery of standard addition experiment, experimental result is shown in Table 2.
The sample recovery of standard addition of table 2
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of method for determining Se content in impure selenium, it is characterised in that comprise the following steps：
A) by impure selenium and water Hybrid Heating, add reducing agent and reacted, obtain sediment；
B) sediment is added oxidant and carry out oxidation reaction, the oxidant is selected from perchloric acid and mistake with after acid dissolving
Composite oxidant, potassium permanganate or the potassium bichromate of hydrogen oxide formation；
C) by step B) oxidation product carry out salinization after add precipitating reagent reacted, precipitated, according to the quality of precipitation
The content for obtaining selenium in impure selenium is calculated, the precipitating reagent is selected from barium nitrate or barium chloride.
2. according to the method described in claim 1, it is characterised in that the oxidant is selected from perchloric acid and hydrogen peroxide formation
The volume ratio of perchloric acid and hydrogen peroxide is (4~6) in composite oxidant, the composite oxidant：(4~6).
3. according to the method described in claim 1, it is characterised in that the reducing agent is selected from hydroxylamine hydrochloride, sulphuric acid leaching, hydration
Hydrazine, stannous chloride.
4. according to the method described in claim 1, it is characterised in that the acid is selected from nitric acid or hydrochloric acid.
5. oxidation product according to the method described in claim 1, it is characterised in that by step B) and sodium hydroxide, hydroxide
Potassium or sodium carbonate mixing carry out salinization.
6. according to the method described in claim 1, it is characterised in that the precipitating reagent is selected from barium nitrate.
7. according to the method described in claim 1, it is characterised in that step A) reaction temperature be 90~100 DEG C, reaction when
Between be 30~60 minutes；
Step B) oxidation reaction temperature be 90~100 DEG C, the time be 20~40 minutes；
Step C) reaction temperature be 90~100 DEG C, the time be 1.5~2 hours.
8. according to the method described in claim 1, it is characterised in that comprise the following steps：
By impure selenium and water Hybrid Heating, add hydroxylamine hydrochloride and reacted, obtain sediment；
The sediment is subjected to oxidation reaction with addition perchloric acid after acid dissolving with hydrogen peroxide；
Above-mentioned oxidation product is reacted with sodium hydroxide and barium nitrate successively, is precipitated, is obtained according to the Mass Calculation of precipitation
The content of selenium into impure selenium.
9. according to the method described in claim 1, it is characterised in that shown in the calculation formula such as formula (I)：
In formula (I), w be impure selenium in selenium percentage composition, %,
m1For the quality of precipitation,
m0For the quality of impure selenium.
10. according to the method described in claim 1, it is characterised in that the impure selenium includes selenium and impurity component, described miscellaneous
Major impurity element in matter composition includes Pb, S, Cu, Te, Fe, As and Sb.
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| CN111983135A (en) * | 2020-07-04 | 2020-11-24 | 福建紫金矿冶测试技术有限公司 | Detection method for determining selenium in crude tellurium dioxide |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02254339A (en) * | 1989-03-29 | 1990-10-15 | Mitsubishi Metal Corp | Apparatus for estimating evaporation residue in volatilizing refined material |
| US20030070943A1 (en) * | 2000-03-07 | 2003-04-17 | Shevchenko Sergey M. | Method and apparatus for measuring deposit forming capacity of fluids using an electrochemically controlled pH change in the fluid proximate to a piezoelectric microbalance |
| CN101149357A (en) * | 2007-11-06 | 2008-03-26 | 苏州大学 | A kind of assay method of selenium content |
| CN101177250A (en) * | 2007-10-31 | 2008-05-14 | 先导（清远）稀有金属化工有限公司 | Production method of barium selenate |
| AU2009230806A1 (en) * | 2008-10-31 | 2010-05-20 | Elanco New Zealand | Improved medicament formulation |
| CN102086029A (en) * | 2010-12-04 | 2011-06-08 | 金川集团有限公司 | Method for extracting selenium from selenium-contained material |
| CN101492181B (en) * | 2009-02-20 | 2011-07-27 | 中南大学 | Method for removing tungsten, vanadium, phosphor and arsenic from molybdate solution by deposition |
| CN102175673A (en) * | 2011-01-18 | 2011-09-07 | 安徽泰格生物技术股份有限公司 | Method for detecting total selenium content |
| CN103418316A (en) * | 2010-01-29 | 2013-12-04 | 张颖 | Preparation method of modified micro-granules |
| CN103592197A (en) * | 2013-11-07 | 2014-02-19 | 铜陵有色金属集团股份有限公司 | Method for analyzing selenium content in crude selenium |
| CN103588181A (en) * | 2013-10-30 | 2014-02-19 | 四川鑫龙碲业科技开发有限责任公司 | Wet method for preparing low-sulfur refined selenium |
| CN103645165A (en) * | 2013-11-26 | 2014-03-19 | 金堆城钼业股份有限公司 | Method for measuring content of selenium in molybdenum and molybdenum product |
| CN104911358A (en) * | 2015-06-10 | 2015-09-16 | 中南大学 | Method for separating arsenic and selenium from copper anode slime alkaline leach liquor |
| CN105000537A (en) * | 2015-06-29 | 2015-10-28 | 中南大学 | Method for separating selenium in alkaline leachate |
| CN106323933A (en) * | 2016-08-12 | 2017-01-11 | 浙江大学 | Method for determining elementary selenium content |
| CN106542506A (en) * | 2016-12-08 | 2017-03-29 | 湖南水口山有色金属集团有限公司 | A kind of method that selenium is reclaimed from heavy tellurium waste liquid |
-
2017
- 2017-04-24 CN CN201710270326.XA patent/CN107101905B/en active Active
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02254339A (en) * | 1989-03-29 | 1990-10-15 | Mitsubishi Metal Corp | Apparatus for estimating evaporation residue in volatilizing refined material |
| US20030070943A1 (en) * | 2000-03-07 | 2003-04-17 | Shevchenko Sergey M. | Method and apparatus for measuring deposit forming capacity of fluids using an electrochemically controlled pH change in the fluid proximate to a piezoelectric microbalance |
| CN101177250A (en) * | 2007-10-31 | 2008-05-14 | 先导（清远）稀有金属化工有限公司 | Production method of barium selenate |
| CN100577559C (en) * | 2007-10-31 | 2010-01-06 | 清远先导稀有材料有限公司 | Production method of barium selenate |
| CN101149357A (en) * | 2007-11-06 | 2008-03-26 | 苏州大学 | A kind of assay method of selenium content |
| AU2009230806A1 (en) * | 2008-10-31 | 2010-05-20 | Elanco New Zealand | Improved medicament formulation |
| CN101492181B (en) * | 2009-02-20 | 2011-07-27 | 中南大学 | Method for removing tungsten, vanadium, phosphor and arsenic from molybdate solution by deposition |
| CN103418316A (en) * | 2010-01-29 | 2013-12-04 | 张颖 | Preparation method of modified micro-granules |
| CN102086029A (en) * | 2010-12-04 | 2011-06-08 | 金川集团有限公司 | Method for extracting selenium from selenium-contained material |
| CN102175673A (en) * | 2011-01-18 | 2011-09-07 | 安徽泰格生物技术股份有限公司 | Method for detecting total selenium content |
| CN103588181A (en) * | 2013-10-30 | 2014-02-19 | 四川鑫龙碲业科技开发有限责任公司 | Wet method for preparing low-sulfur refined selenium |
| CN103592197A (en) * | 2013-11-07 | 2014-02-19 | 铜陵有色金属集团股份有限公司 | Method for analyzing selenium content in crude selenium |
| CN103645165A (en) * | 2013-11-26 | 2014-03-19 | 金堆城钼业股份有限公司 | Method for measuring content of selenium in molybdenum and molybdenum product |
| CN104911358A (en) * | 2015-06-10 | 2015-09-16 | 中南大学 | Method for separating arsenic and selenium from copper anode slime alkaline leach liquor |
| CN105000537A (en) * | 2015-06-29 | 2015-10-28 | 中南大学 | Method for separating selenium in alkaline leachate |
| CN106323933A (en) * | 2016-08-12 | 2017-01-11 | 浙江大学 | Method for determining elementary selenium content |
| CN106542506A (en) * | 2016-12-08 | 2017-03-29 | 湖南水口山有色金属集团有限公司 | A kind of method that selenium is reclaimed from heavy tellurium waste liquid |
Non-Patent Citations (2)
| Title |
|---|
| VICTOR LENHER: "The quantitative determation of selenium tellurium", 《PROCEEDINGS OF THE AMERICAN PHILOSOPHICAL SOCIETY》 * |
| 潘云琼: "间接碘量法测定粗硒中硒的含量", 《环境科学导刊》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111983135A (en) * | 2020-07-04 | 2020-11-24 | 福建紫金矿冶测试技术有限公司 | Detection method for determining selenium in crude tellurium dioxide |
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Inventor after: Wan Shuang Inventor after: Li Xianhe Inventor after: Zhao Jiuke Inventor after: Jiang Hong Inventor after: Qi Yuehua Inventor before: Wan Shuang Inventor before: Li Xianhe Inventor before: Zhao Jiuke Inventor before: Jiang Hong Inventor before: Qi Yuehua |