CN104502298B - A kind of measure cadmium and the method for micro lead in iron ore - Google Patents
A kind of measure cadmium and the method for micro lead in iron ore Download PDFInfo
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- CN104502298B CN104502298B CN201410813789.2A CN201410813789A CN104502298B CN 104502298 B CN104502298 B CN 104502298B CN 201410813789 A CN201410813789 A CN 201410813789A CN 104502298 B CN104502298 B CN 104502298B
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Abstract
The present invention discloses and a kind of measures cadmium and the method for micro lead in iron ore, clears up iron ore sample including with microwave dissolver, then uses graphite furnace atomic absorption spectrophotometer to measure test solution.The process of micro-wave digestion is: is placed in politef counteracting tank by the iron ore sample of drying, uses deionized water moistening, be subsequently adding chloroazotic acid, after vigorous reaction stops, putting in microwave dissolver furnace chamber, set digestion condition as 190 DEG C, the heating-up time is 20min, clearing up the retention time is 20min, it is cooled to room temperature after having cleared up, takes out counteracting tank, after sample in tank is taken out, add water constant volume, i.e. obtains sample liquid to be measured.Sample can be cleared up by present invention Microwave Digestion completely, and in the case of not adding matrix modifier, testing result is consistent with the testing result of additive method, has simply, advantage fast and accurately, it is adaptable to micro lead and Cadmium detrmination in iron ore in batches.
Description
Technical field
The invention belongs to physical and chemical inspection technical field, a kind of measure cadmium and the method for micro lead in iron ore.
Background technology
Iron ore is as the basic material of steel and iron industry, and mineral composition is various, complex chemical composition, either trade relations
Or metallurgical requirements is all the most deeply concerned to its component.The poisonous and harmful element not only shadow such as lead, arsenic, cadmium, hydrargyrum, fluorine and chlorine in iron ore
Ring smelting equipment and product quality, also can pollute surrounding enviroment simultaneously, threaten health of human body.Based on environmental conservation and smelting enterprise
The factors such as industry protection smelting equipment, iron and steel industry industry standard formulated the limitation mark of harmful elements in iron ore in 2014
Accurate.In iron ore, the examination criteria of the element such as lead, arsenic is more, mainly has atomic fluorescence spectrometry, inductively coupled plasma to send out
Penetrate spectrographic method, flame atomic absorption spectrometry, volumetric method, spectrophotography, inductively coupled plasma mass spectrometry method etc..Iron mine
In stone, the examination criteria method of cadmium compares shortage, mainly has atomic fluorescence method and ICP-MS method.The iron ore of other document report
Middle cadmium element method for measuring also has inductively coupled plasma emission spectrography, voltammetry, atomic absorption spectrography (AAS), inductance coupling
Close ICP-MS etc..In these methods, ICP-MS method is expensive, and the expense using process to produce is too high, at home
Produce, detection enterprise popularizes difficulty.Although flame atomic absorption method and inductive coupling plasma emission spectrum method instrumentation
Simply, but the cadmium content ratio in iron ore is relatively low, uses both approaches sensitivity not reach requirement.Zhang Li etc. use hydrogenation
Thing Generation-Atomic Fluorescence Spectrometry measures, although detection limit ratio is relatively low, but preparing of Sulfhydryl Cotton is cumbersome, and process is complicated.
At present, the report of cadmium in graphite furnace atomic absorption spectrometry iron ore is not the most found.
GFAAS is the atomizer utilizing graphite material to make the shapes such as pipe, cup, adds with electric current
Hot atom carries out the method for atomic absorption analysis.Due to sample full entry atomization, and avoid atomic concentration at fire
Dilution in flame gas, sensitivity for analysis has obtained significant raising, and detection limit can reach 10-6～10-4, better than ICP-AES method
1～2 order of magnitude.For measuring trace metal element, better than other many methods in performance, and a small amount of sample can be used for
Analyze and solid sample direct analysis.Compared with atomic emission spectrum and atomic fluorescence spectrometry technology, spectral interference is few, right
Have more preferable selectivity in tested unit, thus its application is quite varied.
Summary of the invention
It is an object of the invention to provide one and have employed micro-wave digestion GFAAS to measure ferrum
Cadmium and the method for micro lead in Ore.
For reaching above-mentioned purpose, the technical solution used in the present invention is:
A kind of measure cadmium and the method for micro lead in iron ore, clear up iron ore sample, then including with microwave dissolver
Use the step that graphite furnace atomic absorption spectrophotometer measures.
In technique scheme:
Described microwave dissolver clears up the process of iron ore:
The solution iron ore sample of drying is placed in politef counteracting tank, uses deionized water moistening, be subsequently adding king
Water, after vigorous reaction stops, putting in microwave dissolver furnace chamber, sets digestion condition as 190 DEG C, and the heating-up time is 20min,
Clearing up the retention time is 20min, is cooled to room temperature after having cleared up, and takes out counteracting tank, and after being taken out by sample in tank, add water constant volume,
I.e. obtain sample liquid to be measured.
Further, if silicone content is higher in ironstone sample, described vigorous reaction adds a small amount of Fluohydric acid. after stopping.
Further, described iron ore sample is preferably dried under the conditions of 105 DEG C.
The process that described graphite furnace atomic absorption spectrophotometer measures is:
Concentration is 1000 μ L/mL lead, cadmium Standard Stock solutions, is diluted to the lead mark that concentration is multiple numerical value respectively
Quasi-working solution and cadmium standard working solution, utilize graphite furnace atomic absorption spectrophotometer mensuration lead, cadmium standard working solution to obtain
Calibration curve, recycling graphite furnace atomic absorption spectrophotometer measures the iron ore sample after micro-wave digestion, passes through comparison calibration
Curve obtains cadmium and the content of lead in iron ore.
Preferably, a series of concentration values of described lead standard working solution are: 0mg/L, 2mg/L, 4mg/L, 6mg/L,
8mg/L.A series of concentration values of described cadmium standard working solution are: 0 μ g/L, 0.5 μ g/L, 1 μ g/L, 2 μ g/L, 4 μ g/L.
Preferably, instrument parameter when described graphite furnace atomic absorption spectrophotometer is measured is:
Cadmium: wavelength 228.8nm, slit 0.7nm, lamp current 4.0mA；Baking temperature 85～120 DEG C, drying time 25s；Ash
Change temperature 500 DEG C, ashing time 20s；Atomization temperature 1500 DEG C, atomization time 5s；Burn residual temperature 2450 DEG C, burn the residual time
3s；Zeeman correcting background, measures peak area；With high-purity argon gas for graphite furnace protective gas, flow 1.8L/min；Sample size then with
20 μ L are optimal；
Lead: wavelength 217.0nm, slit 0.7nm, lamp current 2.0mA；Baking temperature 85～130 DEG C, drying time 25s；Ash
Change temperature 650 DEG C, ashing time 25s；Atomization temperature 1500 DEG C, atomization time 5s；Burn residual temperature 2450 DEG C, burn the residual time
3s；Zeeman correcting background, measures peak area；With high-purity argon gas for graphite furnace protective gas, flow 1.8L/min；Sample size also with
20 μ L are optimal.
Compared to the prior art, the invention have the advantages that
1, the pre-treatment of ironstone sample uses microwave digestion technology, has gathered the property of high-pressure digestion and microwave fast heating
Can, there is sample and decompose quick, complete, simple to operate, volatile element loss is little, and reagent consumption is few, pollutes few, and blank is low,
The distinguishing features such as analysis cost is low；
Have employed GFAAS when 2, measuring cadmium and lead, sensitivity for analysis is high, and amount of samples is few, operation
Simply, compared with atomic emission spectrum and atomic fluorescence spectrometry technology, spectral interference is few, have preferably for tested unit
Selectivity.
Detailed description of the invention
Embodiment 1
1.1 key instrument
AA240Z type graphite furnace atomic absorption spectrophotometer (Varian company of the U.S.)；PSD120 graphite furnace automatic sampler
(Varian company of the U.S.)；O2E-05 type cadmium hollow cathode lamp；WB24A type lead hollow cathode lamp.ETHOS A type microwave dissolver
(LabTech company of the U.S.), is equipped with 12 100mL high-pressure digestion tanks.Milli-Q Advantage A10 ultrapure water system is (beautiful
Millipore Corp. of state): resistivity 18.2M Ω cm.
1.2 main agents
Lead, cadmium Standard Stock solutions (ferrous materials test center of country): be 1000 μ g/mL, be diluted to as required
Different concentration standard working solution (being shown in Table 1).
The concentration of Pb and Cd in table 1 standard working solution
1.3 experimental technique
Weigh 0.5g 105 DEG C dry iron ore samples, be placed in 100mL politef counteracting tank, with go on a small quantity from
Sub-water-wet, adds 10mL chloroazotic acid, (if silicone content is higher in sample, drip 1mL Fluohydric acid .) after vigorous reaction stops, adding
Lid set, is placed in rotating disk, puts in furnace chamber, connects temperature, pressure transducer.Setting digestion condition as 190 DEG C, the heating-up time is
20min, clearing up the retention time is 20min.It is cooled to room temperature after having cleared up, takes out counteracting tank, by whole for Specimen eliminating liquid in tank
It is transferred in 100mL plastics volumetric flask, is diluted with water to scale, shakes up, stand.In company with doing blank experiment.Then graphite furnace is used
Atomic absorption spectrography (AAS) measures lead cadmium in solution under the conditions of selected instrument parameter.
The process that graphite furnace atomic absorption spectrophotometer measures is: it is molten that concentration is 1000 μ L/mL lead, cadmium standard inventory
Liquid, is diluted to lead standard working solution and cadmium standard working solution (being shown in Table 1) that concentration is multiple numerical value respectively, utilizes graphite furnace
Atomic absorption spectrometry lead, cadmium standard working solution obtain calibration curve, and recycling graphite furnace atomic absorption spectrophotometer is surveyed
Fixed iron ore sample after micro-wave digestion, obtains cadmium and the content of lead in iron ore by comparison calibration curve.
Instrument parameter when graphite furnace atomic absorption spectrophotometer is measured is:
Cadmium: wavelength 228.8nm, slit 0.7nm, lamp current 4.0mA；Baking temperature 85～120 DEG C, drying time 25s；Ash
Change temperature 500 DEG C, ashing time 20s；Atomization temperature 1500 DEG C, atomization time 5s；Burn residual temperature 2450 DEG C, burn the residual time
3s；Zeeman correcting background, measures peak area；With high-purity argon gas for graphite furnace protective gas, flow 1.8L/min；Sample size 20 μ
L；
Lead: wavelength 217.0nm, slit 0.7nm, lamp current 2.0mA；Baking temperature 85～130 DEG C, drying time 25s；Ash
Change temperature 650 DEG C, ashing time 25s；Atomization temperature 1500 DEG C, atomization time 5s；Burn residual temperature 2450 DEG C, burn the residual time
3s；Zeeman correcting background, measures peak area；With high-purity argon gas for graphite furnace protective gas, flow 1.8L/min；Sample size 20 μ
L。
1.4 method detection limits, precision, accuracy and the response rate
Under above-mentioned instrument working condition, draw calibration curve, to blank solution replication 11 times, take measurement result
3 times of standard deviation (s) are as detection limit, 10 times of Determination Limit as method.The detection limit of lead and cadmium is respectively 0.25 μ g/
G (Pb) and 0.072 μ g/g (Cd).Lead and Cadmium detrmination lower limit are respectively 0.83 μ g/g (Pb) and 0.24 μ g/g (Cd).
According to above-mentioned experimental technique, for same sample ore METHOD FOR CONTINUOUS DETERMINATION 11 times, investigate method precision.Lead, cadmium are relative
Standard deviation (RSD, n=11) is respectively 0.8% (Pb) and 2.6% (Cd) (being shown in Table 2)；Select two different iron ores, adopt
Measure by this method, from the point of view of table 2 result, consistent with additive method measured value.Sample ore is separately added into isocyatic to be measured
Element, is measured after clearing up process by 1.4 joint experimental techniques, and the method response rate is respectively 96.0% (Pb) and 107.3%
(Cd) (being shown in Table 3), result is more satisfactory.
Table 2 preci-sion and accuracy is tested
Note: the cooperative experiment sample that same Fe-1, Fe-2 provide for Tianjin Entry-Exit Inspection and Quarantine Bureau, reference value is collaborative
Experiment median.
The response rate of table 3 method
Test result indicate that, sample can be cleared up completely with microwave dissolver, and do not adding the feelings of matrix modifier
Under condition, the method is consistent to the testing result of actual sample and the testing result of additive method.This method is simple, quick, accurate,
Lead and Cadmium detrmination be applicable to batch iron ore.
Claims (4)
1. one kind measures cadmium and the method for micro lead in iron ore, it is characterised in that: include clearing up instrument iron ore with micro-wave digestion
Sample, then uses the step that graphite furnace atomic absorption spectrophotometer measures；
The process of described micro-wave digestion iron ore sample is: dried under the conditions of 105 DEG C by iron ore sample, the iron ore of drying
Sample is placed in politef counteracting tank, uses deionized water moistening, is subsequently adding chloroazotic acid, after vigorous reaction stops, putting into
In microwave dissolver furnace chamber, setting digestion condition as 190 DEG C, the heating-up time is 20min, and clearing up the retention time is 20min, clears up
Being cooled to room temperature after completing, take out counteracting tank, after being taken out by sample in tank, add water constant volume, i.e. obtains sample liquid to be measured；
The process that described graphite furnace atomic absorption spectrophotometer measures is: it is molten that concentration is 1000 μ L/mL lead, cadmium standard inventory
Liquid, is diluted to lead standard working solution and cadmium standard working solution that concentration is multiple numerical value respectively, utilizes sampling Graphite Furnace Atomic to inhale
Receive spectrophotometer lead, cadmium standard working solution obtains calibration curve, and recycling graphite furnace atomic absorption spectrophotometer measures through micro-
Ripple clear up after iron ore sample, obtain cadmium and the content of lead in iron ore by comparison calibration curve.
Method the most according to claim 1, it is characterised in that: described vigorous reaction adds Fluohydric acid. after stopping.
Method the most according to claim 1, it is characterised in that:
A series of concentration values of described lead standard working solution are: 0mg/L, 2mg/L, 4mg/L, 6mg/L, 8mg/L；
A series of concentration values of described cadmium standard working solution are: 0 μ g/L, 0.5 μ g/L, 1 μ g/L, 2 μ g/L, 4 μ g/L.
4. according to the method described in claim 1 or 3, it is characterised in that described graphite furnace atomic absorption spectrophotometer is measured
Time instrument parameter be:
Cadmium: wavelength 228.8nm, slit 0.7nm, lamp current 4.0mA；Baking temperature 85～120 DEG C, drying time 25s；Ashing temperature
Spend 500 DEG C, ashing time 20s；Atomization temperature 1500 DEG C, atomization time 5s；Burn residual temperature 2450 DEG C, burn residual time 3s；
Zeeman correcting background, measures peak area；With high-purity argon gas for graphite furnace protective gas, flow 1.8L/min；
Lead: wavelength 217.0nm, slit 0.7nm, lamp current 2.0mA；Baking temperature 85～130 DEG C, drying time 25s；Ashing temperature
Spend 650 DEG C, ashing time 25s；Atomization temperature 1500 DEG C, atomization time 5s；Burn residual temperature 2450 DEG C, burn residual time 3s；
Zeeman correcting background, measures peak area；With high-purity argon gas for graphite furnace protective gas, flow 1.8L/min.
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| CN105300908A (en) * | 2015-11-10 | 2016-02-03 | 合肥通用机械研究院 | Method for determining trace element lead in centrifugal casting furnace tube and matrix modifier applied thereto |
| 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 |
| CN106290194A (en) * | 2016-08-22 | 2017-01-04 | 常州大学 | A kind of method of cadmium content in direct mensuration electron level diethylene glycol dimethyl ether |
| CN109297914A (en) * | 2018-11-16 | 2019-02-01 | 阿拉山口出入境检验检疫局综合技术服务中心 | A method of using the Zn-ef ficiency content in graphite resolution-atomic absorption spectrometry sulphur |
| CN110161017B (en) * | 2019-06-04 | 2022-08-23 | 深圳市环保科技集团股份有限公司 | Method for establishing mathematical model of spectral interference coefficient of iron in cadmium determination by ICP-OES method |
| CN111537328A (en) * | 2020-04-20 | 2020-08-14 | 湛江海关技术中心 | Pretreatment method for chromium ore by microwave digestion acid melting method and chromium production method |
| CN114280222A (en) * | 2021-12-14 | 2022-04-05 | 万宝矿产有限公司 | Method for batch processing of copper ore samples |
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| 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 |
| CN102854238A (en) * | 2012-08-10 | 2013-01-02 | 同济大学 | Method for determination analysis of multiple heavy metals in environmental medium or biological sample |
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