CN117413172A - Method for detecting chromium content in laterite nickel ore - Google Patents
Method for detecting chromium content in laterite nickel ore Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 85
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 84
- 239000011651 chromium Substances 0.000 title claims abstract description 80
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 77
- 229910001710 laterite Inorganic materials 0.000 title abstract description 16
- 239000011504 laterite Substances 0.000 title abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000001514 detection method Methods 0.000 claims abstract description 24
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012086 standard solution Substances 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 48
- 230000029087 digestion Effects 0.000 claims description 32
- 238000009616 inductively coupled plasma Methods 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 15
- 230000003595 spectral effect Effects 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 9
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 4
- 238000005259 measurement Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000012360 testing method Methods 0.000 abstract description 33
- 239000011159 matrix material Substances 0.000 abstract description 21
- 238000004458 analytical method Methods 0.000 abstract description 14
- 238000004090 dissolution Methods 0.000 abstract description 10
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 abstract description 10
- 239000003513 alkali Substances 0.000 abstract description 9
- 230000004927 fusion Effects 0.000 abstract description 8
- 238000002386 leaching Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 238000012827 research and development Methods 0.000 abstract description 4
- 239000000523 sample Substances 0.000 description 57
- 239000002253 acid Substances 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000012488 sample solution Substances 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000012491 analyte Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000033558 biomineral tissue development Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000013558 reference substance Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 238000010200 validation analysis Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011978 dissolution method Methods 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000120 microwave digestion Methods 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000000705 flame atomic absorption spectrometry Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- KAQHZJVQFBJKCK-UHFFFAOYSA-L potassium pyrosulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OS([O-])(=O)=O KAQHZJVQFBJKCK-UHFFFAOYSA-L 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000002133 sample digestion Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Classifications
-
- 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 discloses a method for detecting chromium content in laterite-nickel ore, which belongs to the technical field of detection and analysis, wherein a standard adding method is adopted, namely a matrix in a standard solution is similar to a sample matrix, and meanwhile, analysis parameters are reasonably selected to inhibit or eliminate matrix effects of easily ionized elements and other elements; the method adopts a simple, efficient and low-cost method of sodium peroxide alkali fusion, hot water leaching and hydrochloric acid dissolution to digest laterite nickel ore, and adopts a standard addition method to reduce ionization interference of ICP-OES, thereby meeting the requirements of research and development at the present stage and providing a quick and simpler method for subsequent batch tests.
Description
Technical Field
The invention relates to the technical field of detection and analysis, in particular to a method for detecting chromium content in laterite-nickel ore.
Background
The new energy electric automobile industry in China is rapidly developed, the demand for power batteries is continuously increased, and the demand for positive electrode materials is increased. Of these, the demand for nickel in the ternary cathode material is greatest. At present, the sources of nickel mainly comprise waste batteries and nickel ore resources. Wherein the extraction of nickel from laterite nickel ores is the main current research direction. Chromium, as an impurity in laterite nickel ores, needs to be reduced to a certain extent. How to accurately test chromium in laterite-nickel ore is particularly important in ore dressing.
Due to the stable property of the laterite nickel ore, the laterite nickel ore is difficult to be completely digested by single acid or multiple mixed acids under the conditions of flat plate heating or microwaves, and the main residual elements are chromium and aluminum, so that the filtrate can not be tested after filtration, the sample needs to be completely digested, and the chromium is completely transferred into the solution for testing. At present, three test standards for chromium content in laterite nickel ores are respectively part 5 of SNT 2763.5-2013 laterite nickel mineralization analysis method: determination of copper, zinc and chromium content flame atomic absorption Spectrometry and "SNT 2763.6-2014 laterite Nickel mineralization analysis method part 6: determination of nickel, calcium, titanium, manganese, copper, chromium, zinc, phosphorus content inductively coupled plasma atomic emission spectrometry, YST 820.21-2013, part 21 of the laterite nickel mineralization analytical method: determination of chromium content ferrous ammonium sulphate titration.
The digestion thought adopted by the SN T2763.5-2013 and the SNT 2763.6-2014 is that hydrochloric acid, nitric acid and the like are used for carrying out low-temperature digestion and then filtering to obtain main liquid, filter residues are burnt, sulfuric acid and hydrofluoric acid electric heating plates are added for digestion, potassium pyrosulfate is added for burning, hydrochloric acid is added for heating after burning, a melt is dissolved, the solution is combined with the main liquid after evaporating to remove acid, and then AAS or ICP-OES is used for testing after dilution. The digestion method adopted by YST 820.21-2013 is that sodium peroxide is added into a sample to be heated and roasted, then the sample is melted in a high-temperature furnace, hot water is added to be leached after the sample is burnt, excessive sulfuric acid is added to dissolve sediment, and finally phosphoric acid is added to be heated and decomposed into hydrogen peroxide. The two digestion modes generally have the defects of complex digestion steps, long consumed time, high reagent consumption, high cost and the like, and are not suitable for batch test.
The inductively coupled plasma atomic emission spectrometry (ICP-AES) is a spectrum analysis method using inductively coupled plasma moment as an excitation light source, has the advantages of high accuracy and precision, low detection limit, quick measurement, wide linear range, capability of measuring multiple elements simultaneously and the like, and is widely used for measuring tens of elements in environmental samples, rock, minerals, metals and other samples abroad.
Disclosure of Invention
The method aims to overcome the defects of the prior art and provide a method for detecting the chromium content in the laterite-nickel ore, so that the accurate and stable detection of the chromium content in the laterite-nickel ore is realized.
In order to achieve the above purpose, the technical scheme adopted herein is as follows:
the method for detecting the chromium content in the laterite-nickel ore comprises the following steps:
uniformly mixing laterite-nickel ore with sodium peroxide, roasting, soaking a roasting product in water for reaction, cleaning, and adding hydrochloric acid solution to obtain laterite-nickel ore digestion solution;
diluting the laterite-nickel ore digestion solution to obtain a solution to be measured;
respectively adding a chromium standard solution into the laterite-nickel ore digestion solution to prepare a chromium standard curve solution with the chromium concentration of Amg/L, A +1mg/L, A +2mg/L, A +3mg/L, A +4 mg/L;
respectively introducing the chromium standard curve solution into an inductively coupled plasma emission spectrometer for measurement, and drawing a chromium standard working curve by taking the concentration of the chromium standard curve solution as an abscissa and the spectral emission relative intensity of chromium as an ordinate;
introducing the liquid to be measured into an inductively coupled plasma emission spectrometer, measuring the spectral intensity of the liquid to be measured, and determining the chromium content in the laterite-nickel ore according to a chromium standard working curve;
wherein A is more than or equal to 0 and less than or equal to 10.
The matrix in the standard solution is similar to the matrix of the sample by using a standard addition method, and the matrix effect of the easily ionized elements and other elements can be inhibited or eliminated by reasonably selecting analysis parameters; the method adopts a simple, efficient and low-cost method of sodium peroxide alkali fusion, hot water leaching and hydrochloric acid dissolution to digest laterite nickel ore, and adopts a standard addition method to reduce ionization interference of ICP-OES, thereby meeting the requirements of research and development at the present stage and providing a quick and simpler method for subsequent batch tests.
In the determination method, a large amount of acid is not needed to be digested, and the sample can be completely digested only by using sodium peroxide and hydrochloric acid, so that the problems of complex steps, multiple reagent consumption types, large dosage and high cost of the digestion method in the existing analysis standard are solved. And realizing rapid digestion of the laterite-nickel ore sample.
A large amount of Na ions are present in the sodium peroxide digested sample solution, and if the ICP-OES test is directly performed, a high Na content will cause serious ionization interference. In the measuring method, a sample is added into the target liquid, so that the target liquid matrix and the sample matrix are kept consistent, and ionization interference and other matrix interference are counteracted. The prepared standard solution can be used for testing samples of similar matrixes. Realizes accurate and stable detection of the chromium content in the laterite nickel ore.
Wherein a represents the sample concentration.
The linear correlation coefficient of the detection method is larger than 99.9%, the detection limit of an instrument is 0.0081mg/L, the detection limit of the method is 0.0101%, the quantitative limit of the method reaches 0.0403%, the relative deviation is low, and the detection result is accurate and stable.
In one embodiment, the mass ratio of the laterite-nickel ore to the sodium peroxide is (0.2-0.4): (3-5).
In one embodiment, the baking temperature is 500-700 ℃ and the baking time is 5-15 min. The sample pretreatment method adopts a sodium peroxide firing alkali fusion method, and can be completed in a shorter firing time. And hot water is adopted for leaching after firing, and then concentrated hydrochloric acid is added for heating to digest the sample until the solution is clear and transparent.
In one embodiment, the solid-to-liquid ratio of the laterite-nickel ore to the hydrochloric acid solution (0.2-0.4) g: (20-30) mL.
In one embodiment, the laterite-nickel ore digestion solution is diluted by a factor of 1 to 100.
In one embodiment, the laterite-nickel ore digestion solution is diluted by a factor of 10.
In one embodiment, the chromium standard solution has a chromium concentration of 100mg/L.
In one embodiment, 1.ltoreq.A.ltoreq.10.
In one embodiment, the operating parameters of the inductively coupled plasma emission spectrometer include: the radio frequency power is 1100-1300W.
In one embodiment, the operating parameters of the inductively coupled plasma emission spectrometer include: the radio frequency power is 1150W.
In an embodiment, the operating parameters of the inductively coupled plasma emission spectrometer further include: the atomized air flow is 0.6-0.8L/min, the cooling air flow is 10-20L/min, and the auxiliary air flow is 0.5-1.5L/min.
In an embodiment, the operating parameters of the inductively coupled plasma emission spectrometer further include: the atomizing air flow rate was 0.6L/min, the cooling air flow rate was 12.5L/min, and the auxiliary air flow rate was 0.5L/min.
In an embodiment, the operating parameters of the inductively coupled plasma emission spectrometer further include: the pump speed is 40-50 rpm.
In an embodiment, the operating parameters of the inductively coupled plasma emission spectrometer further include: the detection wavelength was 267.716nm.
In an embodiment, the operating parameters of the inductively coupled plasma emission spectrometer further include: the plasma observation was a vertical observation, and the observation height was 10mm.
By adopting the analysis parameters, the matrix effect of the easily ionized elements and other elements can be inhibited or eliminated, and the detection accuracy and stability are further improved.
The beneficial effects of the method are as follows: (1) The matrix in the standard solution is similar to the matrix of the sample by using a standard addition method, and the matrix effect of the easily ionized elements and other elements can be inhibited or eliminated by reasonably selecting analysis parameters; the method adopts a simple, efficient and low-cost method of sodium peroxide alkali fusion, hot water leaching and hydrochloric acid dissolution to digest laterite nickel ore, and adopts a standard addition method to reduce ionization interference of ICP-OES, thereby meeting the requirements of research and development at the present stage and providing a quick and simpler method for subsequent batch test; (2) In the determination method, a large amount of acid is not needed to be digested, and the sample can be completely digested only by using sodium peroxide and hydrochloric acid, so that the problems of complex steps, multiple reagent consumption types, large dosage and high cost of the digestion method in the existing analysis standard are solved. Realizing rapid digestion of laterite-nickel ore samples; (3) In this context, a large amount of Na ions are present in the sample solution after digestion with sodium peroxide, and if the sample solution is directly subjected to ICP-OES test, a high content of Na may cause serious ionization interference. In the measuring method, a sample is added into the target liquid, so that the target liquid matrix and the sample matrix are kept consistent, and ionization interference and other matrix interference are counteracted. The prepared standard solution can be used for testing samples of similar matrixes. Realizes accurate and stable detection of the chromium content in the laterite nickel ore.
Detailed Description
For a better description of the objects, technical solutions and advantages herein, the following description will be given with reference to specific examples and comparative examples, which are intended to be illustrative of the contents herein in detail, and not limiting thereof.
The experimental reagents and apparatus involved in the implementation herein are common reagents and apparatus unless otherwise specified.
Example 1
The method for detecting the chromium content in the laterite-nickel ore comprises the following steps:
(1) 1g of sodium peroxide is weighed and placed in a 50mL nickel crucible, then 0.2g of laterite-nickel ore sample is paved, the granularity of the laterite-nickel ore sample is required to be smaller than 160 microns (the laterite-nickel ore sample is sieved by a 95-mesh sieve) and is dried to constant weight (moisture is removed), then 2g of sodium peroxide is paved, the mixture is placed in a muffle furnace, and after being burned for 5min at 700 ℃, the sample is taken out and slightly cooled. The nickel crucible was placed in a 250mL beaker along with the sample, the crucible was placed side by side, and the dish was covered. Slowly adding the preheated ultrapure water into a beaker, immersing the crucible, and soaking for about 5min until sodium peroxide and water completely react to generate sodium hydroxide. The sample in the crucible is washed clean with secondary water, and the crucible wall also needs to be washed. 20mLGR hydrochloric acid is added into a beaker, and the mixture is heated on a flat heater for about 3 minutes until the solution is clear and transparent, so as to obtain laterite-nickel ore digestion solution.
(2) Diluting the laterite-nickel ore digestion solution obtained in the step (1) by 10 times to obtain a solution to be measured;
(3) Preparing chromium standard curve solution: transferring 10mL of the solution from the laterite-nickel ore digestion solution in the step (1) into a 100mL volumetric flask, transferring in parallel for 5 times, respectively adding 0mL, 1mL, 2mL, 3mL and 4mL of chromium standard solution into 5 parallel samples, and uniformly shaking with water to fix the volume to scale marks to obtain a chromium standard curve solution;
wherein the concentration of chromium in the chromium standard solution is 100mg/L;
the concentrations of the chromium standard curve solutions are shown in table 1.
TABLE 1
(4) Setting instrument parameters and a method: radio frequency power 1150W, atomizing air flow rate 0.6L/min, cooling air flow rate 12.5L/min, auxiliary air flow rate 0.5L/min, pump speed 45rmp and observation height 10mm. The wavelength Cr 267.716nm was selected and observed vertically.
And (3) sequentially entering the chromium standard curve solution obtained in the step (3) into an inductively coupled plasma emission spectrometer according to a set method, and drawing a chromium working curve by taking the concentration of the chromium standard curve solution as an abscissa and the spectral emission relative intensity of chromium as an ordinate, wherein the fitting coefficient of the standard curve is more than or equal to 0.999.
(5) And (3) introducing the liquid to be detected obtained in the step (2) into an inductively coupled plasma emission spectrometer, measuring the spectral intensity of the sample solution, obtaining the concentration of the sample solution according to the linear relation between the spectral intensity and the concentration, and obtaining the mass percent of chromium element according to the sample amount, the constant volume and the dilution multiple.
Test results
Method validation by this section is all referred to the GBT27417-2017 qualification assessment chemistry analysis method validation and validation guidelines
(1) The detection limits and linear correlation coefficients detected herein are used as follows in table 2. The instrument detection limit, the method detection limit and the method quantitative limit are calculated as follows:
instrument detection limit: the lowest concentration or amount of analyte when the target analyte signal is reliably identified from the background (noise) by the instrument. Table 2 the test results were obtained by testing the sample blank independently 11 times to obtain the standard deviation, and the standard deviation of 3 times is used to represent the detection limit of the instrument.
Method detection limit: to reliably identify or distinguish the analyte determination signal from a particular matrix background by a particular method. Table 2 the test results were obtained after the instrument detection limit was introduced into the fixed volume and the sample mass.
The method is characterized by: the minimum amount of analyte is reliably detected and quantified in a certain way within a certain confidence in a particular matrix. To increase the reliability of the data, the test results of table 2 are expressed in terms of 4-fold method detection limit.
TABLE 2 detection limits and correlation coefficients for spectral lines
| Element/spectral line | Linear correlation coefficient | Instrument detection limit (mg/L) | Method detection limit (%) | Quantitative limit of method (%) |
| Cr/267.716 | ＞0.999 | 0.0081 | 0.0101 | 0.0403 |
(2) The accuracy of the assays using this paper are shown in tables 3 and 4 below. Accuracy can be assessed using the labeled recovery and the reference material. When the content is more than 0.1%, the recovery rate is required to be between 95 and 105 percent.
And (3) adding a mark and recovering rate: and (3) adding a laterite-nickel ore standard sample during sample weighing for a recovery rate test to obtain the whole recovery rate of the method. The mass of the marked element is generally 0.5-2 times of the mass of the element to be detected. The mass of the marked element in the experiment is about 1.4 times of the mass of the element to be detected.
Reference substance test: the reference substance is tested by the method herein and compared to the standard values given, since the standard is free of uncertainty, the deviation of the standard tested by the method herein is indicated by the relative deviation.
The following changes were made to the instrument parameters when making reference substance measurements:
test 1: the atomizing gas flow rate was changed only by 0.7L/min in the same manner as in example 1.
Test 2: the atomizing gas flow rate was changed only by 0.8L/min in the same manner as in example 1.
Test 3: according to the method of example 1, only the cooling air flow rate was changed by 10L/min.
Test 4: according to the method of example 1, only the cooling air flow rate was changed by 20L/min.
Test 5: only the auxiliary air flow rate of 1.0L/min was changed in the same manner as in example 1.
Test 6: only the auxiliary air flow rate of 1.5L/min was changed in the same manner as in example 1.
Table 3 test of the recovery of the addition of the marks
Table 4 standard sample test comparison
(3) The precision of the assays used herein are shown in tables 5 and 6 below. The precision is generally expressed by repeatability and reproducibility, the content is between 1% and 10%, and the variation coefficient in a laboratory is required to be less than 2%.
Repeatability experiments: samples were digested 6 times in parallel and tested at the same time. Calculating the coefficient of variation
Reproducibility experiments: the samples were digested 3 times per day in parallel and two consecutive days, tested. Calculating the coefficient of variation
TABLE 5 results of repeatability experiments
TABLE 6
Comparative example 1
And (3) digesting the laterite-nickel ore sample by adopting a flat acid dissolution method, wherein the acids comprise hydrochloric acid, nitric acid, hydrofluoric acid, perchloric acid and sulfuric acid pentaacid. The method comprises the following specific steps: weighing 0.1-0.2g of sample into a 100mL polytetrafluoroethylene beaker, adding acid corresponding to table 7, placing the beaker on a flat-plate electric heating furnace for heating, digesting until the acid liquor is near dry, and recording time consumption. The beaker is taken down and cooled, the sample in the beaker is transferred to a 100mL volumetric flask for constant volume by using secondary water, whether slag exists after the sample is digested or not is observed, and whether the solution is clear and transparent is detailed in Table 7.
And (3) digesting the laterite-nickel ore sample by adopting a microwave acid dissolution method, wherein the acids comprise hydrochloric acid, nitric acid, hydrofluoric acid and perchloric acid. The method comprises the following specific steps: the sample is weighed 0.1g into a microwave digestion tank, acid corresponding to Table 7 is added for microwave digestion according to the program, the sample is transferred to a polytetrafluoroethylene beaker, 1mL of perchloric acid is added for acid removal until the sample is near dry, and the time consumption is recorded. The beaker is taken down and cooled, the sample in the beaker is transferred to a 100mL volumetric flask for constant volume by using secondary water, whether slag exists after the sample is digested or not is observed, and whether the solution is clear and transparent is detailed in Table 7.
The laterite-nickel ore sample is digested by adopting a method of sodium hydroxide alkali fusion and hydrochloric acid dissolution, and the specific steps are as follows: weighing 0.1g of sample in a 30mL nickel crucible, putting the crucible into a muffle furnace, burning for 2h at 650 ℃, taking out, cooling, adding a proper amount of secondary water into the crucible, heating on a flat heater until sodium hydroxide is dissolved, transferring the sample into a 250mL beaker, adding a 25mL hydrochloric acid flat plate for digestion for 20min, and transferring the sample into a 100mL volumetric flask for constant volume. The samples were observed for slag after digestion, and the solutions were clear and transparent, as detailed in table 7.
TABLE 7
From Table 7, it can be seen that the acid consumption of the acid dissolution of the plate is large, the plate cannot be completely digested, and the fluctuation of the data is large. Microwave acid dissolution is relatively long in time consumption, cannot be completely digested, and is low in data. The sodium hydroxide alkali fusion and hydrochloric acid dissolution are long in time consumption, and the burnt sample is easy to overflow, difficult to leach and low in data. Sodium peroxide alkali fusion and hydrochloric acid dissolution are short in time consumption, complete in sample digestion, easy in sample leaching, and visible, in the digestion method, a large amount of acid is not needed, and the sample can be completely digested only by sodium peroxide and hydrochloric acid, so that the problems of complex steps, multiple reagent consumption types, large consumption and high cost of the digestion method in the existing analysis standard are solved. And realizing rapid digestion of the laterite-nickel ore sample.
Comparative example 2
The method of comparative example 2 is specifically as follows:
(1) 1g of sodium peroxide is weighed and placed in a 50mL nickel crucible, then 0.2g of laterite-nickel ore sample is paved, the granularity of the laterite-nickel ore sample is required to be smaller than 160 microns (the laterite-nickel ore sample is sieved by a 95-mesh sieve) and is dried to constant weight (moisture is removed), then 2g of sodium peroxide is paved, the mixture is placed in a muffle furnace, and after being burned for 5min at 700 ℃, the sample is taken out and slightly cooled. The nickel crucible was placed in a 250mL beaker along with the sample, the crucible was placed side by side, and the dish was covered. Slowly adding the preheated ultrapure water into a beaker, immersing the crucible, and soaking for about 5min until sodium peroxide and water completely react to generate sodium hydroxide. The sample in the crucible is washed clean with secondary water, and the crucible wall also needs to be washed. 20mLGR hydrochloric acid is added into a beaker, and the mixture is heated on a flat heater for about 3 minutes until the solution is clear and transparent, so as to obtain laterite-nickel ore digestion solution.
(2) Diluting the laterite-nickel ore digestion solution obtained in the step (1) by 10 times to obtain a solution to be measured;
(3) Preparing chromium standard curve solution: respectively adding 0mL, 1mL, 2mL, 3mL and 4mL of chromium standard solution into a 100mL volumetric flask, and shaking the secondary water until the volume is fixed to the scale mark to obtain a chromium standard curve solution;
wherein the concentration of chromium in the chromium standard solution is 100mg/L;
the concentrations of the chromium standard curve solutions are shown in table 8.
TABLE 8
(4) Setting instrument parameters and a method: radio frequency power 1150W, atomizing air flow rate 0.6L/min, cooling air flow rate 12.5L/min, auxiliary air flow rate 0.5L/min, pump speed 45rmp and observation height 10mm. The wavelength Cr 267.716nm was selected and observed vertically.
And (3) sequentially entering the chromium standard curve solution obtained in the step (3) into an inductively coupled plasma emission spectrometer according to a set method, and drawing a chromium working curve by taking the concentration of the chromium standard curve solution as an abscissa and the spectral emission relative intensity of chromium as an ordinate, wherein the fitting coefficient of the standard curve is more than or equal to 0.999.
(5) And (3) introducing the liquid to be detected obtained in the step (2) into an inductively coupled plasma emission spectrometer, measuring the spectral intensity of the sample solution, obtaining the concentration of the sample solution according to the linear relation between the spectral intensity and the concentration, and obtaining the mass percent of chromium element according to the sample amount, the constant volume and the dilution multiple.
Table 9 comparison of test results of Standard addition method and Standard Curve method
| Parallel sample | Method of example 1 (%) | Method of comparative example 2 (%) |
| 1 | 1.6299 | 1.5645 |
| 2 | 1.6876 | 1.6616 |
| 3 | 1.6313 | 1.6027 |
| 4 | 1.6527 | 1.6889 |
| 5 | 1.6992 | 1.6761 |
| 6 | 1.6732 | 1.5875 |
| Mean value of | 1.6623 | 1.6302 |
| Extremely poor | 0.0693 | 0.1244 |
| COV | 1.75 | 3.18 |
The sample was prepared by digestion with sodium peroxide alkali fusion, hot water leaching and hydrochloric acid dissolution. The standard solution of 100mg/L chromium purchased by direct dilution is prepared into a chromium test standard solution, a standard curve is drawn, a test sample is tested, 6 groups of repeated test results are compared with the standard addition method (namely, the method of the embodiment 1) and the standard addition method (namely, the method of the comparison example 2) to obtain the standard deviation and the COV, and the test fluctuation is small.
Thus, the matrix effects of the ionizable elements and other elements are suppressed or eliminated herein by using standard addition methods, i.e., allowing the matrix in the standard solution to resemble the sample matrix, while rationally selecting the analysis parameters; the method adopts a simple, efficient and low-cost method of sodium peroxide alkali fusion, hot water leaching and hydrochloric acid dissolution to digest laterite nickel ore, and adopts a standard addition method to reduce ionization interference of ICP-OES, thereby meeting the requirements of research and development at the present stage and providing a quick and simpler method for subsequent batch tests.
Claims (15)
1. The method for detecting the chromium content in the laterite-nickel ore is characterized by comprising the following steps of:
uniformly mixing laterite-nickel ore with sodium peroxide, roasting, soaking a roasting product in water for reaction, cleaning, and adding hydrochloric acid solution to obtain laterite-nickel ore digestion solution;
diluting the laterite-nickel ore digestion solution to obtain a solution to be measured;
respectively adding a chromium standard solution into the laterite-nickel ore digestion solution to prepare a chromium standard curve solution with the chromium concentration of Amg/L, A +1mg/L, A +2mg/L, A +3mg/L, A +4 mg/L;
respectively introducing the chromium standard curve solution into an inductively coupled plasma emission spectrometer for measurement, and drawing a chromium standard working curve by taking the concentration of the chromium standard curve solution as an abscissa and the spectral emission relative intensity of chromium as an ordinate;
introducing the liquid to be measured into an inductively coupled plasma emission spectrometer, measuring the spectral intensity of the liquid to be measured, and determining the chromium content in the laterite-nickel ore according to a chromium standard working curve;
wherein A is more than or equal to 0 and less than or equal to 10.
2. The method for detecting the chromium content in the laterite-nickel ore according to claim 1, wherein the mass ratio of the laterite-nickel ore to sodium peroxide is (0.2-0.4): (3-5).
3. The method for detecting the chromium content in the laterite-nickel ore according to claim 1, wherein the roasting temperature is 500-700 ℃, and the roasting time is 5-15 min.
4. The method for detecting the chromium content in the laterite-nickel ore according to claim 1, wherein the solid-to-liquid ratio (0.2-0.4) g of the laterite-nickel ore and the hydrochloric acid solution is as follows: (20-30) mL.
5. The method for detecting the chromium content in the laterite-nickel ore according to claim 1, wherein the dilution factor of the laterite-nickel ore digestion liquid is 1-100 times.
6. The method for detecting the chromium content in the laterite-nickel ore according to claim 1, wherein the dilution factor of the laterite-nickel ore digestion solution is 10 times.
7. The method for detecting the chromium content in the laterite-nickel ore according to claim 1, wherein the concentration of chromium in the chromium standard solution is 100mg/L.
8. The method for detecting the chromium content in the laterite-nickel ore according to claim 1, wherein A is 1-10.
9. The method for detecting the chromium content in the laterite-nickel ore according to claim 1, wherein the working parameters of the inductively coupled plasma emission spectrometer include: the radio frequency power is 1100-1300W.
10. The method for detecting the chromium content in the laterite-nickel ore according to claim 1, wherein the working parameters of the inductively coupled plasma emission spectrometer include: the radio frequency power is 1150W.
11. The method for detecting the chromium content in the laterite-nickel ore according to claim 1, wherein the working parameters of the inductively coupled plasma emission spectrometer further comprise: the atomized air flow is 0.6-0.8L/min, the cooling air flow is 10-20L/min, and the auxiliary air flow is 0.5-1.5L/min.
12. The method for detecting the chromium content in the laterite-nickel ore according to claim 1, wherein the working parameters of the inductively coupled plasma emission spectrometer further comprise: the atomizing air flow rate was 0.6L/min, the cooling air flow rate was 12.5L/min, and the auxiliary air flow rate was 0.5L/min.
13. The method for detecting the chromium content in the laterite-nickel ore according to claim 1, wherein the working parameters of the inductively coupled plasma emission spectrometer further comprise: the pump speed is 40-50 rpm.
14. The method for detecting the chromium content in the laterite-nickel ore according to claim 1, wherein the working parameters of the inductively coupled plasma emission spectrometer further comprise: the detection wavelength was 267.716nm.
15. The method for detecting the chromium content in the laterite-nickel ore according to claim 1, wherein the working parameters of the inductively coupled plasma emission spectrometer further comprise: the plasma observation was a vertical observation, and the observation height was 10mm.
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