CN116818679A - Method for measuring trace sulfur - Google Patents
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- CN116818679A CN116818679A CN202310086572.5A CN202310086572A CN116818679A CN 116818679 A CN116818679 A CN 116818679A CN 202310086572 A CN202310086572 A CN 202310086572A CN 116818679 A CN116818679 A CN 116818679A
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000011593 sulfur Substances 0.000 title claims abstract description 74
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 40
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052802 copper Inorganic materials 0.000 claims abstract description 43
- 239000010949 copper Substances 0.000 claims abstract description 43
- 238000004458 analytical method Methods 0.000 claims abstract description 21
- 230000003595 spectral effect Effects 0.000 claims abstract description 19
- 238000011088 calibration curve Methods 0.000 claims abstract description 16
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 12
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 9
- 238000012360 testing method Methods 0.000 claims abstract description 6
- 238000007865 diluting Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 69
- 239000012086 standard solution Substances 0.000 claims description 26
- 238000005868 electrolysis reaction Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- 235000019270 ammonium chloride Nutrition 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000005259 measurement Methods 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 150000003568 thioethers Chemical class 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 37
- 230000006872 improvement Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- 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
- G01N1/38—Diluting, dispersing or mixing samples
-
- 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
- G01N1/40—Concentrating samples
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention relates to the technical field of spectrochemical analysis and test, in particular to a method for measuring trace sulfur, which comprises the following steps: s1: preparing a solution; s2: electrolytic copper removal to enrich trace sulfur; s3: establishing a calibration curve; s4: and (3) measuring the sample. The method comprises the steps of dissolving a sample by nitric acid, oxidizing potassium permanganate to enable sulfide in the sample to be completely converted into sulfate ions, utilizing a constant current electrolyzer to electrolyze and remove copper, concentrating and diluting the solution to a certain volume after the solution is discolored, fixing the volume, selecting an analysis spectral line on a spectrometer, selecting the analysis wavelength to be 180.731nm, avoiding spectral interference of coexisting elements on sulfur, deducting a background at a proper position, measuring the relative spectral intensity of sulfur, calculating the mass fraction of sulfur on a working curve, and further measuring trace sulfur.
Description
Technical Field
The invention relates to the technical field of spectrochemical analysis and test, in particular to a method for measuring trace sulfur.
Background
Copper is one of nonferrous metals with excellent comprehensive application performance, is widely applied to the fields of electric power, electronics, energy sources, petrochemical industry, machinery, metallurgy, traffic, light industry, emerging industry and the like, and in recent years, along with the requirements of new energy sources and communication industry on the high conductivity of pure copper, the total amount of impurities contained in the pure copper as a raw material cannot exceed one ten thousandth, and when the mass fraction of sulfur in the pure copper is 0.0004%, no method with proper high precision and good accuracy exists at present, the accurate detection needs cannot be met, and improvement is needed.
The invention discloses an analysis and determination method for sulfur in each valence state in a sodium aluminate solution, wherein the method is characterized in that the sulfur in each valence state in the solution is independently determined, so that the mutual interference among the sulfur in each valence state is avoided, the determination effect is good, the error is small, meanwhile, the method is simple, quick and accurate in operation, has the beneficial effects of good determination effect, small error, simple, quick and accurate in operation, and the method does not relate to the determination of trace sulfur when the mass fraction of sulfur in pure copper is 0.0004%, and the current accurate detection requirement cannot be met.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a method for measuring trace sulfur.
In order to achieve the above purpose, the present invention adopts the following technical scheme: a method for measuring trace sulfur, comprising the steps of:
s1: preparing a solution: weighing pure copper, adding potassium permanganate to quantitatively convert sulfide in the sample into sulfate ions, and adding a depolarizer ammonium chloride to eliminate the influence of nitrous acid on electrolytic copper removal;
s2: electrolytic copper removal and trace sulfur enrichment: controlling the electrolytic current to remove copper by electrolysis, heating, concentrating and removing copper to obtain a solution, and fixing the volume to a certain volume;
s3: establishing a calibration curve: preparing a series of standard solutions according to the concentration range of sulfur after concentration of the solution;
s4: measuring a sample: and selecting analysis spectral lines and background buckling positions of sulfur, and establishing an analysis method for on-machine measurement.
In order to ensure complete oxidation of sulfide in the sample, the improvement of the invention is that in the step S1, 5.0000g of the sample is weighed into a 250mL high-type glass beaker, 35mL of nitric acid (1+1) is added for low-temperature dissolution and evaporation, cooling is carried out, ammonium chloride solution is added to 150mL, about 4mL of potassium permanganate solution is dropped and is continuously stirred, the solution is changed from blue to dark purple, and all sulfide in the oxidized sample is sulfate ions.
In order to ensure that all sulfide in the sample is converted into sulfate ions, the improvement of the invention is that the evaporation process needs to be carried out until the oil-like state of the cup wall appears for 8-10 minutes, the concentration of the ammonium chloride solution is set to be 0.02g/L, and the mass fraction of the potassium permanganate solution is 2%.
In order to improve the treatment effect of copper removal and trace sulfur enrichment by electrolysis, the improvement of the invention is that in the S2, a magnetic stirring rod is put into a beaker, the beaker is placed on an electrolyzer tray, a stirring device is started to stir the solution uniformly, a platinum anode and a platinum cathode are arranged on the electrolyzer, a cathode net is immersed in the solution, two half-piece surface dishes are covered with a high beaker, and the surface of the cathode is about 2.0A/dm 2 Stirring and electrolyzing the solution until the solution is colorless, washing the surface dish, the cup wall and the electrolysis rod with water, and reducing the current density to 1.0A/dm 2 Continuing the electrolysis, if no copper is separated out from the newly immersed electrode part, the electrolysis is complete.
In order to ensure the copper removal effect and improve the accuracy of the detection result, the invention is improved in that the power supply is not cut off after the electrolysis is completed, the electrode is slowly lifted, the electrode is leached by water, the washing liquid is combined with the solution after copper is separated out by electrolysis, the solution is evaporated to a volume below 50mL at low temperature, cooled and then transferred into a 50mL volumetric flask, diluted to a scale by water and uniformly mixed, and a blank test is carried out along with a sample.
In order to ensure the smooth establishment of the calibration curve, the improvement of the invention is that in the process of establishing the calibration curve in the step S3, 0mL, 1.00mL, 5.00mL and 10.00mL of sulfur standard solution (B) and 5.00mL of sulfur standard solution (A) are added into a group of 100mL volumetric flasks, 5mL of nitric acid (1+1) is respectively added, water is used for dilution to scale, and the mixture is uniformly mixed, wherein the concentration of the solution in each volumetric flask is 0ug/mL, 0.10ug/mL, 0.50ug/mL, 1.00ug/mL and 5.00ug/mL.
In order to ensure the concentration of the solution in each volumetric flask, the improvement of the invention comprises adding 0mL, 1.00mL, 5.00mL and 10.00mL of the sulfur standard solution (B) to obtain the concentration of 10ug/mL, and adding 5.00mL of the sulfur standard solution (A) to obtain the concentration of 100ug/mL.
In order to ensure the smooth progress of the measured sample, the invention is improved in that the instrument is opened during the measurement of the sample in the step S4, the analysis spectral line is selected after the instrument is stable, the sulfur element content in the standard solution is input into the equipment analysis software, and the calibration curve equation is established by sucking the standard solution one by one.
In order to improve the accuracy of the sample, the invention improves that the linear correlation coefficient of the curve equation is not lower than 0.999, and the wavelength of the spectral line is 180.731nm.
In order to further ensure the accuracy of the whole analysis process, the invention is improved in that distilled water or water with quite high purity is adopted in the measurement and analysis process.
Compared with the prior art, the invention has the advantages and positive effects that:
in the method, nitric acid is used for dissolving a sample, potassium permanganate is used for oxidizing sulfide in the sample to be completely converted into sulfate ions, a constant current electrolyzer is used for removing copper, after the solution is discolored, the solution is concentrated and diluted to a certain volume, the volume is fixed, when an analysis spectral line is selected on a spectrometer, the analysis wavelength is selected to be 180.731nm, the spectral interference of coexisting elements on sulfur is avoided, meanwhile, the background is deducted at a proper position, the relative spectral intensity of the sulfur is measured, the mass fraction of the sulfur is calculated on a working curve, and further, the trace sulfur is measured.
Drawings
FIG. 1 is a schematic diagram of a preparation flow of a method for determining trace sulfur according to the present invention;
FIG. 2 is a diagram showing the results of the precision measurement in the embodiment of the method for measuring trace sulfur according to the present invention;
FIG. 3 is a graph showing experimental results of the standard recovery rate experiment in the embodiment of the method for measuring trace sulfur.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the description of the present invention, it should be understood that the terms "length," "width," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like indicate orientations or positional relationships based on the orientation or positional relationships shown in the drawings, merely to facilitate describing the present invention and simplify the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the present invention. Furthermore, in the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
Referring to fig. 1, the present invention provides a technical solution: a method for measuring trace sulfur, comprising the steps of:
s1: preparing a solution: weighing pure copper, adding potassium permanganate to quantitatively convert sulfide in the sample into sulfate ions, and adding a depolarizer ammonium chloride to eliminate the influence of nitrous acid on electrolytic copper removal;
s2: electrolytic copper removal and trace sulfur enrichment: controlling the electrolytic current to remove copper by electrolysis, heating, concentrating and removing copper to obtain a solution, and fixing the volume to a certain volume;
s3: establishing a calibration curve: preparing a series of standard solutions according to the concentration range of sulfur after concentration of the solution;
s4: measuring a sample: and selecting analysis spectral lines and background buckling positions of sulfur, and establishing an analysis method for on-machine measurement.
In S1, 5.0000g of the sample is weighed into a 250mL high-speed glass beaker, 35mL of nitric acid (1+1) is added for low-temperature dissolution and evaporation, cooling is carried out, ammonium chloride solution is added to 150mL, about 4mL of potassium permanganate solution is dripped and continuously stirred, the solution is changed from blue to dark purple, all sulfides in the oxidized sample are sulfate ions, the complete oxidation of the sulfides in the sample can be ensured, the evaporation process needs to be evaporated until the oil-like state of the wall of the cup appears for 8-10 minutes, the concentration of the ammonium chloride solution is set to 0.02g/L, the mass fraction of the potassium permanganate solution is 2%, and the complete conversion of the sulfides in the sample into sulfate ions can be further ensured.
S2, placing a magnetic stirring rod into the beaker, placing the beaker on an electrolyzer tray, starting a stirring device to stir the solution uniformly, mounting a platinum anode and a platinum cathode on the electrolyzer to submerge a cathode net in the solution, covering the high beaker with two half-piece watch dishes, and covering the high beaker with a speed of about 2.0A/dm on the surface of the cathode 2 Stirring and electrolyzing the solution until the solution is colorless, washing the surface dish, the cup wall and the electrolysis rod with water, and reducing the current density to 1.0A/dm 2 And continuing electrolysis, if no copper is separated out from the newly immersed electrode part, the complete electrolysis is shown, the treatment effect of copper removal and trace sulfur enrichment by electrolysis can be greatly improved in the whole treatment process, the electrode is not cut off after the complete electrolysis, the electrode is slowly lifted, the electrode is rinsed by water, the washing liquid is combined with the solution after copper separation by electrolysis, the solution is evaporated to a volume of below 50mL at low temperature, cooled and then transferred into a 50mL volumetric flask, diluted to be uniform with water, and the solution is subjected to blank test along with the sample, so that the smooth performance of the blank test along with the sample can be ensured.
In the process of establishing the calibration curve in S3, 0mL, 1.00mL, 5.00mL and 10.00mL of sulfur standard solution (B) and 5.00mL of sulfur standard solution (A) are added into a group of 100mL volumetric flasks, 5mL of nitric acid (1+1) is respectively added, water is used for diluting to scale, the concentration of the solution in each volumetric flask is 0ug/mL, 0.10ug/mL, 0.50ug/mL, 1.00ug/mL and 5.00ug/mL, the concentration of the sulfur standard solution added is 10ug/mL, the concentration of the sulfur standard solution added is 100ug/mL, and the concentration of the sulfur standard solution in 5.00mL can be ensured, so that the smooth establishment of the calibration curve can be ensured.
And S4, opening the instrument when the sample is measured, after the instrument is stable, selecting an analysis spectral line, inputting the content of sulfur element in the standard solution in equipment analysis software, and then sucking the standard solution one by one to establish a calibration curve equation, wherein the linear correlation coefficient of the curve equation is not lower than 0.999, the wavelength of the spectral line is 180.731nm, so that the spectral interference of coexisting elements on sulfur can be avoided, and the data accuracy of the measured sample is ensured.
Distilled water or water with quite purity is adopted in the measuring and analyzing process, and reagent blank can be reduced by utilizing distilled water or water with quite purity, so that the accuracy of the whole analyzing process is further ensured.
Examples
Referring to FIGS. 1-3, an actual sample, SYD2001, was measured on a pure copper sample, as follows:
s1: preparing a solution: sample dissolution: weighing 5.0000g of a sample in a 250mL high-type glass beaker, adding 35mL of nitric acid (1+1) for low-temperature dissolution, evaporating until oil-like state appears on the wall of the beaker for 8-10 minutes, taking down for cooling, adding ammonium chloride solution (0.02 g/L) to 150mL, dripping about 4mL of potassium permanganate (2%) solution, continuously stirring to change the solution from blue to dark purple, completely converting sulfide in the oxidized sample into sulfate ions, and carrying out a blank experiment along with the sample;
s2: electrolytic copper removal and trace sulfur enrichment: placing a magnetic stirring rod into a beaker, placing the beaker on an electrolyzer tray, starting a stirring device to stir the solution uniformly, mounting a platinum anode and a platinum cathode on the electrolyzer to submerge a cathode net in the solution, covering a high beaker with two half-piece watch dishes, and covering the high beaker with a thickness of about 2.0A/dm on the surface of the cathode 2 Stirring and electrolyzing the solution until the solution is colorless, washing the surface dish, the cup wall and the electrolysis rod with water, and reducing the current density to 1.0A/dm 2 Continuing electrolysis, if no copper is separated out from the newly immersed electrode part, indicating that the electrolysis is complete, not cutting off the power supply, slowly lifting the electrode, and leaching the electrode with water. Combining the washing liquid with the solution after copper is electrolyzed and separated, evaporating the solution at a low temperature until the volume is below 50mL, cooling the solution, transferring the solution into a 50mL volumetric flask with the mass fraction of 0.0004% -0.005%, and diluting the solution with water until the solution is uniformly mixed with scales;
s3: establishing a calibration curve: opening the instrument, selecting an analysis spectral line after the instrument automatically completes system initialization, inputting 0, 0.1ug/ml, 0.5ug/ml, 1.0ug/ml and 5.0ug/ml sulfur standard solution concentrations into equipment analysis software, and sucking the standard solutions one by one to establish a calibration curve equation to obtain a calibration curve;
s4: measuring a sample: inputting the quality of a sample into instrument operation software, measuring the intensity of sulfur element on a sample solution and a reagent blank after electrolytic copper removal and concentration, superposing spectrograms on each point of a working curve and the sample, selecting a spectral line without interference and a flat background position to deduct the background, automatically calculating the content of sulfur element in the reagent blank and the sample by the instrument, selecting a standard substance close to the content of the element to be measured of the sample as a control sample after the sample is measured, verifying the accuracy of the result, and measuring the content of sulfur for 7 times on a pure copper SYD2001 sample, wherein the relative standard deviation is the precision;
3 parts of pure copper SYD2001 sample solutions are treated in parallel to carry out a standard adding recovery rate experiment, 2.0ml of a sulfur standard solution (10 ug/ml) is added respectively, the addition amount is equivalent to 20ug of sulfur, a scalar adding amount is measured, and the standard adding recovery rate is calculated.
Working principle: firstly, preparing a solution, weighing pure copper, adding potassium permanganate to quantitatively convert sulfide in a sample into sulfate ions, adding a depolarizer ammonium chloride to eliminate the influence of nitrous acid, then carrying out electrolytic copper removal to enrich trace sulfur, controlling the electrolytic current, carrying out electrolytic copper removal, heating and concentrating the copper-removed solution, fixing the volume to a certain volume, then establishing a calibration curve, preparing a series of standard solutions according to the concentration range of the concentrated sulfur, finally, measuring a sample, selecting an analysis spectral line and a background buckling position of the sulfur, and establishing an analysis method for machine-loading measurement.
The present invention is not limited to the above embodiments, and any equivalent embodiments which can be changed or modified by the technical disclosure described above can be applied to other fields, but any simple modification, equivalent changes and modification made to the above embodiments according to the technical matter of the present invention will still fall within the scope of the technical disclosure.
Claims (10)
1. A method for measuring trace sulfur is characterized by comprising the following steps:
s1: preparing a solution: weighing pure copper, adding potassium permanganate to quantitatively convert sulfide in the sample into sulfate ions, and adding a depolarizer ammonium chloride to eliminate the influence of nitrous acid on electrolytic copper removal;
s2: electrolytic copper removal and trace sulfur enrichment: controlling the electrolytic current to remove copper by electrolysis, heating, concentrating and removing copper to obtain a solution, and fixing the volume to a certain volume;
s3: establishing a calibration curve: preparing a series of standard solutions according to the concentration range of sulfur after concentration of the solution;
s4: measuring a sample: and selecting analysis spectral lines and background buckling positions of sulfur, and establishing an analysis method for on-machine measurement.
2. The method for measuring trace sulfur according to claim 1, wherein: in the step S1, 5.0000g of the sample is weighed into a 250mL high-speed glass beaker, 35mL of nitric acid (1+1) is added for low-temperature dissolution and evaporation, cooling is carried out, ammonium chloride solution is added to 150mL, about 4mL of potassium permanganate solution is dripped and continuously stirred, the solution is changed from blue to dark purple, and all sulfides in the oxidized sample are sulfate ions.
3. The method for measuring trace sulfur according to claim 2, wherein: the evaporation process is needed to evaporate until the oil-like state appears on the wall of the cup for 8-10 minutes, the concentration of the ammonium chloride solution is set to be 0.02g/L, and the mass fraction of the potassium permanganate solution is 2%.
4. The method for measuring trace sulfur according to claim 1, wherein: in the S2 process of copper removal and trace sulfur enrichment by electrolysis, a magnetic stirring rod is placed in a beaker, the beaker is placed on an electrolyzer tray, a stirring device is started to stir the solution uniformly, a platinum anode and a platinum cathode are arranged on the electrolyzer, a cathode net is immersed in the solution, two half-piece watch dishes are used for covering a high beaker, and the surface of the cathode is about 2.0A/dm 2 Stirring at current density of (2)Stirring the solution to be colorless, washing the surface dish, the cup wall and the electrolysis rod with water, and reducing the current density to 1.0A/dm 2 Continuing the electrolysis, if no copper is separated out from the newly immersed electrode part, the electrolysis is complete.
5. The method for measuring trace sulfur according to claim 4, wherein: and after the electrolysis is completed, the power supply is not cut off, the electrode is slowly lifted, the electrode is leached by water, the washing liquid is combined with the solution after copper is separated out by electrolysis, the solution is evaporated to a volume of below 50mL at low temperature, cooled, then the solution is transferred into a 50mL volumetric flask, diluted to a scale by water and uniformly mixed, and a blank test is carried out along with a sample.
6. The method for measuring trace sulfur according to claim 1, wherein: in the process of establishing the calibration curve in the step S3, 0mL, 1.00mL, 5.00mL and 10.00mL of sulfur standard solution (B) and 5.00mL of sulfur standard solution (A) are added into a group of 100mL volumetric flasks, 5mL of nitric acid (1+1) is respectively added, water is used for diluting to scale, and the concentration of the solution in each volumetric flask is 0ug/mL, 0.10ug/mL, 0.50ug/mL, 1.00ug/mL and 5.00ug/mL.
7. The method for measuring trace sulfur according to claim 6, wherein: the concentrations of the added 0mL, 1.00mL, 5.00mL and 10.00mL of the sulfur standard solution (B) were 10ug/mL, and the concentration of the 5.00mL of the sulfur standard solution (A) was 100ug/mL.
8. The method for measuring trace sulfur according to claim 1, wherein: and S4, opening an instrument when a sample is measured, selecting an analysis spectral line after the instrument is stable, inputting the content of sulfur element in the standard solution into equipment analysis software, and sucking the standard solution one by one to establish a calibration curve equation.
9. The method for measuring trace sulfur according to claim 8, wherein: the linear correlation coefficient of the curve equation should be not lower than 0.999, the wavelength of the spectral line being chosen to be 180.731nm.
10. The method for measuring trace sulfur according to claim 1, wherein: distilled water or water with quite high purity is adopted in the measuring and analyzing process.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117147273A (en) * | 2023-10-31 | 2023-12-01 | 成都博瑞科传科技有限公司 | Background sample concentrating device, concentrating method thereof and calibrating method of detection equipment |
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2023
- 2023-02-09 CN CN202310086572.5A patent/CN116818679A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117147273A (en) * | 2023-10-31 | 2023-12-01 | 成都博瑞科传科技有限公司 | Background sample concentrating device, concentrating method thereof and calibrating method of detection equipment |
| CN117147273B (en) * | 2023-10-31 | 2024-02-02 | 成都博瑞科传科技有限公司 | Background sample concentrating device, concentrating method thereof and calibrating method of detection equipment |
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