CN111443056A - Method for measuring mercury content in copper concentrate - Google Patents
Method for measuring mercury content in copper concentrate Download PDFInfo
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- CN111443056A CN111443056A CN202010492429.2A CN202010492429A CN111443056A CN 111443056 A CN111443056 A CN 111443056A CN 202010492429 A CN202010492429 A CN 202010492429A CN 111443056 A CN111443056 A CN 111443056A
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 143
- 239000010949 copper Substances 0.000 title claims abstract description 68
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 67
- 239000012141 concentrate Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000002835 absorbance Methods 0.000 claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000120 microwave digestion Methods 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 14
- 239000010453 quartz Substances 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 18
- 239000012085 test solution Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- 238000012360 testing method Methods 0.000 claims description 12
- 238000005259 measurement Methods 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000012224 working solution Substances 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000000265 homogenisation Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000000643 oven drying Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 239000000523 sample Substances 0.000 abstract description 56
- 239000012488 sample solution Substances 0.000 abstract description 4
- 238000001514 detection method Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 5
- 239000012086 standard solution Substances 0.000 description 5
- 238000003723 Smelting Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000001391 atomic fluorescence spectroscopy Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000009614 chemical analysis method Methods 0.000 description 2
- 238000004993 emission spectroscopy Methods 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000003446 memory effect Effects 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002180 inductively coupled plasma atomic fluorescence spectrometry Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—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
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- 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
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- 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
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Abstract
The invention discloses a method for measuring mercury content in copper concentrate, which comprises the following operation steps of 1) respectively measuring the absorbance of a corresponding mercury in a range of 0 ng-1000 ng at a wavelength of 253.7nm according to the sequence of mercury content from low to high, drawing a standard working curve by taking the corresponding mercury mass concentration as an abscissa and the absorbance as an ordinate, 2) adding a mixed acid solution prepared from hydrochloric acid and nitric acid into a copper concentrate sample to be detected, then putting the mixed material into a microwave digestion instrument for pretreatment, 3) transferring 1m L of a sample solution obtained in the step 2) into a quartz boat of a mercury measuring instrument, measuring the absorbance of the sample solution at the wavelength of 253.7nm on the mercury measuring instrument, reading the corresponding mercury mass concentration value from the standard working curve, and obtaining the mercury mass concentration value in the sample solution, and 4) calculating the mercury content in the copper concentrate sample according to a formula.
Description
Technical Field
The invention relates to a chemical analysis method, in particular to a method for measuring mercury content in copper concentrate.
Background
The copper concentrate is prepared by crushing and ball-milling low-grade copper-containing raw ore, and then separating and trapping copper-containing minerals by using a reagent for flotation so as to improve the copper content to a level that the copper content is not less than 13% (mass fraction), and the copper concentrate can be directly used as a raw material for copper smelting. After a series of mineral separation such as crushing, flotation, separation, concentration and the like, copper concentrate is associated with some harmful elements such as sulfur, lead, cadmium, mercury, arsenic, fluorine and the like which cannot be removed, and in the further smelting and processing process of the copper concentrate, the elements can harm the health of operators and pollute the environment, so that the requirements of China on the harmful elements in the imported copper concentrate are stricter and stricter. Imported copper concentrate must meet the national mandatory standards for the limits of harmful elements, mercury is one of 5 harmful elements, the national mandatory standards for the limits of harmful elements in heavy metal concentrate products specify that the mercury content in copper concentrate is 100 mug/g. As a recognized global pollutant, mercury can migrate and convert among the atmosphere, soil and water, and directly harms human health through food chain enrichment. Experts point out that the main reason of mercury pollution is artificial mercury emission, and the existing non-ferrous metal smelting is an important source of artificial mercury emission, so that mercury in copper concentrate is accurately measured, and quantification and management and control of mercury emission in the copper smelting process are facilitated.
At present, methods for measuring mercury content include cold atomic absorption spectrometry, inductively coupled plasma emission spectrometry, inductively coupled plasma mass spectrometry, atomic fluorescence spectrometry and the like. Cold atomic absorption spectrometry is widely applied before 2005, but the method is gradually replaced by other methods due to high detection limit, complex operation and low precision; the inductively coupled plasma emission spectrometry and the inductively coupled plasma mass spectrometry are mostly suitable for multi-element simultaneous detection, and if the method is used for measuring the single-element mercury in the copper concentrate, the cost is high and the time consumption is long. At present, copper concentrate of ChinaThe content of the toxic and harmful mercury is measured by adopting an atomic fluorescence spectrometry and a solid sample introduction mercury detector method, the mercury measured by the atomic fluorescence spectrometry is easy to have a memory effect, the accuracy of a result is influenced, a detection mechanism cannot provide quick, accurate and objective detection data for a client, and the smooth development of goods value evaluation, withholding, processing and other work of relevant administrative law enforcement departments is influenced to a certain extent; and the copper content in the copper concentrate is too high, Cu2+Cu easily reduced to black by potassium borohydride in the measurement process+And the adsorption on the wall of the sample injection pipeline can not clean the pipeline by using acid after adsorption, thereby seriously polluting equipment. The solid sample introduction mercury detector method is simple and rapid, but the mercury content in the copper concentrate is high and ranges from 0.05 to 500 mu g/g, and the measuring range of the direct solid sample introduction mercury detector method is 0.05 to 20 mu g/g. But actually, the mercury content in many copper concentrates is more than 20 mug/g, if 0.1g of copper concentrate sample is directly weighed on an mercury measuring instrument for measurement, the poison of the mercury in the sample to a catalytic tube and an alignment tube is easily aggravated, and the service life of the alignment tube is shortened, if the sample content is more than 100 mug/g, the alignment tube can be saturated once and cannot work, the alignment tube can only be replaced by a new one for use, the cost of each alignment tube is as high as 2 ten thousand yuan, and the expensive cost is brought to the inspection process.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for measuring the mercury content in copper concentrate, which can improve the accuracy and the measuring range of measurement.
The invention solves the technical problems by the following technical scheme:
the method for measuring the mercury content in the copper concentrate comprises the following operation steps:
1) drawing a standard working curve: respectively absorbing the same amount of mercury standard working solution with different concentrations into a quartz boat of a mercury detector by using a liquid transfer device, enabling the mass concentration range of the corresponding mercury to be 0 ng-1000 ng, respectively measuring the absorbance of the mercury at the position of 253.7nm according to the sequence of the mercury content from low to high, repeatedly measuring each standard curve point for 2 times, taking the average value of the measured values, and drawing a standard working curve by taking the mass concentration of the corresponding mercury as an abscissa and the absorbance as an ordinate;
2) adding a mixed acid solution prepared from hydrochloric acid and nitric acid into a copper concentrate sample to be detected, wherein the using amount ratio of the copper concentrate to the mixed acid solution is that 0.1g of the copper concentrate is 5m L, and the weight ratio of the hydrochloric acid to the nitric acid in the mixed acid solution is 1 part to 3 parts, then putting the mixed material into a microwave digestion instrument for pretreatment, wherein the control condition of the microwave digestion instrument is that the power is 1500W, the temperature is firstly increased to 120 ℃, the constant temperature is kept for 5 minutes at 120 ℃, then is increased to 150 ℃, the constant temperature is kept for 10 minutes at 150 ℃, is increased to 190 ℃, the constant temperature is kept for 20 minutes at 190 ℃, and the temperature increasing time is controlled within 5 minutes each time;
3) transferring the sample liquid 1m L obtained in the step 2) into a quartz boat of a mercury detector, measuring the absorbance of the sample liquid at the wavelength of 253.7nm on the mercury detector, and reading the mass concentration value of the corresponding mercury in a standard curve according to the absorbance value to obtain the mass concentration value of the mercury in the sample liquid;
4) calculating the mercury content w in the copper concentrate sample according to the following formulaHg：
In the formula:
ρHgthe mass concentration of the mercury element in the test solution is in the unit of mu g/g;
v is the total volume of the test solution, and the unit is m L;
V1-removing the volume of the test solution measured in a mercury porosimeter in m L.
In the step 2), the pressure relief speed of the microwave digestion is 5 bar/min.
In step 1) and step 3), the instrument is required to be subjected to blank measurement before the mercury tester is used for testing, namely, mercury remaining in the instrument is required to be removed, and the requirements are as follows: the test was performed without sample entry until the absorbance of the blank was less than 0.0003.
In the step 1) and the step 3), the control conditions of the mercury detector are as follows: the drying temperature is 300 ℃, the drying time is 30s, the decomposition temperature is 750 ℃, the decomposition time is 90s, the heating temperature of the catalytic tube is 615 ℃, the purging pipeline time is 60s, the heating temperature of the homogenization tube is 900 ℃, the heating time of the homogenization tube is 12s, the signal record is 30s, and the carrier gas flow is 200 ml/min.
In the steps 1) and 3), the quartz boat of the mercury detector is subjected to the following processing operations before use: soaking in 50% nitric acid solution, boiling, cleaning for 20min, cleaning with distilled water, oven drying, placing into a high temperature furnace, igniting at 800 deg.C for 10 min, taking out, and cooling.
The method of the invention has the following beneficial effects:
1) the method disclosed by the invention has the advantages that the copper concentrate sample is pretreated by microwave digestion in a closed environment, the loss of volatile mercury caused by conventional wet sample dissolution is effectively avoided, the microwave digestion has the advantages of sample dissolution rapidness, thorough treatment, no damage to dissolution, automation and the like, the mercury in the copper concentrate is dissolved by proper acid in a closed microwave heating state, the loss of volatile mercury elements is effectively avoided, and the measured data is more accurate.
2) According to the method, the mercury content in the copper concentrate is measured by adopting a direct mercury-measuring instrument method of solid sample introduction after the acid-soluble sample is digested by microwaves, and the mercury content in the test solution is measured by adopting the direct mercury-measuring instrument method, so that the interference is small, and the result is accurate.
3) In part of researches, mercury in copper concentrate is measured by adopting a solid sample introduction direct mercury detector method, the content range of the copper concentrate is 0.05-500 mug/g, the measurement range of the direct solid sample introduction mercury detector method is 0.05-20 mug/g, a copper concentrate sample larger than 20 mug/g cannot be measured, however, since the mercury content in the sample is unknown, if 0.1g of the copper concentrate sample is directly weighed on the mercury detector for measurement, the copper concentrate sample with high mercury content is easy to aggravate the poison of mercury in the sample to a catalytic tube and an alignment tube, and the service life of the catalyst tube and the alignment tube is shortened, if the sample content is larger than 100 mug/g, the alignment tube can be saturated once and cannot work, only a new alignment tube can be used, the cost of each alignment tube is as high as 2 ten thousand yuan, and expensive cost is brought to the inspection process. The invention can measure the copper concentrate sample with the mercury content of 0.25-500 mug/g by taking a small amount of test solution on the direct mercury meter after the sample is pretreated, thereby greatly widening the measuring range of the mercury meter and effectively prolonging the service life of the mercury meter.
Drawings
FIG. 1 is a graph of a standard operating curve for low concentration mercury plotted in the method of the present invention.
Fig. 2 is a graph plotting a standard operating curve for high concentration mercury in the method of the present invention.
Detailed Description
The technical solution of the method of the present invention is further described below.
The method for determining the mercury content in the copper concentrate comprises the following specific operation steps:
1) drawing a standard curve, namely respectively sucking the same amount of mercury standard working solutions with different concentrations (the mercury content is 1 mug/m L-25 mug/m L) into a quartz boat of a mercury measuring instrument by using a liquid transfer machine, enabling the mass range of the corresponding mercury to be 0 ng-1000 ng (according to actual needs and instrument configuration), respectively measuring the absorbance of the mercury at the position of 253.7nm according to the sequence of the mercury content from low to high, repeatedly measuring each standard curve point for 2 times, taking the average value of the measured values, and drawing the standard working curve by taking the mass concentration of the corresponding mercury as an abscissa and the absorbance as an ordinate.
2) Adding a mixed acid solution prepared from hydrochloric acid and nitric acid into a copper concentrate sample to be detected, wherein the using amount ratio of the copper concentrate to the mixed acid solution is that 0.1g of the copper concentrate is mixed with 5m L of the mixed acid solution, the weight ratio of the hydrochloric acid to the nitric acid in the mixed acid solution is 1 part to 3 parts, then putting the mixed material into a microwave digestion instrument for pretreatment, wherein the control condition of the microwave digestion instrument is that the power is 1500W, the temperature is firstly increased to 120 ℃, the constant temperature is kept for 5 minutes at 120 ℃, then increased to 150 ℃, the constant temperature is kept for 10 minutes at 150 ℃, then increased to 190 ℃, the constant temperature is kept for 20 minutes at 190 ℃, the temperature increasing time is controlled within 5 minutes each time, after the microwave digestion is finished, the pressure is released at the speed of 5bar/min, the temperature is cooled to 40 ℃, then transferred to a volumetric flask, and diluted by water until the mass concentration of the copper concentrate is 0.1g/50m L, and the mixture is shaken uniformly to obtain a copper concentrate sample solution;
3) transferring the sample liquid 1m L obtained in the step 2) into a quartz boat of a mercury detector, measuring the absorbance of the sample liquid at the wavelength of 253.7nm on the mercury detector, and reading the mass concentration value of the corresponding mercury in a standard curve according to the absorbance value to obtain the mass concentration value of the mercury in the sample liquid;
4) calculating the mercury content w in the copper concentrate sample according to the following formulaHg：
In the formula:
ρHgthe mass concentration of the mercury element in the test solution is in the unit of mu g/g;
v is the total volume of the test solution, and the unit is m L;
V1-removing the volume of the test solution measured in a mercury porosimeter in m L.
In step 1) and step 3), the instrument is required to be subjected to blank measurement before the mercury tester is used for testing, namely, mercury remaining in the instrument is required to be removed, and the requirements are as follows: and (4) testing without entering the sample, wherein the sample can not be tested until the blank light absorption value is less than 0.0003, otherwise, the blank value of the measuring instrument is repeatedly measured until the blank value meets the requirement.
Setting the control conditions of the mercury detector: the drying temperature is 300 ℃, the drying time is 30s, the decomposition temperature is 750 ℃, the decomposition time is 90s, the heating temperature of the catalytic tube is 615 ℃, the purging pipeline time is 60s, the heating temperature of the homogenization tube is 900 ℃, the heating time of the homogenization tube is 12s, the signal record is 30s, and the carrier gas flow is 200 ml/min.
The quartz boat of the mercury detector needs to be processed as follows before use: soaking in 50% nitric acid solution, boiling, cleaning for 20min, cleaning with distilled water, oven drying, placing into a high temperature furnace, igniting at 800 deg.C for 10 min, taking out, and cooling.
The invention adopts a direct mercury-measuring instrument as the prior art, and the measuring principle of the mercury-measuring instrument is as follows: in an oxygen atmosphere, a sample is dried and thermally decomposed at high temperature in a decomposing furnace, generated gas enters a catalytic furnace, is subjected to catalytic decomposition by a catalyst and is purified by an adsorbent to remove impurities, mercury is reduced to mercury atoms, the mercury atoms are brought into an alignment tube by oxygen flow to carry out an amalgam reaction, mercury in the mercury atoms is selectively adsorbed, then the alignment tube is rapidly heated after being treated by an oxygen blowing purification system, mercury vapor is released, the mercury vapor is brought into a single-wavelength optical absorption cell by the oxygen flow to carry out atomic absorption measurement, the absorbance (peak height or peak area) of the mercury is measured at the wavelength of 253.7nm, and then a standard curve method is adopted for quantification.
The following are examples of applications of the process of the invention:
respectively measuring 3 copper concentrate samples with low, medium and high mercury contents to be measured, and operating as follows:
step 1, respectively weighing 0.10g (accurate to 0.0001g) of copper concentrate sample in a test tube, adding 5m L of mixed acid solution prepared from hydrochloric acid and nitric acid, wherein the weight ratio of the hydrochloric acid to the nitric acid in the mixed acid solution is 1 part to 3 parts, placing the copper concentrate sample in a microwave digestion instrument, controlling the microwave digestion instrument under the condition that the power is 1500W, firstly heating to 120 ℃, keeping the temperature at 120 ℃ for 5 minutes at constant temperature, then heating to 150 ℃, keeping the temperature at 150 ℃ for 10 minutes, heating to 190 ℃, keeping the temperature at 190 ℃ for 20 minutes at constant temperature, controlling the heating time within 5 minutes each time, after the microwave digestion is finished, carrying out pressure relief at the speed of 5bar/min, cooling to 40 ℃, transferring to a 50m L volumetric flask, diluting to 50m L scales with water, and shaking up to obtain the test solution.
Step 2, transferring mercury standard solutions with different volumes according to table 1 and placing the mercury standard solutions into two groups of 100m L volumetric flasks, wherein the concentration of the mercury standard solution transferred from the first group of volumetric flasks 1-11 is 1.00 mu g/m L, the concentration of the mercury standard solution transferred from the second group of volumetric flasks 12-25 is 25.00 mu g/m L, adding 1m L potassium dichromate solution (the concentration is 10 g/L) as a protective agent, fixing the volume to 100m L scale with nitric acid (the concentration is 5%), mixing uniformly to obtain mercury standard working solutions, respectively absorbing 100 mu L mercury standard working solutions into a quartz sample boat, respectively sending the quartz sample boat into a pyrolysis furnace for pyrolysis catalysis, measuring the absorbance of mercury on a mercury detector (the measurement parameter is consistent with that of a sample), and placing each mercury standard solution into two groups of 100m L volumetric flasksThe standard working solution is repeatedly measured for 2 times, the average value is taken, the mass (ng) of the corresponding mercury is taken as the abscissa, the absorbance is taken as the ordinate, and a low-concentration mercury standard working curve (shown in figure 1) and a high-concentration mercury standard working curve (shown in figure 2) with the mercury amount of 0-18 ng and 20-1000 ng are drawn. The quadratic regression equation of the standard working curve of the low-concentration mercury is as follows: a 0.00857957+0.06012798 Hg-0.00084712 Hg2The correlation coefficient is 0.9999; the second regression equation of the standard working curve of the high-concentration mercury is A (0.00101372) Hg-4.02806e-07*Hg2The correlation coefficient is 0.9998;
TABLE 1 Mercury Standard working solution compounding Table
From the drawn curve, the mass of the mercury is in the range from 0.6ng to 1000ng, the absorbance of the mercury and the mercury amount form a good linear relation, the correlation coefficient is larger than 0.9990, and the standard curve can be used for a long time after being drawn.
And step 3: a quartz sample boat: soaking in nitric acid solution (50%), boiling, cleaning for 20min, cleaning with distilled water, oven drying, placing into high temperature furnace, igniting at 800 deg.C for 10 min, taking out, and cooling.
Step 4, testing on a mercury tester under the condition of not entering a sample until the blank light absorption value is less than 0.0003, transferring 1m L of the test solution obtained in the step 1 into a quartz boat of the mercury tester, inputting corresponding sample weighing quantities (the sample numbers are 1#, 2#, and 3#), measuring the absorbance of the test sample on the mercury tester at 253.7nm, and reading the mass concentration rho of mercury in the copper concentrate test solution from a standard curveHg。
And 5: calculating the mercury content w in the copper concentrate sample according to the following formulaHgThe results are shown in Table 2, where V is 50m L, V1Is 1m L.
TABLE 2 mercury content of copper concentrate in test solutions and samples
The accuracy verification method of the method comprises the following steps:
(1) sample labeling recovery test: quantitatively adding mercury into a copper concentrate sample, measuring the sample according to the steps 1-5, and examining the correctness of the method by measuring the recovery rate of the mercury, wherein the recovery rate of the mercury is shown in table 3 by adding different amounts of mercury into 2 different samples in the experiment, the sample standard addition recovery rate is 97.41-1000.66%, and the correctness of the detection result is better.
TABLE 3 actual sample addition recovery test results
(2) Method comparison test: to examine the accuracy of the method of the invention, the test solution of step (1) was taken according to the reference: SN/T4364-. However, in the process of atomic fluorescence spectrometry, the sample introduction pipeline is seriously polluted into black, and the sample introduction pipeline needs to be continuously cleaned in the process of measurement so as to eliminate the memory effect of mercury.
TABLE 4 comparison of methods
As can be seen from the analysis results in tables 3-4, the method for determining the mercury in the copper concentrate by combining microwave digestion with a direct mercury-measuring instrument method enlarges the determination range of the traditional chemical analysis method, reduces the error of the analysis method, improves the accuracy of detection, and is suitable for determining the mercury content in the copper concentrate.
Claims (5)
1. A method for determining the mercury content of copper concentrate is characterized by comprising the following operation steps:
1) drawing a standard working curve: respectively absorbing the same amount of mercury standard working solution with different concentrations into a quartz boat of a mercury detector by using a liquid transfer device, enabling the mass concentration range of the corresponding mercury to be 0 ng-1000 ng, respectively measuring the absorbance of the mercury at the position of 253.7nm according to the sequence of the mercury content from low to high, repeatedly measuring each standard curve point for 2 times, taking the average value of the measured values, and drawing a standard working curve by taking the mass concentration of the corresponding mercury as an abscissa and the absorbance as an ordinate;
2) adding a mixed acid solution prepared from hydrochloric acid and nitric acid into a copper concentrate sample to be detected, wherein the using amount ratio of the copper concentrate to the mixed acid solution is that 0.1g of the copper concentrate is 5m L, and the weight ratio of the hydrochloric acid to the nitric acid in the mixed acid solution is 1 part to 3 parts, then putting the mixed material into a microwave digestion instrument for pretreatment, wherein the control condition of the microwave digestion instrument is that the power is 1500W, the temperature is firstly increased to 120 ℃, the constant temperature is kept for 5 minutes at 120 ℃, then is increased to 150 ℃, the constant temperature is kept for 10 minutes at 150 ℃, is increased to 190 ℃, the constant temperature is kept for 20 minutes at 190 ℃, and the temperature increasing time is controlled within 5 minutes each time;
3) transferring the sample liquid 1m L obtained in the step 2) into a quartz boat of a mercury detector, measuring the absorbance of the sample liquid at the wavelength of 253.7nm on the mercury detector, and reading the mass concentration value of the corresponding mercury in a standard curve according to the absorbance value to obtain the mass concentration value of the mercury in the sample liquid;
4) calculating the mercury content w in the copper concentrate sample according to the following formulaHg：
In the formula:
ρHgthe mass concentration of the mercury element in the test solution is in the unit of mu g/g;
v is the total volume of the test solution, and the unit is m L;
V1-removing the volume of the test solution measured in a mercury porosimeter in m L.
2. The method for measuring the mercury content in the copper concentrate according to claim 1, wherein in the step 2), the pressure relief speed of the microwave digestion is 5 bar/min.
3. The method for determining the mercury content in the copper concentrate according to the claim 1 or 2, characterized in that in the step 1) and the step 3), the instrument is required to be subjected to blank measurement before the mercury tester is used for testing, namely, the mercury remained in the instrument is required to be removed, and the following requirements are met: the test was performed without sample entry until the absorbance of the blank was less than 0.0003.
4. The method for determining the mercury content in copper concentrate according to claim 1 or 2, characterized in that in step 1) and step 3), the control conditions of the mercury meter are as follows: the drying temperature is 300 ℃, the drying time is 30s, the decomposition temperature is 750 ℃, the decomposition time is 90s, the heating temperature of the catalytic tube is 615 ℃, the purging pipeline time is 60s, the heating temperature of the homogenization tube is 900 ℃, the heating time of the homogenization tube is 12s, the signal record is 30s, and the carrier gas flow is 200 ml/min.
5. The method for determining the mercury content in copper concentrate according to claim 1 or 2, characterized in that in step 1) and step 3), the quartz boat of the mercury tester is subjected to the following treatment operations before use: soaking in 50% nitric acid solution, boiling, cleaning for 20min, cleaning with distilled water, oven drying, placing into a high temperature furnace, igniting at 800 deg.C for 10 min, taking out, and cooling.
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