CN109781713A - The method that inductively coupled plasma emission spectrography measures multiple metallic element in zinc abstraction acid leaching residue simultaneously - Google Patents
The method that inductively coupled plasma emission spectrography measures multiple metallic element in zinc abstraction acid leaching residue simultaneously Download PDFInfo
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Abstract
The invention belongs to the metallic test analysis technical fields of metallurgy industry, in particular to the method that a kind of inductively coupled plasma emission spectrography measures multiple metallic element in zinc abstraction acid leaching residue simultaneously, it is measured carries out according to inductively coupled plasma emission spectrography testing principle, including experiment condition, the preparation of single element standard solution, the preparation of mixed standard solution, the preparation of series standard working solution A, the preparation of series standard working solution B, sample treatment, working curve is drawn, co-existing element interference is investigated, detection limit situation, precision situation, rate of recovery experiment and steadiness.The method of the invention can detect multiple element in zinc abstraction acid leaching residue simultaneously, and the precision of testing result is high, stability is good in instrument detection process, and enterprise's detection and Solid state fermentation pressure can be effectively relieved in the method for the present invention, not only have great importance, but also very necessary.
Description
Technical field
The invention belongs to the metallic test analysis technical field of metallurgy industry, in particular to a kind of inductively coupled plasma body
The method that emission spectrometry measures multiple metallic element in zinc abstraction acid leaching residue simultaneously.
Background technique
The phase analysis containing zincic acid of 100,000 tons of zinc abstraction branch company oxygen leaching technique outputs of western mining industry, chemical component and zinc
Concentrate raw material is different, shows as complicated component and changeable.Because zinc abstraction residues containing zinc sample does not have national standard detection method, big portion
Point enterprise detects that these material containing zincs only continue to use zinc concentrate national standard or professional standard carries out analysis detection, i.e., each element list
Only analysis detection.Wherein, zinc, ferro element use EDTA titration, and copper, lead, cadmium, cobalt, nickel use atomic absorption spectrography (AAS), oxidation
Calcium, magnesia and aluminium oxide use EDTA titration, and arsenic and antimony are measured using atomic fluorescence spectrometry, these detection methods
It is cumbersome, round of visits is longer, the especially measurement such as calcium oxide, magnesia is serious due to interfering with each other, and indicator color becomes
Change it is unobvious, it is more demanding for instrument detection sensitivity, and detect preci-sion and accuracy it is poor, to detection work belt come
Very big difficulty.Further, since ingredient and content are different in material containing zinc, cannot be reached using what these method test samples had
To satisfied effect.And can all generate large batch of slag specimen containing zinc abstraction daily for the production unit of continuous processing, this is contained
The detection work of zinc abstraction slag specimen brings biggish pressure, these zinc abstraction acid leaching residues detect large labor intensity, detection time
It is long, and inspection cost is higher.Residues containing zinc sample waste not only land occupation but also had endangered ecological environment, if detection determines not in time
Content, biggish burden will be caused to enterprise by being recycled and being reprocessed.Therefore, status is detected in conjunction with zinc abstraction acidleach slag specimen,
The measuring method of copper, lead, iron, cadmium, cobalt, nickel, antimony, calcium, magnesium, aluminium, arsenic, manganese element in zinc abstraction acid leaching residue is studied, enterprise is alleviated
Detection and Solid state fermentation pressure, not only have great importance, but also very necessary.
Summary of the invention
The purpose of the present invention is to provide a kind of inductively coupled plasma emission spectrographies to measure zinc abstraction acidleach simultaneously
The method of multiple metallic element in slag, solution prior art detection method is cumbersome, is difficult to once measure multiple element, and is not suitable for
The problem of multiple metallic element detects in zinc abstraction acid leaching residue sample.
Realization process of the invention is as follows:
A kind of method that inductively coupled plasma emission spectrography measures multiple metallic element in zinc abstraction acid leaching residue simultaneously,
It is measured carries out according to inductively coupled plasma emission spectrography testing principle, including experiment condition, single element standard solution
Preparation, the preparation of mixed standard solution, the preparation of series standard working solution A, the preparation of series standard working solution B, sample
Product processing, working curve drafting, co-existing element interference investigation, the experiment of detection limit situation, precision situation, the rate of recovery and stability
Situation.
Further, it states inductively coupled plasma emission spectrography while measuring multiple metallic element in zinc abstraction acid leaching residue
Method specifically includes following detection process:
(1) experiment condition
1.1 this method scope of applications: this method is suitable for inductively coupled plasma atomic emission spectrum and measures zinc simultaneously
The measurement of copper, lead, iron, cadmium, cobalt, nickel, antimony, calcium, magnesium, aluminium, arsenic, manganese amount in acid leaching residue is smelted, wherein Zn-ef ficiency concentration is not more than
600ug/mL；
The instrument and condition of 1.2 this method: electronics coupled plasma atomic emission spectrometer is U.S.'s thermoelectricity iCAP-
7400 types, 27.12MHZ；Muffle furnace: 1200 DEG C of maximum temperature；Electronic balance: sensibility reciprocal 0.0001g；Baking oven: 50 DEG C~300 DEG C；
U.S.'s thermoelectricity iCAP-7400 type, power 1150W, cooling air 14L/min assist gas 0.7L/min, carrier gas 0.5L/
Min, observed altitude 15mm, time of integration long wave 5s, time of integration shortwave 10s, instrumental resolution≤0.04nm；
Reagent used in 1.3 this method: the density p of hydrochloric acid is 1.19g/mL；The density p of nitric acid is 1.42g/mL, grade
It Wei not GR；Hydrofluoric acid, perchloric acid, dehydrated alcohol, argon gas purity >=99.99%；
The analysis spectral line of 1.4 this method: it is provided according to inductively coupled plasma atomic emission spectrometer operational manual
Condition starts instrument, analysis spectral line Cu:324.754nm；Pb:216.999nm；Fe:238.204nm；Cd:226.502nm；
Co:228.616nm；Ni:231.604nm；Sb:217.581nm；Ca:184.006nm；Mg:285.213nm；Al:
309.271nm；As:189.042nm；Mn:260.569nm；
(2) preparation of single element standard solution
2.1 concentration are 1.00mg/mL copper standard solution:
By the oxide layer on metal copper sheet (1+9) the nitric acid treatment surface that purity is >=99.99%, water and ethyl alcohol are used respectively
Washing air-dries, and accurately weighs 0.2000g treated that (1+1) nitric acid 20mL, lid is added in 250mL beaker in metal copper sheet
Upper watch glass, low-temperature heat, dissolution completely, are removed, cooling, wash watch glass and wall of cup, are moved into 200mL volumetric flask, constant volume shakes
It is even；Wherein described (1+9) nitric acid is by nitric acid: water volume ratio is formulated for 1:9, and (1+1) nitric acid is by nitric acid: water volume ratio
It is formulated for 1:1；The temperature of low-temperature heat is 300 DEG C；
2.2 concentration are 1.00mg/mL lead standard solution:
By the oxide layer on high-purity lead button (1+9) nitric acid treatment surface that purity is >=99.99%, water and ethyl alcohol are used respectively
Washing air-dries；Accurately weigh 0.2000g treated that lead button is added (1+1) nitric acid 20mL, covers table in 250mL beaker
Ware, low-temperature heat, dissolution completely, are removed, cooling, wash watch glass and wall of cup, are moved into 200mL volumetric flask, constant volume shakes up；Its
Described in (1+9) nitric acid be by nitric acid: water volume ratio is formulated for 1:9, and (1+1) nitric acid is by nitric acid: water volume ratio 1:1
It is formulated；The temperature of low-temperature heat is 300 DEG C；
2.3 concentration is 1.00mg/mL cadmium standard solution:
By the oxide layer on high purity cadmium grain (1+9) the nitric acid treatment surface that purity is >=99.99%, water and ethyl alcohol are used respectively
Washing air-dries；Accurately weigh 0.2000g treated that cadmium grain is added (1+1) nitric acid 20mL, covers table in 250mL beaker
Ware, low-temperature heat, dissolution completely, are removed, cooling, wash watch glass and wall of cup, are moved into 200mL volumetric flask, constant volume shakes up；Its
Described in (1+9) nitric acid be by nitric acid: water volume ratio is formulated for 1:9, and (1+1) nitric acid is by nitric acid: water volume ratio 1:1
It is formulated；The temperature of low-temperature heat is 300 DEG C；
2.4 concentration are 1.00mg/mL cobalt standard solution:
The high-purity cobalt powder of 0.2000g is accurately weighed, in 250mL beaker, (1+1) nitric acid 20mL is added, covers watch glass, low temperature
Heating, dissolution completely, are removed, cooling, wash watch glass and wall of cup, are moved into 200mL volumetric flask, constant volume shakes up；Wherein (1+1)
Nitric acid is by nitric acid: water volume ratio is formulated for 1:1；The temperature of low-temperature heat is 300 DEG C；
2.5 concentration are 1.00mg/mL nickel standard solution:
By the oxide layer on high purity nickel (1+9) the nitric acid treatment surface that purity is >=99.99%, washed respectively with water and ethyl alcohol
It washs, air-dry；Accurately weigh 0.2000g treated that nickel is added (1+1) nitric acid 20mL, covers watch glass in 250mL beaker, it is low
Temperature heating, dissolution completely, are removed, cooling, wash watch glass and wall of cup, are moved into 200mL volumetric flask, constant volume shakes up；It is wherein described
(1+9) nitric acid is by nitric acid: water volume ratio is formulated for 1:9, and (1+1) nitric acid is by nitric acid: water volume ratio be 1:1 prepare and
At；The temperature of low-temperature heat is 300 DEG C；
2.6 concentration are 1.00mg/mL antimony standard solution:
It is the oxide layer on >=99.99% high-purity antimony particles (1+9) nitric acid treatment surface by purity, is washed respectively with water and ethyl alcohol
It washs, air-dry；Accurately weigh 0.2000g treated that antimony grain is added (1+1) nitric acid 20mL, covers watch glass in 250mL beaker,
Low-temperature heat, dissolution completely, are removed, cooling, wash watch glass and wall of cup, are moved into 200mL volumetric flask, constant volume shakes up；Wherein institute
Stating (1+9) nitric acid is by nitric acid: water volume ratio is formulated for 1:9, and (1+1) nitric acid is by nitric acid: water volume ratio is 1:1 preparation
It forms；The temperature of low-temperature heat is 300 DEG C；
2.7 concentration are 1.00mg/mL iron standard solution:
Spectroscopic pure di-iron trioxide of the 0.2860g through 900 DEG C of calcination 1h is weighed in 250mL beaker, (1+1) hydrochloric acid is added
20mL low-temperature heat dissolution moves into 200mL volumetric flask after cooling, is diluted with water to scale, shakes up；Wherein (1+1) hydrochloric acid is
By hydrochloric acid: water volume ratio is formulated for 1:1；The temperature of low-temperature heat is 300 DEG C；
2.8 concentration are 1.00mg/mL calcium standard solution:
Spectrum pure calcium carbonate of the 0.4994g through 120 DEG C of drying 2h is accurately weighed in 250mL beaker, addition has removed two
(1+1) hydrochloric acid 20mL is added along wall of cup in the water 20mL of carbonoxide, cap upper surface ware by several times, and removing carbon dioxide is boiled in dissolution,
It removes, it is cooling, surface plate and wall of cup are washed, is moved into 200mL volumetric flask, constant volume shakes up；Wherein (1+1) hydrochloric acid is by hydrochloric acid:
Water volume ratio is formulated for 1:1；
2.9 concentration are 1.00mg/mL magnesium standard solution:
Spectroscopic pure magnesia of the 1.6583g through 800 DEG C of drying 2h is accurately weighed in 250mL beaker, addition has removed two
The water 20mL of carbonoxide is added dropwise (1+1) hydrochloric acid to being completely dissolved, and is stirred continuously, and 10mL hydrochloric acid is added, and heating removes nitrogen oxidation
Object, it is cooling, wall of cup is washed, is moved into 1000mL volumetric flask, constant volume shakes up；Wherein (1+1) hydrochloric acid is by hydrochloric acid: water volume ratio
It is formulated for 1:1；Heating temperature is 300 DEG C.
2.10 concentration are 1.00mg/mL aluminum standard solution:
0.2000g spectrum pure metallic aluminum is accurately weighed in 250mL beaker, it is molten that 10mL hydrochloric acid (1+1) low-temperature heat is added
Solution moves into 200mL volumetric flask after cooling, dilute to scale with water, shakes up；Wherein (1+1) hydrochloric acid is by hydrochloric acid: water volume ratio is
1:1 is formulated；The temperature of low-temperature heat is 300 DEG C；
2.11 concentration are 1.00mg/mL manganese standard solution:
It accurately weighs 0.2000g high pure metal manganese (99.99%) to be placed in 250mL beaker, be added 20mL hydrochloric acid (1+1),
Low-temperature heat dissolution, is cooled to room temperature, and moves into 200mL volumetric flask, is diluted with water to scale, shakes up；Wherein (1+1) hydrochloric acid is
By hydrochloric acid: water volume ratio is formulated for 1:1；The temperature of low-temperature heat is 300 DEG C；
2.12 concentration are 1.00mg/mL arsenic standard solution:
It accurately weighs the arsenic that 0.2000g purity is 99.99% to be placed in 250mL beaker, (1+1) nitric acid 10mL, lid is added
Watch glass, low-temperature heat dissolution completely, are removed, are cooled to room temperature, move into 200mL volumetric flask, 5mL nitric acid is added, is diluted with water
To scale, shake up；Wherein (1+1) nitric acid is by nitric acid: water volume ratio is formulated for 1:1；The temperature of low-temperature heat is 300
℃；
(3) preparation of mixed standard solution
3.1 concentration are 100.00 μ g/mL mixed standard solution A:
Copper standard solution, the lead standard solution, iron standard solution, cadmium of the preparation of 20.00mL step (2) are accurately pipetted respectively
Standard solution, cobalt standard solution, nickel standard solution, antimony standard solution, in 200mL volumetric flask, addition 10mL nitric acid, constant volume,
It shakes up；
3.2 concentration are 100.00 μ g/mL mixed standard solution B:
Calcium standard solution, the magnesium standard solution, aluminum standard solution, arsenic of the preparation of 20.00mL step (2) are accurately pipetted respectively
10mL nitric acid is added in 200mL volumetric flask in standard solution, manganese standard solution, and constant volume shakes up；
(4) preparation of series standard working solution A
4.1 zero standard working solution ρ (Cu, Pb, Fe, Cd, CO, Ni, Sb)=0 μ g/mL:
Nitric acid is added in 100mL volumetric flask in the mixed standard solution A for accurately pipetting the preparation of 0.00mL step (3)
5mL, it is dilute to scale with water, it shakes up；
4.2 hybrid standard working solution ρ (Cu, Pb, Fe, Cd, CO, Ni, Sb)=0.10 μ g/mL:
Nitric acid is added in 100mL volumetric flask in the mixed standard solution A for accurately pipetting the preparation of 0.10mL step (3)
5mL, it is dilute to scale with water, it shakes up；
4.3 hybrid standard working solution ρ (Cu, Pb, Fe, Cd, CO, Ni, Sb)=1.00 μ g/mL:
Nitric acid is added in 100mL volumetric flask in the mixed standard solution A for accurately pipetting the preparation of 1.00mL step (3)
5mL, it is dilute to scale with water, it shakes up；
4.4 hybrid standard working solution ρ (Cu, Pb, Fe, Cd, CO, Ni, Sb)=10.00 μ g/mL:
Nitric acid is added in 100mL volumetric flask in the mixed standard solution A for accurately pipetting the preparation of 10.00mL step (3)
5mL, it is dilute to scale with water, it shakes up；
4.5 hybrid standard working solution ρ (Cu, Pb, Fe, Cd, CO, Ni, Sb)=50.00 μ g/mL:
Copper standard solution, the lead standard solution, iron standard solution, cadmium mark of the preparation of 5.00mL step (2) are accurately pipetted respectively
Nitric acid 5mL is added in 100mL volumetric flask in quasi- solution, cobalt standard solution, nickel standard solution, antimony standard solution, dilute extremely with water
Scale shakes up；
(5) preparation of series standard working solution B
5.1 zero standard working solution ρ (Ca, Mg, Al, As, Mn)=0 μ g/mL:
Nitric acid is added in 100mL volumetric flask in the mixed standard solution B for accurately pipetting the preparation of 0.00mL step (3)
5mL, it is dilute to scale with water, it shakes up；
5.2 hybrid standard working solution ρ (Ca, Mg, Al, As, Mn)=0.10 μ g/mL:
Nitric acid is added in 100mL volumetric flask in the mixed standard solution B for accurately pipetting the preparation of 0.10mL step (3)
5mL, it is dilute to scale with water, it shakes up；
5.3 hybrid standard working solution ρ (Ca, Mg, Al, As, Mn)=0.50 μ g/mL:
Nitric acid is added in 100mL volumetric flask in the mixed standard solution B for accurately pipetting the preparation of 0.50mL step (3)
5mL, it is dilute to scale with water, it shakes up；
5.4 hybrid standard working solution ρ (Ca, Mg, Al, As, Mn)=1.00 μ g/mL:
Nitric acid is added in 100mL volumetric flask in the mixed standard solution B for accurately pipetting the preparation of 1.00mL step (3)
5mL, it is dilute to scale with water, it shakes up；
5.5 hybrid standard working solution ρ (Ca, Mg, Al, As, Mn)=10.00 μ g/mL:
Nitric acid is added in 100mL volumetric flask in the mixed standard solution B for accurately pipetting the preparation of 10.00mL step (3)
5mL, it is dilute to scale with water, it shakes up；
(6) zinc abstraction acid leaching residue sample treatment
0.1000-0.5000g zinc abstraction acid leaching residue sample is accurately weighed in 150mL polytetrafluoroethylene beaker, Jia Shuirun
It is wet, 15mL nitric acid, addition 5mL hydrochloric acid complete to sample dissolution after low-temperature heat 10-20min, 5mL hydrofluoric acid, 5mL high is added
Chloric acid, often plus a kind of reagent is both needed to shake up, and continues low-temperature heat, emits opium to wet salt, removes, cooling, is rinsed with water wall of cup,
9mL hydrochloric acid, 1mL nitric acid is added, low-temperature heat is boiled dissolved salts, removed, cooling；It moves into 100mL volumetric flask, constant volume shakes
Even, filtering obtains zinc abstraction acid leaching residue sample solution；Blank assay is carried out in company with sample；The temperature of low-temperature heat is 300 DEG C；
(7) working curve is drawn
7.1 draw working curve:
(1) stablize 30min after the igniting of electronics coupled plasma atomic emission spectrometer；
(2) five kinds of standard working solutions of 4.1-4.5 prepared in measuring process (four) series standard working solution A, to survey
Measuring resulting concentration is abscissa, and peak strength is ordinate after corresponding correction, draws working curve A；
(3) five kinds of standard working solutions of 5.1-5.5 prepared in measuring process (five) series standard working solution B, to survey
Measuring resulting concentration is abscissa, and peak strength is ordinate after corresponding correction, draws working curve B；
(4) measuring process (six) zinc abstraction acid leaching residue sample solution；
The calculating of 7.2 analysis results:
Calculation formula are as follows:In formula: c0Measure the concentration of blank solution, μ g/
mL；
C- measures the concentration of sample solution, μ g/mL；
The constant volume of v- sample solution, mL；
M- sample mass, g；
By step 7.1 and 7.2 can detect simultaneously copper in zinc abstraction acid leaching residue sample solution, lead, iron, cadmium, cobalt, nickel, antimony,
The content of calcium, magnesium, aluminium, arsenic, manganese totally ten two kinds of elements；
(8) co-existing element interference is investigated
Zinc-base when zinc-base bulk concentration is respectively 200ug/mL, 400ug/mL, 600ug/mL in zinc abstraction acid leaching residue is investigated
Interference of the body to element to be measured, being equivalent to zinc ion content is respectively 20%, 40%, 60%, it is determined that zinc-base bulk concentration is not
It is noiseless to element to be measured when greater than 600ug/mL；
(9) detection limit situation
In the step (1) under the conditions of laboratory apparatus, with being free of blank solution METHOD FOR CONTINUOUS DETERMINATION for 11 times of element to be measured,
Using 3 times of standard deviations of measurement result as detection limit, using 10 times of Determination Limits as this method of standard deviation；
Detection limit: Cu:0.0093ug/mL；Pb:0.0255ug/mL；Fe:0.0198ug/mL；Cd:0.0048ug/mL；
Co:0.0078ug/mL；Ni:0.0048ug/mL；Sb:0.0144ug/mL；Ca:0.0243ug/mL；Mg:0.0021ug/mL；
Al:0.0132ug/mL；As:0.0105ug/mL；Mn:0.0024ug/mL；
Determination Limit: Cu:0.032ug/mL；Pb:0.085ug/mL；Fe:0.066ug/mL；Cd:0.016ug/mL；Co:
0.026ug/mL；Ni:0.016ug/mL；Sb:0.048ug/mL；Ca:0.081ug/mL；Mg:0.007ug/mL；Al:
0.044ug/mL；As:0.035ug/mL；Mn:0.008ug/mL；
(10) precision situation
After electronics coupled plasma atomic emission spectrometer preheats 40min, the standard solution for being 1 μ g/mL with concentration
Duplicate measurements 11 times, relative standard deviation≤1.5%；
The experiment of (11) rate of recovery
To zinc abstraction acid leaching residue sample carry out recovery testu, obtain Cu, Pb, Fe, Cd, Co, Ni, Sb, Ca, Mg, Al,
As, Mn, the rate of recovery respectively 99.60~100.20%, 99.60~100.30%, 99.00~100.00%, 99.40~
99.60%, 95.98~99.87%, 100.00~100.10%, 99.96~100.02%, 100.10~100.60%,
99.20~99.90%, 99.92~100.03%, 100.06~100.10%, 99.60~100.30%, fully meet analysis
The requirement of method；
(12) steadiness
After electronics coupled plasma atomic emission spectrometer preheats 40min, the mixing for being respectively 1 μ g/mL with concentration
Standard working solution ρ (Cu, Pb, Fe, Cd, CO, Ni, Sb), concentration be 1 μ g/mL hybrid standard working solution ρ (Ca, Mg, Al,
As, Mn) in 4h, it measures 1 time, measures 12 times altogether, relative standard deviation≤3%, the linear phase of working curve at interval of 20min
Close coefficients R >=0.999.
Further, in step (6) zinc abstraction acid leaching residue sample handling processes, when member to be measured in zinc abstraction acid leaching residue sample
When plain concentration is lower than 0.10ug/mL, before zinc abstraction acid leaching residue sample solution constant volume, respective element standard solution is added and makes zinc
It smelts concentration of element to be measured in acid leaching residue sample and reaches 0.50ug/mL, the detection of element to be measured is dense in zinc abstraction acid leaching residue sample
Degree deducts the concentration that the standard solution being added introduces, then according to step (7) Calculation results, wherein in zinc abstraction acidleach
The effect that respective element standard solution is added in slag specimen product is to improve the accuracy of analysis result.
The positive effect of the present invention:
(1) contained although having in the prior art using the multielement in ICP-AES measurement zinc concentrate, calcining and regenerated zinc raw material
The method of amount, but the complicated component of zinc abstraction acid leaching residue, the method for continuing to use the prior art are difficult to realize in zinc abstraction acid leaching residue
The detection of multiple element, it is even more impossible to realize while detecting, and the method for the invention can detect simultaneously it is more in zinc abstraction acid leaching residue
Kind element, and the precision of testing result is high, stability is good in instrument detection process, and enterprise's inspection can be effectively relieved in the method for the present invention
Survey and Solid state fermentation pressure, not only have great importance, but also very necessary.
(2) it is difficult to handle zinc abstraction acid leaching residue sample using existing method, the method for the present invention passes through nitric acid, hydrochloric acid, hydrogen fluorine
Acid, the ingenious proportion of perchloric acid and sample treatment, obtain zinc abstraction acid leaching residue sample solution, do not relate in the prior art
And similar method and proportion, there is not any enlightenment yet, sample treatment of the present invention is obtained by test of many times,
With practical operation application value.
Specific embodiment
Below with reference to embodiment, the present invention will be further described.
Prior art detection method is cumbersome, is difficult to once measure multiple element in order to solve, and is not suitable for zinc abstraction acid
The problem of multiple metallic element detects in phase analysis sample, the present invention provide a kind of inductively coupled plasma emission spectrography while surveying
Determine the method for multiple metallic element in zinc abstraction acid leaching residue.
Inductively coupled plasma emission spectrography of the present invention measures multiple metallic element in zinc abstraction acid leaching residue simultaneously
Method, measurement carries out according to inductively coupled plasma emission spectrography testing principle, including experiment condition, single element mark
The preparation of quasi- solution, the preparation of mixed standard solution, the preparation of series standard working solution A, series standard working solution B match
System, sample treatment, working curve drafting, co-existing element interference investigation, detection limit situation, precision situation, the rate of recovery experiment and
Steadiness.Specifically include following detection process:
(1) experiment condition
1.1 this method scope of applications: this method is suitable for inductively coupled plasma atomic emission spectrum and measures zinc simultaneously
The measurement of copper, lead, iron, cadmium, cobalt, nickel, antimony, calcium, magnesium, aluminium, arsenic, manganese amount in acid leaching residue is smelted, wherein Zn-ef ficiency concentration is not more than
600ug/mL；
The instrument and condition of 1.2 this method: electronics coupled plasma atomic emission spectrometer is U.S.'s thermoelectricity iCAP-
7400 types, 27.12MHZ；Muffle furnace: 1200 DEG C of maximum temperature；Electronic balance: sensibility reciprocal 0.0001g；Baking oven: 50 DEG C~300 DEG C；
U.S.'s thermoelectricity iCAP-7400 type, power 1150W, cooling air 14L/min assist gas 0.7L/min, carrier gas 0.5L/
Min, observed altitude 15mm, time of integration long wave 5s, time of integration shortwave 10s, instrumental resolution≤0.04nm；
Reagent used in 1.3 this method: the density p of hydrochloric acid is 1.19g/mL；The density p of nitric acid is 1.42g/mL, grade
It Wei not GR；Hydrofluoric acid, perchloric acid, dehydrated alcohol, argon gas purity >=99.99%；
The analysis spectral line of 1.4 this method: it is provided according to inductively coupled plasma atomic emission spectrometer operational manual
Condition starts instrument, analysis spectral line Cu:324.754nm；Pb:216.999nm；Fe:238.204nm；Cd:226.502nm；
Co:228.616nm；Ni:231.604nm；Sb:217.581nm；Ca:184.006nm；Mg:285.213nm；Al:
309.271nm；As:189.042nm；Mn:260.569nm；
(2) preparation of single element standard solution
2.1 concentration is 1.00mg/mL copper standard solution:
By the oxide layer on metal copper sheet (1+9) the nitric acid treatment surface that purity is >=99.99%, water and ethyl alcohol are used respectively
Washing air-dries, and accurately weighs 0.2000g treated that (1+1) nitric acid 20mL, lid is added in 250mL beaker in metal copper sheet
Upper watch glass, low-temperature heat, dissolution completely, are removed, cooling, wash watch glass and wall of cup, are moved into 200mL volumetric flask, constant volume shakes
It is even；Wherein described (1+9) nitric acid is by nitric acid: water volume ratio is formulated for 1:9, and (1+1) nitric acid is by nitric acid: water volume ratio
It is formulated for 1:1；The temperature of low-temperature heat is 300 DEG C；
2.2 concentration are 1.00mg/mL lead standard solution:
By the oxide layer on high-purity lead button (1+9) nitric acid treatment surface that purity is >=99.99%, water and ethyl alcohol are used respectively
Washing air-dries；Accurately weigh 0.2000g treated that lead button is added (1+1) nitric acid 20mL, covers table in 250mL beaker
Ware, low-temperature heat, dissolution completely, are removed, cooling, wash watch glass and wall of cup, are moved into 200mL volumetric flask, constant volume shakes up；Its
Described in (1+9) nitric acid be by nitric acid: water volume ratio is formulated for 1:9, and (1+1) nitric acid is by nitric acid: water volume ratio 1:1
It is formulated；The temperature of low-temperature heat is 300 DEG C；
2.3 concentration are 1.00mg/mL cadmium standard solution:
By the oxide layer on high purity cadmium grain (1+9) the nitric acid treatment surface that purity is >=99.99%, water and ethyl alcohol are used respectively
Washing air-dries；Accurately weigh 0.2000g treated that cadmium grain is added (1+1) nitric acid 20mL, covers table in 250mL beaker
Ware, low-temperature heat, dissolution completely, are removed, cooling, wash watch glass and wall of cup, are moved into 200mL volumetric flask, constant volume shakes up；Its
Described in (1+9) nitric acid be by nitric acid: water volume ratio is formulated for 1:9, and (1+1) nitric acid is by nitric acid: water volume ratio 1:1
It is formulated；The temperature of low-temperature heat is 300 DEG C；
2.4 concentration are 1.00mg/mL cobalt standard solution:
The high-purity cobalt powder of 0.2000g is accurately weighed, in 250mL beaker, (1+1) nitric acid 20mL is added, covers watch glass, low temperature
Heating, dissolution completely, are removed, cooling, wash watch glass and wall of cup, are moved into 200mL volumetric flask, constant volume shakes up；Wherein (1+1)
Nitric acid is by nitric acid: water volume ratio is formulated for 1:1；The temperature of low-temperature heat is 300 DEG C；
2.5 concentration are 1.00mg/mL nickel standard solution:
By the oxide layer on high purity nickel (1+9) the nitric acid treatment surface that purity is >=99.99%, washed respectively with water and ethyl alcohol
It washs, air-dry；Accurately weigh 0.2000g treated that nickel is added (1+1) nitric acid 20mL, covers watch glass in 250mL beaker, it is low
Temperature heating, dissolution completely, are removed, cooling, wash watch glass and wall of cup, are moved into 200mL volumetric flask, constant volume shakes up；It is wherein described
(1+9) nitric acid is by nitric acid: water volume ratio is formulated for 1:9, and (1+1) nitric acid is by nitric acid: water volume ratio be 1:1 prepare and
At；The temperature of low-temperature heat is 300 DEG C；
2.6 concentration are 1.00mg/mL antimony standard solution:
It is the oxide layer on >=99.99% high-purity antimony particles (1+9) nitric acid treatment surface by purity, is washed respectively with water and ethyl alcohol
It washs, air-dry；Accurately weigh 0.2000g treated that antimony grain is added (1+1) nitric acid 20mL, covers watch glass in 250mL beaker,
Low-temperature heat, dissolution completely, are removed, cooling, wash watch glass and wall of cup, are moved into 200mL volumetric flask, constant volume shakes up；Wherein institute
Stating (1+9) nitric acid is by nitric acid: water volume ratio is formulated for 1:9, and (1+1) nitric acid is by nitric acid: water volume ratio is 1:1 preparation
It forms；The temperature of low-temperature heat is 300 DEG C；
2.7 concentration are 1.00mg/mL iron standard solution:
Spectroscopic pure di-iron trioxide of the 0.2860g through 900 DEG C of calcination 1h is weighed in 250mL beaker, (1+1) hydrochloric acid is added
20mL low-temperature heat dissolution moves into 200mL volumetric flask after cooling, is diluted with water to scale, shakes up；Wherein (1+1) hydrochloric acid is
By hydrochloric acid: water volume ratio is formulated for 1:1；The temperature of low-temperature heat is 300 DEG C；
2.8 concentration are 1.00mg/mL calcium standard solution:
Spectrum pure calcium carbonate of the 0.4994g through 120 DEG C of drying 2h is accurately weighed in 250mL beaker, addition has removed two
(1+1) hydrochloric acid 20mL is added along wall of cup in the water 20mL of carbonoxide, cap upper surface ware by several times, and removing carbon dioxide is boiled in dissolution,
It removes, it is cooling, surface plate and wall of cup are washed, is moved into 200mL volumetric flask, constant volume shakes up；Wherein (1+1) hydrochloric acid is by hydrochloric acid:
Water volume ratio is formulated for 1:1；
2.9 concentration are 1.00mg/mL magnesium standard solution:
Spectroscopic pure magnesia of the 1.6583g through 800 DEG C of drying 2h is accurately weighed in 250mL beaker, addition has removed two
The water 20mL of carbonoxide is added dropwise (1+1) hydrochloric acid to being completely dissolved, and is stirred continuously, and 10mL hydrochloric acid is added, and heating removes nitrogen oxidation
Object, it is cooling, wall of cup is washed, is moved into 1000mL volumetric flask, constant volume shakes up；Wherein (1+1) hydrochloric acid is by hydrochloric acid: water volume ratio
It is formulated for 1:1；Heating temperature is 300 DEG C.
2.10 concentration is 1.00mg/mL aluminum standard solution:
0.2000g spectrum pure metallic aluminum is accurately weighed in 250mL beaker, it is molten that 10mL hydrochloric acid (1+1) low-temperature heat is added
Solution moves into 200mL volumetric flask after cooling, dilute to scale with water, shakes up；Wherein (1+1) hydrochloric acid is by hydrochloric acid: water volume ratio is
1:1 is formulated；The temperature of low-temperature heat is 300 DEG C；
2.11 concentration are 1.00mg/mL manganese standard solution:
It accurately weighs 0.2000g high pure metal manganese (99.99%) to be placed in 250mL beaker, be added 20mL hydrochloric acid (1+1),
Low-temperature heat dissolution, is cooled to room temperature, and moves into 200mL volumetric flask, is diluted with water to scale, shakes up；Wherein (1+1) hydrochloric acid is
By hydrochloric acid: water volume ratio is formulated for 1:1；The temperature of low-temperature heat is 300 DEG C；
2.12 concentration are 1.00mg/mL arsenic standard solution:
It accurately weighs the arsenic that 0.2000g purity is 99.99% to be placed in 250mL beaker, (1+1) nitric acid 10mL, lid is added
Watch glass, low-temperature heat dissolution completely, are removed, are cooled to room temperature, move into 200mL volumetric flask, 5mL nitric acid is added, is diluted with water
To scale, shake up；Wherein (1+1) nitric acid is by nitric acid: water volume ratio is formulated for 1:1；The temperature of low-temperature heat is 300
℃；
(3) preparation of mixed standard solution
3.1 concentration are 100.00 μ g/mL mixed standard solution A:
Copper standard solution, the lead standard solution, iron standard solution, cadmium of the preparation of 20.00mL step (2) are accurately pipetted respectively
Standard solution, cobalt standard solution, nickel standard solution, antimony standard solution, in 200mL volumetric flask, addition 10mL nitric acid, constant volume,
It shakes up；
3.2 concentration are 100.00 μ g/mL mixed standard solution B:
Calcium standard solution, the magnesium standard solution, aluminum standard solution, arsenic of the preparation of 20.00mL step (2) are accurately pipetted respectively
10mL nitric acid is added in 200mL volumetric flask in standard solution, manganese standard solution, and constant volume shakes up；
(4) preparation of series standard working solution A
4.1 zero standard working solution ρ (Cu, Pb, Fe, Cd, CO, Ni, Sb)=0 μ g/mL:
Nitric acid is added in 100mL volumetric flask in the mixed standard solution A for accurately pipetting the preparation of 0.00mL step (3)
5mL, it is dilute to scale with water, it shakes up；
4.2 hybrid standard working solution ρ (Cu, Pb, Fe, Cd, CO, Ni, Sb)=0.10 μ g/mL:
Nitric acid is added in 100mL volumetric flask in the mixed standard solution A for accurately pipetting the preparation of 0.10mL step (3)
5mL, it is dilute to scale with water, it shakes up；
4.3 hybrid standard working solution ρ (Cu, Pb, Fe, Cd, CO, Ni, Sb)=1.00 μ g/mL:
Nitric acid is added in 100mL volumetric flask in the mixed standard solution A for accurately pipetting the preparation of 1.00mL step (3)
5mL, it is dilute to scale with water, it shakes up；
4.4 hybrid standard working solution ρ (Cu, Pb, Fe, Cd, CO, Ni, Sb)=10.00 μ g/mL:
Nitric acid is added in 100mL volumetric flask in the mixed standard solution A for accurately pipetting the preparation of 10.00mL step (3)
5mL, it is dilute to scale with water, it shakes up；
4.5 hybrid standard working solution ρ (Cu, Pb, Fe, Cd, CO, Ni, Sb)=50.00 μ g/mL:
Copper standard solution, the lead standard solution, iron standard solution, cadmium mark of the preparation of 5.00mL step (2) are accurately pipetted respectively
Nitric acid 5mL is added in 100mL volumetric flask in quasi- solution, cobalt standard solution, nickel standard solution, antimony standard solution, dilute extremely with water
Scale shakes up；
(5) preparation of series standard working solution B
5.1 zero standard working solution ρ (Ca, Mg, Al, As, Mn)=0 μ g/mL:
Nitric acid is added in 100mL volumetric flask in the mixed standard solution B for accurately pipetting the preparation of 0.00mL step (3)
5mL, it is dilute to scale with water, it shakes up；
5.2 hybrid standard working solution ρ (Ca, Mg, Al, As, Mn)=0.10 μ g/mL:
Nitric acid is added in 100mL volumetric flask in the mixed standard solution B for accurately pipetting the preparation of 0.10mL step (3)
5mL, it is dilute to scale with water, it shakes up；
5.3 hybrid standard working solution ρ (Ca, Mg, Al, As, Mn)=0.50 μ g/mL:
Nitric acid is added in 100mL volumetric flask in the mixed standard solution B for accurately pipetting the preparation of 0.50mL step (3)
5mL, it is dilute to scale with water, it shakes up；
5.4 hybrid standard working solution ρ (Ca, Mg, Al, As, Mn)=1.00 μ g/mL:
Nitric acid is added in 100mL volumetric flask in the mixed standard solution B for accurately pipetting the preparation of 1.00mL step (3)
5mL, it is dilute to scale with water, it shakes up；
5.5 hybrid standard working solution ρ (Ca, Mg, Al, As, Mn)=10.00 μ g/mL:
Nitric acid is added in 100mL volumetric flask in the mixed standard solution B for accurately pipetting the preparation of 10.00mL step (3)
5mL, it is dilute to scale with water, it shakes up；
(6) zinc abstraction acid leaching residue sample treatment
0.1000-0.5000g zinc abstraction acid leaching residue sample is accurately weighed in 150mL polytetrafluoroethylene beaker, Jia Shuirun
It is wet, 15mL nitric acid, addition 5mL hydrochloric acid complete to sample dissolution after low-temperature heat 10-20min, 5mL hydrofluoric acid, 5mL high is added
Chloric acid, often plus a kind of reagent is both needed to shake up, and continues low-temperature heat, emits opium to wet salt, removes, cooling, is rinsed with water wall of cup,
9mL hydrochloric acid, 1mL nitric acid is added, low-temperature heat is boiled dissolved salts, removed, cooling；It moves into 100mL volumetric flask, constant volume shakes
Even, filtering obtains zinc abstraction acid leaching residue sample solution；Blank assay is carried out in company with sample；The temperature of low-temperature heat is 300 DEG C；
(7) working curve is drawn
7.1 draw working curve:
(1) stablize 30min after the igniting of electronics coupled plasma atomic emission spectrometer；
(2) five kinds of standard working solutions of 4.1-4.5 prepared in measuring process (four) series standard working solution A, to survey
Measuring resulting concentration is abscissa, and peak strength is ordinate after corresponding correction, draws working curve A；
(3) five kinds of standard working solutions of 5.1-5.5 prepared in measuring process (five) series standard working solution B, to survey
Measuring resulting concentration is abscissa, and peak strength is ordinate after corresponding correction, draws working curve B；
(4) measuring process (six) zinc abstraction acid leaching residue sample solution；
The calculating of 7.2 analysis results:
Calculation formula are as follows:In formula: c0Measure the concentration of blank solution, μ g/
mL；
C- measures the concentration of sample solution, μ g/mL；
The constant volume of v- sample solution, mL；
M- sample mass, g；
By step 7.1 and 7.2 can detect simultaneously copper in zinc abstraction acid leaching residue sample solution, lead, iron, cadmium, cobalt, nickel, antimony,
The content of calcium, magnesium, aluminium, arsenic, manganese totally ten two kinds of elements；
(8) co-existing element interference is investigated
Zinc-base when zinc-base bulk concentration is respectively 200ug/mL, 400ug/mL, 600ug/mL in zinc abstraction acid leaching residue is investigated
Interference of the body to element to be measured, being equivalent to zinc ion content is respectively 20%, 40%, 60%, it is determined that zinc-base bulk concentration is not
It is noiseless to element to be measured when greater than 600ug/mL；
(9) detection limit situation
In the step (1) under the conditions of laboratory apparatus, with being free of blank solution METHOD FOR CONTINUOUS DETERMINATION for 11 times of element to be measured,
It is specifically shown in using 3 times of standard deviations of measurement result as detection limit using 10 times of Determination Limits as this method of standard deviation
Table 1；
Detection limit: Cu:0.0093ug/mL；Pb:0.0255ug/mL；Fe:0.0198ug/mL；Cd:0.0048ug/mL；
Co:0.0078ug/mL；Ni:0.0048ug/mL；Sb:0.0144ug/mL；Ca:0.0243ug/mL；Mg:0.0021ug/mL；
Al:0.0132ug/mL；As:0.0105ug/mL；Mn:0.0024ug/mL；
Determination Limit: Cu:0.032ug/mL；Pb:0.085ug/mL；Fe:0.066ug/mL；Cd:0.016ug/mL；Co:
0.026ug/mL；Ni:0.016ug/mL；Sb:0.048ug/mL；Ca:0.081ug/mL；Mg:0.007ug/mL；Al:
0.044ug/mL；As:0.035ug/mL；Mn:0.008ug/mL；
(10) precision situation
After electronics coupled plasma atomic emission spectrometer preheats 40min, the standard solution for being 1 μ g/mL with concentration
Duplicate measurements 11 times, relative standard deviation≤1.5% is specifically shown in Table 2；
The experiment of (11) rate of recovery
To zinc abstraction acid leaching residue sample carry out recovery testu, obtain Cu, Pb, Fe, Cd, Co, Ni, Sb, Ca, Mg, Al,
As, Mn, the rate of recovery respectively 99.60~100.20%, 99.60~100.30%, 99.00~100.00%, 99.40~
99.60%, 95.98~99.87%, 100.00~100.10%, 99.96~100.02%, 100.10~100.60%,
99.20~99.90%, 99.92~100.03%, 100.06~100.10%, 99.60~100.30%, fully meet analysis
The requirement of method, is specifically shown in Table 3；
(12) steadiness
After electronics coupled plasma atomic emission spectrometer preheats 40min, the mixing for being respectively 1 μ g/mL with concentration
Standard working solution ρ (Cu, Pb, Fe, Cd, CO, Ni, Sb), concentration be 1 μ g/mL hybrid standard working solution ρ (Ca, Mg, Al,
As, Mn) in 4h, it measures 1 time, measures 12 times altogether, relative standard deviation≤3%, the linear phase of working curve at interval of 20min
Close coefficients R >=0.999.
The detection limit and Determination Limit (ug/mL) of 1 the method for the present invention of table
The precision test (%) of 2 the method for the present invention of table
3 mark-on reclaims of table test (ug/mL)
Embodiment 2
Remaining step is identical, in step (6) zinc abstraction acid leaching residue sample handling processes, when zinc abstraction acid leaching residue sample
In concentration of element to be measured when being lower than 0.10ug/mL, before zinc abstraction acid leaching residue sample solution constant volume, it is molten that respective element standard is added
Liquid makes concentration of element to be measured in zinc abstraction acid leaching residue sample reach 0.50ug/mL, element to be measured in zinc abstraction acid leaching residue sample
Detectable concentration deduct be added standard solution introduce concentration, then according to step (7) Calculation results, wherein in zinc
Smelting acid leaching residue sample the effect of respective element standard solution is added is to improve the accuracy of analysis result.
The above content is specific preferred embodiment further description to made by the present invention is combined, cannot recognize
Fixed specific implementation of the invention is only limitted to these explanations.For those skilled in the art, do not taking off
Under the premise of from present inventive concept, several simple deduction or replace can also be made, all should be considered as and belong to protection of the invention
Range.
Claims (3)
1. a kind of method that inductively coupled plasma emission spectrography measures multiple metallic element in zinc abstraction acid leaching residue simultaneously,
Be characterized in that: it is measured carries out according to inductively coupled plasma emission spectrography testing principle, including experiment condition, single element
The preparation of standard solution, the preparation of mixed standard solution, the preparation of series standard working solution A, series standard working solution B
Preparation, sample treatment, working curve drafting, co-existing element interference investigation, the experiment of detection limit situation, precision situation, the rate of recovery
And steadiness.
2. inductively coupled plasma emission spectrography measures more metals in zinc abstraction acid leaching residue simultaneously according to claim 1
The method of element, which is characterized in that specifically include following detection process:
(1) experiment condition
1.1 this method scope of applications: this method is suitable for inductively coupled plasma atomic emission spectrum and measures zinc abstraction simultaneously
The measurement of copper, lead, iron, cadmium, cobalt, nickel, antimony, calcium, magnesium, aluminium, arsenic, manganese amount in acid leaching residue, wherein Zn-ef ficiency concentration is not more than
600ug/mL；
The instrument and condition of 1.2 this method: electronics coupled plasma atomic emission spectrometer is U.S.'s thermoelectricity iCAP-7400
Type, 27.12MHZ；Muffle furnace: 1200 DEG C of maximum temperature；Electronic balance: sensibility reciprocal 0.0001g；Baking oven: 50 DEG C~300 DEG C；
U.S.'s thermoelectricity iCAP-7400 type, power 1150W, cooling air 14L/min assist gas 0.7L/min, carrier gas 0.5L/min,
Observed altitude 15mm, time of integration long wave 5s, time of integration shortwave 10s, instrumental resolution≤0.04nm；
Reagent used in 1.3 this method: the density p of hydrochloric acid is 1.19g/mL；The density p of nitric acid is 1.42g/mL, and rank is
GR；Hydrofluoric acid, perchloric acid, dehydrated alcohol, argon gas purity >=99.99%；
The analysis spectral line of 1.4 this method: according to inductively coupled plasma atomic emission spectrometer operational manual rated condition
Start instrument, analysis spectral line Cu:324.754nm；Pb:216.999nm；Fe:238.204nm；Cd:226.502nm；Co:
228.616nm；Ni:231.604nm；Sb:217.581nm；Ca:184.006nm；Mg:285.213nm；Al:309.271nm；
As:189.042nm；Mn:260.569nm；
(2) preparation of single element standard solution
2.1 concentration are 1.00mg/mL copper standard solution:
By the oxide layer on metal copper sheet (1+9) the nitric acid treatment surface that purity is >=99.99%, washed respectively with water and ethyl alcohol
It washs, air-dry, accurately weigh 0.2000g treated that metal copper sheet is added (1+1) nitric acid 20mL, covers in 250mL beaker
Watch glass, low-temperature heat, dissolution completely, are removed, cooling, wash watch glass and wall of cup, are moved into 200mL volumetric flask, constant volume shakes up；
Wherein described (1+9) nitric acid is by nitric acid: water volume ratio is formulated for 1:9, and (1+1) nitric acid is by nitric acid: water volume ratio is
1:1 is formulated；The temperature of low-temperature heat is 300 DEG C；
2.2 concentration are 1.00mg/mL lead standard solution:
By the oxide layer on high-purity lead button (1+9) nitric acid treatment surface that purity is >=99.99%, washed respectively with water and ethyl alcohol
It washs, air-dry；Accurately weigh 0.2000g treated that lead button is added (1+1) nitric acid 20mL, covers watch glass in 250mL beaker,
Low-temperature heat, dissolution completely, are removed, cooling, wash watch glass and wall of cup, are moved into 200mL volumetric flask, constant volume shakes up；Wherein institute
Stating (1+9) nitric acid is by nitric acid: water volume ratio is formulated for 1:9, and (1+1) nitric acid is by nitric acid: water volume ratio is 1:1 preparation
It forms；The temperature of low-temperature heat is 300 DEG C；
2.3 concentration are 1.00mg/mL cadmium standard solution:
By the oxide layer on high purity cadmium grain (1+9) the nitric acid treatment surface that purity is >=99.99%, washed respectively with water and ethyl alcohol
It washs, air-dry；Accurately weigh 0.2000g treated that cadmium grain is added (1+1) nitric acid 20mL, covers watch glass in 250mL beaker,
Low-temperature heat, dissolution completely, are removed, cooling, wash watch glass and wall of cup, are moved into 200mL volumetric flask, constant volume shakes up；Wherein institute
Stating (1+9) nitric acid is by nitric acid: water volume ratio is formulated for 1:9, and (1+1) nitric acid is by nitric acid: water volume ratio is 1:1 preparation
It forms；The temperature of low-temperature heat is 300 DEG C；
2.4 concentration are 1.00mg/mL cobalt standard solution:
The high-purity cobalt powder of 0.2000g is accurately weighed, in 250mL beaker, (1+1) nitric acid 20mL is added, covers watch glass, low temperature adds
Heat, dissolution completely, are removed, cooling, wash watch glass and wall of cup, are moved into 200mL volumetric flask, constant volume shakes up；Wherein (1+1) nitre
Acid is by nitric acid: water volume ratio is formulated for 1:1；The temperature of low-temperature heat is 300 DEG C；
2.5 concentration are 1.00mg/mL nickel standard solution:
By the oxide layer on high purity nickel (1+9) the nitric acid treatment surface that purity is >=99.99%, use respectively water and ethanol washing,
It air-dries；Accurately weigh 0.2000g treated that nickel is added (1+1) nitric acid 20mL, covers watch glass, low temperature in 250mL beaker
Heating, dissolution completely, are removed, cooling, wash watch glass and wall of cup, are moved into 200mL volumetric flask, constant volume shakes up；(1 described in wherein
+ 9) nitric acid is by nitric acid: water volume ratio is formulated for 1:9, and (1+1) nitric acid is by nitric acid: water volume ratio be 1:1 prepare and
At；The temperature of low-temperature heat is 300 DEG C；
2.6 concentration are 1.00mg/mL antimony standard solution:
Be the oxide layer on >=99.99% high-purity antimony particles (1+9) nitric acid treatment surface by purity, use respectively water and ethanol washing,
It air-dries；Accurately weigh 0.2000g treated that antimony grain is added (1+1) nitric acid 20mL, covers watch glass in 250mL beaker, it is low
Temperature heating, dissolution completely, are removed, cooling, wash watch glass and wall of cup, are moved into 200mL volumetric flask, constant volume shakes up；It is wherein described
(1+9) nitric acid is by nitric acid: water volume ratio is formulated for 1:9, and (1+1) nitric acid is by nitric acid: water volume ratio be 1:1 prepare and
At；The temperature of low-temperature heat is 300 DEG C；
2.7 concentration are 1.00mg/mL iron standard solution:
Spectroscopic pure di-iron trioxide of the 0.2860g through 900 DEG C of calcination 1h is weighed in 250mL beaker, (1+1) hydrochloric acid 20mL is added
Low-temperature heat dissolution moves into 200mL volumetric flask after cooling, is diluted with water to scale, shakes up；Wherein (1+1) hydrochloric acid is by salt
Acid: water volume ratio is formulated for 1:1；The temperature of low-temperature heat is 300 DEG C；
2.8 concentration are 1.00mg/mL calcium standard solution:
Spectrum pure calcium carbonate of the 0.4994g through 120 DEG C of drying 2h is accurately weighed in 250mL beaker, addition has removed titanium dioxide
(1+1) hydrochloric acid 20mL is added along wall of cup in the water 20mL of carbon, cap upper surface ware by several times, and dissolution is boiled removing carbon dioxide, removed,
It is cooling, surface plate and wall of cup are washed, is moved into 200mL volumetric flask, constant volume shakes up；Wherein (1+1) hydrochloric acid is by hydrochloric acid: water body
Product ratio is formulated for 1:1；
2.9 concentration are 1.00mg/mL magnesium standard solution:
Spectroscopic pure magnesia of the 1.6583g through 800 DEG C of drying 2h is accurately weighed in 250mL beaker, addition has removed titanium dioxide
The water 20mL of carbon is added dropwise (1+1) hydrochloric acid to being completely dissolved, and is stirred continuously, and 10mL hydrochloric acid is added, and heating removes nitrogen oxides,
It is cooling, wall of cup is washed, is moved into 1000mL volumetric flask, constant volume shakes up；Wherein (1+1) hydrochloric acid is by hydrochloric acid: water volume ratio 1:
1 is formulated；Heating temperature is 300 DEG C.
2.10 concentration are 1.00mg/mL aluminum standard solution:
0.2000g spectrum pure metallic aluminum is accurately weighed in 250mL beaker, 10mL hydrochloric acid (1+1) low-temperature heat dissolution is added, it is cold
But it moves into 200mL volumetric flask afterwards, it is dilute to scale with water, it shakes up；Wherein (1+1) hydrochloric acid is by hydrochloric acid: water volume ratio is matched for 1:1
It makes；The temperature of low-temperature heat is 300 DEG C；
2.11 concentration are 1.00mg/mL manganese standard solution:
It accurately weighs 0.2000g high pure metal manganese (99.99%) to be placed in 250mL beaker, be added 20mL hydrochloric acid (1+1), low temperature
It dissolves by heating, is cooled to room temperature, move into 200mL volumetric flask, be diluted with water to scale, shake up；Wherein (1+1) hydrochloric acid is by salt
Acid: water volume ratio is formulated for 1:1；The temperature of low-temperature heat is 300 DEG C；
2.12 concentration are 1.00mg/mL arsenic standard solution:
It accurately weighs the arsenic that 0.2000g purity is 99.99% to be placed in 250mL beaker, addition (1+1) nitric acid 10mL, lid watch glass,
Low-temperature heat dissolution completely, is removed, is cooled to room temperature, and is moved into 200mL volumetric flask, and 5mL nitric acid is added, is diluted with water to quarter
Degree, shakes up；Wherein (1+1) nitric acid is by nitric acid: water volume ratio is formulated for 1:1；The temperature of low-temperature heat is 300 DEG C；
(3) preparation of mixed standard solution
3.1 concentration are 100.00 μ g/mL mixed standard solution A:
Copper standard solution, the lead standard solution, iron standard solution, cadmium standard of the preparation of 20.00mL step (2) are accurately pipetted respectively
10mL nitric acid is added in 200mL volumetric flask in solution, cobalt standard solution, nickel standard solution, antimony standard solution, and constant volume shakes up；
3.2 concentration is 100.00 μ g/mL mixed standard solution B:
Calcium standard solution, the magnesium standard solution, aluminum standard solution, arsenic standard of the preparation of 20.00mL step (2) are accurately pipetted respectively
10mL nitric acid is added in 200mL volumetric flask in solution, manganese standard solution, and constant volume shakes up；
(4) preparation of series standard working solution A
4.1 zero standard working solution ρ (Cu, Pb, Fe, Cd, CO, Ni, Sb)=0 μ g/mL:
Nitric acid 5mL is added in 100mL volumetric flask in the mixed standard solution A for accurately pipetting the preparation of 0.00mL step (3), uses
Water is dilute to scale, shakes up；
4.2 hybrid standard working solution ρ (Cu, Pb, Fe, Cd, CO, Ni, Sb)=0.10 μ g/mL:
Nitric acid 5mL is added in 100mL volumetric flask in the mixed standard solution A for accurately pipetting the preparation of 0.10mL step (3), uses
Water is dilute to scale, shakes up；
4.3 hybrid standard working solution ρ (Cu, Pb, Fe, Cd, CO, Ni, Sb)=1.00 μ g/mL:
Nitric acid 5mL is added in 100mL volumetric flask in the mixed standard solution A for accurately pipetting the preparation of 1.00mL step (3), uses
Water is dilute to scale, shakes up；
4.4 hybrid standard working solution ρ (Cu, Pb, Fe, Cd, CO, Ni, Sb)=10.00 μ g/mL:
Nitric acid 5mL is added in 100mL volumetric flask in the mixed standard solution A for accurately pipetting the preparation of 10.00mL step (3), uses
Water is dilute to scale, shakes up；
4.5 hybrid standard working solution ρ (Cu, Pb, Fe, Cd, CO, Ni, Sb)=50.00 μ g/mL:
The copper standard solution, lead standard solution, iron standard solution, cadmium standard for accurately pipetting the preparation of 5.00mL step (2) respectively are molten
Nitric acid 5mL is added in 100mL volumetric flask in liquid, cobalt standard solution, nickel standard solution, antimony standard solution, dilute to scale with water,
It shakes up；
(5) preparation of series standard working solution B
5.1 zero standard working solution ρ (Ca, Mg, Al, As, Mn)=0 μ g/mL:
Nitric acid 5mL is added in 100mL volumetric flask in the mixed standard solution B for accurately pipetting the preparation of 0.00mL step (3), uses
Water is dilute to scale, shakes up；
5.2 hybrid standard working solution ρ (Ca, Mg, Al, As, Mn)=0.10 μ g/mL:
Nitric acid 5mL is added in 100mL volumetric flask in the mixed standard solution B for accurately pipetting the preparation of 0.10mL step (3), uses
Water is dilute to scale, shakes up；
5.3 hybrid standard working solution ρ (Ca, Mg, Al, As, Mn)=0.50 μ g/mL:
Nitric acid 5mL is added in 100mL volumetric flask in the mixed standard solution B for accurately pipetting the preparation of 0.50mL step (3), uses
Water is dilute to scale, shakes up；
5.4 hybrid standard working solution ρ (Ca, Mg, Al, As, Mn)=1.00 μ g/mL:
Nitric acid 5mL is added in 100mL volumetric flask in the mixed standard solution B for accurately pipetting the preparation of 1.00mL step (3), uses
Water is dilute to scale, shakes up；
5.5 hybrid standard working solution ρ (Ca, Mg, Al, As, Mn)=10.00 μ g/mL:
Nitric acid 5mL is added in 100mL volumetric flask in the mixed standard solution B for accurately pipetting the preparation of 10.00mL step (3), uses
Water is dilute to scale, shakes up；
(6) zinc abstraction acid leaching residue sample treatment
0.1000-0.5000g zinc abstraction acid leaching residue sample is accurately weighed in 150mL polytetrafluoroethylene beaker, adds water to soak, adds
Enter 15mL nitric acid, dissolved completely after low-temperature heat 10-20min to sample, addition 5mL hydrochloric acid, 5mL hydrofluoric acid, 5mL perchloric acid,
Often plus a kind of reagent is both needed to shake up, and continues low-temperature heat, emits opium to wet salt, removes, cooling is rinsed with water wall of cup, is added
9mL hydrochloric acid, 1mL nitric acid, low-temperature heat are boiled dissolved salts, are removed, cooling；It moves into 100mL volumetric flask, constant volume shakes up, mistake
Filter, obtains zinc abstraction acid leaching residue sample solution；Blank assay is carried out in company with sample；The temperature of low-temperature heat is 300 DEG C；
(7) working curve is drawn
7.1 draw working curve:
(1) stablize 30min after the igniting of electronics coupled plasma atomic emission spectrometer；
(2) five kinds of standard working solutions of 4.1-4.5 prepared in measuring process (four) series standard working solution A, to measure
The concentration obtained is abscissa, and peak strength is ordinate, drafting working curve A after corresponding correction；
(3) five kinds of standard working solutions of 5.1-5.5 prepared in measuring process (five) series standard working solution B, to measure
The concentration obtained is abscissa, and peak strength is ordinate, drafting working curve B after corresponding correction；
(4) measuring process (six) zinc abstraction acid leaching residue sample solution；
The calculating of 7.2 analysis results:
Calculation formula are as follows:
In formula: c0Measure the concentration of blank solution, μ g/mL；
C- measures the concentration of sample solution, μ g/mL；
The constant volume of v- sample solution, mL；
M- sample mass, g；
By step 7.1 and 7.2 can detect simultaneously copper in zinc abstraction acid leaching residue sample solution, lead, iron, cadmium, cobalt, nickel, antimony, calcium,
The content of magnesium, aluminium, arsenic, manganese totally ten two kinds of elements；
(8) co-existing element interference is investigated
Zinc Matrix pair when zinc-base bulk concentration is respectively 200ug/mL, 400ug/mL, 600ug/mL in zinc abstraction acid leaching residue is investigated
The interference of element to be measured, being equivalent to zinc ion content is respectively 20%, 40%, 60%, it is determined that zinc-base bulk concentration is being not more than
It is noiseless to element to be measured when 600ug/mL；
(9) detection limit situation
In the step (1) under the conditions of laboratory apparatus, with being free of, to survey blank solution METHOD FOR CONTINUOUS DETERMINATION for 11 times of element to be measured
3 times of standard deviations of result are determined as detection limit, using 10 times of Determination Limits as this method of standard deviation；
Detection limit: Cu:0.0093ug/mL；Pb:0.0255ug/mL；Fe:0.0198ug/mL；Cd:0.0048ug/mL；Co:
0.0078ug/mL；Ni:0.0048ug/mL；Sb:0.0144ug/mL；Ca:0.0243ug/mL；Mg:0.0021ug/mL；Al:
0.0132ug/mL；As:0.0105ug/mL；Mn:0.0024ug/mL；
Determination Limit: Cu:0.032ug/mL；Pb:0.085ug/mL；Fe:0.066ug/mL；Cd:0.016ug/mL；Co:
0.026ug/mL；Ni:0.016ug/mL；Sb:0.048ug/mL；Ca:0.081ug/mL；Mg:0.007ug/mL；Al:
0.044ug/mL；As:0.035ug/mL；Mn:0.008ug/mL；
(10) precision situation
After electronics coupled plasma atomic emission spectrometer preheats 40min, repeated with the standard solution that concentration is 1 μ g/mL
Measurement 11 times, relative standard deviation≤1.5%；
The experiment of (11) rate of recovery
To zinc abstraction acid leaching residue sample carry out recovery testu, obtain Cu, Pb, Fe, Cd, Co, Ni, Sb, Ca, Mg, Al, As,
Mn, the rate of recovery respectively 99.60~100.20%, 99.60~100.30%, 99.00~100.00%, 99.40~
99.60%, 95.98~99.87%, 100.00~100.10%, 99.96~100.02%, 100.10~100.60%,
99.20~99.90%, 99.92~100.03%, 100.06~100.10%, 99.60~100.30%, fully meet analysis
The requirement of method；
(12) steadiness
After electronics coupled plasma atomic emission spectrometer preheats 40min, the hybrid standard for being respectively 1 μ g/mL with concentration
Working solution ρ (Cu, Pb, Fe, Cd, CO, Ni, Sb), concentration be 1 μ g/mL hybrid standard working solution ρ (Ca, Mg, Al, As,
Mn it) in 4h, measures 1 time, measures 12 times altogether, relative standard deviation≤3% at interval of 20min, working curve is linearly related
Coefficients R >=0.999.
3. inductively coupled plasma emission spectrography measures more metals in zinc abstraction acid leaching residue simultaneously according to claim 2
The method of element, it is characterised in that: in step (6) zinc abstraction acid leaching residue sample handling processes, when in zinc abstraction acid leaching residue sample
When concentration of element to be measured is lower than 0.10ug/mL, before zinc abstraction acid leaching residue sample solution constant volume, respective element standard solution is added
So that concentration of element to be measured reaches 0.50ug/mL in zinc abstraction acid leaching residue sample, element to be measured in zinc abstraction acid leaching residue sample
Detectable concentration deducts the concentration that the standard solution being added introduces, then according to step (7) Calculation results, wherein in zinc smelting
The effect that respective element standard solution is added in refining acid leaching residue sample is to improve the accuracy of analysis result.
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