CN111239240A - Method for determining harmful elements in iron ore - Google Patents
Method for determining harmful elements in iron ore Download PDFInfo
- Publication number
- CN111239240A CN111239240A CN202010107470.3A CN202010107470A CN111239240A CN 111239240 A CN111239240 A CN 111239240A CN 202010107470 A CN202010107470 A CN 202010107470A CN 111239240 A CN111239240 A CN 111239240A
- Authority
- CN
- China
- Prior art keywords
- iron ore
- microwave digestion
- temperature
- solution
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/626—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using heat to ionise a gas
-
- 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
- G01N1/44—Sample treatment involving radiation, e.g. heat
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention discloses a method for determining harmful elements in iron ore, which comprises the following steps: step one, preprocessing an iron ore sample to be detected; step two, drawing a standard curve; step three, predicting an iron ore sample to be detected; step four, accurately measuring the iron ore sample to be measured: taking 4 10mL volumetric flasks, adding 1mL of the pretreatment solution obtained in the first step, sequentially adding 10 microgram/mL of Na, K, Pb and Zn mixed standard solution with a calibrated volume L into the 4 volumetric flasks, wherein L is 0.1, 0.3 and 0.5mL, performing constant volume, respectively measuring the concentrations of Na, K, Pb and Zn as Cm, and calculating the accurate concentration Ci of Na, K, Pb and Zn in the iron ore sample to be measured according to a formula; and averaging the four obtained solubilities and the predicted concentration Cr of a certain element in the iron ore sample obtained in the step three to obtain the concentration of each element in the iron ore sample to be detected. The method can simultaneously determine four harmful elements of sodium, potassium, lead and zinc in the iron ore, and has good determination stability on trace elements.
Description
Technical Field
The present invention relates to a method for measuring a harmful element. More specifically, the invention relates to a method for determining harmful elements in iron ore.
Background
Iron ore detection usually detects the contents of elements such as iron, silicon, aluminum, calcium, magnesium, sulfur, phosphorus and the like according to trade contract requirements, but in practical application, on the basis of urgent requirements for prolonging the service life of a blast furnace and increasing the yield and efficiency of enterprises, harmful elements are also necessary items of various enterprises, wherein sodium, potassium, lead and zinc are reduced into corresponding elements in the blast furnace in the smelting process of the blast furnace, oxides of the elements are changed into steam to volatilize in a high-temperature region of the blast furnace due to low boiling point, a small part of the elements escape out of the furnace along with coal gas as well as other parts of the elements are condensed in a lower-temperature region at the upper part of the blast furnace and are oxidized into corresponding oxides, and a part of the oxides are reduced into elements to volatilize again along with the reduction of furnace charge or iron slag and are continuously enriched in the circulating process, so that the efficiency of the blast furnace and the service life of the blast furnace are influenced. Therefore, the determination of the contents of sodium, potassium, lead and zinc in the iron ore is also common knowledge of various enterprises. The workload of respectively measuring sodium, potassium, lead and zinc is complicated, and the measurement of some trace elements is not accurate enough during measurement.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and to provide at least the advantages described later.
The invention also aims to provide a method for determining harmful elements in iron ore, which can simultaneously determine four harmful elements of sodium, potassium, lead and zinc in the iron ore and has good determination stability on trace elements.
To achieve these objects and other advantages in accordance with the present invention, there is provided a method for determining harmful elements in iron ore, comprising:
step one, preprocessing an iron ore sample to be detected: accurately weighing an iron ore sample to be detected, and placing the iron ore sample into a microwave digestion tank, wherein the first step is as follows: adding hydrochloric acid, nitric acid and graphite in sequence, wherein the volume ratio of the hydrochloric acid to the nitric acid is 1: 3-6, adding 1/5-1/3 of the weight of the graphite and the weight of the iron ore to be detected; placing the microwave digestion tank in a microwave digestion instrument, starting the microwave digestion instrument, and setting a program as follows: the power is 1600W, the temperature is 190 ℃, the temperature rising procedure is 2min to 190 ℃, the temperature is kept for 5min, and the temperature begins to decrease; the second step is that: and sequentially adding nitric acid and hydrofluoric acid, wherein the volume ratio of the nitric acid to the hydrofluoric acid is 2-3: 1, and the concentration of the nitric acid added in the second step is lower than that of the nitric acid added in the first step, placing the microwave digestion tank in a microwave digestion instrument, starting the microwave digestion instrument, and setting the program as follows: the power is 1000W, the temperature is 120 ℃, the temperature rising program is 5min to 120 ℃, the temperature is kept constant for 15min, the temperature begins to be reduced, the digestion tank is taken out, the digestion solution is transferred to a 100mL volumetric flask, and the volume is fixed to obtain the pretreatment solution for later use; while preparing a blank sample solution in the same manner,
step two, drawing a standard curve: taking 4 100mL volumetric flasks, weighing 0.1000g of iron ore sample to be measured according to the method in the step one to prepare standard liquid base solution, placing the microwave digestion tank in a microwave digestion instrument, starting the microwave digestion instrument, and performing the first step: hydrochloric acid, nitric acid and graphite are sequentially added, a micro-electrolysis system is formed by main components of iron simple substance or iron compound in the iron ore and the graphite under an acidic condition, and the digestion rate is increased, wherein the volume ratio of the hydrochloric acid to the nitric acid is 1: 3-6, adding 1/5-1/3 of the weight of the graphite and the weight of the iron ore to be detected; placing the microwave digestion tank in a microwave digestion instrument, starting the microwave digestion instrument, and setting a program as follows: the power is 1600W, the temperature is 190 ℃, the temperature rising procedure is 2min to 190 ℃, the temperature is kept for 5min, and the temperature begins to decrease; the second step is that: sequentially adding nitric acid and hydrofluoric acid, wherein the volume ratio of the nitric acid to the hydrofluoric acid is 2-3: 1, the concentration of the nitric acid added in the second step is higher than that of the nitric acid added in the first step, a microwave digestion tank is placed in a microwave digestion instrument, the microwave digestion instrument is started, and the program is set as follows: the power is 1000W, the temperature is 120 ℃, the temperature rising program is 5min to 120 ℃, the temperature is kept constant for 15min, the digestion tank is taken out, the digestion solution is transferred to 100mL volumetric flasks, 0.0, 0.5, 1.0, 1.5mL of 10 mu g/mL Na, K, Pb and Zn mixed standard solution is sequentially added into 4 volumetric flasks, the volume is constant, the mixture is shaken up, the ion signal intensity is measured by an inductively coupled plasma mass spectrometer, and a standard curve of each element is drawn by taking the element concentration as the abscissa and the signal intensity as the ordinate;
step three, predicting the iron ore sample to be detected: measuring the pretreatment solution obtained in the step one and a blank sample solution, measuring the signal intensity of Na, K, Pb and Zn ions, calculating the concentration Cn of Na, K, Pb and Zn elements according to a standard curve, and calculating the predicted concentration Cr of a certain element in an iron ore sample;
step four, accurately measuring the iron ore sample to be measured: taking 4 10mL volumetric flasks, adding 1mL of the pretreatment solution obtained in the first step, sequentially adding 10 microgram/mL of Na, K, Pb and Zn mixed standard solution with a calibrated volume L into the 4 volumetric flasks, wherein L is 0.1, 0.3 and 0.5mL, performing constant volume, measuring the solution obtained from the 4 volumetric flasks and a blank sample solution, measuring the signal intensity of Na, K, Pb and Zn ions, calculating the concentration of Na, K, Pb and Zn elements as Cm according to a standard curve, and calculating the accurately measured concentration Ci of Na, K, Pb and Zn elements in the iron ore sample to be measured according to the following formula; averaging the four obtained solubilities and the predicted concentration Cr of a certain element in the iron ore sample obtained in the step three to obtain the concentration of each element in the iron ore sample to be detected;
in the formula: ci is the content of a certain element in the iron ore sample, and is mu g/g;
cm is the content of a certain element in the test solution, mu g/mL;
c0 is the content of a certain element in the blank sample solution, mu g/mL;
l is the calibration volume, mL;
v is the volume of the test solution, mL;
and m is the weight of the weighed iron ore and g.
Preferably, the microwave digestion tank in the first step and the second step is also provided with nano ceramic particles. The nano ceramic particles can increase the contact area of digestion reaction and improve the digestion rate. The addition amount of the nano ceramic particles is 1/5-1/2 of the weight of the iron ore sample.
Preferably, the method also comprises the step of optimizing the working parameters of the instrument by using a tuning solution before each measurement, so that the working parameters of the inductively coupled plasma mass spectrometer are determined, wherein M (220) is less than or equal to 2cps, In (115) is more than or equal to 250, 000cps/10 mu g/L, CeO/Ce is less than 3.0 percent, and Ba + +/Ba + < 3.0 percent.
Preferably, the operating parameters of the inductively coupled plasma mass spectrometer are as follows: RF power 100w, cooling air flow 15.00L/min, auxiliary air flow 1.20L/min, carrier air flow 0.90L/min, lens voltage 7.5V, and RPa for Na, K0.11, and RPa for Pb, Zn 0.00.
Preferably, a protective sleeve is further arranged on the microwave digestion tank in the step one.
Preferably, after the microwave digestion tank is placed in the microwave digestion instrument in the step one, an explosion-proof sheet is also required to be placed.
Preferably, R of the standard curve fitting function of each element in the second step2≥0.99。
Preferably, the predicted concentration Cr of an element in the iron ore sample in step three is calculated according to the following formula:
the invention at least comprises the following beneficial effects: firstly, the method can simultaneously determine four harmful elements of sodium, potassium, lead and zinc in the iron ore, and has good determination stability on trace elements; secondly, the invention overcomes the mutual influence among elements and has high accuracy of the measured result; thirdly, the invention has simple operation, high sensitivity, good stability and good reproducibility.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a standard curve of Na element in examples 1 and 2 of the present invention;
FIG. 2 is a standard curve of K element in examples 1 and 2 of the present invention;
FIG. 3 is a calibration curve of Pb element in examples 1 and 2 according to the present invention;
FIG. 4 is a standard curve of Zn element in one embodiment 1 and 2 of the present invention;
FIG. 5 is a standard curve of Na element in comparative example 1 of the present invention;
FIG. 6 is a standard curve of K element in comparative example 1 according to the present invention;
FIG. 7 is a standard curve of Pb element in comparative example 1 according to the present invention;
FIG. 8 is a standard curve of Zn element in comparative example 1 according to the present invention.
Detailed Description
The present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1
Step one, preprocessing an iron ore sample to be detected: the iron ore to be detected is a standard GSBH3006-97, the contents of marked Na, K, Pb and Zn are 0.0378%, 0.0332%, 0.0015% and 0.0093%, 0.1g of the iron ore sample to be detected is accurately weighed and placed in a microwave digestion tank, and the first step is as follows: sequentially adding 1mL of hydrochloric acid, 6mL of nitric acid and 0.02g of graphite; placing the microwave digestion tank in a microwave digestion instrument, starting the microwave digestion instrument, and setting a program as follows: the power is 1600W, the temperature is 190 ℃, the temperature rising procedure is 2min to 190 ℃, the temperature is kept for 5min, and the temperature begins to decrease; the second step is that: then adding 3mL of nitric acid and 1mL of hydrofluoric acid in sequence, wherein the concentration of the nitric acid added in the second step is lower than that of the nitric acid added in the first step, placing the microwave digestion tank in a microwave digestion instrument, starting the microwave digestion instrument, and setting the program as follows: the power is 1000W, the temperature is 120 ℃, the temperature rising program is 5min to 120 ℃, the temperature is kept constant for 15min, the temperature begins to be reduced, the digestion tank is taken out, the digestion solution is transferred to a 100mL volumetric flask, and the volume is fixed to obtain the pretreatment solution for later use; simultaneously preparing a blank sample solution by the same method;
step two, drawing a standard curve: taking 4 100mL volumetric flasks, weighing 0.1g of iron ore sample to be measured according to the method in the step one to prepare standard liquid base solution, placing a microwave digestion tank in a microwave digestion instrument, starting the microwave digestion instrument, and performing the first step: sequentially adding 1mL of hydrochloric acid, 6mL of nitric acid and 0.02g of graphite; placing the microwave digestion tank in a microwave digestion instrument, starting the microwave digestion instrument, and setting a program as follows: the power is 1600W, the temperature is 190 ℃, the temperature rising procedure is 2min to 190 ℃, the temperature is kept for 5min, and the temperature begins to decrease; the second step is that: then adding 3mL of nitric acid and 1mL of hydrofluoric acid in sequence, wherein the concentration of the nitric acid added in the second step is lower than that of the nitric acid added in the first step, placing the microwave digestion tank in a microwave digestion instrument, starting the microwave digestion instrument, and setting the program as follows: the power is 1000W, the temperature is 120 ℃, the temperature rising program is 5min to 120 ℃, the temperature is kept constant for 15min, the digestion tank is taken out, the digestion solution is transferred to 100mL volumetric flasks, 0.0, 0.5, 1.0, 1.5mL of 10 mu g/mL Na, K, Pb and Zn mixed standard solution is sequentially added into 4 volumetric flasks, the volume is constant, the digestion solution is shaken up, the ion signal intensity is measured by an inductively coupled plasma mass spectrometer, the working parameters of the instrument are optimized by using a tuning solution before measurement, the working parameters of the inductively coupled plasma mass spectrometer are determined, and the M (220) is less than or equal to
2cps, In (115) is more than or equal to 250, 000cps/10 mug/L, CeO/Ce is less than 3.0%, Ba + +/Ba + < 3.0%; the inductively coupled plasma mass spectrometer has the following working parameters: RF power 100w, cooling air flow 15.00L/min, auxiliary air flow 1.20L/min, carrier air flow 0.90L/min, lens voltage 7.5V, and RPa of Na, K0.11, and RPa of Pb, Zn 0.00; drawing a standard curve of each element by taking the element concentration as an abscissa and the signal intensity as an ordinate; the standard curve is shown in figures 1-4.
Step three, predicting the iron ore sample to be detected: measuring the pretreatment solution obtained in the step one and a blank sample solution, measuring the signal intensity of Na, K, Pb and Zn ions, calculating the concentration Cn of Na, K, Pb and Zn elements according to a standard curve, and calculating the predicted concentration Cr of a certain element in an iron ore sample;
step four, accurately measuring the iron ore sample to be measured: taking 4 10mL volumetric flasks, adding 1mL of the pretreatment solution obtained in the first step, sequentially adding 10 microgram/mL of Na, K, Pb and Zn mixed standard solution with a calibrated volume L into the 4 volumetric flasks, wherein L is 0.1, 0.3 and 0.5mL, performing constant volume, measuring the solution obtained from the 4 volumetric flasks and a blank sample solution, measuring the signal intensity of Na, K, Pb and Zn ions, calculating the concentration of Na, K, Pb and Zn elements as Cm according to a standard curve, and calculating the accurately measured concentration Ci of Na, K, Pb and Zn elements in the iron ore sample to be measured according to the following formula; and averaging the four obtained solubilities and the predicted concentration Cr of a certain element in the iron ore sample obtained in the step three to obtain the concentration of each element in the iron ore sample to be detected. The results are shown in Table 1.
TABLE 1 measurement results of standard samples
As can be seen from Table 1, the measurement results of Na, K, Pb and Zn elements in the iron ore provided by the invention are basically close to the standard concentration, the relative error of the standard concentration is less than 4%, and the accuracy is high.
Example 2
Step one, preprocessing an iron ore sample to be detected: accurately weighing 0.1g of iron ore sample to be measured, placing the iron ore sample in a microwave digestion tank, and performing the following steps: sequentially adding 1mL of hydrochloric acid, 6mL of nitric acid and 0.02g of graphite; placing the microwave digestion tank in a microwave digestion instrument, starting the microwave digestion instrument, and setting a program as follows: the power is 1600W, the temperature is 190 ℃, the temperature rising procedure is 2min to 190 ℃, the temperature is kept for 5min, and the temperature begins to decrease; the second step is that: then adding 3mL of nitric acid and 1mL of hydrofluoric acid in sequence, wherein the concentration of the nitric acid added in the second step is lower than that of the nitric acid added in the first step, placing the microwave digestion tank in a microwave digestion instrument, starting the microwave digestion instrument, and setting the program as follows: the power is 1000W, the temperature is 120 ℃, the temperature rising program is 5min to 120 ℃, the temperature is kept constant for 15min, the temperature begins to be reduced, the digestion tank is taken out, the digestion solution is transferred to a 100mL volumetric flask, and the volume is fixed to obtain the pretreatment solution for later use; simultaneously preparing a blank sample solution by the same method;
step two, predicting the iron ore sample to be detected: measuring the pretreatment solution obtained in the step one and a blank sample solution, measuring the signal intensity of Na, K, Pb and Zn ions, calculating the concentration Cn of Na, K, Pb and Zn elements according to a standard curve, and calculating the predicted concentration Cr of a certain element in an iron ore sample;
step three, accurately measuring the iron ore sample to be measured: taking 4 10mL volumetric flasks, adding 1mL of the pretreatment solution obtained in the first step, sequentially adding 10 microgram/mL of Na, K, Pb and Zn mixed standard solution with a calibrated volume L into the 4 volumetric flasks, wherein L is 0.1, 0.3 and 0.5mL, performing constant volume, measuring the solution obtained from the 4 volumetric flasks and a blank sample solution, measuring the signal intensity of Na, K, Pb and Zn ions, calculating the concentration of Na, K, Pb and Zn elements as Cm according to a standard curve, and calculating the accurately measured concentration Ci of Na, K, Pb and Zn elements in the iron ore sample to be measured according to the following formula; and averaging the four obtained solubilities and the predicted concentration Cr of a certain element in the iron ore sample obtained in the step three to obtain the concentration of each element in the iron ore sample to be detected.
And step four, accurately weighing the iron ore sample to be measured, performing a standard addition recovery rate test, and determining the recovery rate results of each element as shown in table 2.
TABLE 2 sample determination and recovery test results
The results in table 2 show that the standard recovery rate of Na, K, Pb and Zn is 96.0-106.0%, the determination result is accurate, and the determination requirements of four harmful elements in iron ore are met.
Example 3
Step one, preprocessing an iron ore sample to be detected: accurately weighing 0.1g of iron ore sample to be measured, placing the iron ore sample in a microwave digestion tank, and performing the following steps: sequentially adding 1mL of hydrochloric acid, 4mL of nitric acid, 0.03g of graphite and 0.02g of nano ceramic particles; placing the microwave digestion tank in a microwave digestion instrument, starting the microwave digestion instrument, and setting a program as follows: the power is 1600W, the temperature is 190 ℃, the temperature rising procedure is 2min to 190 ℃, the temperature is kept for 5min, and the temperature begins to decrease; the second step is that: then sequentially adding 2mL of nitric acid and 1mL of hydrofluoric acid, wherein the concentration of the nitric acid added in the second step is lower than that of the nitric acid added in the first step, placing the microwave digestion tank in a microwave digestion instrument, starting the microwave digestion instrument, and setting the program as follows: the power is 1000W, the temperature is 120 ℃, the temperature rising program is 5min to 120 ℃, the temperature is kept constant for 15min, the temperature begins to be reduced, the digestion tank is taken out, the digestion solution is transferred to a 100mL volumetric flask, and the volume is fixed to obtain the pretreatment solution for later use; simultaneously preparing a blank sample solution by the same method;
step two, predicting the iron ore sample to be detected: measuring the pretreatment solution obtained in the step one and a blank sample solution, measuring the signal intensity of Na, K, Pb and Zn ions, calculating the concentration Cn of Na, K, Pb and Zn elements according to a standard curve, and calculating the predicted concentration Cr of a certain element in an iron ore sample;
step three, accurately measuring the iron ore sample to be measured: taking 4 10mL volumetric flasks, adding 1mL of the pretreatment solution obtained in the first step, sequentially adding 10 microgram/mL of Na, K, Pb and Zn mixed standard solution with a calibrated volume L into the 4 volumetric flasks, wherein L is 0.1, 0.3 and 0.5mL, performing constant volume, measuring the solution obtained from the 4 volumetric flasks and a blank sample solution, measuring the signal intensity of Na, K, Pb and Zn ions, calculating the concentration of Na, K, Pb and Zn elements as Cm according to a standard curve, and calculating the accurately measured concentration Ci of Na, K, Pb and Zn elements in the iron ore sample to be measured according to the following formula; and averaging the four obtained solubilities and the predicted concentration Cr of a certain element in the iron ore sample obtained in the step three to obtain the concentration of each element in the iron ore sample to be detected.
And step four, accurately weighing the iron ore sample to be measured, performing a standard addition recovery rate test, wherein the standard addition recovery rate of the elements Na, K, Pb and Zn is measured to be 98.0-104.0%, and the measurement result is accurate, so that the measurement requirements of four harmful elements in the iron ore are met.
Comparative example 1
Step one, preprocessing an iron ore sample to be detected: accurately weighing 0.1g of iron ore sample to be measured in example 2, placing the sample in a microwave digestion tank, and performing the following steps: sequentially adding 1mL of hydrochloric acid and 6mL of nitric acid; placing the microwave digestion tank in a microwave digestion instrument, starting the microwave digestion instrument, and setting a program as follows: the power is 1600W, the temperature is 190 ℃, the temperature rising procedure is 2min to 190 ℃, the temperature is kept for 5min, and the temperature begins to decrease; the second step is that: then adding 3mL of nitric acid and 1mL of hydrofluoric acid in sequence, wherein the concentration of the nitric acid added in the second step is lower than that of the nitric acid added in the first step, placing the microwave digestion tank in a microwave digestion instrument, starting the microwave digestion instrument, and setting the program as follows: the power is 1000W, the temperature is 120 ℃, the temperature rising program is 5min to 120 ℃, the temperature is kept constant for 15min, the temperature begins to be reduced, the digestion tank is taken out, the digestion solution is transferred to a 100mL volumetric flask, and the volume is fixed to obtain the pretreatment solution for later use; simultaneously preparing a blank sample solution by the same method;
step two, drawing a standard curve: taking 4 100mL volumetric flasks, weighing 0.1g of iron ore sample to be measured according to the method in the step one to prepare standard liquid base solution, placing a microwave digestion tank in a microwave digestion instrument, starting the microwave digestion instrument, and performing the first step: sequentially adding 1mL of hydrochloric acid and 6mL of nitric acid; placing the microwave digestion tank in a microwave digestion instrument, starting the microwave digestion instrument, and setting a program as follows: the power is 1600W, the temperature is 190 ℃, the temperature rising procedure is 2min to 190 ℃, the temperature is kept for 5min, and the temperature begins to decrease; the second step is that: then adding 3mL of nitric acid and 1mL of hydrofluoric acid in sequence, wherein the concentration of the nitric acid added in the second step is lower than that of the nitric acid added in the first step, placing the microwave digestion tank in a microwave digestion instrument, starting the microwave digestion instrument, and setting the program as follows: the power is 1000W, the temperature is 120 ℃, the temperature rising program is 5min to 120 ℃, the temperature is kept constant for 15min, the digestion tank is taken out, the digestion solution is transferred to 100mL volumetric flasks, 0.0, 0.5, 1.0 and 1.5mL of 10 mug/mL mixed standard solution of Na, K, Pb and Zn is sequentially added into 4 volumetric flasks, the volume is fixed, the digestion solution is shaken uniformly, the ionic signal intensity is measured through an inductively coupled plasma mass spectrometer, the working parameters of the instrument are optimized by using a tuning solution before the measurement, so that the working parameters of the inductively coupled plasma mass spectrometer are determined, wherein M (220) is less than or equal to 2cps, In (115) is more than or equal to 250, 000cps/10 mug/L, CeO/Ce is less than 3.0%, and Ba +/Ba is less than 3.0%; the inductively coupled plasma mass spectrometer has the following working parameters: RF power 100w, cooling air flow 15.00L/min, auxiliary air flow 1.20L/min, carrier air flow 0.90L/min, lens voltage 7.5V, and RPa of Na, K0.11, and RPa of Pb, Zn 0.00; drawing a standard curve of each element by taking the element concentration as an abscissa and the signal intensity as an ordinate; the standard curve is shown in figures 5-8.
Step three, predicting the iron ore sample to be detected: measuring the pretreatment solution obtained in the step one and a blank sample solution, measuring the signal intensity of Na, K, Pb and Zn ions, calculating the concentration Cn of Na, K, Pb and Zn elements according to a standard curve, and calculating the predicted concentration Cr of a certain element in an iron ore sample;
step four, accurately measuring the iron ore sample to be measured: taking 4 10mL volumetric flasks, adding 1mL of the pretreatment solution obtained in the first step, sequentially adding 10 microgram/mL of Na, K, Pb and Zn mixed standard solution with a calibrated volume L into the 4 volumetric flasks, wherein L is 0.1, 0.3 and 0.5mL, performing constant volume, measuring the solution obtained from the 4 volumetric flasks and a blank sample solution, measuring the signal intensity of Na, K, Pb and Zn ions, calculating the concentration of Na, K, Pb and Zn elements as Cm according to a standard curve, and calculating the accurately measured concentration Ci of Na, K, Pb and Zn elements in the iron ore sample to be measured according to the following formula; and averaging the four obtained solubilities and the predicted concentration Cr of a certain element in the iron ore sample obtained in the step three to obtain the concentration of each element in the iron ore sample to be detected.
Step five, accurately weighing the iron ore sample to be measured, performing a standard addition recovery rate test, and measuring the recovery rate of each element; the results are shown in Table 3.
TABLE 3 sample determination and recovery test results with spiking
The difference between the comparative example 1 and the example 2 is that whether graphite is added during the first-step digestion and the second-step digestion is not added in the comparative example 1, the standard addition recovery rate of Na, K, Pb and Zn elements is measured to be 56.0-92.0%, and the accuracy of the measurement result is not as good as that in the example 2, because in the digestion process, a micro-electrolysis system is formed by the iron simple substance or the iron compound which is the main component in the iron ore and the graphite under the acidic condition, the digestion is facilitated, and the better detection effect is achieved.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.
Claims (8)
1. The method for measuring harmful elements in iron ore is characterized by comprising the following steps:
step one, preprocessing an iron ore sample to be detected: accurately weighing an iron ore sample to be detected, and placing the iron ore sample into a microwave digestion tank, wherein the first step is as follows: adding hydrochloric acid, nitric acid and graphite in sequence, wherein the volume ratio of the hydrochloric acid to the nitric acid is 1: 3-6, adding 1/5-1/3 of the weight of the graphite and the weight of the iron ore to be detected; placing the microwave digestion tank in a microwave digestion instrument, starting the microwave digestion instrument, and setting a program as follows: the power is 1600W, the temperature is 190 ℃, the temperature rising procedure is 2min to 190 ℃, the temperature is kept for 5min, and the temperature begins to decrease; the second step is that: and sequentially adding nitric acid and hydrofluoric acid, wherein the volume ratio of the nitric acid to the hydrofluoric acid is 2-3: 1, and the concentration of the nitric acid added in the second step is lower than that of the nitric acid added in the first step, placing the microwave digestion tank in a microwave digestion instrument, starting the microwave digestion instrument, and setting the program as follows: the power is 1000W, the temperature is 120 ℃, the temperature rising program is 5min to 120 ℃, the temperature is kept constant for 15min, the temperature begins to be reduced, the digestion tank is taken out, the digestion solution is transferred to a 100mL volumetric flask, and the volume is fixed to obtain the pretreatment solution for later use; while preparing a blank sample solution in the same manner,
step two, drawing a standard curve: taking 4 100mL volumetric flasks, weighing 0.1000g of iron ore sample to be measured according to the method in the step one to prepare standard liquid base solution, placing the microwave digestion tank in a microwave digestion instrument, starting the microwave digestion instrument, and performing the first step: adding hydrochloric acid, nitric acid and graphite in sequence, wherein the volume ratio of the hydrochloric acid to the nitric acid is 1: 3-6, adding 1/5-1/3 of the weight of the graphite and the weight of the iron ore to be detected; placing the microwave digestion tank in a microwave digestion instrument, starting the microwave digestion instrument, and setting a program as follows: the power is 1600W, the temperature is 190 ℃, the temperature rising procedure is 2min to 190 ℃, the temperature is kept for 5min, and the temperature begins to decrease; the second step is that: sequentially adding nitric acid and hydrofluoric acid, wherein the volume ratio of the nitric acid to the hydrofluoric acid is 2-3: 1, the concentration of the nitric acid added in the second step is higher than that of the nitric acid added in the first step, a microwave digestion tank is placed in a microwave digestion instrument, the microwave digestion instrument is started, and the program is set as follows: the power is 1000W, the temperature is 120 ℃, the temperature rising program is 5min to 120 ℃, the temperature is kept constant for 15min, the digestion tank is taken out, the digestion solution is transferred to 100mL volumetric flasks, 0.0, 0.5, 1.0, 1.5mL of 10 mu g/mL Na, K, Pb and Zn mixed standard solution is sequentially added into 4 volumetric flasks, the volume is constant, the mixture is shaken up, the ion signal intensity is measured by an inductively coupled plasma mass spectrometer, and a standard curve of each element is drawn by taking the element concentration as the abscissa and the signal intensity as the ordinate;
step three, predicting the iron ore sample to be detected: measuring the pretreatment solution obtained in the step one and a blank sample solution, measuring the signal intensity of Na, K, Pb and Zn ions, calculating the concentration Cn of Na, K, Pb and Zn elements according to a standard curve, and calculating the predicted concentration Cr of a certain element in an iron ore sample;
step four, accurately measuring the iron ore sample to be measured: taking 4 10mL volumetric flasks, adding 1mL of the pretreatment solution obtained in the first step, sequentially adding 10 microgram/mL of Na, K, Pb and Zn mixed standard solution with a calibrated volume L into the 4 volumetric flasks, wherein L is 0.1, 0.3 and 0.5mL, performing constant volume, measuring the solution obtained from the 4 volumetric flasks and a blank sample solution, measuring the signal intensity of Na, K, Pb and Zn ions, calculating the concentration of Na, K, Pb and Zn elements as Cm according to a standard curve, and calculating the accurately measured concentration Ci of Na, K, Pb and Zn elements in the iron ore sample to be measured according to the following formula; averaging the four obtained solubilities and the predicted concentration Cr of a certain element in the iron ore sample obtained in the step three to obtain the concentration of each element in the iron ore sample to be detected;
in the formula: ci is the content of a certain element in the iron ore sample, and is mu g/g;
cm is the content of a certain element in the test solution, mu g/mL;
c0 is the content of a certain element in the blank sample solution, mu g/mL;
l is the calibration volume, mL;
v is the volume of the test solution, mL;
and m is the weight of the weighed iron ore and g.
2. The method for determining harmful elements in iron ore according to claim 1, wherein nano ceramic particles are further arranged in the microwave digestion tank in the first step and the second step.
3. The method of claim 1, further comprising optimizing the operating parameters of the apparatus with a tuning solution before each measurement, such that the operating parameters of the inductively coupled plasma mass spectrometer are determined by M (220) is less than or equal to 2cps, In (115) is greater than or equal to 250,000 cps/10 μ g/L, CeO/Ce is less than 3.0%, and Ba + +/Ba + < 3.0%.
4. The method of claim 3, wherein the inductively coupled plasma mass spectrometer has the following operating parameters: RF power 100w, cooling air flow 15.00L/min, auxiliary air flow 1.20L/min, carrier air flow 0.90L/min, lens voltage 7.5V, and RPa for Na, K0.11, and RPa for Pb, Zn 0.00.
5. The method for determining harmful elements in iron ore according to claim 4, wherein the microwave digestion tank in the first step is further provided with a protective sleeve.
6. The method for determining harmful elements in iron ore according to claim 5, wherein an explosion-proof sheet is additionally arranged after the microwave digestion tank is arranged in the microwave digestion instrument in the step one.
7. The method according to claim 6, wherein R of the standard curve fitting function for each element in the second step2≥0.99。
8. The method according to claim 7, wherein the predicted concentration of Cr in an element in the iron ore sample in step three is calculated according to the following formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010107470.3A CN111239240B (en) | 2020-02-21 | 2020-02-21 | Method for determining harmful elements in iron ore |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010107470.3A CN111239240B (en) | 2020-02-21 | 2020-02-21 | Method for determining harmful elements in iron ore |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111239240A true CN111239240A (en) | 2020-06-05 |
| CN111239240B CN111239240B (en) | 2023-04-07 |
Family
ID=70867596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010107470.3A Active CN111239240B (en) | 2020-02-21 | 2020-02-21 | Method for determining harmful elements in iron ore |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111239240B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112630211A (en) * | 2020-11-25 | 2021-04-09 | 沪东重机有限公司 | Method for measuring internal elements of iron ore |
| CN117074447A (en) * | 2023-08-25 | 2023-11-17 | 中国矿业大学 | Method for detecting content of harmful impurity elements in Huang Jinkuang flotation product |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101303307A (en) * | 2008-07-08 | 2008-11-12 | 株洲硬质合金集团有限公司 | Analyses testing method of aluminum, calcium, iron, molybdenum, niobium, titanium, tungsten impurity elements in chromium carbide |
| CN101793830A (en) * | 2010-03-16 | 2010-08-04 | 武汉钢铁(集团)公司 | Method for measuring sulfur content in iron ore |
| CN102565176A (en) * | 2010-12-17 | 2012-07-11 | 鞍钢股份有限公司 | Method for simultaneously determining harmful elements in iron ore |
| CN103241796A (en) * | 2013-05-31 | 2013-08-14 | 邓杰帆 | Process and device for performing continuous filtration and adsorption treatment on sewage by using graphene |
| CN103252223A (en) * | 2013-05-15 | 2013-08-21 | 东华大学 | Method for regenerating saturated active carbon adsorbing organic matters through microwave activation of potassium persulfate |
| CN104316590A (en) * | 2014-09-16 | 2015-01-28 | 河北中烟工业有限责任公司 | Inductively coupled plasma mass spectrometry method for simultaneous determination of chromium, nickel, arsenic and lead in hot melt adhesive for cigarette |
| CN104730013A (en) * | 2015-03-25 | 2015-06-24 | 广东出入境检验检疫局检验检疫技术中心 | Method for judging effective life of graphite pipe in graphite furnace atomic absorption spectrometer |
| CN105548331A (en) * | 2015-12-10 | 2016-05-04 | 内蒙古包钢钢联股份有限公司 | Method for simultaneous determination of multiple trace elements in iron ore |
| CN108802012A (en) * | 2018-06-07 | 2018-11-13 | 山东省食品药品检验研究院 | The detection method of silica in a kind of food and food additives |
| CN108982204A (en) * | 2018-09-05 | 2018-12-11 | 安徽科达洁能新材料有限公司 | A kind of method that micro-wave digestion-ICP-OES measures microelement in graphite |
| CN109316433A (en) * | 2018-12-05 | 2019-02-12 | 邯郸学院 | A kind of facial treatment mask reducing heavy metal pollution |
-
2020
- 2020-02-21 CN CN202010107470.3A patent/CN111239240B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101303307A (en) * | 2008-07-08 | 2008-11-12 | 株洲硬质合金集团有限公司 | Analyses testing method of aluminum, calcium, iron, molybdenum, niobium, titanium, tungsten impurity elements in chromium carbide |
| CN101793830A (en) * | 2010-03-16 | 2010-08-04 | 武汉钢铁(集团)公司 | Method for measuring sulfur content in iron ore |
| CN102565176A (en) * | 2010-12-17 | 2012-07-11 | 鞍钢股份有限公司 | Method for simultaneously determining harmful elements in iron ore |
| CN103252223A (en) * | 2013-05-15 | 2013-08-21 | 东华大学 | Method for regenerating saturated active carbon adsorbing organic matters through microwave activation of potassium persulfate |
| CN103241796A (en) * | 2013-05-31 | 2013-08-14 | 邓杰帆 | Process and device for performing continuous filtration and adsorption treatment on sewage by using graphene |
| CN104316590A (en) * | 2014-09-16 | 2015-01-28 | 河北中烟工业有限责任公司 | Inductively coupled plasma mass spectrometry method for simultaneous determination of chromium, nickel, arsenic and lead in hot melt adhesive for cigarette |
| CN104730013A (en) * | 2015-03-25 | 2015-06-24 | 广东出入境检验检疫局检验检疫技术中心 | Method for judging effective life of graphite pipe in graphite furnace atomic absorption spectrometer |
| CN105548331A (en) * | 2015-12-10 | 2016-05-04 | 内蒙古包钢钢联股份有限公司 | Method for simultaneous determination of multiple trace elements in iron ore |
| CN108802012A (en) * | 2018-06-07 | 2018-11-13 | 山东省食品药品检验研究院 | The detection method of silica in a kind of food and food additives |
| CN108982204A (en) * | 2018-09-05 | 2018-12-11 | 安徽科达洁能新材料有限公司 | A kind of method that micro-wave digestion-ICP-OES measures microelement in graphite |
| CN109316433A (en) * | 2018-12-05 | 2019-02-12 | 邯郸学院 | A kind of facial treatment mask reducing heavy metal pollution |
Non-Patent Citations (3)
| Title |
|---|
| 孙跃: "《金属腐蚀与控制》", 30 April 2003 * |
| 林婵: "《食品理化检验技术》", 31 January 2019 * |
| 郭劲: "《放电引发非链式脉冲氟化氘激光器》", 31 July 2017 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112630211A (en) * | 2020-11-25 | 2021-04-09 | 沪东重机有限公司 | Method for measuring internal elements of iron ore |
| CN117074447A (en) * | 2023-08-25 | 2023-11-17 | 中国矿业大学 | Method for detecting content of harmful impurity elements in Huang Jinkuang flotation product |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111239240B (en) | 2023-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111239240B (en) | Method for determining harmful elements in iron ore | |
| CN105548331A (en) | Method for simultaneous determination of multiple trace elements in iron ore | |
| CN107436292A (en) | The method for determining sulfur content in covering slag | |
| CN113189085A (en) | Method for measuring Mg activity coefficient of Mg-containing blast furnace slag | |
| CN111257258A (en) | Method for detecting zinc in dust mud based on atomic absorption spectrum | |
| CN112014379A (en) | Method for measuring calcium oxide in limestone and dolomite | |
| CN103808791A (en) | Method for determining iron content in silicon nitride material | |
| CN111855351A (en) | Method for measuring total arsenic content in zeolite powder | |
| CN111307787A (en) | Method for measuring molybdenum content in molybdenum waste residue | |
| CN114739982A (en) | Method for detecting element content in glass | |
| CN102914533A (en) | Method for measuring high content lead in iron-containing dust and mud | |
| CN110095419A (en) | The detection method of lead, cadmium in automotive material | |
| CN108802012A (en) | The detection method of silica in a kind of food and food additives | |
| CN112683611B (en) | Digestion solution and method for determining element content in refined aluminum ingot for remelting | |
| CN112129744B (en) | Chemical phase analysis method for lithium in ore | |
| CN113189086A (en) | Method for measuring MgO activity in high-aluminum blast furnace slag | |
| CN110412116B (en) | Method for testing content of sulfur element and application thereof | |
| CN113777095A (en) | Method for detecting content of potassium and sodium in molybdenum trioxide for high-solubility catalyst | |
| CN111239172A (en) | Method for determining phosphorus content in coal | |
| CN112730385A (en) | Detection method for determining contents of silicon and phosphorus elements in ferrochrome by utilizing ICP (inductively coupled plasma) | |
| CN118347958A (en) | Method for measuring carbon-sulfur content in coal and coke by infrared carbon-sulfur analyzer | |
| CN113640454B (en) | Rapid test method for calcium oxide content in limestone | |
| CN114674810A (en) | Method for measuring amounts of vanadium pentoxide, copper, molybdenum, nickel and zinc in stone coal vanadium ore | |
| CN114878671A (en) | Method for determining rhenium and scandium in geochemical sample | |
| CN115950719A (en) | Method for determining acid-insoluble aluminum in aluminum-magnesium-calcium alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |